CN112090398A - Photocatalytic adsorbent, preparation method thereof and application thereof in sewage treatment - Google Patents
Photocatalytic adsorbent, preparation method thereof and application thereof in sewage treatment Download PDFInfo
- Publication number
- CN112090398A CN112090398A CN202010983076.6A CN202010983076A CN112090398A CN 112090398 A CN112090398 A CN 112090398A CN 202010983076 A CN202010983076 A CN 202010983076A CN 112090398 A CN112090398 A CN 112090398A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- halloysite nanotube
- aerogel
- cds
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 50
- 239000010865 sewage Substances 0.000 title claims abstract description 35
- 239000002071 nanotube Substances 0.000 claims abstract description 219
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 217
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 206
- 239000004964 aerogel Substances 0.000 claims abstract description 184
- -1 arsenic ions Chemical class 0.000 claims abstract description 66
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 164
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 105
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 89
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 239000007864 aqueous solution Substances 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 50
- 238000001914 filtration Methods 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 229960001031 glucose Drugs 0.000 claims description 46
- 239000008103 glucose Substances 0.000 claims description 46
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 41
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 36
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 33
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 30
- 238000011068 loading method Methods 0.000 claims description 28
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 28
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 28
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 26
- 229960002089 ferrous chloride Drugs 0.000 claims description 26
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 26
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 26
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 20
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 16
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 16
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- PMJIKKNFJBDSHO-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxy-3-methylpentane-1,5-diol Chemical compound NCCC[Si](OCC)(OCC)OC(C)(CCO)CCO PMJIKKNFJBDSHO-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 229960003638 dopamine Drugs 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 60
- 230000000694 effects Effects 0.000 abstract description 25
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 19
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 17
- 150000002500 ions Chemical class 0.000 abstract description 13
- 229910052785 arsenic Inorganic materials 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 11
- 241000894006 Bacteria Species 0.000 abstract description 8
- 230000005291 magnetic effect Effects 0.000 abstract description 8
- 241000195493 Cryptophyta Species 0.000 abstract description 7
- 230000001954 sterilising effect Effects 0.000 abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 7
- 230000005389 magnetism Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 35
- 239000002351 wastewater Substances 0.000 description 14
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000003672 processing method Methods 0.000 description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 230000005294 ferromagnetic effect Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229940000489 arsenate Drugs 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
- B01J20/0266—Compounds of S
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Dispersion Chemistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Toxicology (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a photocatalytic adsorbent, a preparation method thereof and application thereof in sewage treatment, wherein the adsorbent is loaded with Fe3O4Graphene oxide-halloysite nanotube aerogel of-CdS-Ag, the specific surface area of which is 3200-3510m2Per g, density of 0.15-0.17mg/cm3. The photocatalytic adsorbent prepared by the invention has the advantages of simple preparation process, low cost and strong operability, and the obtained adsorbent can quickly adsorb and remove heavy metal ions in sewage, such as arsenic ions, cobalt ions, miscellaneous algae and bacteria, organic pollutants and CO2The magnetic field-based photocatalytic adsorbent has high-efficiency adsorption effect, magnetism and sterilization, can be used for removing cobalt ions from sewage, and can be used for efficiently removing the photocatalytic adsorbent after sewage purification, so that aftertreatment is facilitated, and the magnetic field-based photocatalytic adsorbent has wide application prospect.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a photocatalytic adsorbent, a preparation method thereof and application thereof in sewage treatment.
Background
With the continuous acceleration of the industrialization of China, more and more industries related to sewage discharge are involved, including mining, metal smelting, chemical engineering, printing and dyeing, leather, pesticides, feeds and the like, and problems of illegal mining, standard exceeding and pollution discharge and the like of some pollution enterprises are prominent, so that organic pollutants and heavy metal pollution events are in high tendency. The pollution of water caused by unreasonable discharge of industrial wastewater is always a serious environmental problem, heavy metal ions have high toxicity at low concentration, can be accumulated in biological organisms to cause a series of disorders and diseases, the molecular structure of the dye contains unsaturated groups N ≡ N, C = C, -N = O and the like, has different chromaticity, polarity and acid-base property, and the common method is difficult to effectively destroy the conjugated system structure. Therefore, the decomposition of organic pollutants from industrial wastewater, and the separation and removal of heavy metal ions are very important for environmental protection and human health. Arsenic is a semimetal element, odorless and tasteless, commonly found in natural waters and industrial wastewater, and is considered to be the most toxic inorganic pollutant. Arsenic element in an inorganic state mainly exists in a water body in two forms of arsenite and arsenate, the toxicity of the arsenite is 10 times higher than that of the arsenite, and the arsenite can generate great harm to human bodies after being exposed in a high-arsenic environment for a long time.
At present, methods for treating heavy metals mainly include a chemical precipitation method, an activated carbon adsorption method, an ion exchange method and the like. The chemical precipitation method mainly uses limestone alkaline substances to precipitate and separate heavy metal ions, but the heavy metal ions separated from the water body are precipitated into silt of the river bottom, and still cause harm to the environment and organisms; the activated carbon adsorption method and the ion exchange method can well separate heavy metals from water, but the cost is too high, and the application is limited. The existing method for removing cobalt ions in wastewater mainly comprises heat treatment, extraction, adsorption, ion exchange, electrolytic reduction, membrane separation and the like. The heat treatment process comprises evaporation, incineration and vitrification, and a large amount of energy is consumed in the heat treatment process. The ion exchange method needs to develop a new type of ion exchange resin with higher selectivity to remove cobalt ions in the wastewater, and also needs to reduce the process cost. The adsorption method has the advantages of simple process operation, relatively low cost, cyclic utilization and the like, and is proved to be an effective method for removing heavy metal ions including cobalt ions in wastewater.
The photocatalysis technology is a green technology with important application prospect in the fields of energy and environment. In recent years, research and development of photocatalysis application technology are rapid, the novel technology has the advantages of low energy consumption, simple operation process, mild reaction conditions and the like, organic matters in water, air and soil can be completely oxidized into nontoxic and harmless substances at room temperature, and secondary pollution is avoided. Especially has outstanding performance in the aspect of degrading organic pollutants, and can effectively degrade various organic wastewater including antibiotic pharmaceutical wastewater, sulfur-containing fuel wastewater, fermentation production wastewater, fine chemical wastewater and the like so as to reach the discharge standard.
The photocatalysis technology and the adsorption technology are combined into one, so that organic pollutants in sewage can be effectively degraded, and heavy metal ions in the sewage can be efficiently adsorbed, so that the sewage treatment technology is simpler, more convenient and more efficient.
Disclosure of Invention
The invention aims to provide a photocatalytic adsorbent, a preparation method thereof and application thereof in sewage treatment, the photocatalytic adsorbent has the characteristics of simple preparation process, low cost and strong operability, and the obtained adsorbent can quickly adsorb and remove heavy metal ions in sewage, such as arsenic ions, cobalt ions, miscellaneous algae and bacteria, organic pollutants and CO2The magnetic field-based photocatalytic adsorbent has high-efficiency adsorption effect, magnetism and sterilization, can be used for removing cobalt ions from sewage, and can be used for efficiently removing the photocatalytic adsorbent after sewage purification, so that aftertreatment is facilitated, and the magnetic field-based photocatalytic adsorbent has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a photocatalytic adsorbent, wherein the adsorbent is loaded with Fe3O4The graphene oxide-halloysite nanotube aerogel of-CdS-Ag comprises the following preparation methods:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 1-3h to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube;
s3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing a graphene oxide aqueous solution, a carboxyl halloysite nanotube aqueous solution and pure water, stirring for reaction for 1-3h, filtering, treating in a freeze dryer, taking out, and grinding to obtain a graphene oxide-halloysite nanotube aerogel;
s4, loading Fe3O4-CdS-glucosePreparing glucose oxidized graphene-halloysite nanotube aerogel: adding graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion uniformly, adding a composite silane coupling agent, heating to 45-70 ℃, reacting for 0.5-1h, filtering, repeatedly washing a solid with pure water, adding a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose, performing ultrasonic stirring reaction for 1-2h, dropwise adding a chromium chloride solution, performing ultrasonic reaction while dropwise adding, dropwise adding an ammonia water solution, heating to 70-90 ℃, performing ultrasonic reaction while dropwise adding, filtering, repeatedly washing the solid with pure water for 1-3h to obtain a Fe-loaded Fe3O4-graphene oxide of CdS-glucose-halloysite nanotube aerogel;
s5, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of CdS-Ag: will carry Fe3O4Adding graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing ultrasonic treatment to fully disperse the graphene oxide-halloysite nanotube aerogel of-CdS-Ag, dropwise adding silver ammonia solution while stirring, increasing the ultrasonic power to 1500-2000W, performing ultrasonic reaction for 1-3h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded Fe3O4Graphene oxide-halloysite nanotube aerogel of CdS-Ag.
As a further improvement of the invention, the concentration of the graphene oxide aqueous solution is 10-20 mg/mL; the mixed acid is prepared from phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10 (3-5): (1-3) mixing and preparing, wherein the concentration of the hydrochloric acid is 1-3 mol/L; the concentration of the carboxyl halloysite nanotube aqueous solution is 3-5 mg/mL.
As a further improvement of the present invention, the volume ratio of the graphene oxide aqueous solution, the carboxyl halloysite nanotube aqueous solution and pure water in step S3 is (30-50): (15-30): (10-30); the treatment method in the freeze dryer comprises the steps of firstly keeping the temperature at minus 10- (-15) DEG C for 20-30min, then reducing the temperature to minus 20- (-35) DEG C at 3-5 ℃/min, keeping the temperature for 10-20h, then heating the temperature to the room temperature at 3-5 ℃, and taking out the product.
As a further improvement of the invention, the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group or an epoxy group, and the mass ratio of the silane coupling agent to the hydroxyl group or the epoxy group is 1: (1-2), wherein the silane coupling agent with a mercapto group is gamma-mercaptopropyltriethoxysilane or gamma-mercaptopropyltrimethoxysilane; the silane coupling agent with hydroxyl or epoxy is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or bis- (2-hydroxyethyl) -3-aminopropyl triethoxy silane.
As a further improvement of the present invention, in the mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose in step S4, the mass concentration of the sodium sulfide is 0.1 to 0.2mol/L, the mass concentration of the sodium hexametaphosphate is 0.1 to 0.3mol/L, the mass concentration of the ferrous chloride is 0.15 to 0.3mol/L, and the mass concentration of the glucose is 0.01 to 0.05 mol/L; the mass concentration of the chromium chloride solution is 0.1-0.2mol/L, and the mass concentration of the ammonia water solution is 2-5 mol/L.
As a further improvement of the invention, the preparation method of the silver-ammonia solution in the step S5 is that firstly, 0.1-0.5mol/L NaOH solution is used for washing a reaction container, 1-3mol/L silver nitrate solution is added, then 2-5mol/L ammonia water is dropwise added, and the mixture is shaken while being dropwise added until all the initially generated precipitate is dissolved, so that the silver-ammonia solution is prepared.
The invention further protects the photocatalytic adsorbent prepared by the preparation method, and the specific surface area of the photocatalytic adsorbent is 3200-3510m2Per g, density of 0.15-0.17mg/cm3。
As a further improvement of the invention, the load of Fe3O4The graphene oxide-halloysite nanotube aerogel of-CdS-Ag also supports dopamine.
The invention further provides a preparation method of the photocatalytic adsorbent, which comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 1-3h to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube;
s3, preparing the dopamine-graphene oxide-halloysite nanotube aerogel: uniformly mixing a graphene oxide aqueous solution, a carboxyl halloysite nanotube aqueous solution and pure water, adjusting the pH value to 7.5-8.5 by using a phosphate buffer system, adding a dopamine solution under ultrasonic waves, stirring for reacting for 1-3h, transferring into a reaction kettle for sealing, keeping the temperature at 200 ℃ for 3-5h to form gel, sequentially washing by using ethanol and water, treating in a freeze dryer, taking out, and grinding to obtain a dopamine-graphene oxide-halloysite nanotube aerogel;
s4, loading Fe3O4-preparation of dopamine-graphene oxide-halloysite nanotube aerogel of CdS-glucose: adding dopamine-graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion uniformly, adding a composite silane coupling agent, heating to 45-70 ℃, reacting for 0.5-1h, filtering, repeatedly washing a solid with pure water, adding a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose, performing ultrasonic stirring reaction for 1-2h, dropwise adding a chromium chloride solution, performing ultrasonic reaction while dropwise adding, dropwise adding an ammonia water solution, heating to 70-90 ℃, performing ultrasonic reaction while dropwise adding, filtering after 1-3h, repeatedly washing the solid with pure water to obtain a Fe-loaded Fe3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-glucose;
s5, loading Fe3O4-preparation of dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag: will carry Fe3O4Adding dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing ultrasonic treatment to fully disperse the dopamine-graphene oxide-halloysite nanotube aerogel, dropwise adding silver ammonia solution while stirring, increasing the ultrasonic power to 1500-2000W, performing ultrasonic reaction for 1-3h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded nano-tubes3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag.
The invention further protects the application of the photocatalytic adsorbent in sewage treatment.
The invention has the following beneficial effects: the invention is madeThe obtained aerogel is usually a spatial porous network structure formed by mutually connecting graphene oxide molecules and halloysite nanotubes, a basic structural unit is a sheet layer with a unique two-dimensional honeycomb lattice, the layers are mutually stacked to form the spatial porous network structure, the halloysite nanotubes and the graphene oxide are bonded, the mechanical property and the stability of the aerogel are improved to a great extent, the pore structure and the specific surface area of the aerogel are increased, the aerogel can bear the weight which is 17000 times of the self 15000-doped weight, and the aerogel comprises a plurality of pores, mesopores, macropores and micropores, which provide the aerogel with a very large specific surface area and can reach 3510m2The density of the aerogel is reduced by the macropores, and can be as low as 0.15mg/cm3The structure avoids the agglomeration between layers, improves the quality transmission and electron transmission effects of the aerogel, and can effectively improve the carrier to the anhydrous mixed bacteria, the mixed algae substances and the CO2Meanwhile, due to hydroxyl and carboxyl on the surface of the graphene oxide and a carbonyl structure on the surface of the halloysite nanotube, a negative electricity center of the graphene oxide has better adsorption capacity on most heavy metals.
The invention adopts ferrous chloride and ammonia water to react to generate ferric hydroxide, slowly oxidizes the ferric hydroxide under the heating condition to generate ferromagnetic substance ferroferric oxide, chromium chloride and sodium sulfide react under the action of sodium hexametaphosphate to generate photocatalyst cadmium sulfide, glucose and ferroferric oxide are coupled with carrier aerogel under the action of a silane coupling agent with hydroxyl, cadmium sulfide is coupled with the carrier aerogel under the action of a silane coupling agent with sulfydryl, so that the effect of high-efficiency loading is realized, the loaded aerogel can effectively adsorb arsenic (V) ions in wastewater under the action of ferroferric oxide, and efficiently adsorb arsenic (III) ions in the wastewater under the synergistic action of chromium sulfide, on the other hand, due to the existence of ferroferric oxide, the supported aerogel can realize high-efficiency ferromagnetic separation, so that the effect of quickly removing the photocatalytic adsorbent after sewage treatment is realized; the photocatalyst chromium sulfide can also realize the function of efficiently decomposing organic pollutants in water, so that the content of COD in the anhydrous water can be effectively reduced;
fe load3O4Adding graphene oxide-halloysite nanotube aerogel of-CdS-glucose into water, dropwise adding silver ammonia solution under an ultrasonic condition, and generating elemental nano silver in situ to obtain Fe-loaded nano silver3O4The graphene oxide-halloysite nanotube aerogel of-CdS-Ag is beneficial to efficient sterilization in water due to the Ag ions, so that sewage is further purified;
further, loading dopamine on aerogel to obtain Fe load3O4Dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag can enhance CO-pair of aerogel after being modified by dopamine2The adsorption effect of (3);
the photocatalytic adsorbent prepared by the invention has the advantages of simple preparation process, low cost and strong operability, and the obtained adsorbent can quickly adsorb and remove heavy metal ions in sewage, such as arsenic ions, cobalt ions, miscellaneous algae and bacteria, organic pollutants and CO2The magnetic field-based photocatalytic adsorbent has high-efficiency adsorption effect, magnetism and sterilization, can be used for removing cobalt ions from sewage, and can be used for efficiently removing the photocatalytic adsorbent after sewage purification, so that aftertreatment is facilitated, and the magnetic field-based photocatalytic adsorbent has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of a graphene oxide-halloysite nanotube aerogel prepared in example 3 of the present invention;
FIG. 2 is a graph showing the comparison of COD contents of the respective groups in test example 2 of the present invention;
FIG. 3 is a graph comparing the BOD5 content of each group in test example 2 of the present invention;
FIG. 4 is a graph showing a comparison of SS contents among groups in test example 2 of the present invention;
FIG. 5 is a graph comparing the total nitrogen content of each group in test example 2 of the present invention;
FIG. 6 is a graph comparing the total phosphorus content of each group in test example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparing graphene oxide by a Hummers method:
step one, weighing 10G of natural graphite powder (G), 4G of potassium persulfate and 10G of phosphorus pentoxide, adding the natural graphite powder (G), the potassium persulfate and the phosphorus pentoxide into a three-neck flask filled with 24mL of sulfuric acid under the condition of stirring, firstly reacting for 3h in a constant-temperature water bath at 60 ℃, then moving the three-neck flask into a constant-temperature water bath at 25 ℃ for reacting for 5h, performing suction filtration, washing the three-neck flask to be neutral by using ionized water, and drying the three-neck flask in the air to obtain pre-oxidized graphite (P-G);
step two, weighing lg of pre-oxidized graphite, adding the pre-oxidized graphite into a three-neck flask filled with 25mL of sulfuric acid under the condition of stirring, putting the three-neck flask into an ice-water bath, adding 3g of potassium permanganate after the pre-oxidized graphite is completely dissolved, reacting for 2 hours, moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40 minutes, finally adding deionized water, continuing to react for 1 hour at 35 ℃, and finally dropwise adding 30% of H2O2So that the solution turned bright yellow until no more gas was formed. The mixture was filtered by centrifugation while hot and washed to neutrality with a large amount of 5% hydrochloric acid and deionized water. And (3) after the final precipitate is subjected to ultrasonic oscillation for lh, pouring the precipitate into a culture dish, and drying for 24 hours at 90 ℃ to obtain flaky Graphite Oxide (GO).
EXAMPLE 1 preparation of photocatalytic adsorbent
The photocatalytic adsorbent is loaded with Fe3O4Graphene oxide-halloysite nanotube aerogel of CdS-Ag.
Fe load3O4Graphite oxide of-CdS-AgThe preparation method of the alkene-halloysite nanotube aerogel comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning a halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 1h to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 3 mg/mL;
the mixed acid is prepared from phosphoric acid, acetic acid and hydrochloric acid according to a volume ratio of 10: 3: 1, wherein the concentration of the hydrochloric acid is 1 mol/L.
S3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing 30mL of graphene oxide aqueous solution, 15mL of carboxyl halloysite nanotube aqueous solution and 10mL of pure water, stirring for reaction for 1h, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide-halloysite nanotube aerogel;
the treatment method in the freeze dryer comprises maintaining at-10 deg.C for 20min, cooling to-20 deg.C at 3 deg.C/min, maintaining for 10 hr, heating to room temperature at 3 deg.C, and taking out;
s4, loading Fe3O4-preparation of graphene oxide-halloysite nanotube aerogel of CdS-glucose: adding 1g of graphene oxide-halloysite nanotube aerogel into water, uniformly dispersing by 500W ultrasonic waves, adding 0.05g of a composite silane coupling agent, heating to 45 ℃, reacting for 0.5h, filtering, repeatedly washing the solid by pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of sodium sulfide is 0.1mol/L, the mass concentration of sodium hexametaphosphate is 0.1mol/L, the mass concentration of ferrous chloride is 0.15mol/L, and the mass concentration of glucose is 0.01 mol/L), stirring by ultrasonic waves for reaction for 1h, dropwise adding 50mL0.1mol/L of a chromium chloride solution, dropwise adding and ultrasonic fully reacting, dropwise adding 20mL of a 2mol/L ammonia water solution, heating to 70 ℃, dropwise adding and ultrasonic fully reacting, filtering after 1h, repeatedly washing the solid by pure water, obtaining the load Fe3O4-CdS-glucoseThe graphene oxide-halloysite nanotube aerogel of (a);
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with an epoxy group, and the mass ratio of the silane coupling agent to the epoxy group is 1: 1, the silane coupling agent with sulfydryl is gamma-mercaptopropyltriethoxysilane; the silane coupling agent with epoxy groups is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane;
s5, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of CdS-Ag: 1g of the alloy is loaded with Fe3O4Adding graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing 500W ultrasonic treatment to fully disperse the graphene oxide-halloysite nanotube aerogel, dropwise adding 10mL silver ammonia solution while stirring, increasing the ultrasonic power to 1500W, performing ultrasonic reaction for 1h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded Fe3O4-graphene oxide of CdS-Ag-halloysite nanotube aerogel;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.1mol/L NaOH solution, adding 1mol/L silver nitrate solution, then dropwise adding 2mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
EXAMPLE 2 preparation of photocatalytic adsorbent
The photocatalytic adsorbent is loaded with Fe3O4Graphene oxide-halloysite nanotube aerogel of CdS-Ag.
Fe load3O4The preparation method of the graphene oxide-halloysite nanotube aerogel of-CdS-Ag comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 20 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 3 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 5 mg/mL;
the mixed acid is prepared from phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10: 5: 3, wherein the concentration of the hydrochloric acid is 1-3 mol/L.
S3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing 50mL of graphene oxide aqueous solution, 15-30mL of carboxyl halloysite nanotube aqueous solution and 30mL of pure water, stirring for reacting for 3h, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide-halloysite nanotube aerogel;
the treatment method in the freeze dryer comprises maintaining at-15 deg.C for 30min, cooling to-35 deg.C at 5 deg.C/min, maintaining for 20 hr, heating to room temperature at 5 deg.C, and taking out;
s4, loading Fe3O4-preparation of graphene oxide-halloysite nanotube aerogel of CdS-glucose: adding 1g of graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion uniformly at 700W, adding 0.05g of a composite silane coupling agent, heating to 70 ℃ to react for 1h, filtering, repeatedly washing the solid with pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of sodium sulfide is 0.2mol/L, the mass concentration of sodium hexametaphosphate is 0.3mol/L, the mass concentration of ferrous chloride is 0.3mol/L, and the mass concentration of glucose is 0.05 mol/L), performing ultrasonic stirring reaction for 2h, dropwise adding 50mL of 0.2mol/L chromium chloride solution, performing ultrasonic reaction while dropwise adding, dropwise adding 20mL of 2-5mol/L ammonia water solution, heating to 90 ℃, performing ultrasonic reaction while dropwise adding, filtering after 3h, repeatedly washing the solid with pure water, obtaining the load Fe3O4-graphene oxide of CdS-glucose-halloysite nanotube aerogel;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 2, the silane coupling agent with sulfydryl is gamma-mercaptopropyltriethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s5, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of CdS-Ag: 1g of the alloy is loaded with Fe3O4Graphene oxide-erlotin of-CdS-AgAdding the stone nanotube aerogel into pure water, performing 700W ultrasonic treatment to fully disperse the aerogel, dropwise adding 20mL of silver ammonia solution while stirring, increasing the ultrasonic power to 2000W, performing ultrasonic reaction for 1-3h, filtering, repeatedly washing with pure water, drying, and grinding to obtain the Fe-loaded aerogel3O4-graphene oxide of CdS-Ag-halloysite nanotube aerogel;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.5mol/L NaOH solution, adding 3mol/L silver nitrate solution, then dropwise adding 5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
EXAMPLE 3 preparation of photocatalytic adsorbent
The photocatalytic adsorbent is loaded with Fe3O4Graphene oxide-halloysite nanotube aerogel of CdS-Ag.
Fe load3O4The preparation method of the graphene oxide-halloysite nanotube aerogel of-CdS-Ag comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 15 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 2 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 4 mg/mL;
the mixed acid is prepared by mixing phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10:4:2, wherein the concentration of the hydrochloric acid is 2 mol/L.
S3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing 40mL of graphene oxide aqueous solution, 22mL of carboxyl halloysite nanotube aqueous solution and 20mL of pure water, stirring for reaction for 2h, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide-halloysite nanotube aerogel, wherein an SEM image of the graphene oxide-halloysite nanotube aerogel is shown in figure 1, so that a porous honeycomb structure is easily formed;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
s4, loading Fe3O4-preparation of graphene oxide-halloysite nanotube aerogel of CdS-glucose: adding 1g of graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion by 600W, adding 0.05g of a composite silane coupling agent, heating to 65 ℃ for reaction for 0.75h, filtering, repeatedly washing the solid with pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of sodium sulfide is 0.15mol/L, the mass concentration of sodium hexametaphosphate is 0.2mol/L, the mass concentration of ferrous chloride is 0.22mol/L, and the mass concentration of glucose is 0.03 mol/L), performing ultrasonic stirring reaction for 1.5h, dropwise adding 50mL0.15mol/L of a chromium chloride solution, dropwise adding ammonia water while performing ultrasonic reaction, heating to 80 ℃ while performing ultrasonic reaction, after 2h, filtering, repeatedly washing the solid with pure water, obtaining the load Fe3O4-graphene oxide of CdS-glucose-halloysite nanotube aerogel;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s5, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of CdS-Ag: 1g of the alloy is loaded with Fe3O4Adding graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing 600W ultrasonic treatment to fully disperse the graphene oxide-halloysite nanotube aerogel, dropwise adding 15mL silver ammonia solution while stirring, increasing the ultrasonic power to 1700W, performing ultrasonic reaction for 2h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded Fe3O4-graphene oxide of CdS-Ag-halloysite nanotube aerogel;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.3mol/L NaOH solution, adding 2mol/L silver nitrate solution, then dropwise adding 3.5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
Example 4
The photocatalytic adsorbent is loaded with Fe3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag.
Fe load3O4The preparation method of dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 15 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 2 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 4 mg/mL;
the mixed acid is prepared by mixing phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10:4:2, wherein the concentration of the hydrochloric acid is 2 mol/L.
S3, preparing the dopamine-graphene oxide-halloysite nanotube aerogel: uniformly mixing 40mL of graphene oxide aqueous solution, 22mL of carboxyl halloysite nanotube aqueous solution and 20mL of pure water, adjusting the pH value to 8 by using a phosphate buffer system, adding 10mL of 2mol/L dopamine solution under ultrasonic treatment, stirring for reacting for 2 hours, transferring into a reaction kettle for sealing, keeping the temperature at 200 ℃ for 4 hours to form gel, sequentially washing by using ethanol and water, treating in a freeze dryer, taking out, and grinding to obtain dopamine-graphene oxide-halloysite nanotube aerogel;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
the phosphate buffer system is a solution consisting of sodium dihydrogen phosphate and disodium hydrogen phosphate;
s4, loading Fe3O4-preparation of dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag: adding 1g of dopamine-graphene oxide-halloysite nanotube aerogel into water to obtain 600W super aerogelUniformly dispersing by sound, adding 0.05g of composite silane coupling agent, heating to 65 ℃ for reaction for 0.75h, filtering, repeatedly washing the solid by pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of the sodium sulfide is 0.15mol/L, the mass concentration of the sodium hexametaphosphate is 0.2mol/L, the mass concentration of the ferrous chloride is 0.22mol/L and the mass concentration of the glucose is 0.03 mol/L), dropwise adding 50mL0.15mol/L of chromium chloride solution after ultrasonic stirring reaction for 1.5h, dropwise adding 20mL3.5mol/L of ammonia water solution after ultrasonic reaction while dropwise adding, heating to 80 ℃, fully reacting while dropwise adding ultrasonic reaction while adding, filtering after 2h, repeatedly washing the solid by pure water to obtain Fe-loaded Fe3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s5, loading Fe3O4-preparation of dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag: 1g of the alloy is loaded with Fe3O4Adding dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing ultrasonic treatment at 600W to fully disperse the dopamine-graphene oxide-halloysite nanotube aerogel, dropwise adding 15mL of silver ammonia solution while stirring, increasing the ultrasonic power to 1700W, performing ultrasonic reaction for 2h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded Fe3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.3mol/L NaOH solution, adding 2mol/L silver nitrate solution, then dropwise adding 3.5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
Comparative example 1
Compared with example 3, no graphene oxide was added, and the other conditions were the same.
The photocatalytic adsorbent is loaded with Fe3O4-halloysite nanotube aerogel of CdS-Ag.
Fe load3O4The preparation method of the halloysite nanotube aerogel of-CdS-Ag comprises the following steps:
s1, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 2 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 4 mg/mL;
the mixed acid is prepared by mixing phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10:4:2, wherein the concentration of the hydrochloric acid is 2 mol/L.
S2, preparing the halloysite nanotube aerogel: uniformly mixing 172mL of carboxyl halloysite nanotube aqueous solution and 20mL of pure water, stirring for reaction for 2h, filtering, treating in a freeze dryer, taking out, and grinding to obtain a halloysite nanotube aerogel;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
s3, loading Fe3O4-preparation of halloysite nanotube aerogel of CdS-glucose: adding 1g of halloysite nanotube aerogel into water, uniformly dispersing by 600W ultrasonic, adding 0.05g of composite silane coupling agent, heating to 65 ℃, reacting for 0.75h, filtering, repeatedly washing the solid with pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of sodium sulfide is 0.15mol/L, the mass concentration of sodium hexametaphosphate is 0.2mol/L, the mass concentration of ferrous chloride is 0.22mol/L, and the mass concentration of glucose is 0.03 mol/L), after the reaction is carried out for 1.5h by ultrasonic stirring, 50mL0.15mol/L of chromium chloride solution is dropwise added, ultrasonic reaction is carried out while dropwise adding, then 20mL3.5mol/L of ammonia water solution is dropwise added, heating is carried out to 80 ℃, ultrasonic reaction is carried out while dropwise adding, 2h later, filtering is carried out, and the solid is repeatedly washed by pure water, thus obtaining the load Fe.3O4-halloysite nanotube aerogel of CdS-glucose;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s4, loading Fe3O4-preparation of halloysite nanotube aerogel of CdS-Ag: 1g of the alloy is loaded with Fe3O4Adding halloysite nanotube aerogel of-CdS-Ag into pure water, performing ultrasonic treatment at 600W to fully disperse the halloysite nanotube aerogel, dropwise adding 15mL of silver ammonia solution while stirring, increasing the ultrasonic power to 1700W, performing ultrasonic reaction for 2h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded Fe3O4-halloysite nanotube aerogel of CdS-Ag;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.3mol/L NaOH solution, adding 2mol/L silver nitrate solution, then dropwise adding 3.5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
Comparative example 2
Compared with example 3, no halloysite nanotubes were added, and all other conditions were consistent.
The photocatalytic adsorbent is loaded with Fe3O4-graphene oxide aerogel of CdS-Ag.
Fe load3O4The preparation method of the graphene oxide aerogel of-CdS-Ag comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 15 mg/mL;
s2, preparing the graphene oxide aerogel: uniformly mixing 45.9mL of graphene oxide aqueous solution and 20mL of pure water, stirring for reaction for 2h, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide aerogel;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
s4, loading Fe3O4-preparation of graphene oxide aerogel of CdS-glucose: adding 1g of graphene oxide aerogel into water, uniformly dispersing by 600W ultrasonic waves, adding 0.05g of composite silane coupling agent, heating to 65 ℃, reacting for 0.75h, filtering, repeatedly washing the solid with pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of sodium sulfide is 0.15mol/L, the mass concentration of sodium hexametaphosphate is 0.2mol/L, the mass concentration of ferrous chloride is 0.22mol/L, and the mass concentration of glucose is 0.03 mol/L), after the reaction is carried out for 1.5h by ultrasonic stirring, 50mL0.15mol/L of chromium chloride solution is dropwise added, ultrasonic reaction is carried out while dropwise adding, then 20mL3.5mol/L of ammonia water solution is dropwise added, heating is carried out to 80 ℃, ultrasonic reaction is carried out while dropwise adding, 2h later, filtering is carried out, and the solid is repeatedly washed by pure water, thus obtaining the load Fe.3O4-graphene oxide aerogel of CdS-glucose;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s5, loading Fe3O4Preparation of graphene oxide aerogel of CdS-Ag: 1g of the alloy is loaded with Fe3O4Adding graphene oxide aerogel of-CdS-Ag into pure water, performing ultrasonic treatment at 600W to fully disperse the graphene oxide aerogel, dropwise adding 15mL of silver ammonia solution while stirring, increasing the ultrasonic power to 1700W, performing ultrasonic reaction for 2h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded aerogel3O4-graphene oxide gel of CdS-Ag;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.3mol/L NaOH solution, adding 2mol/L silver nitrate solution, then dropwise adding 3.5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
Comparative example 3
Compared with the embodiment 3, the composite silane coupling agent is the silane coupling agent gamma-mercaptopropyl-trimethoxysilane with sulfydryl, and other conditions are consistent.
Comparative example 4
Compared with the embodiment 3, the composite silane coupling agent is the silane coupling agent bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane with all hydroxyl groups, and other conditions are consistent.
Comparative example 5
Compared with example 3, no CdS was added and all other conditions were consistent.
The photocatalytic adsorbent is loaded with Fe3O4-Ag graphene oxide-halloysite nanotube aerogel.
Fe load3O4The preparation method of the graphene oxide-halloysite nanotube aerogel of Ag comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 15 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 2 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 4 mg/mL;
the mixed acid is prepared by mixing phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10:4:2, wherein the concentration of the hydrochloric acid is 2 mol/L.
S3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing 40mL of graphene oxide aqueous solution, 22mL of carboxyl halloysite nanotube aqueous solution and 20mL of pure water, stirring for reaction for 2 hours, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide-halloysite nanotube aerogel;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
s4, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of glucose: 1g of graphene oxide-halloysite sodiumAdding 600W of aerogel of a rice tube into water, performing ultrasonic dispersion uniformly, adding 0.05g of composite silane coupling agent, heating to 65 ℃ for reaction for 0.75h, filtering, repeatedly washing a solid with pure water, adding 50mL of a mixed solution of sodium hexametaphosphate, ferrous chloride and glucose (the mass concentration of the sodium hexametaphosphate is 0.2mol/L, the mass concentration of the ferrous chloride is 0.37mol/L and the mass concentration of the glucose is 0.03 mol/L), performing ultrasonic stirring reaction for 1.5h, dropwise adding 50mL3.5mol/L of ammonia water solution, heating to 80 ℃, performing ultrasonic reaction while dropwise adding, filtering after 2h, repeatedly washing the solid with pure water to obtain Fe-loaded Fe3O4-graphene oxide of glucose-halloysite nanotube aerogel;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s5, loading Fe3O4-preparation of graphene oxide of Ag-halloysite nanotube aerogel: 1g of the alloy is loaded with Fe3O4Adding the-Ag graphene oxide-halloysite nanotube aerogel into pure water, performing 600W ultrasonic treatment to fully disperse the-Ag graphene oxide-halloysite nanotube aerogel, dropwise adding 15mL silver ammonia solution while stirring, increasing the ultrasonic power to 1700W, performing ultrasonic reaction for 2 hours, filtering, repeatedly washing with pure water, drying and grinding to obtain the Fe-loaded Fe3O4-graphene oxide of Ag-halloysite nanotube aerogel;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.3mol/L NaOH solution, adding 2mol/L silver nitrate solution, then dropwise adding 3.5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
Comparative example 6
In comparison with example 3, Fe was not added3O4The other conditions were all the same.
The photocatalytic adsorbent is graphene oxide-halloysite nanotube aerogel loaded with CdS-Ag.
The preparation method of the CdS-Ag loaded graphene oxide-halloysite nanotube aerogel comprises the following steps:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 15 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 2 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 4 mg/mL;
the mixed acid is prepared by mixing phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10:4:2, wherein the concentration of the hydrochloric acid is 2 mol/L.
S3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing 40mL of graphene oxide aqueous solution, 22mL of carboxyl halloysite nanotube aqueous solution and 20mL of pure water, stirring for reaction for 2 hours, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide-halloysite nanotube aerogel;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
s4, preparing the oxidized graphene-halloysite nanotube aerogel loaded with CdS-glucose: adding 1g of graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion by 600W, adding 0.05g of a composite silane coupling agent, heating to 65 ℃ to react for 0.75h, filtering, repeatedly washing the solid with pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate and glucose (the mass concentration of the sodium sulfide is 0.37mol/L, the mass concentration of the sodium hexametaphosphate is 0.2mol/L, and the mass concentration of the glucose is 0.03 mol/L), performing ultrasonic stirring reaction for 1.5h, then dropwise adding 50mL0.15mol/L of a chromium chloride solution, performing ultrasonic reaction while dropwise adding, filtering after 2h, repeatedly washing the solid with pure water to obtain the CdS-glucose loaded graphene oxide-halloysite nanotube aerogel;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane;
s5, preparing the oxidized graphene-halloysite nanotube aerogel loaded with CdS-Ag: adding 1g of CdS-Ag loaded graphene oxide-halloysite nanotube aerogel into pure water, performing 600W ultrasonic treatment to fully disperse the graphene oxide-halloysite nanotube aerogel, dropwise adding 15mL of silver ammonia solution while stirring, increasing the ultrasonic power to 1700W, performing ultrasonic reaction for 2h, filtering, repeatedly washing with pure water, drying and grinding to obtain the CdS-Ag loaded graphene oxide-halloysite nanotube aerogel;
the preparation method of the silver-ammonia solution comprises the steps of firstly washing a reaction container by using 0.3mol/L NaOH solution, adding 2mol/L silver nitrate solution, then dropwise adding 3.5mol/L ammonia water, and oscillating while dropwise adding until the initially generated precipitate is completely dissolved to prepare the silver-ammonia solution.
Comparative example 7
Compared with example 3, Ag was not added and all other conditions were the same.
The photocatalytic adsorbent is loaded with Fe3O4Graphene oxide of CdS-halloysite nanotube aerogel.
Fe load3O4The preparation method of the graphene oxide-halloysite nanotube aerogel of-CdS comprises the following steps of:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 15 mg/mL;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 2 hours to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube with the concentration of 4 mg/mL;
the mixed acid is prepared by mixing phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10:4:2, wherein the concentration of the hydrochloric acid is 2 mol/L.
S3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing 40mL of graphene oxide aqueous solution, 22mL of carboxyl halloysite nanotube aqueous solution and 20mL of pure water, stirring for reaction for 2 hours, filtering, treating in a freeze dryer, taking out, and grinding to obtain graphene oxide-halloysite nanotube aerogel;
the processing method in the freeze dryer comprises maintaining at-12 deg.C for 25min, cooling to-27 deg.C at 4 deg.C/min, maintaining for 15 hr, heating to room temperature at 4 deg.C, and taking out;
s4, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of CdS: adding 1g of graphene oxide-halloysite nanotube aerogel into water, uniformly dispersing by 600W ultrasonic, adding 0.05g of composite silane coupling agent, heating to 65 ℃ to react for 0.75h, filtering, repeatedly washing the solid with pure water, adding 50mL of a mixed solution of sodium sulfide, sodium hexametaphosphate and ferrous chloride (the mass concentration of sodium sulfide is 0.15mol/L, the mass concentration of sodium hexametaphosphate is 0.2mol/L and the mass concentration of ferrous chloride is 0.22 mol/L), stirring by ultrasonic for reaction for 1.5h, dropwise adding 50mL0.15mol/L of chromium chloride solution, dropwise adding and fully reacting by ultrasonic while dropwise adding, dropwise adding 20mL3.5mol/L of ammonia water solution, heating to 80 ℃, sufficiently reacting by ultrasonic while dropwise adding, filtering after 2h, repeatedly washing the solid with pure water to obtain Fe-loaded Fe3O4-graphene oxide of CdS-halloysite nanotube aerogel;
the composite silane coupling agent is a combination of a silane coupling agent with a mercapto group and a silane coupling agent with a hydroxyl group, and the mass ratio of the silane coupling agent to the hydroxyl group is 1: 1.5, the silane coupling agent with the mercapto is gamma-mercaptopropyl trimethoxysilane; the silane coupling agent with hydroxyl is bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane.
Test example 1 adsorption kinetics experiment
(1) Adsorption rate of cobalt ion:
preparing stock solutions containing cobalt ions (II) at a concentration of 50mg/L, adding 30mL of the stock solutions to 11 Erlenmeyer flasks, adding 0.01g of the adsorbents obtained in examples 1-4 and comparative examples 1-7 and a commercially available adsorbent, adjusting the pH to 6.0 with 0.01mol/L hydrochloric acid, and subjecting the Erlenmeyer flasks to constant-temperature shaking adsorption at 25 ℃. The erlenmeyer flasks were removed in the order of 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 90 minutes, and 120 minutes, and after magnetic separation, the cobalt ion concentration of the supernatant was measured by an ultraviolet spectrophotometer, and the saturation adsorption amount was calculated, and the results are shown in tables 1 and 2.
TABLE 1 adsorption rate of cobalt ions as a function of time
TABLE 2 saturated adsorption capacity of cobalt ions
It can be seen that the adsorbent prepared by the embodiment of the invention can realize rapid adsorption of cobalt ions in an aqueous solution within one hour, the adsorption rate can reach 99% within 40min at the fastest, and the adsorption amount is 157.9-172.5mg/mg calculated according to the saturated adsorption amount, which indicates that the adsorption performance is good.
(2) Organic matter adsorption amount:
the results of adsorbing amounts of n-hexane, cyclohexane, turpentine, paraffin oil, methyl silicone oil, etc. by the adsorbents obtained in examples 1 to 3 of the present invention and comparative examples 1 to 7 and commercially available adsorbents are shown in table 3 below.
TABLE 3
It can be seen that the adsorbent prepared by the embodiment of the invention can realize high-efficiency adsorption on n-hexane, cyclohexane, turpentine, paraffin oil and methyl silicone oil within one hour, and can respectively reach 92.7mg/mg, 98.7mg/mg, 113.6mg/mg, 103.7mg/mg and 96.2mg/mg, which shows that the adsorption performance is very good
(3) Adsorption rate of arsenate ions:
preparing stock solutions with the concentration of arsenic (III) acid radical ions of 100mg/L, adding 30mL of the stock solutions into 11 conical flasks, adding 0.01g of the adsorbents obtained in examples 1-4 and comparative examples 1-7 and a commercially available adsorbent, adjusting the pH to 6.0 with 0.01mol/L hydrochloric acid, and carrying out constant-temperature shaking adsorption at 25 ℃ in the conical flasks. The erlenmeyer flask was taken out in the order of 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 90 minutes, and 120 minutes, and after magnetic separation, the arsenate ion concentration of the supernatant was measured with an ultraviolet spectrophotometer, and the saturation adsorption amount was calculated, and the results are shown in tables 4 and 5:
TABLE 4 adsorption rate of arsenate ion as a function of time
TABLE 5 saturated adsorption capacity of arsenate ion
It can be seen that the adsorbent prepared by the embodiment of the invention can realize rapid adsorption of arsenate ions in an aqueous solution within one hour, 99% of adsorption rate can be reached within 30min at the fastest speed, and the adsorption amount is 253.5-292.2mg/mg according to the calculation of saturated adsorption amount, which indicates that the adsorption performance is good.
(3) Adsorption rate of methylene blue:
preparing stock solutions with methylene blue concentration of 200mg/L, adding 30mL of the stock solutions into 11 conical flasks, adding 0.01g of the adsorbents obtained in examples 1-4 and comparative examples 1-7 and a commercially available adsorbent, and subjecting the conical flasks to constant-temperature shaking adsorption at 25 ℃. The erlenmeyer flasks were taken out in the order of 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 90 minutes, and 120 minutes, and after magnetic separation, the methylene blue concentration of the supernatant was measured by an ultraviolet spectrophotometer, and the removal rate after adsorption was measured, and the results are shown in tables 6 and 7.
TABLE 6 adsorption rate of methylene blue as a function of time
TABLE 7 removal rate of methylene blue after adsorption
It can be seen that the adsorbent prepared by the embodiment of the invention can quickly adsorb methylene blue in an aqueous solution within one hour, the adsorption rate can reach 99% within 30min at the fastest, the removal rate after adsorption can reach 90-98%, and the adsorption performance and the degradation performance are good.
Test example 2
The results of the pollutant content tests of the treated sewage and raw water of examples 1 to 3 and comparative examples 1 to 7 of the present invention are shown in FIGS. 2 to 6. Note that: p <0.01, compared to raw water; p is <0.05 compared to raw water.
As can be seen from FIGS. 2 to 6, the method of the present invention is adopted to purify the aquaculture wastewater, so that the Chemical Oxygen Demand (COD) content is less than 21 mg/L; the biochemical oxygen demand BOD5 is less than 5 mg/L; suspended matter SS is less than 9 mg/L; the total nitrogen content is less than 12 mg/L; the total phosphorus content is less than 1.5 mg/L.
Compared with the embodiment 3, the comparative examples 1 and 2 are respectively not added with graphene oxide or halloysite nanotubes, the formed structure porosity is poor, the specific surface area is not large, and therefore, the adsorption effect on each index is obviously reducedThe pores provide great specific surface area for the aerogel, and can reach 3510m2The density of the aerogel is reduced by the macropores, and can be as low as 0.15mg/cm3The structure avoids the agglomeration between layers, improves the quality transmission and electron transmission effects of the aerogel, and can effectively improve the carrier to the anhydrous mixed bacteria, the mixed algae substances and the CO2Meanwhile, due to hydroxyl and carboxyl on the surface of the graphene oxide and a carbonyl structure on the surface of the halloysite nanotube, a negative electricity center of the graphene oxide has better adsorption capacity on most heavy metals;
compared with the example 3, the composite silane coupling agent is only the silane coupling agent gamma-mercaptopropyl trimethoxy silane with sulfydryl or the silane coupling agent bis (2-hydroxyethyl) -3-aminopropyl triethoxy silane with hydroxyl respectively, the coupling of cadmium sulfide and carrier aerogel is better under the existence of the gamma-mercaptopropyl trimethoxy silane, but the coupling of ferroferric oxide and glucose is not favored, meanwhile, the coupling of the bis (2-hydroxyethyl) -3-aminopropyl triethoxy silane is better for the coupling of the ferroferric oxide and the glucose and the carrier aerogel, but the coupling of the cadmium sulfide is not favored, therefore, the adsorption effect of the comparative example 3 on arsenic ions and cobalt ions is obviously reduced, the adsorption effect of the comparative example 4 on organic matters and the adsorption and degradation effect of methylene blue are obviously reduced, and has certain influence on the adsorption of other substances in the sewage.
Comparative examples 5 to 7 compared with example 3, without CdS and Fe respectively3O4Or Ag, the adsorption effect of the comparative example 5 on arsenic ions, the adsorption of organic matters and the adsorption and degradation of methylene blue are obviously reduced, the adsorption effect of the comparative example 6 on arsenic ions and cobalt ions is obviously reduced, and the degradation effect of the comparative example 7 on COD and BOD5 in sewage is obviously reduced. Ag has the sterilization effect in sewage, and the reduction of bacteria can obviously reduce the content of COD and BOD5 in the sewage; the CdS photocatalyst chromium sulfide can also realize the effect of efficiently decomposing organic pollutants in water, so that the COD content in the anhydrous water can be effectively reduced; supporting aerogel in Fe3O4Can effectively adsorb arsenic in the wastewaterV) ions and efficiently adsorbing arsenic (III) ions in the wastewater under the synergistic effect of chromium sulfide, and on the other hand, due to the existence of ferroferric oxide, the loaded aerogel can realize efficient ferromagnetic separation, so that the effect of quickly removing the photocatalytic adsorbent after sewage treatment is realized.
Test example 3
Using Trister II 3020 specific surface area and pore Structure Analyzer (Mike instruments, USA), N2Adsorption-desorption specific surface area test the specific surface areas of the adsorbents in examples 1 to 4 and comparative examples 1 to 7 and the commercially available porous adsorbents were analyzed, and the results are shown in table 8:
| group of | Specific surface area (m)2/g） |
| Example 1 | 3425 |
| Example 2 | 3452 |
| Example 3 | 3510 |
| Example 4 | 3472 |
| Comparative example 1 | 1526 |
| Comparative example 2 | 1725 |
| Comparative example 3 | 3024 |
| Comparative example 4 | 3135 |
| Comparative example 5 | 2956 |
| Comparative example 6 | 3015 |
| Comparative example 7 | 3102 |
| Is commercially available | 1025 |
As can be seen from the above table, the adsorbent prepared in the embodiment of the present invention has a very high specific surface area, is easier to adsorb impurities, heavy metals, and the like in sewage, and facilitates loading Fe3O4CdS and Ag.
Test example 4
0.01g of the adsorbents obtained in examples 1 to 4 and comparative examples 1 to 7 and a commercially available adsorbent were mixed at a low pressure of (<200 kPa), 298K, CO was performed on each sample before and after modification2Static adsorption test, the results are shown in Table 9.
TABLE 9
| Group of | CO2Adsorption amount (mg/mg) |
| Examples1 | 946 |
| Example 2 | 957 |
| Example 3 | 982 |
| Example 4 | 1572 |
| Comparative example 1 | 452 |
| Comparative example 2 | 511 |
| Comparative example 3 | 675 |
| Comparative example 4 | 723 |
| Comparative example 5 | 715 |
| Comparative example 6 | 810 |
| Comparative example 7 | 798 |
| Is commercially available | 472 |
As can be seen from the above table, the sorbents produced in examples 1-4 of the inventionThe adsorbent has better CO adsorption effect2Wherein, in example 4, the effect on CO2The adsorption capacity of the catalyst can reach 1572mg/mg, so that dopamine is loaded on the aerogel to obtain Fe load3O4Dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag can enhance CO-pair of aerogel after being modified by dopamine2The adsorption effect of (1).
Compared with the prior art, the aerogel prepared by the invention is usually a spatial porous network structure formed by mutually connecting graphene oxide molecules and halloysite nanotubes, the basic structural unit is a sheet layer with a unique two-dimensional honeycomb lattice, the layers are mutually stacked to form the spatial porous network structure, the halloysite nanotubes and graphene oxide are bonded, the mechanical property and the stability of the aerogel are improved to a great extent, the pore structure and the specific surface area of the aerogel are increased, the aerogel can bear the weight which is 17000 times of the 15000-fold weight of the aerogel, and the aerogel comprises a plurality of pores, mesopores, macropores, and the pores and the mesopores provide a great specific surface area for the aerogel, and can reach 3510m2The density of the aerogel is reduced by the macropores, and can be as low as 0.15mg/cm3The structure avoids the agglomeration between layers, improves the quality transmission and electron transmission effects of the aerogel, and can effectively improve the carrier to the anhydrous mixed bacteria, the mixed algae substances and the CO2Meanwhile, due to hydroxyl and carboxyl on the surface of the graphene oxide and a carbonyl structure on the surface of the halloysite nanotube, a negative electricity center of the graphene oxide has better adsorption capacity on most heavy metals.
The invention adopts ferrous chloride and ammonia water to react to generate ferric hydroxide, slowly oxidizes the ferric hydroxide under the heating condition to generate ferromagnetic substance ferroferric oxide, chromium chloride and sodium sulfide react under the action of sodium hexametaphosphate to generate photocatalyst cadmium sulfide, glucose and ferroferric oxide are coupled with carrier aerogel under the action of a silane coupling agent with hydroxyl, cadmium sulfide is coupled with the carrier aerogel under the action of a silane coupling agent with sulfydryl, so that the effect of high-efficiency loading is realized, the loaded aerogel can effectively adsorb arsenic (V) ions in wastewater under the action of ferroferric oxide, and efficiently adsorb arsenic (III) ions in the wastewater under the synergistic action of chromium sulfide, on the other hand, due to the existence of ferroferric oxide, the supported aerogel can realize high-efficiency ferromagnetic separation, so that the effect of quickly removing the photocatalytic adsorbent after sewage treatment is realized; the photocatalyst chromium sulfide can also realize the function of efficiently decomposing organic pollutants in water, so that the content of COD in the anhydrous water can be effectively reduced;
fe load3O4Adding graphene oxide-halloysite nanotube aerogel of-CdS-glucose into water, dropwise adding silver ammonia solution under an ultrasonic condition, and generating elemental nano silver in situ to obtain Fe-loaded nano silver3O4The graphene oxide-halloysite nanotube aerogel of-CdS-Ag is beneficial to efficient sterilization in water due to the Ag ions, so that sewage is further purified;
further, loading dopamine on aerogel to obtain Fe load3O4Dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag can enhance CO-pair of aerogel after being modified by dopamine2The adsorption effect of (3);
the photocatalytic adsorbent prepared by the invention has the advantages of simple preparation process, low cost and strong operability, and the obtained adsorbent can quickly adsorb and remove heavy metal ions in sewage, such as arsenic ions, cobalt ions, miscellaneous algae and bacteria, organic pollutants and CO2The magnetic field-based photocatalytic adsorbent has high-efficiency adsorption effect, magnetism and sterilization, can be used for removing cobalt ions from sewage, and can be used for efficiently removing the photocatalytic adsorbent after sewage purification, so that aftertreatment is facilitated, and the magnetic field-based photocatalytic adsorbent has wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the photocatalytic adsorbent is characterized in that the adsorbent is Fe-loaded3O4The graphene oxide-halloysite nanotube aerogel of-CdS-Ag comprises the following preparation methods:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 1-3h to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube;
s3, preparing the graphene oxide-halloysite nanotube aerogel: uniformly mixing a graphene oxide aqueous solution, a carboxyl halloysite nanotube aqueous solution and pure water, stirring for reaction for 1-3h, filtering, treating in a freeze dryer, taking out, and grinding to obtain a graphene oxide-halloysite nanotube aerogel;
s4, loading Fe3O4-preparation of graphene oxide-halloysite nanotube aerogel of CdS-glucose: adding graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion uniformly, adding a composite silane coupling agent, heating to 45-70 ℃, reacting for 0.5-1h, filtering, repeatedly washing a solid with pure water, adding a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose, performing ultrasonic stirring reaction for 1-2h, dropwise adding a chromium chloride solution, performing ultrasonic reaction while dropwise adding, dropwise adding an ammonia water solution, heating to 70-90 ℃, performing ultrasonic reaction while dropwise adding, filtering, repeatedly washing the solid with pure water for 1-3h to obtain a Fe-loaded Fe3O4-graphene oxide of CdS-glucose-halloysite nanotube aerogel;
s5, loading Fe3O4Preparation of graphene oxide-halloysite nanotube aerogel of CdS-Ag: will carry Fe3O4Adding graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing ultrasonic treatment to fully disperse the graphene oxide-halloysite nanotube aerogel of-CdS-Ag, dropwise adding silver ammonia solution while stirring, increasing the ultrasonic power to 1500-2000W, performing ultrasonic reaction for 1-3h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded Fe3O4Graphene oxide-halloysite nanotube aerogel of CdS-Ag.
2. The preparation method according to claim 1, wherein the concentration of the graphene oxide aqueous solution is 10-20 mg/mL; the mixed acid is prepared from phosphoric acid, acetic acid and hydrochloric acid according to the volume ratio of 10 (3-5): (1-3) mixing and preparing, wherein the concentration of the hydrochloric acid is 1-3 mol/L; the concentration of the carboxyl halloysite nanotube aqueous solution is 3-5 mg/mL.
3. The method according to claim 1, wherein the volume ratio of the graphene oxide aqueous solution, the carboxyl halloysite nanotube aqueous solution and pure water in step S3 is (30-50): (15-30): (10-30); the treatment method in the freeze dryer comprises the steps of firstly keeping the temperature at minus 10- (-15) DEG C for 20-30min, then reducing the temperature to minus 20- (-35) DEG C at 3-5 ℃/min, keeping the temperature for 10-20h, then heating the temperature to the room temperature at 3-5 ℃, and taking out the product.
4. The production method according to claim 1, wherein the composite silane coupling agent is a combination of a silane coupling agent having a mercapto group and a silane coupling agent having a hydroxyl group or an epoxy group, and the mass ratio is 1: (1-2), wherein the silane coupling agent with a mercapto group is gamma-mercaptopropyltriethoxysilane or gamma-mercaptopropyltrimethoxysilane; the silane coupling agent with hydroxyl or epoxy is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or bis- (2-hydroxyethyl) -3-aminopropyl triethoxy silane.
5. The production method according to claim 1, wherein the amount concentration of the substance of sodium sulfide in the mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose in step S4 is 0.1 to 0.2mol/L, the amount concentration of the substance of sodium hexametaphosphate is 0.1 to 0.3mol/L, the amount concentration of the substance of ferrous chloride is 0.15 to 0.3mol/L, and the amount concentration of the substance of glucose is 0.01 to 0.05 mol/L; the mass concentration of the chromium chloride solution is 0.1-0.2mol/L, and the mass concentration of the ammonia water solution is 2-5 mol/L.
6. The method of claim 1, wherein the silver ammonia solution is prepared in step S5 by washing the reaction vessel with 0.1-0.5mol/L NaOH solution, adding 1-3mol/L silver nitrate solution, adding 2-5mol/L ammonia water dropwise, and shaking the mixture while adding dropwise until the initially formed precipitate is completely dissolved.
7. The photocatalytic adsorbent prepared by the preparation method according to any one of claims 1 to 6, wherein the photocatalytic adsorbent has a specific surface area of 3200-3510m2Per g, density of 0.15-0.17mg/cm3。
8. The photocatalytic adsorbent according to claim 7, characterized in that the supported Fe3O4The graphene oxide-halloysite nanotube aerogel of-CdS-Ag also supports dopamine.
9. A method for preparing the photocatalytic adsorbent according to claim 8, comprising the steps of:
s1, preparing graphene oxide: preparing graphene oxide by using a Hummers method, and preparing the graphene oxide into a graphene oxide aqueous solution;
s2, preparing a carboxyl halloysite nanotube: purifying and cleaning the halloysite nanotube, adding the halloysite nanotube into mixed acid, acidifying for 1-3h to obtain a carboxyl halloysite nanotube, and preparing an aqueous solution of the carboxyl halloysite nanotube;
s3, preparing the dopamine-graphene oxide-halloysite nanotube aerogel: uniformly mixing a graphene oxide aqueous solution, a carboxyl halloysite nanotube aqueous solution and pure water, adjusting the pH value to 7.5-8.5 by using a phosphate buffer system, adding a dopamine solution under ultrasonic waves, stirring for reacting for 1-3h, transferring into a reaction kettle for sealing, keeping the temperature at 200 ℃ for 3-5h to form gel, sequentially washing by using ethanol and water, treating in a freeze dryer, taking out, and grinding to obtain a dopamine-graphene oxide-halloysite nanotube aerogel;
s4, loading Fe3O4-preparation of dopamine-graphene oxide-halloysite nanotube aerogel of CdS-glucose: adding dopamine-graphene oxide-halloysite nanotube aerogel into water, performing ultrasonic dispersion uniformly, adding a composite silane coupling agent, heating to 45-70 ℃, reacting for 0.5-1h, filtering, repeatedly washing a solid with pure water, adding a mixed solution of sodium sulfide, sodium hexametaphosphate, ferrous chloride and glucose, performing ultrasonic stirring reaction for 1-2h, dropwise adding a chromium chloride solution, performing ultrasonic reaction while dropwise adding, dropwise adding an ammonia water solution, heating to 70-90 ℃, performing ultrasonic reaction while dropwise adding, filtering after 1-3h, repeatedly washing the solid with pure water to obtain a Fe-loaded Fe3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-glucose;
s5, loading Fe3O4-preparation of dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag: will carry Fe3O4Adding dopamine-graphene oxide-halloysite nanotube aerogel of-CdS-Ag into pure water, performing ultrasonic treatment to fully disperse the dopamine-graphene oxide-halloysite nanotube aerogel, dropwise adding silver ammonia solution while stirring, increasing the ultrasonic power to 1500-2000W, performing ultrasonic reaction for 1-3h, filtering, repeatedly washing with pure water, drying, and grinding to obtain Fe-loaded nano-tubes3O4-dopamine-graphene oxide-halloysite nanotube aerogel of CdS-Ag.
10. Use of a photocatalytic adsorbent according to claim 7 or 8 in sewage treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010983076.6A CN112090398B (en) | 2020-09-18 | 2020-09-18 | Photocatalytic adsorbent, preparation method thereof and application thereof in sewage treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010983076.6A CN112090398B (en) | 2020-09-18 | 2020-09-18 | Photocatalytic adsorbent, preparation method thereof and application thereof in sewage treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112090398A true CN112090398A (en) | 2020-12-18 |
| CN112090398B CN112090398B (en) | 2021-10-12 |
Family
ID=73758902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010983076.6A Active CN112090398B (en) | 2020-09-18 | 2020-09-18 | Photocatalytic adsorbent, preparation method thereof and application thereof in sewage treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112090398B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582110A (en) * | 2022-10-18 | 2023-01-10 | 江苏和合环保集团有限公司 | Photocatalytic adsorption material prepared by recycling titanium-containing blast furnace slag and preparation method thereof |
| CN115746863A (en) * | 2022-10-28 | 2023-03-07 | 湖南大学 | Halloysite nanotube-based oxidant sustained-release capsule and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140133094A (en) * | 2013-05-09 | 2014-11-19 | 경북대학교 산학협력단 | Composites of Bacterial Cellulose and Reinforcement Materials and Method for Preparing the Same |
| CN104772120A (en) * | 2015-03-25 | 2015-07-15 | 上海应用技术学院 | Visible photocatalysis renewable graphene-based hydrogel adsorbent, and preparation method and application thereof |
| CN106362803A (en) * | 2016-08-26 | 2017-02-01 | 江苏大学 | Ag-PANI embedded imprinting CdS/Fe3O4/C of Z-like heterojunction and preparation method of Ag-PANI embedded imprinting CdS/Fe3O4/C |
| CN106621835A (en) * | 2016-12-21 | 2017-05-10 | 华南理工大学 | Silver-loaded halloysite-polyvinyl alcohol ultrafiltration membrane and preparation and application thereof |
| CN109276994A (en) * | 2017-07-20 | 2019-01-29 | 陈阳 | A kind of material for air purification that catalytic decomposition ability is strong and preparation method |
| CN109307699A (en) * | 2018-09-21 | 2019-02-05 | 西北师范大学 | The preparation and application of electrochemical sensor based on halloysite nanotubes and graphene |
| CN109692148A (en) * | 2017-10-20 | 2019-04-30 | 天津城建大学 | Three-dimensional netted graphene-galapectite aerogel composite and preparation method thereof |
-
2020
- 2020-09-18 CN CN202010983076.6A patent/CN112090398B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140133094A (en) * | 2013-05-09 | 2014-11-19 | 경북대학교 산학협력단 | Composites of Bacterial Cellulose and Reinforcement Materials and Method for Preparing the Same |
| CN104772120A (en) * | 2015-03-25 | 2015-07-15 | 上海应用技术学院 | Visible photocatalysis renewable graphene-based hydrogel adsorbent, and preparation method and application thereof |
| CN106362803A (en) * | 2016-08-26 | 2017-02-01 | 江苏大学 | Ag-PANI embedded imprinting CdS/Fe3O4/C of Z-like heterojunction and preparation method of Ag-PANI embedded imprinting CdS/Fe3O4/C |
| CN106621835A (en) * | 2016-12-21 | 2017-05-10 | 华南理工大学 | Silver-loaded halloysite-polyvinyl alcohol ultrafiltration membrane and preparation and application thereof |
| CN109276994A (en) * | 2017-07-20 | 2019-01-29 | 陈阳 | A kind of material for air purification that catalytic decomposition ability is strong and preparation method |
| CN109692148A (en) * | 2017-10-20 | 2019-04-30 | 天津城建大学 | Three-dimensional netted graphene-galapectite aerogel composite and preparation method thereof |
| CN109307699A (en) * | 2018-09-21 | 2019-02-05 | 西北师范大学 | The preparation and application of electrochemical sensor based on halloysite nanotubes and graphene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582110A (en) * | 2022-10-18 | 2023-01-10 | 江苏和合环保集团有限公司 | Photocatalytic adsorption material prepared by recycling titanium-containing blast furnace slag and preparation method thereof |
| CN115746863A (en) * | 2022-10-28 | 2023-03-07 | 湖南大学 | Halloysite nanotube-based oxidant sustained-release capsule and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112090398B (en) | 2021-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Janani et al. | Advancements in heavy metals removal from effluents employing nano-adsorbents: way towards cleaner production | |
| Yang et al. | Adsorption and reduction of Cr (VI) by a novel nanoscale FeS/chitosan/biochar composite from aqueous solution | |
| Tyagi et al. | Strategies for nitrate removal from aqueous environment using nanotechnology: a review | |
| CN112090398B (en) | Photocatalytic adsorbent, preparation method thereof and application thereof in sewage treatment | |
| CN112808233A (en) | Fe3O4Preparation method of-biochar composite nano material and method for degrading organic pollutants in water body | |
| Tang et al. | Fabrication of carboxymethyl cellulose and chitosan modified Magnetic alkaline Ca-bentonite for the adsorption of hazardous doxycycline | |
| Nirmala et al. | Removal of toxic metals from wastewater environment by graphene-based composites: A review on isotherm and kinetic models, recent trends, challenges and future directions | |
| Ghosh et al. | Recent progress on the remediation of metronidazole antibiotic as emerging contaminant from water environments using sustainable adsorbents: a review | |
| Hashemian | MnFe2O4/bentonite nano composite as a novel magnetic material for adsorption of acid red 138 | |
| CN113908835A (en) | Preparation and application of active composite material based on non-free-radical efficient mineralization sulfonamide antibiotics | |
| CN109304143B (en) | Preparation method of iron-loaded mesoporous carbon material, product and application thereof | |
| CN113856621B (en) | Preparation and application of Fe-S co-doped biochar material for simultaneously removing Pb-As composite pollution | |
| Zhang et al. | A novel pigeon waste based biochar composite for the removal of heavy metal and organic compound: Performance, products and mechanism | |
| JP2004524967A (en) | Biochemical treatment of wastewater using nanomaterials | |
| CN110862137A (en) | Preparation of sulfuration modified nano zero-valent iron and application of sulfuration modified nano zero-valent iron in treatment of antibiotic resistance gene | |
| CN114835477B (en) | Multifunctional water purification ceramic material | |
| CN102744030B (en) | Graphite oxide-containing nano-material, its preparation method, water treatment agent and its water treatment method | |
| Krstić | Some effective methods for treatment of wastewater from Cu production | |
| Li et al. | Natural Mineral for Remediation of Ironand Manganese-Contaminated Groundwaters. | |
| CN111875052B (en) | Montmorillonite-pyrite composite biological carrier material and preparation method and application method thereof | |
| CN110642448B (en) | Purification method for recycling aquaculture wastewater | |
| CN109928518B (en) | Efficient water purifying agent | |
| Nayeri et al. | A comprehensive review on the recent development of inorganic nano-adsorbents for the removal of heavy metals from water and wastewater | |
| CN112958036A (en) | Zero-valent iron-manganese composite modified carbon nanotube and preparation method and application thereof | |
| CN113289502A (en) | Preparation method of amyloid fiber ferric oxide composite membrane and method for removing phosphate in tail water of municipal sewage treatment plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Cunjin Inventor after: Wang Xuhua Inventor after: Wang Cunhou Inventor after: Zhou Gexiang Inventor after: Hu Mingyun Inventor before: Dong Xihong Inventor before: Jin Feng Inventor before: Wang Cunjian Inventor before: Zhou Gexiang Inventor before: Hu Mingyun |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |