CN111359591A - Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof - Google Patents
Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof Download PDFInfo
- Publication number
- CN111359591A CN111359591A CN202010220852.7A CN202010220852A CN111359591A CN 111359591 A CN111359591 A CN 111359591A CN 202010220852 A CN202010220852 A CN 202010220852A CN 111359591 A CN111359591 A CN 111359591A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- superparamagnetic
- sodium alginate
- water
- solution
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 59
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 59
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 71
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 25
- 239000011574 phosphorus Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 13
- 230000005291 magnetic effect Effects 0.000 abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 abstract description 9
- 239000010452 phosphate Substances 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000003403 water pollutant Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 65
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- -1 lanthanum nitrate modified graphene Chemical class 0.000 description 4
- KQROHCSYOGBQGJ-UHFFFAOYSA-N 5-Hydroxytryptophol Chemical compound C1=C(O)C=C2C(CCO)=CNC2=C1 KQROHCSYOGBQGJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000012851 eutrophication Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012933 kinetic analysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- WYWFMUBFNXLFJK-UHFFFAOYSA-N [Mo].[Sb] Chemical compound [Mo].[Sb] WYWFMUBFNXLFJK-UHFFFAOYSA-N 0.000 description 1
- VKYVBLORDYZASI-UHFFFAOYSA-L [O-]C(C(C(C([O-])=O)O)O)=O.N.[O-2].[K+].[Sb+3] Chemical compound [O-]C(C(C(C([O-])=O)O)O)=O.N.[O-2].[K+].[Sb+3] VKYVBLORDYZASI-UHFFFAOYSA-L 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 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
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- C02F2101/105—Phosphorus compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a superparamagnetic graphene oxide/sodium alginate composite gel material and a preparation method thereof, researches the adsorption effect and the adsorption mechanism of the superparamagnetic graphene oxide/sodium alginate composite gel material on inorganic phosphate, and belongs to the technical field of environmental protection. According to the invention, the magnetic nano particles, the graphene oxide and the gel are combined, so that the dispersion effect of the magnetic nano material is improved, the phenomenon that the magnetic nano particles are easy to agglomerate together and cannot be effectively dispersed is solved, and the adsorption effect is enhanced. The gel material can adsorb eutrophic water phosphate and avoid secondary pollution caused by continuous and repeated existence of phosphorus element in water, and has good application prospect in removing water pollutants. Has certain significance for realizing the cyclic utilization of water resources and the recycling of the adsorption material and the phosphorus element. Meanwhile, the application and development of the magnetic nano material modified by the high molecular polymer in the field of removing inorganic phosphate in water bodies are promoted.
Description
Technical Field
The invention relates to a superparamagnetic graphene oxide/sodium alginate composite gel material and a preparation method thereof, belonging to the technical field of environmental protection.
Background
In recent years, a large amount of nitrogen and phosphorus elements in domestic sewage are discharged into rivers, lakes and reservoirs, so that water eutrophication is easily caused, the quality of underground water is further deteriorated, and the water supply safety of drinking water of residents is threatened. The 2015 publication of environmental status of China shows that the I-III water quality ratio is 64.5%, the IV and V types are 26.7% and the poor V type water quality ratio is 8.8% of 967 national control surface water monitoring sections of 423 main rivers and 62 major lakes (reservoirs) in China. The contribution rate of nitrogen and phosphorus of the domestic sewage of Dian lake, Taihu lake and nest lake with serious eutrophication in China reaches more than 80 percent. According to statistics, the total phosphorus concentration of water quality in lakes and reservoirs nationwide is 0.018-0.97mg/L, which is generally higher than the critical phosphorus threshold value (0.02mg/L) of eutrophication. At present, the phosphorus pollution of seven water systems in China is serious, the total phosphorus concentration in the water body is 0.126-0.286mg/L in the river reach of Guangzhou, and more than ten times of red tides occur at the river mouth every year. The annual average value of the total phosphorus concentration in the water bodies of the Yangtze river and the yellow river is 0.117mg/L and 2.81mg/L respectively. Therefore, the phosphorus pollution of rivers and lakes in China is very serious, and the control of the phosphorus pollution of water bodies becomes an important task for preventing and treating the water pollution. Meanwhile, phosphorus is a non-renewable resource, and phosphorus pollution causes great resource waste.
Graphene (GR) is sp2The thickness of the monoatomic layer formed by hybridized carbon atoms is arranged into a two-dimensional honeycomb crystal, the carbon material is a lamellar high-specific surface area carbon material, and the theoretical specific surface area can reach 2630m2Has very high adsorption capacity, good chemical stability and mechanical property. The GR is oxidized to obtain Graphene Oxide (GO), the surface of the GO contains rich oxygen-containing functional groups such as carbonyl, hydroxyl, epoxy and the like, the GO is easy to combine with metal sulfides, metal atoms, oxides and the like to form GO intercalation composite materials, various toxic and harmful substances in water can be effectively adsorbed and removed, but the self dispersibility of the GO is poor, the GO intercalation composite materials can be directly prepared in aqueous solution, the graphene composite materials formed by adding one or more other materials are mutually beneficial to the performance, a synergistic effect is generated, the comprehensive performance of the composite materials is superior to that of the original composition materials, and therefore different application requirements are met. The patent application of the invention with the publication number of CN1075198339A proposes an application study of preparing a phosphate ion grid by using lanthanum nitrate and lanthanum nitrate modified graphene oxide as a phosphorus locking agent to prevent phosphorus from being released from lake sediment into a water body, however, lanthanum has acute toxicity and has a large toxic effect on water body organisms, and the popularization and application of lanthanum nitrate modified graphene oxide are to be further investigated. Therefore, the novel green environment-friendly material is searched for modifying the graphene to realize the treatment of the phosphorus pollution of the water body and the effective recovery of the phosphorus, so that the purification of the water body is not slow.
The hydrogel is used as a novel low-cost pollution-free adsorption material, and has great potential in the field of pollution treatment. The superparamagnetic nano material has special magnetic properties, can enable the adsorbing material to be recycled under the action of an external magnetic field, avoids being retained in the environment, can be reused after adsorbed pollutants are removed, and has good application prospect. If the superparamagnetic graphene gel is prepared by loading the magnetic nanoparticles with the modified graphene gel, the problem of agglomeration of the magnetic nanoparticles is effectively solved, the adsorption efficiency is improved, secondary pollution can be avoided, and recycling is realized. Currently, the modified composite membrane is prepared by graphene oxide/sodium alginate gel (GO/SA gel) and stainless steel mesh as a supporting material, and is used for oil-water separation research of oil-polluted water sources, however, the modified membrane is weak in water pressure resistance, is easy to be washed by water flow, and needs to be further enhanced in mechanical performance. The patent applications of the invention with the publication numbers of CN104785177A and CN105797685A both provide a preparation method of the composite double-network graphene oxide/sodium alginate gel beads, which has certain pollutant adsorption capacity, but the separation means is single, and the separation cannot be carried out quickly and efficiently after the adsorption is finished, so that the resource waste is great, and the popularization and application range of the composite double-network graphene oxide/sodium alginate gel beads is limited.
The magnetic graphene aerogel material serving as a novel functional magnetic material can be applied to the fields of water treatment, photoelectric materials, wave-absorbing materials and the like, and has a certain application value and market prospect. The invention patent of CN 104226281B discloses a composite hydrogel for adsorbing heavy metal ions and a preparation method thereof, and the invention patent application of CN 107759808A discloses a preparation method of sodium alginate/L-cysteine/reduced graphene oxide magnetic water/aerogel, wherein the preparation methods all relate to magnetic graphene oxide gel materials, but the preparation methods are relatively complex, the cost is high, the composite gel stability is poor, and the composite gel is not beneficial to practical engineering application. Therefore, there is a need in the art for a composite gel with simple preparation process, lower cost and better performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a superparamagnetic GO/SA composite gel prepared by combining a superparamagnetic nano material with graphene oxide and hydrogel, and further improves the mechanical property through low-temperature drying, thereby being beneficial to promoting the application and development of a magnetic nano material modified by a high molecular polymer in the field of removing inorganic phosphate in a water body. The gel material can adsorb eutrophic water phosphate and avoid secondary pollution caused by continuous and repeated existence of phosphorus element in water, and has certain significance for realizing water resource recycling and recycling of the adsorbing material and the phosphorus element.
In order to achieve the above object, a first aspect of the present invention provides a superparamagnetic graphene oxide/sodium alginate composite gel material, wherein the gel material is prepared from superparamagnetic graphene oxide and a sodium alginate solution by an ultrasonic reaction at 55-65 ℃; the weight ratio of the superparamagnetic graphene oxide to the sodium alginate solution is 1: 4; the ratio of sodium alginate to water in the sodium alginate solution is 2: 5.
the superparamagnetic graphene oxide consists of a graphene oxide aqueous solution and FeCl2·4H2And O is prepared to obtain: adding FeCl into graphene oxide aqueous solution2·4H2And O, reacting for 4 hours at the temperature of 80 ℃, and centrifuging, washing and drying to obtain the catalyst. The graphene oxide aqueous solution and FeCl2·4H2The proportion of O is as follows: 3:1.
The invention provides a preparation method of a superparamagnetic graphene oxide/sodium alginate composite gel material, which comprises the following steps:
a. preparation of superparamagnetic graphene oxide: adjusting the pH value of the graphene oxide aqueous solution to 11 by using ammonia water, adding FeCl2·4H2And O, stirring and reacting in a water bath at the temperature of 80 ℃ for 4 hours, finally centrifugally washing the product by using distilled water, and drying in vacuum at room temperature for 12 hours.
b. Preparation of superparamagnetic graphene/sodium alginate composite gel: adding sodium alginate solution into a container, adding superparamagnetic graphene oxide while stirring at 60 ℃, after full reaction and ultrasound, dropwise adding CaCl into the solution2And (4) fully reacting in the solution to obtain the catalyst.
The graphene oxide aqueous solution is obtained by adding graphite oxide into deionized water and ultrasonically stripping for 20-30 min.
The preparation method of the superparamagnetic graphene oxide/sodium alginate composite gel material comprises the following specific steps:
(1) preparing graphene oxide: weighing 0.75g of graphite powder, adding the graphite powder into 100ml of mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (the volume ratio is 9:1), and cooling to 0 ℃ in ice bath; slowly adding 4.5g of potassium permanganate into the mixed solution, strictly controlling the adding speed, controlling the temperature to be below 10 ℃, and ensuring the reaction time to be about 2 hours; placing the reaction vessel in an air bath at 50 ℃ for shaking reaction for 24 hours; after the reaction is finished, pouring the solution into a container containing 100ml of ice water and 2ml of hydrogen peroxide, and discarding the upper solution after cooling; washing the precipitate with 10% dilute hydrochloric acid until no sulfate ion is detected; and then repeatedly cleaning and centrifuging by using a large amount of deionized water, freezing and drying the obtained graphite oxide under vacuum, and adding the graphite oxide into the deionized water for ultrasonic stripping for 20-30 min to obtain a graphene oxide aqueous solution.
(2) Preparation of superparamagnetic graphene oxide: adjusting pH of graphene oxide aqueous solution to 11 with ammonia water, adding FeCl2·4H2And O, stirring and reacting in a water bath at the temperature of 80 ℃ for 4 hours, finally centrifugally washing the product by using distilled water, and drying in vacuum at room temperature for 12 hours.
(3) Preparation of superparamagnetic graphene/sodium alginate composite gel: adding 2g of sodium alginate solution (the ratio of sodium alginate to water is 2: 5) into a container, putting the container into a water bath kettle, adding 0.5g of superparamagnetic graphene oxide while stirring at the temperature of 60 ℃, reacting for 25 minutes, performing ultrasonic treatment for 30 minutes, and dropwise adding 2% CaCl into the obtained solution through a needle tube2In the solution, the reaction was carried out for 2 hours.
FeCl in the reaction process2·4H2The ferrous iron in O is oxidized to generate Fe under the alkaline condition3O4，Fe3O4Strong acting force exists between the nano particles and the graphene oxide molecules. The superparamagnetic graphene oxide/sodium alginate composite gel material prepared by the invention has the following advantages:
1. the composite gel material has good compatibility and better molecular miscibility. The method improves the dispersion effect of the magnetic nano material, solves the problem that the magnetic nano particles are easy to agglomerate together and cannot be effectively dispersed, and enhances the adsorption effect. The time required by adsorption saturation is about 1h, and the adsorption device can adsorb liquid with 3-5 times of the volume of the adsorption device, and has excellent adsorption effect.
2. In the preparation process, the invention is dried at low temperature, the storage time is 0-6 months, and the mechanical property is good.
3. Compared with the prior art, the method has the advantages of simple process, lower cost and better performance, and is convenient for mass production, preparation, popularization and application.
Drawings
FIG. 1: superparamagnetic graphene gel magnetic attraction diagrams.
FIG. 2: superparamagnetic graphene gel water absorption diagram.
FIG. 3: a superparamagnetic graphene gel force diagram; the left side is sodium alginate gel, and the right side is superparamagnetic graphene gel.
FIG. 4: and (3) a superparamagnetic graphene gel XRD characterization pattern.
FIG. 5: superparamagnetic graphene gel SEM characterization picture.
FIG. 6: phosphate standard curve for experimental example 4.
FIG. 7: the pH value has an influence on the adsorption of the superparamagnetic graphene gel.
FIG. 8: adsorption time versus adsorption effect curve of composite gel.
FIG. 9: first order kinetic analysis curve of superparamagnetic graphene gel.
FIG. 10: secondary kinetic analysis curve of superparamagnetic graphene gel.
FIG. 11: a Langmuir isothermal adsorption equation for inorganic phosphate adsorption was fitted to the curve.
FIG. 12: freundlich isothermal adsorption equation for inorganic phosphate adsorption curves were fitted.
Detailed Description
The superparamagnetic graphene/sodium alginate composite gel material of the present invention is further described in detail below with reference to specific examples and experiments, so as to better understand the technical scheme and effects of the present invention.
Example I, preparation of superparamagnetic graphene/sodium alginate composite gel material and adsorption performance investigation
(1) Preparing graphene oxide: weighing 0.75g of graphite powder, adding the graphite powder into 100ml of mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (the volume ratio is 9:1), and cooling to 0 ℃ in ice bath; slowly adding 4.5g of potassium permanganate into the mixed solution, strictly controlling the adding speed, controlling the temperature to be below 10 ℃, and ensuring the reaction time to be about 2 hours; placing the reaction vessel in an air bath at 50 ℃ for shaking reaction for 24 hours; after the reaction is finished, pouring the solution into a container containing 100ml of ice water and 2ml of hydrogen peroxide, and discarding the upper solution after cooling; washing the precipitate with 10% dilute hydrochloric acid until no sulfate ion is detected; and then repeatedly cleaning and centrifuging by using a large amount of deionized water, freezing and drying the obtained graphite oxide in vacuum, and adding the graphite oxide into the deionized water for ultrasonic stripping for 20-30 min to obtain a graphene oxide aqueous solution.
(2) Preparation of superparamagnetic graphene oxide: taking graphene oxide aqueous solution, adjusting the pH to 11 by using ammonia water, adding FeCl2·4H2O, graphene oxide aqueous solution and FeCl2·4H2The proportion of O is as follows: 3:1, stirring and reacting for 4h in a water bath at the temperature of 80 ℃, finally centrifuging and washing the product by using distilled water, and drying for 12h in vacuum at room temperature.
(3) Preparation of superparamagnetic graphene/sodium alginate composite gel: adding 2g of sodium alginate solution (the ratio of sodium alginate to water is 2: 5) into a container, putting the container into a water bath kettle, adding 0.5g of superparamagnetic graphene oxide while stirring at the temperature of 60 ℃, reacting for 25 minutes, performing ultrasonic treatment for 30 minutes, and dropwise adding 2% CaCl into the obtained solution through a needle tube2In the solution, the reaction was carried out for 2 hours.
Experimental example 1: appearance characterization of superparamagnetic graphene/sodium alginate composite gel
(1) The prepared superparamagnetic graphene/sodium alginate composite gel is attracted by a magnet, and as shown in fig. 1, the magnetic material is attracted, so that the gel material has magnetism, the special magnetic property of the magnetic nano material enables the adsorbing material to be recycled under the action of an external magnetic field, and the adsorbed pollutants can be removed and then can be reused.
(2) The superparamagnetic graphene/sodium alginate composite gel has a good water absorption effect, the time required for adsorption saturation is about 1h, the superparamagnetic graphene/sodium alginate composite gel can adsorb liquid with 3-5 times of self volume, and the superparamagnetic graphene/sodium alginate composite gel has an excellent adsorption effect. The adsorbed product is spherical and has smooth surface, as shown in FIG. 2.
(3) Compared with the common gel material, the superparamagnetic graphene/sodium alginate composite gel material has obviously enhanced strength under the deformation condition of bearing the same pressure (1.2N) as shown in figure 3, and is beneficial to actual use and recovery.
Experimental example 2: XRD spectrogram of superparamagnetic graphene/sodium alginate composite gel
The main diffraction peak of the graphene oxide is consulted, and the contrast with the picture shows that the intensity of the diffraction peak of the graphene oxide is seriously reduced, because the amorphous regions are increased after the graphene oxide and the sodium alginate material are mixed, and simultaneously, the crystallinity is reduced. Consult Fe3O4The main diffraction peak of the nano particles is compared with the XRD spectrogram, and Fe can be found3O4The characteristic diffraction peaks of the nanoparticles exist, the mechanism of the nanoparticles is almost unchanged, and the superparamagnetic graphene gel (PVA) porous structure can effectively protect Fe3O4Nanoparticles. However, the intensity of the diffraction peak was reduced, which proves that Fe3O4Interaction force exists between the nano particles and graphene oxide molecules, and the nano particles and the graphene oxide molecules are not simply coated with Fe3O4Nanoparticles (as shown in fig. 4).
Experimental example 3: super paramagnetic graphene/sodium alginate composite gel SEM characterization picture
From the SEM characterization chart of the superparamagnetic graphene/sodium alginate composite gel in FIG. 5, the porous structure of the superparamagnetic graphene gel can be seen, and the structure increases the specific surface area and is beneficial to the absorption of phosphorus.
Example two, study of adsorption performance of superparamagnetic graphene/sodium alginate composite gel material
Experimental example 4: determination of inorganic phosphate adsorption performance of superparamagnetic graphene/sodium alginate composite gel
The determination of phosphorus in water, generally based on the form in which it exists, determines total phosphorus, soluble orthophosphate and soluble total phosphate, respectively. This time, the molybdenum-antimony anti-spectrophotometry is adopted to measure the total phosphorus in water, orthophosphate reacts with molybdic acid and ammonium tartaric acid antimony potassium oxide under the acidic condition to generate phosphomolybdic heteropoly acid, and the phosphomolybdic heteropoly acid is reduced by a reducing agent ascorbic acid to become a purple complex, which is generally called phosphomolybdic blue.
(1) Drawing of standard curve
Weighing a certain mass of superior pure monopotassium phosphate, drying for two hours at 110 ℃, cooling to room temperature, weighing 4.397g of the superior pure monopotassium phosphate, dissolving in water, transferring to a 1000mL volumetric flask, and fixing the volume to obtain a phosphate stock solution with the concentration of 1000 mg/L. 50ml colorimetric tubes with plugs are added with 0, 0.50, 1.00, 3.00, 5.00, 10.0 and 15.0ml of phosphate standard use solution respectively. 1ml of ascorbic acid solution was added to the cuvette and mixed well. After 30s, 2ml of molybdate solution was added and mixed well, and left for 15 min. Absorbance was measured using a 10mm or 30mm cuvette with a zero concentration solution as a reference at a wavelength of 700 nm.
FIG. 6 is obtained as a phosphate standard curve. The relationship between the concentration of the monopotassium phosphate and the absorbance is as follows: y 0.1427x + 0.0135. The concentration can be calculated by directly measuring the absorbance of the solution by a standard curve.
(2) Calculating the adsorption capacity P of the superparamagnetic nanocomposite during adsorption equilibrium:
wherein V is the volume of the solution, L; m is the mass (g) of the adsorption gel; c0And CeInitial and equilibrium concentrations of phosphate in solution (mg/L), respectively.
Experimental example 5: influence of pH value on adsorption of superparamagnetic graphene/sodium alginate composite gel
Weighing 2g of superparamagnetic graphene gel and 50mL of potassium dihydrogen phosphate solution (10mg/L), setting the temperature at 25 ℃, setting different pH values of 5, 6, 7, 8 and 9, continuously stirring and adsorbing for 20min, taking 5mL, and measuring the absorbance. According to the experimental result, the amount of adsorbed phosphate is calculated by looking up the standard curve, when the pH is 7, the superparamagnetic graphene gel has the best adsorption effect on phosphate, and the adsorption effect is smaller as the pH deviates from 7 (as shown in fig. 7). This shows that the water is neutral, which is beneficial to the adsorption of the composite gel to phosphorus. It is possible that the hydrogen ions and hydroxide ions contained in the meta-acid or meta-alkaline solution occupy the limited adsorption sites in the composite hydrogel, hindering the binding of phosphorus to the adsorption sites.
Experimental example 6: adsorption influence of adsorption time on superparamagnetic graphene/sodium alginate composite gel
Weighing 2g of superparamagnetic graphene gel and 50mL of potassium dihydrogen phosphate solution (10mg/L), setting the temperature at 25 ℃, the pH value at 7, and setting the adsorption time at 10min, 20min, 30min, 60min and 120 min. The results in FIG. 8 show that the adsorption rate of the composite gel to phosphate is high in the initial stage, and the adsorption amount is basically kept unchanged when the time exceeds 60min, which indicates that the adsorption equilibrium is reached.
Experimental example 7: adsorption kinetics of superparamagnetic graphene/sodium alginate composite gel
The kinetics of the adsorption process are very important for the adsorption process. The dynamic adsorption process of experiment 6 was analyzed by using first and second order kinetic models to investigate the adsorption kinetics of phosphate in the composite hydrogel. The secondary dynamics of the superparamagnetic graphene gel obtained from fig. 9 and 10 are more significant, which indicates that the fitting effect of the secondary dynamics model is better. Therefore, the super-paramagnetic graphene gel is used for absorbing inorganic phosphate in a water body by two-stage dynamics.
Experimental example 8: adsorption isothermal analysis of superparamagnetic graphene/sodium alginate composite gel
Fitting the adsorption isotherms to the experimental data can help understand the nature of the composite material to adsorb inorganic phosphate. The Langmuir isothermal adsorption equation and the Fruendlich isothermal adsorption equation are widely applied.
The linear form of the Langmuir isothermal adsorption equation is as follows:
the Fruendlich isothermal adsorption equation is in linear form as follows:
the Langmuir isothermal adsorption equation fitting result has a better linear relation as can be seen from a Langmuir isothermal adsorption equation fitting curve and a Freundlich isothermal adsorption equation fitting curve drawn from data measured by superparamagnetic graphene gel. The Langmuir isothermal adsorption equation fit results in a linear correlation coefficient of 0.999, which is greater than the linear fit coefficient of the Fruendlich isothermal adsorption equation 0.9972 (FIGS. 11, 12). Therefore, the adsorption behavior of the superparamagnetic graphene gel on inorganic phosphate in water can be better described by a Langmuir isothermal adsorption equation. The Langmuir theory of adsorption assumes negligible interactions between adsorbed molecules, that solutes are approximately equal in volume to solvent molecules or have the same adsorption sites, and that is mainly suitable for homogeneous surfaces, and is monolayer adsorption. The Fruendlich isothermal adsorption equation assumes a heterogeneous adsorption process and is an empirical equation based on multi-molecular-layer adsorption, and because the surfaces of the adsorbents have different adsorption sites, the adsorption energy is different. Although the Fruendlich isothermal adsorption equation has a fitting coefficient not as high as that of Langmuir isothermal adsorption equation, the correlation reaches 0.99, so that physical adsorption and chemical adsorption may exist on the surface of the adsorbent at the same time.
Claims (7)
1. A superparamagnetic graphene oxide/sodium alginate composite gel material is characterized in that the gel material is prepared by carrying out ultrasonic reaction on superparamagnetic graphene oxide and a sodium alginate solution at the temperature of 55-65 ℃; the weight ratio of the superparamagnetic graphene oxide to the sodium alginate solution is 1: 4; the ratio of sodium alginate to water in the sodium alginate solution is 2: 5.
2. the superparamagnetic graphene oxide/sodium alginate composite gel material as claimed in claim 1, wherein the superparamagnetic graphene oxide is prepared from graphene oxide aqueous solution and FeCl2·4H2And O is prepared to obtain: adding FeCl into graphene oxide aqueous solution2·4H2And O, reacting for 4 hours at the temperature of 80 ℃, and centrifuging, washing and drying to obtain the catalyst.
3. The superparamagnetic graphene oxide/sodium alginate composite gel material as claimed in claim 1 or 2, wherein said graphene oxide aqueous solution and FeCl2·4H2The proportion of O is as follows: 1:3.
4. A preparation method of a superparamagnetic graphene oxide/sodium alginate composite gel material is characterized by comprising the following steps:
a. preparation of superparamagnetic graphene oxide: adjusting the pH value of the graphene oxide aqueous solution to 11 by using ammonia water, adding FeCl2·4H2And O, stirring and reacting in a water bath at the temperature of 80 ℃ for 4 hours, finally centrifugally washing the product by using distilled water, and drying in vacuum at room temperature for 12 hours.
b. Preparation of superparamagnetic graphene/sodium alginate composite gel: adding sodium alginate solution into a container, adding superparamagnetic graphene oxide while stirring at 60 ℃, after full reaction and ultrasound, dropwise adding CaCl into the solution2And (4) fully reacting in the solution to obtain the catalyst.
5. The preparation method of claim 4, wherein the graphene oxide aqueous solution is obtained by adding graphite oxide into deionized water and ultrasonically stripping for 20-30 min.
6. The preparation method as claimed in claim 4, which comprises the following steps:
(1) preparing graphene oxide: weighing 0.75g of graphite powder, adding the graphite powder into 100ml of mixed solution of concentrated sulfuric acid and concentrated phosphoric acid (the volume ratio is 9:1), and cooling to 0 ℃ in ice bath; slowly adding 4.5g of potassium permanganate into the mixed solution, strictly controlling the adding speed, controlling the temperature to be below 10 ℃, and ensuring the reaction time to be about 2 hours; placing the reaction vessel in an air bath at 50 ℃ for shaking reaction for 24 hours; after the reaction is finished, pouring the solution into a container containing 100ml of ice water and 2ml of hydrogen peroxide, and discarding the upper solution after cooling; washing the precipitate with 10% dilute hydrochloric acid until no sulfate ion is detected; and then repeatedly cleaning and centrifuging by using a large amount of deionized water, freezing and drying the obtained graphite oxide under vacuum, and adding the graphite oxide into the deionized water for ultrasonic stripping for 20-30 min to obtain a graphene oxide aqueous solution.
(2) Preparation of superparamagnetic graphene oxide: adjusting pH of graphene oxide aqueous solution to 11 with ammonia water, adding FeCl2·4H2And O, stirring and reacting in a water bath at the temperature of 80 ℃ for 4 hours, finally centrifugally washing the product by using distilled water, and drying in vacuum at room temperature for 12 hours.
(3) Preparation of superparamagnetic graphene/sodium alginate composite gel: adding 2g of sodium alginate solution (the ratio of sodium alginate to water is 2: 5) into a container, putting the container into a water bath kettle, adding 0.5g of superparamagnetic graphene oxide while stirring at the temperature of 60 ℃, reacting for 25 minutes, performing ultrasonic treatment for 30 minutes, and dropwise adding 2% CaCl into the obtained solution through a needle tube2In the solution, the reaction was carried out for 2 hours.
7. The application of the superparamagnetic graphene oxide/sodium alginate composite gel material as defined in claim 1, which is characterized in that the superparamagnetic graphene oxide/sodium alginate composite gel material is used for removing inorganic phosphate in a water body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010220852.7A CN111359591A (en) | 2020-03-26 | 2020-03-26 | Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010220852.7A CN111359591A (en) | 2020-03-26 | 2020-03-26 | Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111359591A true CN111359591A (en) | 2020-07-03 |
Family
ID=71198973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010220852.7A Pending CN111359591A (en) | 2020-03-26 | 2020-03-26 | Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111359591A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871389A (en) * | 2020-08-06 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent |
| CN113999434A (en) * | 2021-11-10 | 2022-02-01 | 招商局重庆交通科研设计院有限公司 | Preparation method of calcium alginate asphalt self-healing capsule with excellent thermal stability |
| CN115121230A (en) * | 2022-07-07 | 2022-09-30 | 北京师范大学珠海校区 | Lanthanum-modified graphene oxide hydrogel and preparation method and application thereof |
| CN115591535A (en) * | 2022-11-09 | 2023-01-13 | 同济大学（Cn） | LDH/GO-melamine foam and application thereof in removing phosphate in water body |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601899A (en) * | 2013-11-26 | 2014-02-26 | 哈尔滨工业大学 | Method for preparing graphene oxide enhanced magnetic hydrogel |
| CN103977748A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Magnetic aerogel and preparation method thereof |
| CN105688813A (en) * | 2016-03-07 | 2016-06-22 | 西北工业大学 | Magnetic graphene adsorbing material for adsorbing phosphorus in water, preparation method and adsorption method |
| CN106633108A (en) * | 2016-11-23 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of aminated graphene-sodium alginate composite gel ball |
| KR20180000383A (en) * | 2016-06-22 | 2018-01-03 | 주식회사 나노스페이스 | Graphene oxide involved porous magnetic materials and the preparation of the same |
| CN107759808A (en) * | 2017-09-18 | 2018-03-06 | 同济大学 | The preparation method of sodium alginate/L cysteines/redox graphene magnetic water/aeroge |
| CN108355623A (en) * | 2018-03-23 | 2018-08-03 | 西安交通大学 | Magnetic oxygenated graphene-Chitosan Composites and its preparation method and application |
| CN109012618A (en) * | 2018-09-12 | 2018-12-18 | 宝泰隆新材料股份有限公司北京分公司 | A kind of preparation method and application of graphene oxide/sodium alginate gel ball |
-
2020
- 2020-03-26 CN CN202010220852.7A patent/CN111359591A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601899A (en) * | 2013-11-26 | 2014-02-26 | 哈尔滨工业大学 | Method for preparing graphene oxide enhanced magnetic hydrogel |
| CN103977748A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Magnetic aerogel and preparation method thereof |
| CN105688813A (en) * | 2016-03-07 | 2016-06-22 | 西北工业大学 | Magnetic graphene adsorbing material for adsorbing phosphorus in water, preparation method and adsorption method |
| KR20180000383A (en) * | 2016-06-22 | 2018-01-03 | 주식회사 나노스페이스 | Graphene oxide involved porous magnetic materials and the preparation of the same |
| CN106633108A (en) * | 2016-11-23 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of aminated graphene-sodium alginate composite gel ball |
| CN107759808A (en) * | 2017-09-18 | 2018-03-06 | 同济大学 | The preparation method of sodium alginate/L cysteines/redox graphene magnetic water/aeroge |
| CN108355623A (en) * | 2018-03-23 | 2018-08-03 | 西安交通大学 | Magnetic oxygenated graphene-Chitosan Composites and its preparation method and application |
| CN109012618A (en) * | 2018-09-12 | 2018-12-18 | 宝泰隆新材料股份有限公司北京分公司 | A kind of preparation method and application of graphene oxide/sodium alginate gel ball |
Non-Patent Citations (1)
| Title |
|---|
| HUONG CHI VU等: "Magnetite graphene oxide encapsulated in alginate beads for enhanced adsorption of Cr(VI) and As(V) from aqueous solutions:Role of crosslinking metal cations in pH control", 《CHEMICAL ENGINEERING JOURNAL》, vol. 307, pages 220 - 229, XP029774640, DOI: 10.1016/j.cej.2016.08.058 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871389A (en) * | 2020-08-06 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent |
| CN111871389B (en) * | 2020-08-06 | 2022-06-21 | 哈尔滨工业大学 | Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent |
| CN113999434A (en) * | 2021-11-10 | 2022-02-01 | 招商局重庆交通科研设计院有限公司 | Preparation method of calcium alginate asphalt self-healing capsule with excellent thermal stability |
| CN115121230A (en) * | 2022-07-07 | 2022-09-30 | 北京师范大学珠海校区 | Lanthanum-modified graphene oxide hydrogel and preparation method and application thereof |
| CN115121230B (en) * | 2022-07-07 | 2023-11-28 | 北京师范大学珠海校区 | Lanthanum-modified graphene oxide hydrogel and preparation method and application thereof |
| CN115591535A (en) * | 2022-11-09 | 2023-01-13 | 同济大学（Cn） | LDH/GO-melamine foam and application thereof in removing phosphate in water body |
| CN115591535B (en) * | 2022-11-09 | 2023-12-05 | 同济大学 | LDH/GO-melamine foam and application thereof in removing phosphate in water body |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du et al. | Activation of porous magnetized biochar by artificial humic acid for effective removal of lead ions | |
| Ma et al. | One-step fabrication of β-cyclodextrin modified magnetic graphene oxide nanohybrids for adsorption of Pb (II), Cu (II) and methylene blue in aqueous solutions | |
| CN111359591A (en) | Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof | |
| Xue et al. | Adsorption of heavy metals in water by modifying Fe3O4 nanoparticles with oxidized humic acid | |
| Zhang et al. | Ultrathin gC 3 N 4 nanosheets coupled with amorphous Cu-doped FeOOH nanoclusters as 2D/0D heterogeneous catalysts for water remediation | |
| Hong et al. | Investigation of the efficient adsorption performance and adsorption mechanism of 3D composite structure La nanosphere-coated Mn/Fe layered double hydrotalcite on phosphate | |
| Liang et al. | Synthesis of a novel three-dimensional porous carbon material and its highly selective Cr (VI) removal in wastewater | |
| Yuan et al. | Facile preparation of MoS2@ Kaolin composite by one-step hydrothermal method for efficient removal of Pb (II) | |
| Zhang et al. | Retracted Article: Superior adsorption capacity of hierarchical iron oxide@ magnesium silicate magnetic nanorods for fast removal of organic pollutants from aqueous solution | |
| Zhou et al. | rGO/CNQDs/ZIF-67 composite aerogel for efficient extraction of uranium in wastewater | |
| Yang et al. | Xanthate modified magnetic activated carbon for efficient removal of cationic dyes and tetracycline hydrochloride from aqueous solutions | |
| CN102824883B (en) | Composite aerogel of graphene/Prussian-blue complexes, and preparation method and application thereof | |
| Li et al. | Methylene blue adsorption from an aqueous solution by a magnetic graphene oxide/humic acid composite | |
| Jin et al. | Removal of Cu (II) ions from aqueous solution by magnetic chitosan-tripolyphosphate modified silica-coated adsorbent: characterization and mechanisms | |
| Liu et al. | Synthesis of magnetic polyaniline/graphene oxide composites and their application in the efficient removal of Cu (II) from aqueous solutions | |
| Liao et al. | The construction of magnetic hydroxyapatite-functionalized pig manure-derived biochar for the efficient uranium separation | |
| Du et al. | PVP modified rGO/CoFe2O4 magnetic adsorbents with a unique sandwich structure and superior adsorption performance for anionic and cationic dyes | |
| Rong et al. | Highly efficient removal of cationic, anionic and neutral dyes by hierarchically porous structured three-dimensional magnetic sulfur/nitrogen co-doped reduced graphene oxide nanohybrid | |
| He et al. | A reusable Fe3O4/GO-COOH nanoadsorbent for Ca2+ and Cu2+ removal from oilfield wastewater | |
| Das et al. | Adsorptive removal of Uranium (VI) using zeolitic imidazole framework (ZIF)-67 from alkaline leach liquor | |
| CN105585711B (en) | A kind of magnetic polyaniline/graphene composite material and its preparation method and application | |
| Zhao et al. | Efficient adsorption of Congo red by micro/nano MIL-88A (Fe, Al, Fe-Al)/chitosan composite sponge: Preparation, characterization, and adsorption mechanism | |
| Jiang et al. | Structural insight into the alginate derived nano-La (OH) 3/porous carbon composites for highly selective adsorption of phosphate | |
| Zhang et al. | Green and simple synthesis of poly (catechol-tetraethylenepentamine)@ aminopropyl-modified silica composite for removing toxic Cr (VI) | |
| Sun et al. | The influential factors towards graphene oxides removal by activated carbons: Activated functional groups vs BET surface area |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200703 |