CN114832784B - Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof - Google Patents
Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof Download PDFInfo
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- CN114832784B CN114832784B CN202210561038.0A CN202210561038A CN114832784B CN 114832784 B CN114832784 B CN 114832784B CN 202210561038 A CN202210561038 A CN 202210561038A CN 114832784 B CN114832784 B CN 114832784B
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- phosphoric acid
- acid modified
- modified silica
- material according
- silicon dioxide
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- -1 Phosphoric acid modified silicon dioxide Chemical class 0.000 title claims abstract description 67
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000004005 microsphere Substances 0.000 title claims abstract description 58
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 11
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 239000000356 contaminant Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 150000007530 organic bases Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 42
- 239000011651 chromium Substances 0.000 description 33
- 238000001179 sorption measurement Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 239000013310 covalent-organic framework Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000011534 incubation Methods 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000012552 review Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000000383 hazardous chemical Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 208000015606 cardiovascular system disease Diseases 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 235000010213 iron oxides and hydroxides Nutrition 0.000 description 1
- 239000004407 iron oxides and hydroxides Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000590 oncogenic Toxicity 0.000 description 1
- 230000002246 oncogenic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 210000003932 urinary bladder Anatomy 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a phosphoric acid modified silicon dioxide microsphere, and a preparation method and application thereof. During preparation, firstly, introducing 3-aminopropyl on the surface of the silica microsphere, and then grafting phosphoric acid on the surface of the 3-aminopropyl functionalized silica microsphere to prepare the silica microsphere material with the surface modified with phosphoric acid. The material has simple preparation process and mild reaction condition, and is successfully applied to the removal of oxygen-containing acid radical ion pollutants in water.
Description
Technical Field
The invention belongs to the field of water treatment, in particular to a phosphoric acid modified silicon dioxide microsphere and a preparation method thereof, and application thereof in oxygen acid ion adsorption of water.
Background
Water pollution is a global significant problem, causing serious health and environmental hazards. The U.S. national environmental protection agency views some inorganic contaminants, particularly the oxyacid radical ions, as contaminants requiring preferential control among the inorganic contaminants of the water (documents 1.Keith et.al"ES&T Special Report:Priority pollutants:I-a perspective view", (Environmental Science & Technology) 1979,13, (4), 416-423. Documents 2.Mon et.al"Metal-organic framework technologies for water remediation: towards a sustainable ecosystem", (Journal of Materials Chemistry A) 2018,6, (12), 4912-4947).
Industrial waste water contaminated with oxyacid radical ions, e.g. CrO 4 2- /Cr 2 O 7 2- HAsO 4 2- /H 2 AsO 4 - /H 3 AsO 3 Severely threatens human health and the natural environment. Arsenic, as a "class a" human carcinogen, can lead to cancer (skin, liver, lung, bladder), cardiovascular and nervous system diseases, and immune problems.
Hexavalent chromium is an oncogenic and mutagenic substance. In China, 5% of the land contaminated with potentially toxic elements is chromium contaminated land (document 3.Bailey et.al"A review of potentially low-cost sorbents for heavy metals '," Water Research "1999,33, (11), 2469-2479. Document 4.Zhuang et.al"High-performance adsorption of chromate by hydrazone-linked guanidinium-based ionic covalent organic frameworks: selective ion exchange', "Separation and Purification Technology" 2021,274,118993. Document 5.Greenstein et.al"Performance comparison of hematite (α -Fe) 2 O 3 ) Polymer composite and core-shell nanofibers as point-of-use filtration platforms for metal sequestration "," Water Research "2019,148,492-503"). In addition, some radioactive oxo acid ion contaminants (SeO) were also detected in the nuclear wastewater 3 2- /SeO 4 2- ) (document 6.Peak et.al"Mechanisms of selenate adsorption on iron oxides and hydroxides '," Environmental Science and Technology "2002,36, (7) 1460-1466. Document 7.Ling et.al"Influence of coexisting ions on the electron efficiency of sulfidated zerovalent iron toward Se (VI) removal', "Chemical Engineering Journal" 2019,378,122124.). Thus, there is an urgent need to explore effective techniques to remove these contaminants from water bodies, thereby meeting our need for clean water. Over the past few decades, numerous techniques have been explored to remove these highly toxic oxyacid radical ions from water, including adsorption, biological treatment, chemical oxidation/reduction, membrane filtration, and the like (8.Hu et.al"Efficient elimination of organic and inorganic pollutants by Biochar and Biochar-based materials,", biochar 2020,2, (11), 47-64, 9.Mishra et.al"Ferrous sulfide and carboxyl-functional alized ferroferric oxide incorporated PVDF-based nanocomposite membranes for simultaneous removal of highly toxic heavy-metal ions from industrial ground water "," Journal of Membrane Science "2020,593,117422"), but most of these methods have some limitations. For example, biological treatment has a problem of generating other secondary pollutants and a large amount of sludge (document 10.Narayani et.al"Chromium-Resistant Bacteria and Their Environmental Condition for Hexavalent Chromium Removal: A Review", "Environmental Science and Technology" 2013,43, (9), 955-1009). Chemical oxidation/reduction produces more toxic substances. Membrane filtration is the adsorption of organics by the hydrophobicity of the membrane, thus reducing the adsorption of heavy metal ions. In addition, the membranes need to be replaced periodically, which is costly. Compared with other methods, the adsorption method has the advantages of simple operation, low energy consumption, recycling and small secondary pollution, and is considered as the most promising application technology (document 11.Bolisetty et.al"Sustainable technologies for water purification from heavy metals:review and analysis'," Chemical Society Reviews "2019,48, (2) 463-487). Conventional adsorbent materials typically suffer from several problems: (I) lower chemical and thermal stability; (II) low adsorption capacity; (III) relatively slow adsorption kinetics and relatively poor selectivity; (IV) the recycling performance is poor. Therefore, the design and development of new adsorbents with high stability, good selectivity and large adsorption capacity have been a research hotspot in the field of oxyacid radical ion removal.
Currently, researchers have designed and prepared different types of adsorbent materials to remove metal oxyanion contaminants from wastewater, such as Metal Organic Frameworks (MOFs) materials, covalent Organic Frameworks (COFs) materials, organic-inorganic hybrid materials, metal oxides, molecularly Imprinted Polymers (MIPs), and layered double metal hydroxide (LDHs) materials. (document 12.Lv et.al"Nanoscale zero valent iron supported on MgAl-LDH-decorated reduced graphene oxide: enhanced performance in Cr (VI) removal, mechanism and regeneration'," Journal of Hazardous Materials "2019,373,176-186.). The cationized MOFs materials synthesized from metal cations and nitrogen-containing ligands can be synthesized by anionsSub-exchange to selectively adsorb SeO in a body of water 4 2- 、HAsO 4 2- 、MnO 4 - And Cr (V) 2 O 7 2- Iso-oxo acid ions (documents 13.Sharma et.al"A water-stable ionic MOF for the selective capture of toxic oxoanions of Se (VI) and As (V) and crystallographic insight into the ion-exchange mechanism '," Angewandte Chemie International Edition "2020,132, (20), 7862-7866. Documents 14.Kumar et.al"Fluorine-containing triazole-reduced silver (I) -based cationic metal-organic framework for separating organic dyes and removing oxoanions from water', "Inorganic Chemistry" 2021,60, (10), 7070-7081.). Cationic COFs materials can selectively remove HAsO from water bodies by anion exchange and hydrogen bonding 4 2- ,SeO 4 2- 、Cr 2 O 7 2- 、CrO 4 2- 、ReO 4 - And MnO 4 - (documents 15.Deng et.al"Hydrolytically stable nanotubular cationic metal-organic framework for rapid and efficient removal of toxic oxo-anions and dyes from water '," Inorganic Chemistry Frontiers ". 2019,58, (4), 2899-2909. Documents 16.Jansone et.al"Guanidinium-based ionic covalent organic framework for rapid and selective removal of toxic Cr (VI) oxoanions from water', "Environmental Science)&Technology 2018,53, (2), 878-883, document 17.Mollick et.al"Nanotrap grafted anion exchangeable hybrid materials for efficient removal of toxic oxoanions from water", "ACS Central Science" 2020,6, (9), 1534-1541. Although MOFs and COFs materials have adjustable pore channels and large specific surface area, and have a certain application prospect in the aspect of removing oxygen acid ions, the synthesis cost is high, and the large-scale preparation is difficult. Metal oxides, while capable of interacting with a wide variety of oxyacid radical ions, are relatively poorly selective. For example, alpha-MnO 2 The nanofibers can remove As (III) and As (V), although both As (III) and As (V) can be in the alpha-MnO range 2 (100) And (110) forming a complex, but the complex formed at the (100) plane is more stable (document 18.Luo et.al“Arsenic adsorption onα-MnO 2 nanofibers and the significance of (100) facet as compared with (110) "," Chemical Engineering Journal "2018,331,492-500. MIPs are highly selective for target oxo acid ions. The selectivity of MIPs depends on the spatial morphology of the MIPs material and on the strength of van der waals forces and hydrogen bonding between the template oxoacid ions and the functional monomers, which are only good for adsorption of template oxoacid ions and have a poor broad spectrum in terms of adsorption of oxoacid ions (documents 19.Fang et.al"Development of an anion imprinted polymer for high and selective removal of arsenite from wastewater '," Science of The Total Environment "2018,639,110-117. Documents 20.Huang et.al"A novel ion-imprinted polymer based on graphene oxide-mesoporous silica nanosheet for fast and efficient removal of chromium (VI) from aqueous solution', "Journal of Colloid and Interface Science" 2018,514,544-553.).
In summary, the forces between the adsorption sites and the oxyacid radical ions in the adsorbent, the stability of the adsorbent, the broad spectrum and the cost are important factors affecting the performance of the adsorbent and its application.
The report that the 3-aminopropyl is grafted on the surface of the silicon dioxide, and the phosphoric acid is grafted on the surface of the silicon dioxide by utilizing the reaction of the amino group and phosphorus oxychloride is not found at all, so as to prepare the silicon dioxide microsphere modified by the phosphoric acid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a phosphoric acid modified silicon dioxide microsphere, a preparation method and application thereof, which can be used for adsorbing and removing oxygen-containing acid ion pollutants in water.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a phosphoric acid modified silica microsphere, the structure of which is schematically shown as follows:
as a preferred embodiment of the present application, the phosphoric acid modified silica microsphere is prepared by grafting phosphoric acid on silica through a silylation reaction and a nucleophilic substitution reaction of amino groups on the surface of the silica microsphere raw material.
As a preferred embodiment of the present application, the silica microsphere materials used are commercially available or self-prepared.
Preferably, the particle size of the silica microsphere raw material is 5 μm, the pore diameter is 10nm, and the specific surface area is 300m 2 /g。
In the second aspect, the invention also provides a preparation method of the phosphoric acid modified silica microsphere material, wherein after 3-aminopropyl is modified on the surface of the silica, phosphorus oxychloride is added, phosphoric acid is grafted on the surface of the silica microsphere through nucleophilic substitution reaction of amino, and the phosphoric acid modified silica microsphere is formed on the surface of the silica microsphere.
As a preferred technical scheme of the application, the preparation method of the phosphoric acid modified silica microsphere comprises the following specific steps:
(1) Modifying 3-aminopropyl functional groups on the surface of the silicon dioxide microsphere:
dispersing the silica microspheres in an organic solvent, dropwise adding 3-aminopropyl trimethoxy silane, carrying out reflux reaction on the mixture for 16-72h, taking out the silica microspheres, washing the silica microspheres, and drying to obtain the 3-aminopropyl modified silica microspheres; wherein the mass volume ratio (m/v) of the silicon dioxide to the 3-aminopropyl trimethoxysilane is 5-10 g: 2-8 mL, preferably 5-10 g:4mL;
(2) Preparation of phosphoric acid modified silica microspheres:
adding the 3-aminopropyl modified silica microspheres dried in the step (1) into a reaction vessel, adding an organic solvent, preferably acetonitrile, into the reaction vessel, performing ultrasonic dispersion, adding an acid binding agent, slowly dropwise adding phosphorus oxychloride into the reaction vessel, reacting for 4-48 hours, preferably 24 hours, in an oil bath at 40+/-5 ℃, washing the product, and drying to obtain phosphoric acid modified silica microspheres; wherein the mass volume ratio (m/v) of the 3-aminopropyl modified silicon dioxide microsphere to phosphorus oxychloride is 1.0-5.0 g: 2-10 mL.
As a preferred technical scheme of the application, the organic solvent used in the step (1) is one or more of toluene, methanol, ethanol and isopropanol.
Preferably, the organic solvent is toluene or ethanol; toluene is more preferred.
Wherein, when the reaction solvent is toluene, the reaction temperature is 110+/-10 ℃.
When the reaction solvent is ethanol, the reaction temperature is 20 to 80 ℃, preferably room temperature (20 to 25 ℃).
As a preferred technical scheme of the application, in the step (1), the silica microspheres can be dispersed in an organic solvent by adopting an ultrasonic dispersion mode.
In the preferred embodiment of the present application, in the step (1), the reaction is followed by washing with absolute ethanol.
In the preferred embodiments of the present application, in the step (1) and the step (2), the drying may be performed by a common drying method such as vacuum drying or freeze drying.
Preferably, the drying temperature is 40-80 ℃ when vacuum drying is selected.
In the step (2), the acid-binding agent is an organic base, specifically methylamine, dimethylamine, triethylamine, pyridine, etc.
Preferably, the acid binding agent is triethylamine.
The invention also discloses the phosphoric acid modified silicon dioxide microsphere prepared by the preparation method.
In a third aspect, the invention also provides the use of the phosphoric acid modified silica microspheres to remove oxo acid ion contaminants from a body of water.
Advantageous effects
Compared with the prior art, the phosphoric acid modified silicon dioxide microsphere and the preparation method and application thereof provided by the invention have the following advantages:
1. the material of the invention has relatively wide applicable pH range, larger saturated adsorption quantity of the oxo acid ions and Cr 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Is full of (1)And the adsorption amounts are respectively 84.15, 24.67 and 66.76mg/g, and after the cyclic use is carried out for 4 times, the removal rate of the oxygen-containing acid ions can still reach more than 86 percent;
2. the method has the advantages of few steps of the synthetic route, mild reaction conditions and high reaction efficiency, and is favorable for the rapid and efficient synthesis of the phosphoric acid modified silica microspheres.
3. The phosphoric acid modified silicon dioxide microsphere provided by the invention has the advantages of simple preparation method, low preparation cost and large-scale production;
4. the modified silica microsphere provided by the invention has excellent selectivity and can be used for preparing NO 3 - And SO 4 2- Under the interference of (2) to Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- The removal rate of (2) is kept stable;
5. three oxygen atoms in tetrahedral phosphoric acid in the synthesized material can be fully coordinated with elements such as chromium, arsenic, selenium and the like in tetrahedral or triangular pyramid type oxyacid radical ions to form a stable octahedral configuration, thereby being beneficial to adsorbing the oxyacid radical ions.
Drawings
FIG. 1 is a schematic representation of the preparation of phosphoric acid modified silica microspheres;
FIG. 2 shows 3mg SiO at different pH values 2 @NH 2 @H 2 PO 3 For (a) 200 mug/L Cr in aqueous solution 2 O 7 2- ,(b)1mg/L AsO 4 3- ,(c)200μg/L SeO 4 2- Is not limited by the removal efficiency of (2);
FIG. 3 is 3mg SiO 2 @NH 2 @H 2 PO 3 For Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Saturated adsorption capacity of (2);
FIG. 4 is 3mg SiO 2 @NH 2 @H 2 PO 3 For 200 mug/L Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- The number of times of recycling of the adsorption;
FIG. 5 is 3mg SiO 2 @NH 2 @H 2 PO 3 At 1mg/L NO 3 - And SO 4 2- To Cr in aqueous solution under the interference of (2) 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Is selected from the group consisting of (1).
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instrumentation used are not manufacturer specific and are considered to be commercially available conventional products.
Example 1 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 6.2g of silica microspheres in 70mL of anhydrous toluene under the action of ultrasound, dropwise adding 4mL of 3-aminopropyl trimethoxysilane, refluxing the final mixture in an oil bath at 103 ℃ for 24h, taking out the silica microspheres, washing the silica microspheres with absolute ethanol, and then drying the silica microspheres in a vacuum drying oven at 80 ℃ for 24h to obtain 3-aminopropyl functionalized silica microspheres (SiO 2 @NH 2 )；
2) 2g of SiO is taken 2 @NH 2 Dispersing into 70mL acetonitrile under the action of ultrasound, adding 16mL triethylamine, slowly dripping 6mL phosphorus oxychloride into the mixture, reacting for 24 hours in an oil bath at 40 ℃, washing the product with acetonitrile, water and absolute ethyl alcohol in sequence, and then drying the product in a vacuum drying oven at 80 ℃ for 24 hours to obtain a phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
Example 2 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 5g of silica microspheres in 30mL of anhydrous toluene under the action of ultrasound, dropwise adding 4mL of 3-aminopropyl trimethoxysilane, refluxing the final mixture in an oil bath at 103 ℃ for 24h, taking out the silica microspheres, washing the silica microspheres with absolute ethyl alcohol, and then drying the silica microspheres in a vacuum drying oven at 80 ℃ for 24h to obtain 3-aminopropyl functionalized silica microspheres (SiO 2 @NH 2 )；
2) 1g of SiO is taken 2 @NH 2 Dispersing into 30mL of acetonitrile under the action of ultrasonic wave, adding 16mL of triethylamine, slowly dripping 6mL of phosphorus oxychloride into the mixture,reacting in 40 deg.C oil bath for 24 hr, washing the product with acetonitrile, water and absolute ethyl alcohol, and drying in vacuum drying oven at 80 deg.C for 24 hr to obtain phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
EXAMPLE 3 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 10g of silica microspheres in 100mL of anhydrous toluene under the action of ultrasound, dropwise adding 4mL of 3-aminopropyl trimethoxysilane, refluxing the final mixture in an oil bath at 103 ℃ for 24h, taking out the silica microspheres, washing the silica microspheres with absolute ethyl alcohol, and then drying the silica microspheres in a vacuum drying oven at 80 ℃ for 24h to obtain 3-aminopropyl functionalized silica microspheres (SiO 2 @NH 2 )；
2) 2g of SiO is taken 2 @NH 2 Dispersing into 50mL of acetonitrile under the action of ultrasound, adding 16mL of triethylamine, slowly dripping 6mL of phosphorus oxychloride into the mixture, reacting for 24 hours in an oil bath at 40 ℃, washing the product with acetonitrile, water and absolute ethyl alcohol in sequence, and then drying the product in a vacuum drying oven at 80 ℃ for 24 hours to obtain a phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
Example 4 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 6.2g of silica microspheres in 70mL of absolute ethyl alcohol under the action of ultrasound, dropwise adding 4mL of 3-aminopropyl trimethoxysilane, stirring the final mixture at room temperature for 72h, taking out the silica microspheres, washing the silica microspheres with absolute ethyl alcohol, and then drying the silica microspheres in a vacuum drying oven at 80 ℃ for 24h to obtain 3-aminopropyl functionalized silica microspheres (SiO 2 @NH 2 )；
2) 2g of SiO is taken 2 @NH 2 Dispersing into 70mL acetonitrile under the action of ultrasound, adding 16mL triethylamine, slowly dripping 6mL phosphorus oxychloride into the mixture, reacting for 24 hours in an oil bath at 40 ℃, washing the product with acetonitrile, water and absolute ethyl alcohol in sequence, and then drying the product in a vacuum drying oven at 80 ℃ for 24 hours to obtain a phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
Characterization of the product
In the potentiometric analysis (Table 1), siO 2 Potential measurement of-5.26.1.5 mV in SiO 2 @NH 2 The potential became 27mV, indicating that the 3-aminopropyl trimethoxysilane was successfully grafted to the silica microsphere surface; with SiO 2 @NH 2 In contrast, siO 2 @NH 2 @H 2 PO 3 The intermediate potential was changed to-11.9 mV again, indicating that the phosphoric acid was successfully added to SiO 2 @NH 2 And (3) upper part.
TABLE 1 SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 Potential measurement of (2)
Performance testing
1. Material pair Cr at different solution pH 2 O 7 2- ,AsO 4 3- And SeO 4 2- Is not limited by the removal efficiency:
respectively preparing 200 mug/L Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- Each of the seven tubes was 40mL and the pH of each tube was adjusted to 2,3, 4,5, 6, 7, 8. Respectively weighing SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 3mg of the material was placed in 10mL centrifuge tubes, respectively, and 5mL of an oxo acid ion standard solution of the corresponding pH was added thereto. The resulting samples were then placed in a multitube vortex mixer and incubated with shaking at 2500rpm for 2h. After the incubation, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3min. The supernatant was filtered through a 0.22 μm aqueous filter, and 100. Mu.L of concentrated nitric acid was added to the obtained filtrate, followed by mixing, and the concentration of the oxyacid radical ions was measured by ICP-OES. The pH experiments for each solution were repeated 3 times. Standard curve concentration of oxyacid radical ion: preparing 0,5, 10, 50, 100, 150 and 200 mug/L Cr respectively 2 O 7 2- ,AsO 4 3- And SeO 4 2- The pH of each set was adjusted to 2,3, 4,5, 6, 7, 8, respectively, for each 5mL of solution.
The results are shown in FIG. 2a, siO 2 @NH 2 @H 2 PO 3 Material vs. Cr in the pH range examined 2 O 7 2- Is better than SiO in the removal efficiency 2 SiO 2 @NH 2 A material. Especially for Cr in a solution of pH 4 2 O 7 2- Is 100% of the removal efficiency of SiO 2 SiO 2 @NH 2 For Cr 2 O 7 2- The removal efficiencies of (a) were 9.06% and 4.17%, respectively. In FIG. 2b, siO 2 @NH 2 @H 2 PO 3 Material other than for AsO in a solution at pH 2 4 3- Is lower than SiO 2 @NH 2 In addition, the material has a pH value of the other pH range of the material 4 3- Is better than SiO in the removal rate 2 SiO 2 @NH 2 . In particular for AsO in a solution of pH 4 4 3- Is 88% of the removal efficiency of SiO 2 SiO 2 @NH 2 For AsO 4 3- The removal efficiencies of (a) were 5.33% and 7.20%, respectively. In FIG. 2c, siO 2 @NH 2 @H 2 PO 3 Material other than for SeO at pH 2 4 2- Is to remove SiO 2 @NH 2 In addition, the SeO is processed in other pH ranges 4 2- Is better than SiO in the removal efficiency 2 SiO 2 @NH 2 . SiO in particular in a solution at pH 3 2 @NH 2 @H 2 PO 3 For SeO 4 2- 77.30% of SiO 2 SiO 2 @NH 2 For SeO 4 2- The removal efficiencies of (2) were 0 and 32.75%, respectively.
2.3 materials for Cr with different concentrations in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Saturated adsorption amount of (2):
separately formulate ph=4, cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- Seven tubes of the standard solution, 40mL per tube, and the concentration of each tube is 5, 10, 25, 50, 75, 100 and 125mg/L respectively. Respectively weighing 3mg of SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 Placed in a 10mL centrifuge tube, and 5mL of a corresponding concentration of oxyacid radical ion solution was added thereto. The resulting samples were then placed in a multitube vortex mixer and incubated with shaking at 2500rpm for 2h. After the incubation, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3min. The supernatant was filtered through a 0.22 μm aqueous filter, and 100. Mu.L of concentrated nitric acid was added to the obtained filtrate, followed by mixing, and the concentration of the oxyacid radical ions was measured by ICP-OES. The saturated adsorption amount experiment of the material on the oxo acid ions is repeated for 3 times respectively. Standard curve concentration of oxyacid radical ion: preparing Cr with pH=4 and concentration of 0,1, 5, 10, 20, 50, 100, 150mg/L 2 O 7 2- ,AsO 4 3- And SeO 4 2- The solutions were 5mL each.
The results are shown in FIG. 3, siO 2 @NH 2 @H 2 PO 3 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption capacity of (2) is 84.15, 25.67 and 71.21mg/g respectively; and SiO 2 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- Saturated adsorption amounts of 0, 3.04 and 11.11mg/g respectively; siO (SiO) 2 @NH 2 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption amounts of (C) were 15.58, 18.17 and 21.93mg/g, respectively. The results demonstrate that SiO 2 @NH 2 @H 2 PO 3 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption quantity of the catalyst is better than that of SiO 2 And SiO 2 @NH 2 。
3.3mg SiO 2 @NH 2 @H 2 PO 3 For 200 mug/L Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Number of times of cyclic use of adsorption:
respectively preparing pH=4 and concentration of 200 mug/L Cr 2 O 7 2- ,AsO 4 3- ,SeO 4 2- 40mL each. Weigh 3mg SiO 2 @NH 2 @H 2 PO 3 Placed in 10mL centrifuge tubes, and 5mL of the prepared oxyacid radical ion solution was added thereto, respectively. The mixed sample is placed in a multitube vortex mixer and incubated for 2h under shaking at 2500 rpm. After the incubation, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3min. The supernatant was filtered through a 0.22 μm aqueous filter, and 100. Mu.L of concentrated nitric acid was added to the obtained filtrate, followed by mixing, and the concentration of the oxyacid radical ions was measured by ICP-OES. SiO with adsorbed oxyacid radical ion 2 @NH 2 @H 2 PO 3 The material is washed with 0.5mM HCl solution for 3 times, so as to release the oxo acid ions adsorbed by the material, then washed with deionized water for 3 times, then added with 5mL of the oxo acid ion solution of the same type, and the incubation, centrifugation, filtration and detection operations are repeated, wherein the content of oxo acid ions in the obtained filtrate reflects the result of the second adsorption of the material. The above release, incubation, centrifugation and detection operations were repeated in cycles twice, and the results obtained represent the adsorption performance of the material for the third and fourth times, respectively, on the same concentration of oxo-acid ions. Standard curve concentration of oxyacid radical ion: preparing pH=4, and concentration of 0,5, 10, 50, 100, 150, 200 μg/L Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The solutions were 5mL each.
The result of recycling the material is shown in FIG. 4, which shows that SiO 2 @NH 2 @H 2 PO 3 After recycling for 4 times, the catalyst is used for Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The removal efficiency of the catalyst can still reach 77.13%, 93.85% and 84.02%.
4.3mg SiO 2 @NH 2 @H 2 PO 3 At 1mg/L NO 3 - And SO 4 2- To Cr in aqueous solution under the interference of (2) 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Is selected from the group consisting of:
a mixed solution of three oxyacid radical ions at a concentration of 1mg/L and pH=4 was prepared in 40mL: 1) NO (NO) 3 - 、SO 4 2- 、Cr 2 O 7 2- ，2)NO 3 - 、SO 4 2- 、AsO 4 3- ，3)NO 3 - 、SO 4 2- 、SeO 4 2- . Weigh 3mg SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 The solution was placed in 10mL centrifuge tubes, and 10mL of the prepared oxyacid radical ion solution was added to the centrifuge tubes containing the material. The resulting samples were placed in a multitube vortex mixer and incubated with shaking at 2500rpm for 2h. After the incubation, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3min. The supernatant was filtered with a 0.22 μm aqueous filter head, and 100. Mu.L of concentrated nitric acid was added to the resulting liquid, followed by measuring the oxyanion concentration thereof by ICP-OES. Standard curve concentration of oxyacid radical ion: three mixed solutions were prepared at a pH=4 and a concentration of 0, 10, 50, 100, 200, 500, 800, 1000. Mu.g/L, respectively, in an amount of 10mL.
The test results are shown in FIG. 5, at 1mg/L NO 3 - And SO 4 2- SiO under interference of (2) 2 @NH 2 @H 2 PO 3 For Cr in solution 2 O 7 2- ,AsO 4 3- And SeO 4 2- The removal effect of (2) was 98.02%,80.00%,84.12%, respectively, and these results indicate SiO 2 @NH 2 @H 2 PO 3 In the process of removing Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The time selectivity is higher.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included in the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (13)
1. A phosphoric acid modified silicon dioxide microsphere material has the following structure:
the particle size of the silica microsphere raw material is 5 mu m, the pore diameter is 10nm, and the specific surface area is 300m 2 /g；
The phosphoric acid modified silicon dioxide microsphere material is prepared by the following steps: after 3-aminopropyl is modified on the surface of silicon dioxide, phosphorus oxychloride is added, phosphoric acid is grafted on the surface of the silicon dioxide microsphere through nucleophilic substitution reaction of amino, and the silicon dioxide microsphere modified by phosphoric acid is formed on the surface of the silicon dioxide microsphere.
2. The phosphoric acid modified silica microsphere material according to claim 1, wherein the preparation comprises the following specific steps:
(1) Modifying 3-aminopropyl functional groups on the surface of the silicon dioxide microsphere:
dispersing the silica microspheres in an organic solvent, dropwise adding 3-aminopropyl trimethoxy silane, carrying out reflux reaction on the mixture for 16-72h, taking out the silica microspheres, washing the silica microspheres, and drying to obtain the 3-aminopropyl modified silica microspheres; wherein the mass volume ratio (m/v) of the silicon dioxide to the 3-aminopropyl trimethoxysilane is 5-10 g: 2-8 mL;
(2) Preparation of phosphoric acid modified silica microspheres:
adding the 3-aminopropyl modified silica microspheres dried in the step (1) into a reaction vessel, adding an organic solvent into the reaction vessel, performing ultrasonic dispersion, adding an acid binding agent, slowly dropwise adding phosphorus oxychloride into the reaction vessel, reacting for 4-48 hours in an oil bath at 40+/-5 ℃, washing and drying the product to obtain phosphoric acid modified silica microspheres; wherein the mass volume ratio (m/v) of the 3-aminopropyl modified silicon dioxide microsphere to phosphorus oxychloride is 1.0-5.0 g: 2-10 mL.
3. A phosphoric acid modified silica microsphere material according to claim 2, wherein the organic solvent used in step (1) is one or more of toluene, methanol, ethanol, isopropanol.
4. A phosphoric acid modified silica microsphere material according to claim 3, wherein in step (1), the organic solvent is toluene or ethanol.
5. The phosphoric acid modified silica microsphere material according to claim 4, wherein in the step (1), the organic solvent is toluene.
6. A phosphoric acid modified silica microsphere material according to claim 3, wherein the reaction temperature is 110±10 ℃ when the organic solvent is toluene; when the organic solvent is ethanol, the reaction temperature is 20-80 ℃.
7. A phosphoric acid modified silica microsphere material according to any one of claims 2 to 6, wherein in step (1), the silica microspheres are dispersed in an organic solvent by ultrasonic dispersion.
8. The phosphoric acid modified silica microsphere material according to claim 2, wherein in the step (1), the mass-to-volume ratio (m/v) of silica to 3-aminopropyl trimethoxysilane is 5 to 10g:4mL.
9. A phosphoric acid modified silica microsphere material according to claim 2, wherein in step (2), the organic solvent is acetonitrile.
10. A phosphoric acid modified silica microsphere material according to any one of claims 2-6, wherein in step (2), the acid binding agent is an organic base, in particular one or more of methylamine, dimethylamine, triethylamine and pyridine.
11. A phosphoric acid modified silica microsphere material according to claim 10, wherein in said step (2), said acid binding agent is triethylamine.
12. A phosphoric acid modified silica microsphere material according to claim 2, wherein in said step (2), said reaction is carried out in an oil bath at 40±5 ℃ for 24 hours.
13. Use of the phosphoric acid modified silica microsphere material according to any one of claims 1 to 6, the phosphoric acid modified silica microsphere material according to claim 7, the phosphoric acid modified silica microsphere material according to claim 8 or 9, the phosphoric acid modified silica microsphere material according to claim 10, or the phosphoric acid modified silica microsphere material according to any one of claims 11 to 12 for removing oxo acid ion contaminants in a water body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210561038.0A CN114832784B (en) | 2022-05-23 | 2022-05-23 | Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof |
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