CN109107574A - Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application - Google Patents
Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application Download PDFInfo
- Publication number
- CN109107574A CN109107574A CN201810861350.5A CN201810861350A CN109107574A CN 109107574 A CN109107574 A CN 109107574A CN 201810861350 A CN201810861350 A CN 201810861350A CN 109107574 A CN109107574 A CN 109107574A
- Authority
- CN
- China
- Prior art keywords
- silver
- oxysalt
- preparation
- graphene oxide
- graphite oxide
- 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 207
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 128
- 239000004332 silver Substances 0.000 title claims abstract description 128
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 89
- 239000010439 graphite Substances 0.000 title claims abstract description 89
- 239000004964 aerogel Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- 230000015556 catabolic process Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 239000000356 contaminant Substances 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 17
- 229940043267 rhodamine b Drugs 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 7
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 5
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000352 supercritical drying Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 40
- 229910000161 silver phosphate Inorganic materials 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005286 illumination Methods 0.000 description 8
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000505 pernicious effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011240 wet gel Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of preparation method of silver-based oxysalt/graphite oxide aerogel and its aeroge obtained and applications, are related to novel nano-material preparation and application field.Silver-based oxysalt/graphite oxide aerogel preparation method, comprising the following steps: the mixture of silver-based oxysalt, graphene oxide and water is dried, silver-based oxysalt/graphite oxide aerogel is obtained；The mass ratio of silver-based oxysalt, graphene oxide and water is (1.5~5): (0.7~1.3): (40~70).The preparation method has simple process and low cost, highly-safe, and experimental facilities requirement is low, the advantages that being convenient for industrialized production.The preparation method can also regulate and control the structure and shape of aeroge, silver-based oxysalt/graphite oxide aerogel of preparation has many advantages, such as that structural integrity, stability are good, specific surface area is high, light absorptive is good and catalytic activity is high, can be applied to photocatalysis degradation organic contaminant.
Description
Technical field
The present invention relates to novel nano-material preparation and application fields, in particular to a kind of silver-based oxysalt/oxygen
The preparation method of graphite alkene aeroge and its aeroge obtained and application.
Background technique
Aeroge is that a kind of density is ultralow, water can largely be kept not to be dissolved in water, and the three dimensional network that can be swollen again
Shape nano solid porous polymer material has good electric conductivity and thermal conductivity.Stanford University s.s.Kistler in 1931
It is put forward for the first time the concept of aeroge, and is successfully prepared the aeroges such as silica using supercritical drying.Not with research
It is disconnected to go deep into, prepare the aeroges such as silicon systems, carbon system, sulphur system, metal oxidation system.Preparing for aeroge is more complicated, usually
Wet gel is made up in it of the gel process of colloidal sol before this, passes through certain solvent switch later, by surface in grid-gap
The relatively large solvent filter of tension comes out, and aeroge then is made using a series of more complicated processing.
Graphene aerogel is a kind of tridimensional network for being prepared and being formed by graphene, usually with graphene oxide water
Solution is raw material, is made using hydro-thermal or the method for electronation, then by the methods of freeze-drying or supercritical drying.Often now
Aeroge is made with graphene and some Material claddings with catalytic activity to increase catalytic performance, but existing for degrading
The preparation process of the composite material aeroge of organic pollutant is complicated, preparation cost is high and there are security risks, and is prepared into
To aeroge do not obtain satisfactory effect in terms of pernicious gas detection, gas absorption, gas catalysis, this
It is a little there are the problem of limit the practical application of aeroge.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of silver-based oxysalt/graphite oxide aerogel,
By the mixture being obtained by mixing to a certain amount of silver-based oxysalt, graphene oxide and water, it is dried to obtain silver-based and contains
Oxygen hydrochlorate/graphite oxide aerogel has method simple, at low cost, highly-safe, and experimental facilities requirement is low, convenient for industry
The advantages that metaplasia produces.
The second object of the present invention is to provide a kind of silver-based oxysalt/graphite oxide aerogel, aeroge tool
Have the advantages that structural integrity, stability are good, specific surface area is high, light absorptive is good and catalytic activity is high.
The third object of the present invention is to provide silver-based oxysalt/graphite oxide aerogel organic in photocatalytic degradation
Application in pollutant.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, the present invention provides a kind of preparation method of silver-based oxysalt/graphite oxide aerogel, it will be silver-colored
The mixture of base oxysalt, graphene oxide and water is dried, and obtains silver-based oxysalt/graphite oxide aerogel；
The mass ratio of silver-based oxysalt, graphene oxide and water is (1.5~5): (0.7~1.3): (40~70).
Further, on the basis of technical solution provided by the invention, the matter of silver-based oxysalt, graphene oxide and water
Amount is than being (1.5~4): (0.8~1.2): (45~60).
Further, on the basis of technical solution provided by the invention, the matter of silver-based oxysalt, graphene oxide and water
Amount is than being (1.5~3): (1~1.2): (50~60).
Further, on the basis of technical solution provided by the invention, silver-based oxysalt include silver orthophosphate, silver vanadate,
One kind, preferably silver orthophosphate in silver carbonate or wolframic acid silver.
Further, on the basis of technical solution provided by the invention, drying mode includes vacuum freeze drying or super faces
Boundary is dry.
Second aspect, the present invention provides a kind of silver-based oxysalt/graphite oxide aerogel, the silver-based is oxygen-containing
Hydrochlorate/graphite oxide aerogel is prepared into using the preparation method of above-mentioned silver-based oxysalt/graphite oxide aerogel
It arrives.
Further, on the basis of technical solution provided by the invention, silver-based oxysalt is supported on the graphite oxide
In the layer structure of alkene.
The third aspect, the present invention provides silver-based oxysalt/graphite oxide aerogels in the organic dirt of photocatalytic degradation
Contaminate the application in object；
Further, on the basis of technical solution provided by the invention, organic pollutant includes that the volatility in air has
Organic pollutant in machine pollutant or water body.
Compared with prior art, the invention has the benefit that
(1) preparation method of silver-based oxysalt/graphite oxide aerogel provided by the invention passes through to a certain amount of
The mixture that silver-based oxysalt, graphene oxide and water are obtained by mixing is dried to obtain silver-based oxysalt/graphite oxide
Alkene aeroge has simple process and low cost, safety without other reagents are added and can be prepared by using other processing methods
Property it is high, experimental facilities require it is low, the advantages that being convenient for industrialized production.
(2) preparation method of silver-based oxysalt/graphite oxide aerogel provided by the invention is contained by adjusting silver-based
The adding proportion of oxygen hydrochlorate and graphene oxide can have the function that regulate and control aerogel structure, and the use for passing through different vessels
Achieve the purpose that regulate and control aeroge shape.The preparation method can regulate and control the structure and shape of aeroge, prepare through the invention
It is multiple that method can obtain the gelatinous silver-based oxysalt/graphene oxide of airsetting that structural integrity, stability are good, specific surface area is high
Object is closed, silver-based oxysalt/graphene oxide compound of airsetting colloidal state has better light absorptive and catalytic activity.
(3) oxysalt of silver-based made from the method for the present invention/graphite oxide aerogel can to the degradation efficiency of rhodamine B
Up to 96.878%, the degradation efficiency of PARA FORMALDEHYDE PRILLS(91,95) is up to 86.1%.
Detailed description of the invention
Fig. 1 is silver orthophosphate/graphite oxide aerogel scanning electron microscope diagram piece prepared by the embodiment of the present invention 5,
Wherein left side is the SEM photograph under 2000 times, and right side is the SEM photograph under 10000 times；
Fig. 2 is silver orthophosphate/graphite oxide aerogel transmission electron microscope picture prepared by the embodiment of the present invention 5,
Wherein left side is the TEM photo under length of the scale 50nm, and right side is the TEM photo under length of the scale 5nm；
Fig. 3 is silver orthophosphate/graphite oxide aerogel EDS picture prepared by the embodiment of the present invention 5；
Fig. 4 be the embodiment of the present invention 5 prepare silver orthophosphate/graphite oxide aerogel mapping picture, wherein a, b,
C, d is respectively the mapping picture of silver, phosphorus, carbon and oxygen element；
Fig. 5 is that silver orthophosphate/graphite oxide aerogel prepared by the embodiment of the present invention 5 is having light (Light) and unglazed
(Dark) catalytic degradation rhodamine B effect picture under the conditions of；
Fig. 6 for silver orthophosphate/graphite oxide aerogel prepared by the embodiment of the present invention 5 and embodiment 6, urge under light illumination by light
Change degradation of formaldehyde effect picture.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of preparation of silver-based oxysalt/graphite oxide aerogel is provided
The mixture of silver-based oxysalt, graphene oxide and water is dried method, obtains silver-based oxysalt/graphite oxide
Alkene aeroge；The mass ratio of silver-based oxysalt, graphene oxide and water is (1.5~5): (0.7~1.3): (40~70).
Silver-based oxysalt refers to the semiconductor material of the metal oxide based on silver, and the low energy valence band of upper part is by only
Special Ag 3d track and O2p orbital hybridization is constituted, and it reduce valence band locations and valence band energy.The conduction band of bottom is by s and p track
It constitutes, making it have higher energy causes light induced electron to separate with hole, and then there is silver-based oxysalt excellent light to urge
Change performance.But the exclusive use of silver-based oxysalt is unstable during visible light catalytic, can be reduced or resolve into silver-colored simple substance,
Light absorption is influenced, the progress of reaction is unfavorable for.
Silver-based oxysalt includes but is not limited to silver orthophosphate (Ag3PO4), silver vanadate (Ag3VO3), silver carbonate (Ag2CO3) or
Wolframic acid silver (Ag2WO4)。
Graphene oxide (Graphene Oxide, GO) is a kind of material with two-dimensional layered structure, oxygen-containing with silver-based
After hydrochlorate is compound, the probability that silver-based oxysalt is reduced can be reduced, to effectively mention as the transmission channel of light induced electron
The stability and photocatalysis performance of high silver-based oxysalt.Meanwhile the large specific surface area of graphene oxide, improve organic contamination
The absorption of object can also greatly improve the photocatalytic degradation efficiency of composite material.
Graphene oxide is not construed as limiting, graphene oxide that is commercially available or voluntarily preparing may be selected.
Aeroge density is small, preparation is simple, preparation cost is low, practical, is a kind of good nanoscale new material.
Due to its great specific surface area, the ability of adsorbed gas is stronger, when gas concentration is low, will can be enriched on a small quantity volume, thus
It is improved in the sensitivity of gas application aspect, therefore graphene oxide and silver-based oxysalt are compounded to form aeroge, it can
For pernicious gas detection, gas absorption and gas catalytic degradation etc. in environment.
The typical but non-limiting for example, 1.5:0.7:40 of the mass ratio of silver-based oxysalt, graphene oxide and water,
1.5:1:50,2:1:60,2.5:1.3:70,3:1.3:50 or 5:1:60.
The preparation method of silver-based oxysalt/graphite oxide aerogel provided by the invention passes through to a certain amount of silver-based
The mixture that oxysalt, graphene oxide and water are obtained by mixing is dried to obtain silver-based oxysalt/graphene oxide gas
Gel, it is highly-safe with simple process and low cost without other reagents are added and can be prepared by using other processing methods,
Experimental facilities requirement is low, the advantages that being convenient for industrialized production.
In a preferred embodiment, the mass ratio of silver-based oxysalt, graphene oxide and water is (1.5~4):
(0.8~1.2): (45~60).
In a kind of more preferably embodiment, the mass ratio of silver-based oxysalt, graphene oxide and water is (1.5
~3): (1~1.2): (50~60).
It can make the silver-based being prepared by the mass ratio of further preferred silver-based oxysalt, graphene oxide and water
Oxysalt/graphite oxide aerogel has more stable complete structure, higher specific surface area and catalytic activity.
In a preferred embodiment, the preferred silver orthophosphate of silver-based oxysalt.
Silver orthophosphate, silver vanadate, silver carbonate or wolframic acid silver all have good photocatalytic activity, wherein the photocatalysis of silver orthophosphate
Active best, preferably silver orthophosphate can make the specific surface area height for the silver orthophosphate graphite oxide aerogel being prepared, light absorptive
The advantages that good and catalytic activity is high is more prominent.
In a preferred embodiment, drying mode includes but is not limited to vacuum freeze drying or supercritical drying；
Preferably, drying mode is vacuum freeze drying.
It is preferred that drying mode can shorten the time of preparation process, make the silver-based being prepared oxysalt/graphite oxide
The structural integrity of alkene aeroge, stability is good and specific surface area is high.
Preferably, a kind of preparation method of typical silver-based oxysalt/graphite oxide aerogel, including following step
It is rapid:
(a) it adds graphene oxide into deionized water, at room temperature 1~3h of ultrasonic disperse, obtains uniform graphite oxide
Alkene dispersion liquid；
(b) silver-based oxysalt is added into graphene oxide dispersion, 2~4h of ultrasonic disperse, obtains at 20~40 DEG C
To finely dispersed mixed liquor；
(c) mixed liquor is subjected to vacuum freeze drying, obtains silver-based oxysalt/graphite oxide aerogel；
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is (1.5~5): (0.7~1.3): (40~
70)。
This typically prepares silver-based oxysalt/graphite oxide aerogel preparation method, defines the condition of reaction
And step, make preparation method simple process and low cost, highly-safe, experimental facilities requirement is low, the advantages that being convenient for industrialized production
It is more prominent, and make the silver-based being prepared oxysalt/graphite oxide aerogel structural integrity, stability and catalysis
Activity is higher.
In a preferred embodiment, graphene oxide is prepared using improved Hummers method.
Hummers method refers to that graphite is raw material to force son acid and nitrate as reaction system, and strong oxidizer is added, adopts
With gradient heating, i.e., successively aoxidized by (0 DEG C) of ice bath reaction, (35 DEG C) of middle low temperature (98 DEG C) reactions, high temperature reactions
Graphene.
Improved Hummers method refers to that material quality has difference with Hummers method than the condition with reaction, simplifies reaction
Step and shorten the reaction time.
In a preferred embodiment, graphene oxide is prepared using improved Hummers method, including following step
It is rapid:
After mixing by strong protonic acid, graphite and nitrate, strong oxidizer is added to be reacted after mixing, obtains
Graphene oxide.
Strong protonic acid refers to acid functionality H0Bronsted acid less than or equal to -4 may include inorganic or organic strong
Bronsted acid, preferably inorganic strong protonic acid, including but not limited to sulfuric acid, perchloric acid or nitric acid, preferably sulfuric acid.
Nitrate includes but is not limited to one of sodium nitrate, potassium nitrate or magnesium nitrate, preferably sodium nitrate.
Strong oxidizer includes but is not limited to one of potassium permanganate, potassium hyperchlorate or hypochlorous acid, preferably potassium permanganate.
It is preferred that preparing graphene oxide using improved Hummers method, and preferably engage in system, raw material and the catalysis of reaction
The step of agent can shorten the reaction time, simplify reaction, make the graphene oxide being prepared keep complete good structure and
Performance.
In a preferred embodiment, the above-mentioned method for preparing graphene oxide, it is also necessary to it is dilute that deionized water be added
It releases, adds remaining strong oxidizer after hydrogen peroxide removal reaction.The preferred step can remove impurity, make to be prepared
Graphene oxide purity it is higher.
In a preferred embodiment, the preparation method of graphene oxide further includes purifying and drying, is aoxidized
The step of graphene；
Preferably, purification step includes washing and is separated by solid-liquid separation.
Washing includes the steps that pickling and washing in purification step, pickling can preferred dilute hydrochloric acid, the preferred deionized water of water,
It is separated by solid-liquid separation preferred centrifuge separation, purifying can remove remaining acid ion and metal ion etc. in reaction product, make to prepare
Obtained graphene oxide purity is higher.
In a preferred embodiment, drying condition include: drying temperature be 50~70 DEG C, drying time be 20~
30h。
Preferably, it is 55~65 DEG C that drying condition, which includes: drying temperature, and drying time is 22~26h.
Typical but non-limiting drying temperature is, for example, 50 DEG C, 52 DEG C, 54 DEG C, 56 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 64
DEG C, 66 DEG C, 68 DEG C or 70 DEG C；
Drying time is typical but non-limiting be, for example, 22h, 23h, for 24 hours, 25h or 26h.
Dry temperature and time is defined and preferably, the time for preparing graphene oxide can be shortened, save at
This, makes the graphene oxide being prepared keep complete good structure and performance.
Preferably, a kind of preparation method of typical graphene oxide, comprising the following steps:
(a) under the conditions of ice-water bath, sulfuric acid is added in graphite powder and sodium nitrate mixture, is uniformly mixed 30~50min,
Obtain the first mixed liquor；
(b) potassium permanganate is slowly added in the first mixed liquor, the rate for controlling addition makes temperature at 20 DEG C hereinafter, obtaining
Second mixed liquor；
(c) the second above-mentioned mixed liquor is transferred under 30~40 DEG C of water-baths, mixes 80~120min；
(d) suitable deionized water is added into step (3) resulting solution, continuess to mix 10~20min, then slowly
The H that suitable mass fraction is 30% is added2O2Solution；
(e) suitable dilute hydrochloric acid is added into step (4) resulting solution and is purified, then washed, solid-liquid point
From and it is dry, obtain graphene oxide；
Wherein, the ratio between additive amount of the concentrated sulfuric acid, graphite powder, sodium nitrate and potassium permanganate is (40~60) mL:(1~3) g:
(0.5~1.5) g:(4~8) g.
The preparation method of the typical graphene oxide is used with sulfuric acid (H2SO4) and sodium nitrate (NaNO3) it is reactant
System, graphite powder is raw material, potassium permanganate (KMnO4) it is oxidant, it defines the modes such as condition and the subsequent purification of reaction, shortens
The time of preparation method, reduces cost, keep the structure for the graphene oxide being prepared and performance more preferable.
According to the second aspect of the invention, a kind of silver-based oxysalt/graphite oxide aerogel, the silver-based are provided
Oxysalt/graphite oxide aerogel is the system using silver-based oxysalt/graphite oxide aerogel provided by the invention
What Preparation Method was prepared.
Preferably, the silver-based oxysalt/graphite oxide aerogel structure obtained using this method is presented silver-based and contained
Oxygen hydrochlorate is supported in the layer structure of graphene oxide.
The gelatinous silver-based of airsetting that structural integrity, stability are good, specific surface area is high can be obtained by the method for the invention to contain
Silver-based oxysalt/graphene oxide compound of oxygen hydrochlorate/graphene oxide compound, airsetting colloidal state has better extinction
Property and catalytic activity.
Fig. 2 is the transmission electron microscope picture of silver orthophosphate/graphite oxide aerogel prepared by the present invention, high-resolution
Down it can be seen that the Ag of 0.310nm3PO4Lattice fringe it is corresponding with 210 planes.
Fig. 3 be silver orthophosphate/graphite oxide aerogel prepared by the present invention EDS picture, it will be apparent that illustrate silver, carbon,
Oxygen, phosphorus each element are in Ag3PO4Accounting in/GO aeroge.Fig. 4 is silver orthophosphate/graphite oxide aerogel prepared by the present invention
Mapping picture；Apparent silver, carbon, oxygen, P elements can be found, and Elemental redistribution is more uniform, load is preferable.
According to the third aspect of the present invention, silver-based oxysalt/graphite oxide aerogel is provided to drop in photocatalysis
Solve the application in organic pollutant；
Preferably, organic pollutant includes the organic pollutant in the volatile organic contaminant or water body in air；
Preferably, the volatile organic contaminant in air includes one of formaldehyde, toluene, dimethylbenzene or ammonia or more
Kind, preferably formaldehyde；
Preferably, the organic pollutant in water body includes dyestuff, and dyestuff includes in rhodamine B, methylene blue or methyl orange
One or more, preferred rhodamine B.
Silver-based oxysalt/the graphite oxide aerogel obtained by the method for the invention is organic to the volatility in air
The visible light photocatalytic degradation of organic pollutant in pollutant and water body is high-efficient, has a good application prospect.The present invention mentions
Silver-based oxysalt/graphite oxide aerogel of confession to the degradation efficiency of rhodamine B up to 96.878%, the degradation of PARA FORMALDEHYDE PRILLS(91,95)
Efficiency is up to 86.1%.
In order to further appreciate that the present invention, the method for the present invention and effect are done further in detail combined with specific embodiments below
Explanation.Each raw material of the present invention can pass through commercially available acquisition.
Embodiment 1
A kind of preparation method of silver orthophosphate/graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 1h, obtains uniform graphene oxide point
Dispersion liquid；
(2) silver orthophosphate is added in graphene oxide dispersion, ultrasonic disperse 2h at 40 DEG C obtains finely dispersed mixing
Liquid；
(3) mixed liquor is subjected to vacuum freeze drying；Obtain silver orthophosphate/graphite oxide aerogel.
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is 1.5:1:40.
Embodiment 2
A kind of preparation method of silver orthophosphate/graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 3h, obtains uniform graphene oxide point
Dispersion liquid；
(2) silver orthophosphate is added in graphene oxide dispersion, ultrasonic disperse 4h at 20 DEG C obtains finely dispersed mixing
Liquid；
(3) mixed liquor is subjected to vacuum freeze drying, obtains silver orthophosphate/graphite oxide aerogel；
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is 5:1:70.
Embodiment 3
A kind of preparation method of silver orthophosphate/graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 2h, obtains uniform graphene oxide point
Dispersion liquid；
(2) silver orthophosphate is added in graphene oxide dispersion, ultrasonic disperse 2h at 25 DEG C obtains finely dispersed mixing
Liquid；
(3) mixed liquor is subjected to vacuum freeze drying, obtains silver orthophosphate/graphite oxide aerogel；
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is 2:1:50.
Embodiment 4
A kind of preparation method of silver orthophosphate/graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 2h, obtains uniform graphene oxide point
Dispersion liquid；
(2) silver orthophosphate is added in graphene oxide dispersion, ultrasonic disperse 2h at 35 DEG C obtains finely dispersed mixing
Liquid；
(3) mixed liquor is subjected to vacuum freeze drying, obtains silver orthophosphate/graphite oxide aerogel；
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is 4:1:65.
Embodiment 5
A kind of preparation method of silver orthophosphate/graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 2h, obtains uniform graphene oxide point
Dispersion liquid；
(2) silver orthophosphate is added in graphene oxide dispersion, ultrasonic disperse 3h at 30 DEG C obtains finely dispersed mixing
Liquid；
(3) mixed liquor is subjected to vacuum freeze drying, obtains silver orthophosphate/graphite oxide aerogel；
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is 3.7:1:60.
Embodiment 6
A kind of preparation method of silver orthophosphate/graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 2h, obtains uniform graphene oxide point
Dispersion liquid；
(2) silver orthophosphate is added in graphene oxide dispersion, ultrasonic disperse 3h at 30 DEG C obtains finely dispersed mixing
Liquid；
(3) mixed liquor is subjected to vacuum freeze drying, obtains silver orthophosphate/graphite oxide aerogel；
Wherein, the mass ratio of silver-based oxysalt, graphene oxide and water is 5:1:60.
Embodiment 7
The difference of the present embodiment and embodiment 5 is that supercritical drying substitutes vacuum freeze drying.
Embodiment 8
The difference of the present embodiment and embodiment 5 is that silver vanadate substitutes silver orthophosphate.
Embodiment 9
The difference of the present embodiment and embodiment 5 is that silver carbonate substitutes silver orthophosphate.
Embodiment 10
The difference of the present embodiment and embodiment 5 is that wolframic acid silver substitutes silver orthophosphate.
Comparative example 1
A kind of preparation method of graphite oxide aerogel, comprising the following steps:
(1) it adds graphene oxide into deionized water, at room temperature ultrasonic disperse 2h, obtains uniform graphene oxide point
The mass ratio of dispersion liquid, graphene oxide and water is 16.7；
(2) graphene oxide dispersion is subjected to vacuum freeze drying, obtains graphite oxide aerogel.
Comparative example 2
This comparative example is that the mass ratio of silver orthophosphate and graphene oxide is 0.5:1:60 with the difference with embodiment 5.
Comparative example 3
This comparative example is that the mass ratio of silver orthophosphate and graphene oxide is 5.5:1:60 with the difference with embodiment 5.
Comparative example 4
This comparative example is that the mass ratio of graphene oxide and water is 3.7:1:30 with the difference with embodiment 5.
Comparative example 5
This comparative example is that the mass ratio of graphene oxide and water is 3.7:1:80 with the difference with embodiment 5.
Comparative example 6
Patent CN107486225A embodiment 2, comprising the following steps:
(1) 20mg/mL silver nitrate solution is uniformly mixed with 2mg/mL graphene oxide water solution, it is molten obtains presoma
Liquid；
(2) precursor solution is instilled in 80mg/mL potassium hydroxide solution, reacts 2h at room temperature, obtains three-dimensional structure also
Former graphene oxide/metal silver nano-grain hydrogel；
(3) three are obtained after three-dimensional structure redox graphene/metal silver nano-grain hydrogel being taken out cleaning, drying
Tie up construction recovery graphene oxide/nanometer metallic silver aeroge；
Wherein, silver nitrate solution and the mass ratio of graphene oxide water solution are 2:1；
The volume ratio of the additive amount of precursor solution and potassium hydroxide solution is 1:10.
The experiment of 1 scanning electron microscope of experimental example
Embodiment 1-10 and comparative example the 1-6 aeroge being prepared are scanned Electronic Speculum test experience, observe sample
Micromorphology.
The micromorphology of 1 aeroge of table
| Experimental group | Micromorphology |
| Embodiment 1 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 2 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 3 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 4 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 5 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 6 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 7 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Embodiment 8 | Spherical Ag3VO3It is supported in the layer structure of GO |
| Embodiment 9 | Spherical Ag2CO3It is supported in the layer structure of GO |
| Embodiment 10 | Spherical Ag2WO4It is supported in the layer structure of GO |
| Comparative example 1 | It is laminar structured |
| Comparative example 2 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Comparative example 3 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Comparative example 4 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Comparative example 5 | Spherical Ag3PO4It is supported in the layer structure of GO |
| Comparative example 6 | Spherical Ag particulate load is in the layer structure of GO |
It can be seen that silver-based oxysalt/graphite oxide that embodiment 1-10 is prepared from the scanning electron microscope result of table 1
The micromorphology of alkene aeroge is illustrated as spherical silver-based oxysalt and is supported in the layer structure of graphene oxide.Comparative example
The micromorphology of the graphite oxide aerogel of 1 preparation in laminar structured, the aeroge that comparative example 2-6 is prepared it is microcosmic
Form is illustrated as spherical silver-based oxysalt or metallic silver nanometer particle load in the layer structure of graphene oxide.
Fig. 1 is shown the embodiment of the present invention 5 and prepares Ag3PO4The scanning electron microscope diagram piece of/GO aeroge, left and right two
Side is respectively the SEM photograph amplified under 2000 times and 10000 times, and GO is most of at complete slice as carrier as can be seen from Figure
Shape, it is well arranged.Ag3PO4Nano particle portion size is uneven, and most of spherical in shape, particle has a degree of aggregation, point
It dissipates and is supported in GO layer structure.
The micromorphology of graphene oxide prepared by comparative example 1 can be used as good base material in laminar structured,
For constructing composite material.The micromorphology of silver-based oxysalt is substantially spherical in shape, and specific surface area is larger, and light with higher
Silver-based oxysalt and graphene oxide are combined the light that alkene aeroge has given full play to silver-based oxysalt by catalytic activity
The advantages of catalytic performance and graphene oxide and aeroge, makes silver-based oxysalt/graphene oxide gas prepared by the present invention
Gel has many advantages, such as that structural integrity, stability are good, specific surface area is high, light absorptive is good and catalytic activity is high.
2 catalytic degradation rhodamine B of experimental example
The embodiment 1-10 and comparative example 1-6 aeroge prepared is used for the catalysis degeneration experiment of rhodamine B, experiment to have
It is carried out under the conditions of two kinds of no light, the results are shown in Table 2.
The degradation rate of 2 rhodamine B of table
The aeroge of embodiment 1-10 preparation exists to the degradation rate of rhodamine B as can be seen from Table 2 under no light condition
Between 34.249%-35.674%, have under the conditions of light between 95.548%-96.878%.The airsetting of comparative example 2-6 preparation
Glue is to the degradation rate of rhodamine B, under no light condition between 30.922%-34.032%, has and exists under the conditions of light
Between 90.735%-95.271%.
In embodiment 1-10, Ag that embodiment 5 is prepared3PO4The degradation rate of/GO aeroge is higher than prepared by embodiment 6
Ag3PO4/ GO aeroge, the main distinction of embodiment 5 and 6 are Ag3PO4Different with the mass ratio of GO, this shows silver-based oxyacid
The mass ratio of silver-based oxysalt and graphene oxide will affect the photochemical catalyst of aeroge in salt/graphite oxide aerogel
Catalysis degradation modulus.
The degradation rate of GO aeroge prepared by comparative example 1 is primarily referred to as GO aeroge and leads to the suction-operated of rhodamine B
The variation for causing rhodamine B concentration, regards the degradation rate of GO aeroge as.From fig. 5, it can be seen that GO aeroge is in no light and has
Under conditions of illumination, the concentration of rhodamine B reduces degree and is not much different, this is because the absorption property of GO aeroge is stronger, and
It is not illuminated by the light condition influence.Under illumination condition, the Ag of the preparation of embodiment 53PO4Degradation rate of/GO the aeroge to rhodamine B
Most fast, the degradation rate maximum being finally reached is up to 96.878%.In the case where illumination, Ag3PO4/ GO aeroge is to Luo Dan
The concentration variation of bright B influences less, this is because the absorption property of composite material it is not simple GO it is good, and no light can shadow
The Photocatalytic Degradation Property of the composite material is rung, degradation efficiency is most down to 35.674%.
The degradation rate of the aeroge of comparative example 2-5 preparation is significantly lower than the aeroge of embodiment 1-10 preparation, and comparative example
The mass ratio of silver-based oxysalt and graphene oxide does not exist in silver-based oxysalt/graphite oxide aerogel of 2-5 preparation
Within the scope of protection of the invention.This shows that silver-based oxysalt/graphite oxide aerogel must item defined in the present invention
Can just there be higher catalytic activity under part.
The degradation rate of the rhodamine B of aeroge prepared by comparative example 6 is significantly lower than the embodiment 1-10 aeroge prepared
Degradation rate, this shows that silver-based oxysalt/graphite oxide aerogel provided by the invention has stronger visible catalytic activity,
Catalytic degradation efficiency is high, the aeroge prepared better than comparative example 6.
3 catalytic degradation formaldehyde of experimental example
The embodiment 1-10 and comparative example 1-6 aeroge prepared is used for the catalysis degeneration experiment of formaldehyde, experiment to have light
It is carried out according under the conditions of, when 180min the results are shown in Table 3.
The degradation rate of 3 formaldehyde of table
| Experimental group | There is illumination degrading rate (%) |
| Embodiment 1 | 67.629 |
| Embodiment 2 | 80.525 |
| Embodiment 3 | 68.351 |
| Embodiment 4 | 75.733 |
| Embodiment 5 | 70.352 |
| Embodiment 6 | 86.089 |
| Embodiment 7 | 70.168 |
| Embodiment 8 | 69.632 |
| Embodiment 9 | 70.065 |
| Embodiment 10 | 69.523 |
| Comparative example 1 | 10.059 |
| Comparative example 2 | 60.285 |
| Comparative example 3 | 65.552 |
| Comparative example 4 | 62.285 |
| Comparative example 5 | 60.937 |
| Comparative example 6 | 52.763 |
From table 3 it can be seen that the degradation rate of the aeroge PARA FORMALDEHYDE PRILLS(91,95) of embodiment 1-10 preparation exists under illumination condition
Between 67.629%-86.089%.The degradation rate of the aeroge PARA FORMALDEHYDE PRILLS(91,95) of comparative example 2-6 preparation is in 52.763%-
Between 65.552%.
The degradation rate of GO aeroge prepared by comparative example 1 is primarily referred to as the suction-operated of GO aeroge PARA FORMALDEHYDE PRILLS(91,95) and leads to first
The degradation rate of GO aeroge is regarded in the variation of aldehyde concentration as.Fig. 6 is that the embodiment of the present invention 5 and embodiment 6 prepare silver orthophosphate/oxygen
Graphite alkene aeroge formaldehyde degradation by photocatalytic oxidation process effect picture under light illumination.Fig. 6 can be seen that under illumination condition, Ag3PO4/ GO gas
Gel is affected to the concentration of formaldehyde in air in three hours than pure GO aeroge, and pure GO aeroge is empty after handling three hours
Content of formaldehyde is 2.709mg/m in gas3, 0.0045mol Ag in embodiment 53PO4+ 0.5g GO aeroge is empty after handling three hours
Content of formaldehyde is 0.893mg/m in gas3, 0.006molAg in embodiment 63PO4Air after+0.5g GO aeroge is handled three hours
Middle content of formaldehyde is 0.419mg/m3, thus illustrate, loaded Ag3PO4GO aeroge to the volatile organic matter-in air
The degradation effect of formaldehyde is very significant.And load 0.006mol Ag3PO4GO aeroge degradation effect than load
0.0045mol Ag3PO4GO aeroge degradation effect it is more preferable, illustrate Ag3PO4Photocatalysis performance in the composite plays
Critically important effect.But Ag in embodiment 63PO4Aerogel structure is relatively unstable under the ratio with GO, due to silver orthophosphate
Addition, graphene oxide intensity can be influenced to a certain extent, and will affect the adsorption function of graphene, so silver-based is oxygen-containing
The mass ratio of silver-based oxysalt and graphene oxide will have a direct impact on the structure of aeroge in hydrochlorate/graphite oxide aerogel
And catalytic performance.
The degradation rate of the aeroge PARA FORMALDEHYDE PRILLS(91,95) of comparative example 2-5 preparation is significantly lower than the aeroge of embodiment 1-10 preparation, and
The quality of silver-based oxysalt and graphene oxide in silver-based oxysalt/graphite oxide aerogel of comparative example 2-5 preparation
Than not within the scope of protection of the invention.This shows that silver-based oxysalt/graphite oxide aerogel must advise in the present invention
Can just there be higher catalytic activity under conditions of fixed.
Degradation of the degradation rate of aeroge PARA FORMALDEHYDE PRILLS(91,95) prepared by comparative example 6 significantly lower than the aeroge of embodiment 1-10 preparation
Rate, this shows that silver-based oxysalt/graphite oxide aerogel provided by the invention has stronger visible catalytic activity, catalysis
Degradation efficiency is high, the aeroge prepared better than comparative example 6.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of silver-based oxysalt/graphite oxide aerogel, which comprises the following steps:
The mixture of silver-based oxysalt, graphene oxide and water is dried, silver-based oxysalt/graphene oxide is obtained
Aeroge；
The mass ratio of the silver-based oxysalt, the graphene oxide and the water is (1.5~5): (0.7~1.3): (40
~70).
2. the preparation method of silver-based oxysalt/graphite oxide aerogel described in accordance with the claim 1, which is characterized in that
The mass ratio of the silver-based oxysalt, the graphene oxide and the water is (1.5~4): (0.8~1.2): (45~
60)。
3. the preparation method of silver-based oxysalt/graphite oxide aerogel described in accordance with the claim 1, which is characterized in that
The mass ratio of the silver-based oxysalt, the graphene oxide and the water is (1.5~3): (1~1.2): (50~60).
4. special according to the preparation method of the described in any item silver-based oxysalt/graphite oxide aerogels of claim 1-3
Sign is that the silver-based oxysalt includes one kind, preferably silver orthophosphate during silver orthophosphate, silver vanadate, silver carbonate or wolframic acid are silver-colored.
5. special according to the preparation method of the described in any item silver-based oxysalt/graphite oxide aerogels of claim 1-3
Sign is that the drying mode includes vacuum freeze drying or supercritical drying；
Preferably, the drying mode is vacuum freeze drying.
6. special according to the preparation method of the described in any item silver-based oxysalt/graphite oxide aerogels of claim 1-3
Sign is that the graphene oxide is prepared using improved Hummers method；
Preferably, the preparation method of the graphene oxide, comprising the following steps:
After mixing by strong protonic acid, graphite and nitrate, strong oxidizer is added to be reacted, obtains graphene oxide；
Preferably, strong protonic acid includes inorganic proton acid；It is further preferred that inorganic proton acid includes sulfuric acid, perchloric acid or nitre
One of acid, preferably sulfuric acid；
Preferably, nitrate includes one of sodium nitrate, potassium nitrate or magnesium nitrate, preferably sodium nitrate；
Preferably, strong oxidizer includes one of potassium permanganate, potassium hyperchlorate or hypochlorous acid, preferably potassium permanganate.
7. silver-based oxysalt/graphite oxide aerogel preparation method according to claim 6, which is characterized in that
The preparation method of graphene oxide further includes the step of purified after reacting and dried, obtain graphene oxide；
Preferably, the purification step includes washing and is separated by solid-liquid separation；
Preferably, it is 50~70 DEG C, preferably 55~65 DEG C that the drying condition, which includes: drying temperature,；Drying time be 20~
30h, preferably 22~26h.
8. a kind of silver-based oxysalt/graphite oxide aerogel, which is characterized in that using described in any one of claim 1-7
Silver-based oxysalt/graphite oxide aerogel preparation method be prepared.
9. silver-based oxysalt/graphite oxide aerogel according to claim 8, which is characterized in that the silver-based contains
Oxygen hydrochlorate is supported in the layer structure of the graphene oxide.
10. a kind of preparation method of the described in any item silver-based oxysalt/graphite oxide aerogels of claim 1-7 is made
Silver-based oxysalt/graphite oxide aerogel or claim 8 or 9 described in silver-based oxysalt/graphene oxide gas
Application of the gel in photocatalysis degradation organic contaminant；
Preferably, organic pollutant includes the organic pollutant in the volatile organic contaminant or water body in air；
Preferably, the volatile organic contaminant in air includes one of formaldehyde, toluene, dimethylbenzene or ammonia or a variety of, excellent
Select formaldehyde；
Preferably, the organic pollutant in water body includes dyestuff；It is further preferred that dyestuff include rhodamine B, methylene blue or
One of methyl orange is a variety of, preferably rhodamine B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810861350.5A CN109107574A (en) | 2018-08-01 | 2018-08-01 | Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810861350.5A CN109107574A (en) | 2018-08-01 | 2018-08-01 | Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109107574A true CN109107574A (en) | 2019-01-01 |
Family
ID=64863781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810861350.5A Pending CN109107574A (en) | 2018-08-01 | 2018-08-01 | Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109107574A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975906A (en) * | 2019-12-24 | 2020-04-10 | 湖南农业大学 | Silver vanadate/silver carbonate p-n heterojunction composite photocatalyst and preparation method and application thereof |
| CN111036256A (en) * | 2019-12-19 | 2020-04-21 | 昆明理工大学 | Preparation method of vanadate composite Mxene aerogel photocatalyst |
| CN111952595A (en) * | 2020-07-21 | 2020-11-17 | 华南理工大学 | Dendritic-crystal-free metal negative electrode carrier based on tip effect and preparation method thereof |
| CN113385161A (en) * | 2021-07-02 | 2021-09-14 | 青岛瑞利特新材料科技有限公司 | Formaldehyde removal material of graphene nano composite gel and preparation process |
| CN115779972A (en) * | 2022-12-27 | 2023-03-14 | 中南大学 | Graphene oxide-based composite aerogel catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013116733A1 (en) * | 2012-02-03 | 2013-08-08 | The Massachusetts Institute Of Technology | Aerogels and methods of making same |
| CN105562053A (en) * | 2016-01-04 | 2016-05-11 | 西南石油大学 | Preparation method of macroscopic aerogel photocatalyst material |
| CN106890657A (en) * | 2017-01-06 | 2017-06-27 | 华南理工大学 | A kind of graphene oxide/silver phosphate/composite photo-catalyst and preparation and application |
| CN107159068A (en) * | 2017-06-21 | 2017-09-15 | 北京石油化工学院 | A kind of preparation method of graphene composite aerogel |
-
2018
- 2018-08-01 CN CN201810861350.5A patent/CN109107574A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013116733A1 (en) * | 2012-02-03 | 2013-08-08 | The Massachusetts Institute Of Technology | Aerogels and methods of making same |
| CN105562053A (en) * | 2016-01-04 | 2016-05-11 | 西南石油大学 | Preparation method of macroscopic aerogel photocatalyst material |
| CN106890657A (en) * | 2017-01-06 | 2017-06-27 | 华南理工大学 | A kind of graphene oxide/silver phosphate/composite photo-catalyst and preparation and application |
| CN107159068A (en) * | 2017-06-21 | 2017-09-15 | 北京石油化工学院 | A kind of preparation method of graphene composite aerogel |
Non-Patent Citations (2)
| Title |
|---|
| I.S.YAHIA, ET AL: "The photocatalytic activity of graphene oxide/Ag3PO4 nano-composite: Loading effect", 《OPTIK》 * |
| LI YANG, ET AL: "Enhanced visible-light photocatalytic performance of a monolithic tungsten oxide/graphene oxide aerogel for nitric oxide oxidation", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036256A (en) * | 2019-12-19 | 2020-04-21 | 昆明理工大学 | Preparation method of vanadate composite Mxene aerogel photocatalyst |
| CN110975906A (en) * | 2019-12-24 | 2020-04-10 | 湖南农业大学 | Silver vanadate/silver carbonate p-n heterojunction composite photocatalyst and preparation method and application thereof |
| CN110975906B (en) * | 2019-12-24 | 2023-05-26 | 湖南农业大学 | Silver vanadate/silver carbonate p-n heterojunction composite photocatalyst and preparation method and application thereof |
| CN111952595A (en) * | 2020-07-21 | 2020-11-17 | 华南理工大学 | Dendritic-crystal-free metal negative electrode carrier based on tip effect and preparation method thereof |
| CN113385161A (en) * | 2021-07-02 | 2021-09-14 | 青岛瑞利特新材料科技有限公司 | Formaldehyde removal material of graphene nano composite gel and preparation process |
| CN115779972A (en) * | 2022-12-27 | 2023-03-14 | 中南大学 | Graphene oxide-based composite aerogel catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109107574A (en) | Silver-based oxysalt/graphite oxide aerogel preparation method and its aeroge obtained and application | |
| Long et al. | Oxidation of SO 2 to SO 3 catalyzed by graphene oxide foams | |
| US20130230709A1 (en) | Porous graphene material and preparation method and uses as electrode material thereof | |
| Sun et al. | Multi-crystalline N-doped Cu/CuxO/C foam catalyst derived from alkaline N-coordinated HKUST-1/CMC for enhanced 4-nitrophenol reduction | |
| CN108421545B (en) | Application of manganese dioxide composite material | |
| Zhou et al. | Facile synthesis of ultrathin SnNb 2 O 6 nanosheets towards improved visible-light photocatalytic H 2-production activity | |
| Nie et al. | Platinum supported on reduced graphene oxide as a catalyst for hydrogenation of nitroarenes | |
| Liu et al. | Bismuth oxyiodide–graphene nanocomposites with high visible light photocatalytic activity | |
| He et al. | Controllable synthesis, characterization, and CO oxidation activity of CeO2 nanostructures with various morphologies | |
| Chen et al. | Highly active catalysts based on 3D hierarchically ordered porous carbon with entrapped Fe2O3 nanoparticles for the thermal decomposition of ammonium perchlorate | |
| Patil et al. | Nitrogen and sulphur co-doped multiwalled carbon nanotubes as an efficient electrocatalyst for improved oxygen electroreduction | |
| Zou et al. | Controllable interface engineering of g-C3N4/CuS nanocomposite photocatalysts | |
| Han et al. | Controlled synthesis of double-shelled CeO 2 hollow spheres and enzyme-free electrochemical bio-sensing properties for uric acid | |
| Yang et al. | Construction of core-shell mesoporous carbon nanofiber@ nickel cobaltite nanostructures as highly efficient catalysts towards 4-nitrophenol reduction | |
| CN102581297A (en) | Method for preparing controllable green synthetic metallic nano-materials based on graphene oxide | |
| Zhao et al. | Multiple Au cores in CeO2 hollow spheres for the superior catalytic reduction of p-nitrophenol | |
| Li et al. | Platinum nano-catalysts deposited on reduced graphene oxides for alcohol oxidation | |
| CN103553023A (en) | Preparation method of nitrogen hybridized spherical mesoporous carbon | |
| CN106359373A (en) | Porous graphene zinc-oxide-loaded antibacterial composite material and preparation method thereof | |
| Miao et al. | MnO2/MWCNTs nanocomposites as highly efficient catalyst for indoor formaldehyde removal | |
| Gong et al. | Critical review of catalytic degradation of formaldehyde via MnO2: From the perspective of process intensification | |
| KR20060127408A (en) | Process for purifying carbon nanotubes made on refractory oxide supports | |
| Yu et al. | Hollow copper–ceria microspheres with single and multiple shells for preferential CO oxidation | |
| Li et al. | Highly effective catalytic reduction of nitrobenzene compounds with gold nanoparticle-immobilized hydroxyapatite nanowire-sintered porous ceramic beads | |
| Zhao et al. | Facile synthesis of Co-N4-doped mesoporous carbon for oxygen reduction reaction |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190101 |