CN110237853A - A kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst and its application in VOCs purification - Google Patents
A kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst and its application in VOCs purification Download PDFInfo
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- CN110237853A CN110237853A CN201910615439.8A CN201910615439A CN110237853A CN 110237853 A CN110237853 A CN 110237853A CN 201910615439 A CN201910615439 A CN 201910615439A CN 110237853 A CN110237853 A CN 110237853A
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- Prior art keywords
- silver
- chromic acid
- gadolinium
- acid gadolinium
- phosphoric acid
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- XFQMCTLETCOYPP-UHFFFAOYSA-L [Gd].[Cr](=O)(=O)(O)O Chemical compound [Gd].[Cr](=O)(=O)(O)O XFQMCTLETCOYPP-UHFFFAOYSA-L 0.000 title claims abstract description 64
- 239000004332 silver Substances 0.000 title claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 58
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 11
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000007540 photo-reduction reaction Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 10
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000161 silver phosphate Inorganic materials 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 239000011651 chromium Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 25
- 238000003756 stirring Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 229910001961 silver nitrate Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- -1 silver orthophosphate Compound Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion 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
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- JAOZQVJVXQKQAD-UHFFFAOYSA-K gadolinium(3+);phosphate Chemical compound [Gd+3].[O-]P([O-])([O-])=O JAOZQVJVXQKQAD-UHFFFAOYSA-K 0.000 description 1
- RQXZRSYWGRRGCD-UHFFFAOYSA-H gadolinium(3+);tricarbonate Chemical compound [Gd+3].[Gd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RQXZRSYWGRRGCD-UHFFFAOYSA-H 0.000 description 1
- 210000004919 hair shaft Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/39—
Abstract
The invention discloses a kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst and its application in VOCs purification, the form of presentation of the compound is GdCrO3/Ag/Ag3PO4.The preparation method is as follows: 1) take gadolinium source and chromium source in mortar according to the ratio of 1:1, suitable urea is added, grinding is uniformly placed in particular atmosphere high temperature and roasts, and obtains chromic acid gadolinium；2) Argent grain is loaded on chromic acid gadolinium, obtains chromic acid gadolinium/silver composite；3) silver orthophosphate is loaded on chromic acid gadolinium/silver, obtains chromic acid gadolinium/silver/phosphoric acid silver composite.GdCrO produced by the present invention3/Ag/Ag3PO4In simple substance Ag plasma resonance occurs under excited by visible light and generates thermoelectron-hole pair.Thermoelectron-hole is to the semiconductor GdCrO for being connected to energy gap separation3And Ag3PO4Without sacrificing their oxidation or reduction potential, to enhance the photocatalytic redox ability of compound.GdCrO3/Ag/Ag3PO4It is used for photocatalysis degradation organic contaminant.It is under radiation of visible light and mild reaction conditions, and such as 90oC, typical case's organic gaseous contamination object such as complete catalytic purification toluene, dimethylbenzene and benzene.
Description
Technical field
The present invention relates to a kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst and its applications in VOCs purification, belong to
In catalysis material and environmental protection technical field.
Background technique
Photocatalytic pollutant degradation technology has the characteristics that mild condition energy consumption of reaction is low, is the technology for most having application prospect
One of.But traditional photochemical catalyst, such as TiO2, there are the quick compound, quantum yield of photo-generate electron-hole pair is low and purification efficiency
The problems such as low.The building of the heterogeneous system of compound is considered as effective ways of the reduction photo-generate electron-hole to recombination rate, such as
By constructing Z-type hetero-junctions In2O3-Ag-Ag3PO4(Chemical Engineering Journal,2017, 320, 644-
, or tradition II type hetero-junctions Ag 652.)2S/Ag3PO4(Applied Catalysis B: Environmental, 2017,
209,566-578.) Ag can be promoted3PO4The separative efficiency of upper photoproduction electron-hole pair.However, these existing heterogeneous systems
The case where Constructed wetlands and technology original oxidation of generally existing its compositing monomer of sacrifice or reduction potential, fail effectively to promote light
The performance of catalytic purification organic pollutant.
Summary of the invention
For the heterogeneous system problem encountered of compound in the above photocatalysis field, the present invention provides a kind of chromic acid
Gadolinium/silver/phosphoric acid silver composite photochemical catalyst (GdCrO3/Ag/Ag3PO4) and its preparation method and application.The complex catalysts
It is in terms of 100% by the weight of catalyst in agent, the weight fraction of simple substance Ag is 0.1% ~ 20%, the weight fraction of silver orthophosphate is 1% ~
40.0%.Simple substance Ag in the compound occur under excited by visible light plasma resonance effect generate thermoelectron-hole to
Receive Ag3PO4The light induced electron of generation, and pass it to GdCrO3Photohole on, by energy gap separate GdCrO3With
Ag3PO4Respective oxidation or reduction potential are connected and taken full advantage of, efficient GdCrO is prepared3/Ag/Ag3PO4Compound object light
Catalysis material.
Above-mentioned chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst preparation method, comprising the following steps:
(1) it takes gadolinium source and chromium source in mortar according to the ratio of 1:1, suitable urea is added, grinding is uniformly placed on specific gas
The roasting of atmosphere high temperature, obtains chromic acid gadolinium；
(2) Argent grain is loaded on chromic acid gadolinium, obtains chromic acid gadolinium/silver composite；
(3) silver orthophosphate is loaded on chromic acid gadolinium/silver, obtains chromic acid gadolinium/silver/phosphoric acid silver composite.
Wherein, gadolinium nitrate, gadolinium chloride, Gadolinium monophosphate, gadolinium carbonate, Digadolinium trisulfate etc., preferably nitre can be selected in the gadolinium source of step (1)
Sour gadolinium；Chromic nitrate, chromium chloride, chromium phosphate, chromium carbonate, chromium sulfate etc., preferably chromic nitrate can be selected in chromium source.Calcination atmosphere is sky
Gas can also be replaced with the mixed gas for the different proportion that oxygen and inert gas form, and calcination temperature is 150 ~ 1100oC, roasting
The burning time is 0.1 ~ 24 h.It is preferred that maturing temperature is 700 ~ 900oC, calcining time are 3 ~ 6 h.
In step (2), silver-colored source can be silver nitrate, silver chlorate, silver orthophosphate, silver sulfate etc., preferably silver nitrate and to be made into presoma molten
Liquid.Using liquid phase reduction, select glucose solution as reducing agent, silver is reducing loaded on chromic acid gadolinium.Also it can be selected
NaBH4Or other reducing agents, or select other restoring method such as photoreduction method, calcining reduction method by Ag particulate load to chromic acid
On gadolinium.
The method of the compound chromic acid gadolinium/silver of silver orthophosphate in step (3) is liquid phase deposition.Select disodium hydrogen phosphate aqueous solution
With silver nitrate aqueous solution as precursor solution, in chromic acid gadolinium/silver liquid phase reactive deposition silver orthophosphate.Also solid-phase grinding can be selected
Composite algorithm compound phosphoric acid silver on silver/chromic acid gadolinium.
The GdCrO of perovskite structure is prepared with roasting method3It is disclosed report, such as Hou (Applied Catalysis B: Environmental, 2018,232,124-134.) and report roasting method preparation pure phase GdCrO3Method.In liquid phase
In reduction method, glucose is also disclosed report as reducing agent reduction silver ion elemental silver, such as Bi (Chemistry-A European Journal, 2012,18,14272-14275.) and use glucose solution in the Ag of cubic type3PO4Upper selection
Property reduction prepare elemental silver.Above-mentioned roasting and liquid phase reduction is also those skilled in the art's common experimental condition.But the present invention
By accurately controlling the ratio of composite materials component, the additional amount and reducing condition, phosphate radical original position partial corrosion chromium in silver-colored source
The processes such as sour gadolinium/silver and silver orthophosphate in-situ deposition have obtained chromic acid gadolinium/silver/phosphoric acid silver composite for the first time.
It is also another object of the present invention to provide chromic acid gadolinium/silver/phosphoric acid silver composite applications.
Chromic acid gadolinium provided by the present invention/silver/phosphoric acid silver composite application is that it volatilizees in photocatalytic degradation air
Application in property organic gaseous contamination object (or VOCs), such as toluene, dimethylbenzene, benzene gas pollutant.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that (1) chromic acid gadolinium/silver/phosphoric acid silver composite
Preparation process it is simple, experimental period is short, and in addition to chromic acid gadolinium is related to high―temperature nuclei, remaining step can carry out at room temperature, just
In industry's enlarging production.(2) chromic acid gadolinium/silver/phosphoric acid silver composite for being prepared of the present invention can be in radiation of visible light and mild
Under reaction condition, such as 90oC, the typical case such as complete catalytic purification toluene, dimethylbenzene and benzene VOCs.
Specific embodiment
The present invention is described in further detail below with reference to specific embodiment, but implementation method spirit of the invention
It is living, it is not limited only to the concrete operations mode described in this, others are any without departing from the spirit and principles of the present invention
Made changes, modifications, substitutions, combinations, simplifications should be equivalent substitute mode, be included in protection scope of the present invention
Within.
Embodiment 1
A kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst: (1) gadolinium nitrate and chromic nitrate that molar ratio is 1:1 are weighed in containing
Have and be transferred to 3 h of lower 850 DEG C of roastings of air atmosphere in Muffle furnace after grinding uniformly in the mortar of appropriate urea, obtains chromic acid gadolinium；
(2) 0.6 g chromic acid gadolinium is added to the silver-colored ammonia prepared by the weak aqua ammonia of 30 mL, 42.47 g/L silver nitrate aqueous solution and 0.5mol/L
The glucose solution for adding 297.25 g/L of 20 mL after 30 min is stirred in solution, and is continued to stir 5 min and obtained chromium
Sour gadolinium/silver composite；(3) 0.3 g chromic acid gadolinium/silver composite is added to the disodium hydrogen phosphate aqueous solution of 9.47 g/L of 30 mL
The 5.67 g/L silver nitrate aqueous solutions of 15 mL are added dropwise again after 30 min of middle stirring, and continue to obtain chromic acid after stirring 30 min
Gadolinium/silver/phosphoric acid silver composite, with the weight of catalyst for 100%, the mass fraction of simple substance Ag is 4.2%, the quality point of silver orthophosphate
Number is 25.9%.
Comparative example 1
Compare a kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst.Chromic acid gadolinium in 0.3 g embodiment 1 is added 30mL's
After stirring 30 min in the disodium hydrogen phosphate aqueous solution of 9.47 g/L, then be added dropwise to 30 mL 5.67 g/L silver nitrates it is water-soluble
Liquid, and continue to obtain chromic acid gadolinium/phosphoric acid silver composite after stirring 30 min.
Comparative example 2
Compare a kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst.Weigh molar ratio be 1:1 gadolinium nitrate and chromic nitrate in
3 h of lower 850 DEG C of roastings of air atmosphere in Muffle furnace are transferred to after grinding uniformly in mortar containing appropriate urea, obtain chromic acid
Gadolinium；(2) 0.6 g chromic acid gadolinium is added and is prepared by the 42.47 g/L silver nitrate aqueous solutions of 30 mL and the weak aqua ammonia of 0.5 mol/L
Silver ammino solution in stir the glucose solution that 297.25 g/L of 20 mL are added after 30 min, and continue stirring 5
Min obtains chromic acid gadolinium/silver composite.
Comparative example 3
Compare a kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst.(1) by the 14.2 g/L disodium hydrogen phosphate water of 30 mL
Solution is added dropwise in the 42.47 g/L silver nitrate aqueous solutions of 30 mL, and 30 min of stirring obtain silver orthophosphate；(2) by 0.3 g silver orthophosphate
It is added in the silver ammino solution prepared by the 21.23 g/L silver nitrate aqueous solutions of 30 mL and the weak aqua ammonia of 0.5 mol/L and stirs 30
The glucose solution of 148.63 g/L of 20 mL is added after min, and is continued 5 min of stirring and obtained silver orthophosphate/silver composite.
Embodiment 2
A kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst: (1) gadolinium nitrate and chromic nitrate that molar ratio is 1:1 are weighed in containing
Have and be transferred to 6 h of lower 700 DEG C of roastings of air atmosphere in Muffle furnace after grinding uniformly in the mortar of appropriate urea, obtains chromic acid gadolinium；
(2) 0.6 g chromic acid gadolinium is added after stirring 30 min by the 15.0 g/L silver nitrate aqueous solutions of 30 mL and adds 10 mL's
The NaBH of 5.0 g/L4Aqueous solution, and continue 10 min of stirring and obtain chromic acid gadolinium/silver composite；(3) 0.3 g chromic acid gadolinium/silver is multiple
It closes object and the mixed mill of 0.05 g silver orthophosphate uniformly closes, 500 in nitrogen atmosphereoC calcines 2 h and obtains chromic acid gadolinium/silver/silver orthophosphate
Compound, with the weight of catalyst for 100%, the mass fraction of simple substance Ag is 11.1%, and the mass fraction of silver orthophosphate is 14.3%.
Embodiment 3
A kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst: (1) gadolinium nitrate and chromic nitrate that molar ratio is 1:1 are weighed in containing
Have and be transferred to 4.5 h of lower 800 DEG C of roastings of air atmosphere in Muffle furnace after grinding uniformly in the mortar of appropriate urea, obtains chromic acid
Gadolinium；(2) the 24.0 g/L silver nitrate water-ethanol mixed solutions by 30 mL, the illumination 30 under Xe lamp is added in 0.6 g chromic acid gadolinium
Chromic acid gadolinium/silver composite is obtained after min；(3) 0.3 g chromic acid gadolinium/silver composite is added to the phosphoric acid hydrogen of 14.21 g/L of 30 mL
The 8.51 g/L silver nitrate aqueous solutions of 15 mL are added dropwise after stirring 30 min in two sodium water solutions, and continue to obtain after stirring 30 min
To chromic acid gadolinium/silver/phosphoric acid silver composite, with the weight of catalyst for 100%, the mass fraction of simple substance Ag is 0.4%, silver orthophosphate
Mass fraction is 33.3%.
Embodiment 4
A kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst and preparation method thereof: (1) gadolinium nitrate that molar ratio is 1:1 is weighed
It is transferred to the lower 900 DEG C of calcinings 2 of air atmosphere in Muffle furnace after grinding uniformly in the mortar containing appropriate urea with chromic nitrate
H obtains chromic acid gadolinium；(2) after the 30.0 g/L silver nitrate ethanol waters meeting hair shaft by 30 mL being added in 0.6 g chromic acid gadolinium, in
500 o2 h of air calcination restores to obtain chromic acid gadolinium/silver composite under C；(3) 0.3 g chromic acid gadolinium/silver composite is added 30 mL's
The 11.34 g/L silver nitrate aqueous solutions that 15 mL are added dropwise after 30 min are stirred in the disodium hydrogen phosphate aqueous solution of 18.94 g/L, and
Continue to obtain chromic acid gadolinium/silver/phosphoric acid silver composite after stirring 30 min, with the weight of catalyst for 100%, the quality of simple substance Ag
Score is 12.3%, and the mass fraction of silver orthophosphate is 40.0%.
Catalyst described in 0.2 g embodiment 1-4 and comparative example 1-3 is taken respectively, and uniform coating is in 7.0 cm2Surface plate
On, it is placed in reactor bottom, with gaseous mixture (O2:N2=1:3) purge CO in 30 min removing reaction kettle2.Toluene, dimethylbenzene or
Benzene visible light catalytic reaction experiment condition: toluene gas is by being bubbled, by gaseous mixture (O2:N2=1:3) it is blown into reaction kettle, dimethylbenzene
It is added outside reactor with benzene by liquid-transfering gun.The initial concentration of toluene, dimethylbenzene or benzene in a kettle is all ~ 700 ppm, light
It is protected from light 30 min of processing at room temperature according to preceding reaction kettle, so that toluene, dimethylbenzene or benzene is reached adsorption-desorption in catalyst surface and put down
Weighing apparatus.The xenon lamp of 300 W of UVIR-cut400 filter plate is loaded onto as simulated visible light source (λ=400 ~ 780 nm, light intensity 100
mw·cm-2), 90 oCUnder the conditions of react 2 h, pass through gas-chromatography (GC7900, FID) and detect toluene, dimethylbenzene or benzene concentration
CO is detected with gas-chromatography (GC2060, FID)2The elimination factor of yield and be used to convert toluene, dimethylbenzene or benzene.
Activity evaluation under 1 chromic acid gadolinium of table/silver/phosphoric acid silver composite photochemical catalyst radiation of visible light
Claims (6)
1. a kind of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst, it is characterised in that: with the weight of catalyst for 100%, simple substance
The weight fraction of silver is 0.1% ~ 20%, and the weight fraction of silver orthophosphate is 1% ~ 40.0%.
2. the preparation method of chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst as described in claim 1 the following steps are included:
(1) it takes gadolinium nitrate and chromic nitrate in mortar according to the ratio of 1:1, suitable urea is added, grinding, which is uniformly placed on, to be contained
The roasting of oxygen atmosphere high temperature, obtains chromic acid gadolinium；
(2) Argent grain is loaded on chromic acid gadolinium, obtains chromic acid gadolinium/silver composite；
(3) silver orthophosphate is loaded on chromic acid gadolinium/silver, obtains chromic acid gadolinium/silver/phosphoric acid silver composite.
3. preparation method according to claim 2, which is characterized in that the calcination temperature in step (1) is 150 ~ 1100oC calcines as 0.1 ~ 24 h.
4. preparation method according to claim 2, which is characterized in that use liquid phase reduction, photoreduction in step (2)
The restoring method such as method or gas phase reduction process load to silver ion reduction on chromic acid gadolinium.
5. preparation method according to claim 2, which is characterized in that loaded on chromic acid gadolinium/silver described in step (3)
The method of silver orthophosphate is liquid phase deposition or solid-phase grinding composite algorithm.
6. application of the claim 1 ~ 5 chromic acid gadolinium/silver/phosphoric acid silver composite photochemical catalyst in VOCs purification.
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