CN107442105B - It can be used for preparing tungsten manganese calcium/mesoporous tungsten trioxide compound and preparation method thereof of light anode - Google Patents
It can be used for preparing tungsten manganese calcium/mesoporous tungsten trioxide compound and preparation method thereof of light anode Download PDFInfo
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- CN107442105B CN107442105B CN201710608650.8A CN201710608650A CN107442105B CN 107442105 B CN107442105 B CN 107442105B CN 201710608650 A CN201710608650 A CN 201710608650A CN 107442105 B CN107442105 B CN 107442105B
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- tungsten trioxide
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 91
- GNOAGEUIAVUWRB-UHFFFAOYSA-N [Ca].[Mn].[W] Chemical compound [Ca].[Mn].[W] GNOAGEUIAVUWRB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- -1 tungsten trioxide compound Chemical class 0.000 title claims abstract description 23
- SAXPPRUNTRNAIO-UHFFFAOYSA-N [O-2].[O-2].[Ca+2].[Mn+2] Chemical compound [O-2].[O-2].[Ca+2].[Mn+2] SAXPPRUNTRNAIO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- TUEGREKNWIPDRA-UHFFFAOYSA-N [Ca].[Mn] Chemical compound [Ca].[Mn] TUEGREKNWIPDRA-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000001639 calcium acetate Substances 0.000 claims description 9
- 235000011092 calcium acetate Nutrition 0.000 claims description 9
- 229960005147 calcium acetate Drugs 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WDYDGOPLWKQFKI-UHFFFAOYSA-N [O].[Ca].[Mn] Chemical compound [O].[Ca].[Mn] WDYDGOPLWKQFKI-UHFFFAOYSA-N 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims 4
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 38
- 239000001301 oxygen Substances 0.000 abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 abstract description 38
- 238000000926 separation method Methods 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- DEKNNPQZTNWERU-UHFFFAOYSA-N [O-2].[Ca+2].[Mn+2].[W+4].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ca+2].[Mn+2].[W+4].[O-2].[O-2].[O-2] DEKNNPQZTNWERU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 239000001257 hydrogen Substances 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- GSGIQJBJGSKCDZ-UHFFFAOYSA-H hexachlororhenium Chemical compound Cl[Re](Cl)(Cl)(Cl)(Cl)Cl GSGIQJBJGSKCDZ-UHFFFAOYSA-H 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000012300 argon atmosphere Substances 0.000 description 8
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000007171 acid catalysis Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000252506 Characiformes Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 239000003643 water by type 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses tungsten manganese calcium/mesoporous tungsten trioxide compounds that can be used for preparing light anode and preparation method thereof, in the tungsten manganese calcium/mesoporous tungsten trioxide compound, including mesoporous tungsten trioxide, manganese calcium oxide.Mesoporous tungsten trioxide has shorter electron transfer distance, and island tungsten manganese calcium oxide has lower oxygen deposition potential as is produced from oxygen activity center site, so with light anode made of the compound there is very high photocatalysis to produce oxygen activity.This tri compound semiconductor catalyst is compared with corresponding one-component catalyst, pass through the compound defect for overcoming single catalyst of manganese calcium and tungsten oxide, have many advantages, such as that separation of charge is high-efficient, overpotential for oxygen evolution is small, catalytic activity and stability are good, is a kind of new catalytic material of great desired preparation photochemistry pond light anode.
Description
Technical field
The present invention relates to a kind of ternary complex catalysts, and in particular to one kind can be used for preparing photochemical catalyzing photochemistry
The optical anode material catalyst in pond and preparation method thereof.
Background technique
Hydrogen is a kind of clean energy, and calorific value is high, environmental-friendly, convenient transportation, and combustion product is water, not to environment
Generate any harm.Water reserve is enriched, is easy to get, is cheap on the earth.Catalysis water decomposition generates under sunlight irradiation
Hydrogen and oxygen are a kind of methods for preferably converting solar energy into chemical energy.Photocatalysis point with industrialization practical value
The reaction of Xie Shui carries out in photoelectrochemistrpool pool.The reaction that photoelectrochemistrpool pool decomposes water includes the reduction reaction and light of photocathode water
Two half-reactions of oxidation reaction of anode water.Water oxidation reaction process in light anode is four electron reactions, which restricts
The progress of entire reaction.Therefore, obtaining can effectively realize that photocatalysis water oxygenization generates the light anode catalyst of oxygen especially
It is important.Existing tungsten oxide catalyst there are the absorption coefficients of light low, light induced electron and hole easily compound, oxygen are precipitated on tungsten oxide
The disadvantages of current potential is higher.
Summary of the invention
The present invention provides a kind of mesoporous tungsten trioxides and Layered Manganese calcium oxide to be compounded in mesoporous tungsten trioxide surface shape
At the preparation method of island tungsten manganese calcium ternary complex；This tri compound semiconductor catalyst is urged with corresponding one-component
Agent is compared, by the compound defect for overcoming single catalyst of manganese calcium and tungsten oxide, analysis oxygen high-efficient with separation of charge
The advantages that overpotential is small, catalytic activity and stability are good is a kind of novel the urging of great desired preparation photochemistry pond light anode
Change material.
The technical solution adopted by the present invention is that:
A kind of tungsten manganese calcium/mesoporous tungsten trioxide compound can be used for preparing light anode, including active constituent I, activity at
Divide II, wherein active constituent I is mesoporous tungsten trioxide；Active constituent II be Layered Manganese calcium oxide, mass percent be 1.5~
12%, preferably 7~11 % can give full play to the catalysis advantage of compound, obtain the product of high yield.
In tungsten manganese calcium/mesoporous tungsten trioxide compound disclosed by the invention, mesoporous tungsten trioxide has shorter electron transfer
Distance, island tungsten manganese calcium oxide have lower oxygen deposition potential, so with the compound as is produced from oxygen activity center site
There is manufactured light anode very high photocatalysis to produce oxygen activity.Therefore it can be used for preparing light anode the invention also discloses described
Tungsten manganese calcium/mesoporous tungsten trioxide compound preparation optical anode material in application and anode-catalyzed as photoelectrochemistrpool pool
The application of agent.
The above-mentioned tungsten manganese calcium/mesoporous tungsten trioxide compound preparation method that can be used for preparing light anode is, by manganese calcium oxygen
It is scattered in solvent after compound and mesoporous tungsten trioxide mixed grinding, is centrifugated after reaction；It then will be after centrifugal solids drying
It is calcined in inert gas, obtains the tungsten manganese calcium/mesoporous tungsten trioxide compound that can be used for preparing light anode.
In the present invention, the mesoporous tungsten trioxide is prepared using phosphotungstic acid and mesoporous silicon oxide as raw material；With a water acetic acid
Calcium and four water manganese acetates are that raw material prepares the manganese calcium oxide under potassium hydroxide, potassium permanganate；The condition of the calcining
It is 1 ~ 4 h of calcining at 200 ~ 600 DEG C.
Further, after phosphotungstic acid being mixed in a solvent with mesoporous silicon oxide, centrifugal treating, after centrifugal solids are dry
3 ~ 6 h are calcined at 400 ~ 600 DEG C, and then calcined solid is distributed in hydrofluoric acid, is centrifugated after stirring, is situated between
Hole tungstic acid；One water calcium acetate and four water manganese acetates are dissolved in water, KOH aqueous solution is then added, then be added dropwise
KMnO4Aqueous solution is centrifugated after reaction, and centrifugal solids are washed for several times through deionized water, dry vacuum, then in an inert atmosphere
2 ~ 8 h are calcined at 300 ~ 600 DEG C, obtain manganese calcium oxide.
The above-mentioned tungsten manganese calcium/mesoporous tungsten trioxide compound preparation method that can be used for preparing light anode specifically includes as follows
Step:
(1) preparation of mesoporous tungsten trioxide
Under magnetic agitation, phosphotungstic acid and aperture is added into dehydrated alcohol as the mesopore silicon oxide (KIT-6) of 7-8 nm, stirs
It after mixing 1 ~ 3 h, is centrifuged, dry, solid calcines 3 ~ 6 h, cooled to room temperature at 400 ~ 600 DEG C.The solid that will be obtained again
It is distributed in hydrofluoric acid (1 ~ 5 mol/L), is centrifugated after 6 h are stirred at room temperature.Solid is after deionized water is washed for several times, In
Dry 10 h, obtain mesoporous tungsten trioxide at 150 DEG C；Yield is about 80-90 %.
(2) preparation of manganese calcium oxide
Under magnetic stirring, a water calcium acetate and four water manganese acetates are dissolved in after deionized water and are slowly added to KOH aqueous solution (1-
10 mol/L), brown suspension is obtained, then KMnO is added dropwise4(0.02-0.1 mol/L) aqueous solution, persistently it is stirred to react 5 ~
After 10h, centrifuge separation, solid washs for several times through deionized water, dry vacuum, then in the tube furnace of argon atmosphere in 300 ~
2 ~ 8 h are calcined at 600 DEG C, obtain manganese calcium oxide；Yield is about 90-95 %.
(3) tungsten manganese calcium/mesoporous tungsten trioxide complex catalyst preparation
Mesoporous tungsten trioxide and manganese calcium oxide are put into and are added in ball grinder, in 300 ~ 500 on star-like ball mill
It under rpm after grinding at room temperature 3-10 h, is dispersed in deionized water, ultrasonic reaction 5-20 h.Centrifuge separation, solid is through dry vacuum
Afterwards, 1 ~ 4 h is calcined at 200 ~ 600 DEG C in the tube furnace of argon atmosphere, obtains tungsten manganese calcium/Jie that can be used for preparing light anode
Hole tungstic acid compound.Yield is about 90-98 %.
The invention also discloses a kind of light-catalyzed reaction anodes and preparation method thereof, by manganese calcium oxide and mesoporous three oxidation
It is scattered in solvent after tungsten mixed grinding, is centrifugated after reaction；Then it will be calcined in inert gas after centrifugal solids drying,
Obtain the tungsten manganese calcium/mesoporous tungsten trioxide compound that can be used for preparing light anode；Tungsten manganese calcium/mesoporous tungsten trioxide compound is molten
Liquid is coated on clean electro-conductive glass, and dry roasting obtains light-catalyzed reaction anode.
In the present invention, the mesoporous tungsten trioxide is prepared using phosphotungstic acid and mesoporous silicon oxide as raw material；With a water acetic acid
Calcium and four water manganese acetates are raw material, under potassium hydroxide, potassium permanganate effect, prepare the manganese calcium oxide；The calcining
Condition is that 1 ~ 4 h is calcined at 200 ~ 600 DEG C.
Further, after phosphotungstic acid being mixed in a solvent with mesoporous silicon oxide, centrifugal treating, after centrifugal solids are dry
3 ~ 6 h are calcined at 400 ~ 600 DEG C, and then calcined solid is distributed in hydrofluoric acid, is centrifugated after stirring, is situated between
Hole tungstic acid；One water calcium acetate and four water manganese acetates are dissolved in water, KOH aqueous solution is then added, then be added dropwise
KMnO4Aqueous solution is centrifugated after reaction, and centrifugal solids are washed for several times through deionized water, dry vacuum, then in an inert atmosphere
2 ~ 8 h are calcined at 300 ~ 600 DEG C, obtain manganese calcium oxide.
Specifically comprise the following steps:
(1) preparation of mesoporous tungsten trioxide
Under magnetic agitation, phosphotungstic acid and aperture is added into dehydrated alcohol as the mesopore silicon oxide (KIT-6) of 7-8 nm, stirs
It after mixing 1 ~ 3 h, is centrifuged, dry, solid calcines 3 ~ 6 h, cooled to room temperature at 400 ~ 600 DEG C.The solid that will be obtained again
It is distributed in hydrofluoric acid (1 ~ 5 mol/L), is centrifugated after 6 h are stirred at room temperature.Solid is after deionized water is washed for several times, In
Dry 10 h, obtain mesoporous tungsten trioxide at 150 DEG C；Yield is about 80-90 %.
(2) preparation of manganese calcium oxide
Under magnetic stirring, a water calcium acetate and four water manganese acetates are dissolved in after deionized water and are slowly added to KOH aqueous solution (1-
10 mol/L), brown suspension is obtained, then KMnO is added dropwise4(0.02-0.1 mol/L) aqueous solution, persistently it is stirred to react 5 ~
After 10h, centrifuge separation, solid washs for several times through deionized water, dry vacuum, then in the tube furnace of argon atmosphere in 300 ~
2 ~ 8 h are calcined at 600 DEG C, obtain manganese calcium oxide；Yield is about 90-95 %.
(3) tungsten manganese calcium/mesoporous tungsten trioxide complex catalyst preparation
Mesoporous tungsten trioxide and manganese calcium oxide are put into and are added in ball grinder, in 300 ~ 500 on star-like ball mill
It under rpm after grinding at room temperature 3-10 h, is dispersed in deionized water, ultrasonic reaction 5-20 h.Centrifuge separation, solid is through dry vacuum
Afterwards, 1 ~ 4 h is calcined at 200 ~ 600 DEG C in the tube furnace of argon atmosphere, obtains tungsten manganese calcium/Jie that can be used for preparing light anode
Hole tungstic acid compound.Yield is about 90-98 %.
(4) preparation of light-catalyzed reaction anode
Tungsten manganese calcium/mesoporous tungsten trioxide complex solution is coated on clean electro-conductive glass, dry roasting obtains
Light-catalyzed reaction anode.
In the present invention, when preparing mesoporous tungsten trioxide, the mass ratio of phosphotungstic acid and mesoporous silicon oxide is 1: 0.8~2；System
When standby manganese calcium oxide, the mass ratio of a water calcium acetate and four water manganese acetates is 1: 3~6.
Catalyst disclosed by the invention is made of mesoporous tungsten trioxide, Layered Manganese calcium oxide compound, has high light
Catalytic activity and stability；The mesoporous tungsten trioxide of preparation and the manganese calcium oxide of stratiform are heavy by physical grinding, ultrasound removing
Island tungsten manganese calcium ternary complex is formd on mesoporous tungsten trioxide surface after long-pending and high-temperature calcination, can be used as preparation optical electro-chemistry
The light anode catalysis material in pond, the light anode prepared using the composite material is good with stability, optical response range is wide, catalysis is lived
Property it is high, preparation method is simple, without precious metal, free from environmental pollution the features such as.The invention also discloses the light-catalyzed reaction sun
Application of the pole in photochemical catalyzing.
The invention also discloses a kind of three electrode photoelectric chemical baths, including to electrode, reference electrode and above-mentioned light anode；
Described is Pt electrode to electrode, and reference electrode is saturated calomel electrode.The invention also discloses the three electrode photoelectrics chemical baths
Application in photochemical catalyzing.
The present invention has following characteristics:
1. complex catalyst disclosed by the invention has good photocatalysis performance, rich reserves, cheap and easy to get,
As photochemical catalyst have the characteristics that band gap is relatively narrow, light abstraction width is big, it is environmental-friendly, prepare simple, without precious metal, can make
It is used as the anode material that photocatalysis produces oxygen extensively for preparation photoelectrochemistrpool pool optical anode material.
2. photocatalysis of the invention the experimental results showed that, surface have island tungsten manganese calcium complexes porous tungstic acid
Catalysis material is high with photogenerated charge separative efficiency, overpotential for oxygen evolution is low, catalytic activity and stability are good, at normal temperatures and pressures
The advantages that water decomposition can be catalyzed.
Detailed description of the invention
Fig. 1 is mesoporous tungsten trioxide (A) and tungsten manganese calcium/mesoporous tungsten trioxide compound (B) transmission electron microscope picture；
Fig. 2 is tungsten manganese calcium/mesoporous tungsten trioxide compound analysis chart, wherein (A) is scanning electron microscope (SEM) photograph, (B) is
The EDX elemental analysis figure of MnCaWO, (C) are distribution map of the W element on MnCaWO, and (D) is point of the O element on MnCaWO
Butut, (E) are distribution map of the Mn element on MnCaWO, and (F) is distribution map of the Ca element on MnCaWO.
Specific embodiment
Embodiment one
After 12g phosphotungstic acid, 8g KIT-6 are mixed with 200 mL dehydrated alcohols, 2 h of magnetic agitation, centrifuge separation, solid warp
Deionized water is washed for several times, the dry 10h at 60 DEG C.5 h, cooled to room temperature are roasted at 550 DEG C again.Gained is yellowish
Color solid is distributed in 200 mL hydrofluoric acid (2mol/L) and is stirred to react 6h, centrifuge separation.Solid washs for several times through deionized water,
Vacuum drying, obtains mesoporous tungsten trioxide.
Mono- water calcium acetate of 1.2g, tetra- water manganese acetate of 3.98g are dissolved in 30mL deionized water, under magnetic stirring, slowly added
After KOH (8.6 mol/L) aqueous solution for entering 30mL, brown suspension is obtained.100 mL KMnO are added dropwise into suspension4
Aqueous solution (0.06 mol/L), room temperature magnetic agitation 8h, centrifuge separation, solid wash for several times through deionized water, dry vacuum, then
4h is calcined at 400 DEG C, obtains Layered Manganese calcium oxide.
1.82g mesoporous tungsten trioxide and 0.18 g Layered Manganese calcium oxide are added in 50 mL ball grinders, in star-like ball
After grinding 4h under 500 rpm on grinding machine, solid is scattered in ultrasound 10h in the water of 40mL.Centrifuge separation, solid is through deionized water
It washs for several times, dry vacuum, then calcines 2 h at 250 DEG C in the tube furnace of argon atmosphere, obtain tungsten manganese calcium/mesoporous three oxidation
Tungsten compound has the porous tungstic acid catalysis material (MnCaWO) of island tungsten manganese calcium complexes for surface, wherein manganese calcium
Oxide mass score is 9 wt.%.
Electro-conductive glass FTO is first cleaned into 15min with acetone and EtOH Sonicate respectively, then is cleaned by ultrasonic with Piranha solution
(solution that the concentrated sulfuric acid and dioxygen water volume ratio are 3:1) 1h, taking-up is cleaned with deionized water, dry.30mg MnCaWO is compound
Catalyst is dispersed in 6mL ethylene glycol-ethyl alcohol-PVP (20 mL:80 mL:30 mg) solution, is ground 10min, is utilized spin coating
Machine is spin-coated on FTO glass with 2000 rpm revolving speeds, 30 min is heated at 80 DEG C, solvent is allowed to volatilize, be dried in vacuo at 60 DEG C
It after 2h, is placed in the tube furnace of argon atmosphere and roasts 2h at 250 DEG C, obtain MnCaWO/FTO electrode.
Light-catalyzed reaction carries out in three electrode photoelectric chemical baths, three electrode photoelectric chemical baths, including to electrode, reference electricity
Pole and above-mentioned light anode.Pt piece is used as to electrode, and for saturated calomel electrode as reference electrode, light anode is MnCaWO/FTO electricity
Pole.Photoelectrochemistrpool pool side is connected by gas-guide tube with gas-chromatography six-way valve.Light source is 300 W simulated solar irradiation lamps.Light is urged
Change reaction condition: 30 mL of reaction solution, 0.5 mol/mL metabisulfite solution (pH ~ 1).Light source is with light anode optical transmission window distance
20 cm.Illuminating area is 19 cm2, optical electro-chemistry pool device connect with electrochemical workstation (CHI660D).First to anti-before illumination
System is answered to lead to 1 h of argon gas, with the air in exclusion system.Light-catalyzed reaction carries out at normal temperature, with gas chromatograph detection pair
The production quantity of hydrogen and oxygen on electrode and light anode.Illumination reaction 2h, applied voltage be 0.9 V vs. RHE when, hydrogen with
Oxygen output is respectively 1.9 and 0.7 μm of ol；When applied voltage is 1.0 V vs. RHE, hydrogen and oxygen output are respectively 5.3
With 1.5 μm of ol；When applied voltage is 1.1 V vs. RHE, hydrogen and oxygen output are respectively 6.0 and 2.1 μm of ol；Outer power-up
When pressure is 1.2 V vs. RHE, hydrogen and oxygen output are respectively 6.3 and 2.3 μm of ol.
Embodiment two
1.9g mesoporous tungsten trioxide and 0.10g Layered Manganese calcium oxide are added in 50 mL ball grinders, in star-like ball milling
4h is ground under 500 rpm on machine, remaining step is the same as example 1.Preparing surface has the more of island tungsten manganese calcium complexes
Hole tungstic acid catalysis material, wherein manganese calcium oxide mass fraction is 5 wt.%.Light anode preparation and photo catalysis reactor
And photocatalytic reaction conditions are also the same as example 1.Illumination reaction 2h, when applied voltage is 0.9V vs. RHE, hydrogen and oxygen
Gas yield is respectively 1.1 and 0.4 μm of ol；When applied voltage is 1.0 V vs. RHE, hydrogen and oxygen output be respectively 2.0 with
0.9 µmol；When applied voltage is 1.1V vs. RHE, hydrogen and oxygen output are respectively 2.5 and 1.1 μm of ol；Applied voltage
When for 1.2V vs. RHE, hydrogen and oxygen output are respectively 2.8 and 1.1 μm of ol.
Embodiment three
After 1.2g phosphotungstic acid, 2.4g KIT-6 are mixed with 30mL dehydrated alcohol, 2 h of magnetic agitation, centrifuge separation, solid warp
Deionized water is washed for several times, the dry 10h at 60 DEG C.5 h, cooled to room temperature are roasted at 400 DEG C again.Gained is yellowish
Color solid is distributed in 20 mL hydrofluoric acid (2mol/L) and is stirred to react 6h, centrifuge separation.Solid washs for several times through deionized water,
Vacuum drying, obtains mesoporous tungsten trioxide.The mesoporous three oxygen tungsten of the 1.86g that the method is obtained and the 0.14 of the preparation of one method of embodiment
G Layered Manganese calcium oxide is added in 50 mL ball grinders, grinds 4h under 500 rpm on star-like ball mill, with embodiment one
Method, which prepares surface, has manganese calcium oxide mass fraction in the porous tungstic acid catalysis material of island tungsten manganese calcium complexes
For 7 wt.%.Light anode preparation, photo catalysis reactor and photocatalytic reaction conditions are the same as example 1.Illumination reaction 2h, outside
When making alive is 0.9V vs. RHE, hydrogen and oxygen output are respectively 1.6,0.6 μm of ol；Applied voltage 1.0V vs. RHE
When, hydrogen and oxygen output are respectively 2.8,1.2 μm of ol；When applied voltage 1.1V vs. RHE, hydrogen and oxygen output are distinguished
It is 4.0,1.6 μm of ol；When 1.2 V vs. RHE of applied voltage, hydrogen and oxygen output are respectively 4.1,1.9 μm of ol.
Example IV
Mono- water calcium acetate of 1.2g, tetra- water manganese acetate of 6.68g are dissolved in 30 mL deionized waters, under magnetic stirring, slowly added
After KOH (5 mol/L) aqueous solution for entering 30 mL, brown suspension is obtained.100 mL KMnO are added dropwise into suspension4
Aqueous solution (0.08 mol/L), room temperature magnetic agitation 8h, centrifuge separation, solid wash for several times through deionized water, dry vacuum, then
2 h are calcined at 250 DEG C in the tube furnace of argon atmosphere, obtain Layered Manganese calcium oxide.The 0.22 g manganese that the method is obtained
Calcium oxide and the mesoporous three oxygen tungsten of 1.78g of one method of embodiment preparation are added in 50 mL ball grinders with one method system of embodiment
Standby surface has the porous tungstic acid catalysis material of island tungsten manganese calcium complexes, and wherein the mass fraction of manganese calcium oxide is
11 wt.%.Also embodiment one is identical for light anode preparation, photo catalysis reactor and photocatalytic reaction conditions.Illumination reaction 2h, it is additional
When voltage is 0.9V vs. RHE, hydrogen and oxygen output are respectively 1.7,0.5 μm of ol；When applied voltage 1.0V vs. RHE,
Hydrogen and oxygen output are respectively 4.0,1.3 μm of ol；When 1.1 V vs. RHE of applied voltage, hydrogen is respectively with oxygen output
4.8,1.7 μm of ol；When 1.2 V vs. RHE of applied voltage, hydrogen and oxygen output are respectively 5.0,2.0 μm of ol.
Embodiment five
The 1.9 g mesoporous tungsten trioxides and one method of embodiment of one method of embodiment preparation prepare 0.10 g Layered Manganese calcium oxide
It is added in 50 mL ball grinders, after grinding 4 h under 500 rpm on star-like ball mill, solid is scattered in the water of 40 mL
10 h of ultrasound.Centrifuge separation, solid wash for several times through deionized water, dry vacuum, then in 500 in the tube furnace of argon atmosphere
2 h are calcined at DEG C, preparation surface has the porous tungstic acid catalysis material of island tungsten manganese calcium complexes, and wherein manganese calcium aoxidizes
The mass fraction of object is 5 wt.%.Light anode preparation and photo catalysis reactor and photocatalytic reaction conditions are the same as example 1.
Illumination reaction 2h, when applied voltage is 0.9V vs. RHE, hydrogen and oxygen output are respectively 1.1,0.4 μm of ol；Applied voltage
When for 1.0V vs. RHE, hydrogen and oxygen output are respectively 1.8,0.6 μm of ol；When applied voltage is 1.1 V vs. RHE,
Hydrogen and oxygen output are respectively 2.3,1.0 μm of ol；When applied voltage is 1.2 V vs. RHE, hydrogen and oxygen output are distinguished
It is 2.6,1.1 μm of ol.
Comparative example one
30 mg mesoporous tungsten trioxides of one method of embodiment preparation prepare WO3/ FTO light anode.Light anode preparation and photocatalysis
Reactor and photocatalytic reaction conditions are the same as example 1.Illumination reaction 2h, when applied voltage is 0.9V vs.RHE, hydrogen
It is respectively 1.0,0.3 μm of ol with oxygen output；When applied voltage is 1.0 V vs. RHE, hydrogen is respectively with oxygen output
1.7,0.5 μm of ol；When applied voltage is 1.1V vs. RHE, hydrogen and oxygen output are respectively 2.2,0.9 μm of ol；Outer power-up
When pressure is 1.2V vs. RHE, hydrogen and oxygen output are respectively 2.5,1.0 μm of ol.
The present invention prepares mesoporous WO using hard template method3, manganese calcium oxide is prepared using alkaline sedimentation oxidizing process, using super
Sound is removed sedimentation and is formed after manganese calcium oxide and mesoporous tungsten trioxide compound through high-temperature roasting on porous tungstic acid surface
Form island tungsten manganese calcium semiconductor compound；With photogenerated charge separative efficiency is high, overpotential for oxygen evolution is low, catalytic activity and stabilization
Property is good, can be catalyzed the advantages that water decomposition at normal temperatures and pressures.
Claims (9)
1. a kind of tungsten manganese calcium/mesoporous tungsten trioxide compound that can be used for preparing light anode, including mesoporous tungsten trioxide, manganese calcium oxygen
Compound；The mass fraction of the manganese calcium oxide is 1.5~12%；After manganese calcium oxide and mesoporous tungsten trioxide mixed grinding
It is scattered in solvent, is centrifugated after reaction；Then it will be calcined in inert gas after centrifugal solids drying, obtaining, which can be used for, makes
Tungsten manganese calcium/mesoporous tungsten trioxide compound of standby light anode；The condition of the calcining is that 1~4 h is calcined at 200~600 DEG C.
2. can be used for preparing tungsten manganese calcium/mesoporous tungsten trioxide compound of light anode according to claim 1, feature exists
In preparing the mesoporous tungsten trioxide using phosphotungstic acid and mesoporous silicon oxide as raw material；With a water calcium acetate and four water manganese acetates
The manganese calcium oxide is prepared under potassium hydroxide, potassium permanganate for raw material.
3. can be used for preparing tungsten manganese calcium/mesoporous tungsten trioxide compound of light anode according to claim 2, feature exists
In, after phosphotungstic acid is mixed in a solvent with mesoporous silicon oxide, centrifugal treating, after centrifugal solids are dry at 400~600 DEG C
3~6 h are calcined, then calcined solid is distributed in hydrofluoric acid, is centrifugated after stirring, mesoporous tungsten trioxide is obtained；
One water calcium acetate and four water manganese acetates are dissolved in water, KOH aqueous solution is then added, then KMnO is added dropwise4Aqueous solution, instead
Should after be centrifugated, centrifugal solids are washed for several times through deionized water, dry vacuum, then in an inert atmosphere at 300~600 DEG C
2~8 h are calcined, manganese calcium oxide is obtained.
4. can be used for preparing tungsten manganese calcium/mesoporous tungsten trioxide compound of light anode described in claim 1 in preparation light anode material
In material application or in the application as photoelectrochemistrpool pool anode catalyst.
5. a kind of light-catalyzed reaction anode, which is characterized in that the preparation method of the light-catalyzed reaction anode is to aoxidize manganese calcium
It is scattered in solvent after object and mesoporous tungsten trioxide mixed grinding, is centrifugated after reaction；Then by centrifugal solids it is dry after
It is calcined in inert gas, obtains the tungsten manganese calcium/mesoporous tungsten trioxide compound that can be used for preparing light anode；By tungsten manganese calcium/mesoporous
Tungstic acid complex solution is coated on clean electro-conductive glass, and dry roasting obtains light-catalyzed reaction anode；It is described to forge
The condition of burning is that 1~4 h is calcined at 200~600 DEG C.
6. light-catalyzed reaction anode according to claim 5, which is characterized in that using phosphotungstic acid and mesoporous silicon oxide as raw material
Prepare the mesoporous tungsten trioxide；Using a water calcium acetate and four water manganese acetates as raw material, under potassium hydroxide, potassium permanganate, system
The standby manganese calcium oxide.
7. light-catalyzed reaction anode according to claim 6, which is characterized in that by phosphotungstic acid and mesoporous silicon oxide molten
After mixing in agent, centrifugal treating calcines 3~6 h after centrifugal solids are dry, then by calcined solid at 400~600 DEG C
It is distributed in hydrofluoric acid, is centrifugated after stirring, obtain mesoporous tungsten trioxide；One water calcium acetate and four water manganese acetates are dissolved in
In water, KOH aqueous solution is then added, then KMnO is added dropwise4Aqueous solution is centrifugated after reaction, and centrifugal solids are through deionization
Water washing for several times, dries vacuum, then calcines 2~8 h at 300~600 DEG C in an inert atmosphere, obtains manganese calcium oxide.
8. a kind of three electrode photoelectric chemical baths, including to the sun of light-catalyzed reaction described in electrode, reference electrode and claim 5
Pole.
9. three electrode photoelectric chemical baths described in light-catalyzed reaction anode or claim 8 described in claim 5 are in photocatalysis point
The application of Xie Shuizhong.
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