CN105833908A - Doped heteropolyacid catalyst and method for photolyzing water to generate hydrogen under visible light - Google Patents
Doped heteropolyacid catalyst and method for photolyzing water to generate hydrogen under visible light Download PDFInfo
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- CN105833908A CN105833908A CN201610275018.1A CN201610275018A CN105833908A CN 105833908 A CN105833908 A CN 105833908A CN 201610275018 A CN201610275018 A CN 201610275018A CN 105833908 A CN105833908 A CN 105833908A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006303 photolysis reaction Methods 0.000 claims description 10
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- B01J27/186—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
- B01J27/19—Molybdenum
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a doped heteropolyacid catalyst and a method for photolyzing water to generate hydrogen under visible light .A preparation method of the catalyst includes the steps of dissolving Na4SiMo12O40.2H2O in deionized water to be heated to be 80-85 DEG C, adding HF in the solution to be stirred for 1 h at the rotation speed of 200 rpm, then conducting filtering to obtain NaMoFOM filtrate, adding Ni(CH3CO2)2 powder to the filtrate to be dissolved, heating the mixed solution to be 80-85 DEG C to be stirred for 1 h at the rotation speed of 200 rpm, then conducting filtering to obtain NaNiMoFOM filtrate, mixing the NaNiMoFOM filtrate with acetic acid, heating the mixed solution to be 50-60 DEG C to be stirred for 30 min at the rotation speed of 200 rpm, conducting cooling, and putting the solution at room temperature to be evaporated and crystallized for 2 d to obtain crystals, namely the Ni-doped heteropolyacid catalyst H12NiMo17F6O55.20H2O .The doped heteropolyacid catalyst is low in manufacturing cost and simple in doping method, the doped catalyst is used for photolyzing water to generate hydrogen under visible light, the H2 conversion rate can be 15% or above, efficiency is high, and conversion tendency is stable .
Description
Technical field
The method that the present invention relates to photocatalytic water catalyst and photolysis water hydrogen gas under visible light, refers specifically to a kind of doping miscellaneous many
The method of acid catalyst and under visible light photolysis water hydrogen gas.
Background technology
The most less along with non-renewable energy resources, reasonable development and utilize new forms of energy to become a kind of trend.Hydrogen is as uniquely
The reproducible energy, has the feature such as cleaning, efficient, high heating value, environmental friendliness.Tradition silicol process mainly has fossil fuel system
Hydrogen and water electrolysis hydrogen production, wherein fossil fuel hydrogen manufacturing is that application is most, and has become commercial scale, but fossil fuel hydrogen manufacturing
Exist technique fall behind, deficiency in economic performance and the shortcoming such as seriously polluted；Water electrolysis hydrogen production be a kind of clean completely and turned by electric energy
Turning to the hydrogen manufacturing mode of chemical energy, but to be exactly power consumption too much for its disadvantage, Financial cost is high.
Photolysis water hydrogen method is extensively studied as a kind of new hydrogen production method, and solar energy is as a kind of the cleanest renewable
The energy.What people found and developed up to now can be used in the photocatalyst of photocatalytic water, is only capable of absorbing ultraviolet light, but purple
Outer light ratio shared by sunlight is less.Can seldom report by decomposition water under visible light, the most do not pass through carrier
TiO2Or SiO2The doping heteropolyacid catalyst of synthesis have not been reported, and the invention provides a kind of non-loading type doping heteropoly acid
The method of catalyst and under visible light photolysis water hydrogen gas.
Summary of the invention
The technical problem to be solved be the present situation for prior art provide a kind of low cost, preparation process simple,
Hydrogen yield height and the doping heteropolyacid catalyst for being catalyzed photolysis water hydrogen gas under visible ray of conversion trend stability.
Another technical problem to be solved by this invention is to provide a kind of low cost, preparation process is simple, hydrogen conversion is high
And convert the processing method of photolysis water hydrogen gas under visible ray of trend stability.
The present invention solves the technical scheme that above-mentioned technical problem used: this doping heteropolyacid catalyst, it is characterised in that should
The preparation method of catalyst is as follows:
1) it is Na by mixing ratio4SiMo12O40·2H2O: the mixed liquor of deionized water=44g: 100mL, is heated to 80-85 DEG C；
Adding 14mL 40%HF makes pH value maintain 4.5-5.0, and this solution filters after stirring 1h at 200 rpm, obtains
NaMoFOM filtrate.
2) by described NaMoFOM filtrate and Ni (CH3CO2)2Mixing, mixing ratio is filtrate: Ni (CH3CO2)2=80mL:
7g, heats mixed liquor to 80-85 DEG C, filters at 200 rpm, obtain NaNiMoFOM filtrate after stirring 1h.
3) being mixed with acetic acid by described NaNiMoFOM filtrate 60mL, mixed volume is than for filtrate: acetic acid=1: 2, adds
Hot mixing liquid to 50-60 DEG C, stirs 30min at 200 rpm, cooling, puts evaporative crystallization 2 days at room temperature, obtains crystalline substance
Body i.e. nickel doping heteropolyacid catalyst H12NiMo17F6O55·20H2O。
Use the method that described nickel doping heteropolyacid catalyst carries out photolysis water hydrogen gas, it is characterised in that comprise the steps:
In the cylindrical quartz Photoreactor of a 50ml, putting into reactant mixed proportion is nickel doping heteropolyacid catalyst:
Methanol solution: deionized water=0.5-0.7g: 6mL: 20mL, is then removed by bubbling ultrapure argon continuous bubbling 30min and dissolves
Oxygen.After stirring 15min under 1MPa air pressure, 200rpm, it is cutting of the special xenon lamp of visible ray PL-X300D by light source
The photochemical reactor of glass filter only carries out irradiation and the reaction of visible ray, reacts 4h, extract 0.5ml gas every 1h
Body, carries out quantitative determining the H of sample under different time by Japan's Shimadzu GC-2010 gas chromatograph2Burst size, measures sample
The photocatalytic activity of product.
Compared with prior art, the invention provides a kind of brand-new doping heteropolyacid catalyst, this catalyst low cost of manufacture,
Doping method simple possible, the catalyst after doping to the conversion ratio of photolysis water hydrogen gas under visible light up to more than 15%,
And efficiency is high, convert trend stability.
Accompanying drawing explanation
Fig. 1 is the UV-Vis figure of nickel doping heteropolyacid catalyst
Fig. 2 is the SEM figure of nickel doping heteropolyacid catalyst
Fig. 3 is the response time-hydrogen conversion figure of nickel doping heteropolyacid catalyst
Detailed description of the invention
Embodiment 1
Prepare nickel doping heteropolyacid catalyst as follows:
It is Na by mixing ratio4SiMo12O40·2H2O: the mixed liquor of deionized water=44g: 100mL, is heated to 80-85 DEG C；
Adding 14mL 40%HF makes pH value maintain 4.5-5.0, and this solution filters after stirring 1h at 200 rpm, obtains
NaMoFOM filtrate.By described NaMoFOM filtrate and Ni (CH3CO2)2Mixing, mixing ratio is filtrate: Ni (CH3CO2)2
=80mL: 7g, heat mixed liquor to 80-85 DEG C, filter after stirring 1h at 200 rpm, obtain NaNiMoFOM filter
Liquid.Being mixed with acetic acid by described NaNiMoFOM filtrate 60mL, mixed volume ratio is for filtrate: acetic acid=1: 2, heating is mixed
Close liquid to 50-60 DEG C, stir 30min at 200 rpm, cooling, put evaporative crystallization 2 days at room temperature, obtain crystal i.e.
Nickel doping heteropolyacid catalyst, divides WFJ 2100 UV, visible light that this catalyst provides in Shanghai You Nike Instrument Ltd.
Being analyzed test in light photometer, Fig. 1 is the UV-Vis figure of nickel doping heteropolyacid catalyst.As shown in Figure 1, this enforcement
Nickel doping heteropolyacid catalyst prepared by example has absorption in visible light wave strong point, and absworption peak position is in about 500nm, explanation
This catalyst is the most active.
Embodiment 2
The present embodiment be determined by experiment nickel doping heteropolyacid catalyst molecular formula:
The heteropolyacid catalyst that adulterated by the nickel of embodiment 1 is analyzed test, knot in Thermo X-7ICP elemental analyser
Fruit is shown in Table 1.Separately take this photocatalyst crystals of 2g at 80 DEG C, calcine 2h, obtain 1.764g powder, this photocatalyst crystals is described
Containing 20 water of crystallization.
The icp analysis test result of table 1 nickel doping heteropolyacid catalyst
| Element | H | Ni | Mo | F | O |
| Content (%) | 1.70 | 1.93 | 53.40 | 3.73 | 39.24 |
Test and experiment is analyzed, it may be determined that the molecular formula of this doping heteropolyacid catalyst is by described:
H12NiMo17F6O55·20H2O。
Embodiment 3
The heteropolyacid catalyst that the nickel of embodiment 1 adulterated is carried out point in Hitachi high-new scanning electron microscope SEM SU3500
Analysis test, the most each parameter is as follows, accelerating potential: 20kV, enlargement ratio: 25～200.000, resolution: 3.5nm,
Vacuum: 6 × 10-6Pa.Fig. 2 be nickel doping heteropolyacid catalyst SEM figure, as can be seen from Figure 2 nickel be doped in
In the heteropoly acid group of layer structure, it is further characterized by nickel and has been entrained in heteropolyacid catalyst.
Embodiment 4
In the cylindrical quartz Photoreactor of a 50ml, putting into reactant mixed proportion is nickel doping heteropolyacid catalyst:
Methanol solution: deionized water=0.5-0.7g: 6mL: 20mL, is then removed by bubbling ultrapure argon continuous bubbling 30min and dissolves
Oxygen.After stirring 15min under 1MPa air pressure, 200rpm, it is cutting of the special xenon lamp of visible ray PL-X300D by light source
The photochemical reactor of glass filter only carries out irradiation and the reaction of visible ray, reacts 4h, extract 0.5ml gas every 1h
Body, carries out quantitative determining the H2 burst size of sample under different time by Japan's Shimadzu GC-2010 gas chromatograph, measures sample
The photocatalytic activity of product, Fig. 3 is the response time-hydrogen conversion figure of nickel doping heteropolyacid catalyst.From figure 3, it can be seen that
When being reacted to 4h, the conversion ratio of hydrogen is 15%, increases over time, H2Conversion ratio constantly increasing, reach
More than 15%.
Claims (2)
1. a doping heteropolyacid catalyst, it is characterised in that the preparation method of this catalyst is as follows:
1) it is Na by mixing ratio4SiMo12O40·2H2O: the mixed liquor of deionized water=44g: 100mL, is heated to 80-85 DEG C；
Adding 14mL 40%HF makes pH value maintain 4.5-5.0, and this solution filters after stirring 1h at 200 rpm, obtains
NaMoFOM filtrate.
2) by described NaMoFOM filtrate and Ni (CH3CO2)2Mixing, mixing ratio is filtrate: NiCH3CO2)2=80mL:
7g, heats mixed liquor to 80-85 DEG C, filters at 200 rpm, obtain NaNiMoFOM filtrate after stirring 1h.
3) being mixed with acetic acid by described NaNiMoFOM filtrate 60mL, mixed volume is than for filtrate: acetic acid=1: 2, adds
Hot mixing liquid to 50-60 DEG C, stirs 30min at 200 rpm, cooling, puts evaporative crystallization 2 days at room temperature, obtains crystalline substance
Body i.e. nickel doping heteropolyacid catalyst H12NiMo17F6O55·20H2O。
2. using the method that nickel as claimed in claim 1 doping heteropolyacid catalyst carries out photolysis water hydrogen gas, its feature exists
In comprising the steps:
In the cylindrical quartz Photoreactor of a 50ml, putting into reactant mixed proportion is nickel doping heteropolyacid catalyst:
Methanol solution: deionized water=0.5-0.7g: 6mL: 20mL, is then removed by bubbling ultrapure argon continuous bubbling 30min and dissolves
Oxygen.After stirring 15min under 1MPa air pressure, 200rpm, it is cutting of the special xenon lamp of visible ray PL-X300D by light source
The photochemical reactor of glass filter only carries out irradiation and the reaction of visible ray, reacts 4h, extract 0.5ml gas every 1h
Body, carries out quantitative determining the H of sample under different time by Japan's Shimadzu GC-2010 gas chromatograph2Burst size, hydrogen
Conversion ratio reaches more than 15%.
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| CN112934262A (en) * | 2021-02-01 | 2021-06-11 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622371A (en) * | 2016-10-12 | 2017-05-10 | 上海应用技术大学 | (R)-1-(1-phenethyl)thiourea modified Al-Anderson type heteropolyacid catalyst and preparation method and application thereof |
| CN112934262A (en) * | 2021-02-01 | 2021-06-11 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
| CN112934262B (en) * | 2021-02-01 | 2021-10-26 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
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