CN116328778A - Plasmon metallic copper-metal oxide composite structure catalyst and method for catalyzing gas phase formic acid to prepare hydrogen under room temperature visible light - Google Patents
Plasmon metallic copper-metal oxide composite structure catalyst and method for catalyzing gas phase formic acid to prepare hydrogen under room temperature visible light Download PDFInfo
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000002244 precipitate Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 2
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 42
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 25
- 235000005074 zinc chloride Nutrition 0.000 abstract description 21
- 239000011592 zinc chloride Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract description 4
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 2
- 229960001763 zinc sulfate Drugs 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000011787 zinc oxide Substances 0.000 description 11
- 229960003280 cupric chloride Drugs 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 150000004972 metal peroxides Chemical class 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007792 gaseous phase Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- -1 copper modified oxygen Chemical class 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
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- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- 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
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- 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
- C01B2203/1076—Copper or zinc-based catalysts
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Abstract
A plasmon metal copper-metal oxide composite structure catalyst and a method for catalyzing gas phase formic acid to prepare hydrogen under room temperature visible light belong to the technical field of copper-based plasmon photocatalysts. The method comprises using metal salt (zinc chloride, zinc sulfate, zinc nitrate, zirconyl chloride, cerium nitrate, etc.) as source of metal oxide semiconductor, modifying metal oxide with copper source (copper chloride, copper sulfate, copper nitrate, etc.), and H 2 O 2 The metal oxide generates a large amount of oxygen holes by treatment and vacuum annealing, so that the plasmon metal copper-metal oxide composite structure catalyst is obtained, has good catalytic activity, selectivity and stability, realizes the catalytic gas phase formic acid hydrogen production under room temperature visible light, still shows good catalytic activity under room temperature (20 ℃), the conversion rate is nearly 100%, the selectivity is 96.3%, and the hydrogen generated by the reactionThe speed is more than 300 mmol/(g.h), and the method has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of copper-based plasmon photocatalyst, and particularly relates to a plasmon metallic copper-metal oxide composite structure catalyst and a method for catalyzing gas phase formic acid to prepare hydrogen at room temperature under visible light.
Background
In the current era of ever decreasing fossil fuel resources and global warming, the search for a sustainable energy source is more urgent than ever before. Hydrogen (H) 2 ) As a promising intermediate energy storage alternative, its high energy content and high efficiency make it a solution capable of replacing fossil fuels as a source of mobile energy for transportation. Conventional hydrogen storage methods have weight, cost and safety issues. Alternatively, chemical hydrogen storage has attracted considerable attention, formic Acid (FA) being one of the compounds promising to achieve this goal. Formic acid is the simplest carboxylic acid, and because of its low toxicity, stability, high mass capacity (4.4 wt%) and high volume capacity (53 g/L), its simple and readily available source (formic acid is readily available from biomass oxidation), is an important hydrogen storage material for mobile applications, so finding a catalyst for efficient hydrogen production from formic acid is of great importance in hydrogen storage and applications.
Formic acid high-efficiency hydrogen production catalyst mainly comprises a homogeneous catalyst and a heterogeneous catalyst, and Formic Acid (FA) has attracted people to explore hydrogen production by more than 50 years ago. The formic acid hydrogen production homogeneous catalytic system starts from the research of Pt, ru and Ir phosphine complexes reported by Coffey in 1967, and until the research of Laurenczy and Beller in 2008, formic acid FA starts to serve as a liquid organic hydrogen carrier. Leading each research group to develop new active homogeneous catalysts and to considerable progress. However, the homogeneous catalyst is difficult to recycle, and a large amount of organic matters are used in the preparation process, so that the environment is greatly influenced.
Heterogeneous systems can catalyze formic acid to produce hydrogen under milder conditions. The catalyst is mainly composed of metal oxide and supported metal nano particles, and the noble metal-based catalyst is generally considered as the most effective catalyst in a heterogeneous system, and is easier to recycle and more stable than a homogeneous catalyst. However, noble metal resources are limited, the price is high, and the large-scale use is not facilitated, so that the research and development of non-noble metal catalysts are continuously carried out. While most non-noble metal catalysts are extremely unstable in systems with pH less than 7, it is very important to develop a highly efficient, low cost, stable non-noble metal catalyst. Copper (Cu) with abundant reserves and low cost has a very strong and adjustable localized surface plasmon resonance effect and has excellent catalytic performance for various reactions. The copper-based plasmon photocatalyst can be used as a promising platform for effectively driving chemical reactions by light in combination with light capturing capability and catalytic function.
The photocatalytic formic acid hydrogen production is used as a current research hot spot, and green rich sunlight is used as energy to efficiently produce hydrogen at room temperature. The invention provides a non-noble metal copper-based plasmon photocatalyst which is low in cost, high in efficiency, simple and easy to obtain, and is used for preparing hydrogen by photocatalysis gas phase formic acid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a plasmon metal copper-metal oxide composite structure catalyst and a method for catalyzing formic acid to prepare hydrogen at room temperature under visible light, wherein the plasmon metal copper-metal oxide composite structure catalyst has good catalytic activity, selectivity and stability, and realizes gas phase formic acid dehydrogenation under mild conditions.
The invention relates to a plasmon metal copper-metal oxide composite structure catalyst, which uses metal salt (zinc chloride and the like) as a source of a metal oxide semiconductor, uses a copper source (copper chloride and the like) to modify metal oxide, and uses H 2 O 2 The metal oxide generates a large amount of oxygen holes by treatment and vacuum annealing, so that the plasmon metal copper-metal oxide composite structure catalyst is obtained.
The plasmon metal copper-metal oxide composite structure catalyst is prepared by the following steps:
(1) Adding an alkali solution into a mixed solution of water-soluble metal salt and water-soluble copper salt, wherein the concentration of alkali in the alkali solution is 2M, the sum of the concentration of metal salt and copper salt in the mixed solution of water-soluble metal salt and water-soluble copper salt is 2M, and the dosage mole ratio of the metal salt to the copper salt is 0.2-5: 100; stirring for 0.5-4 h at room temperature to fully react to generate metal hydroxide precipitate, filtering to separate precipitate, and washing with distilled water to remove impurities;
(2) Dispersing the precipitate obtained in the step (1) in 1M H 2 O 2 In the aqueous solution, then keeping the aqueous solution for 1 to 4 hours in an oil bath at 70 to 90 ℃, and then separating the precipitate by suction filtration to obtain copper doped peroxide powder; annealing the obtained copper doped peroxide powder for 1-4 hours under the vacuum condition of 200-600 ℃, thereby obtaining the copper modified oxygen vacancy oxide catalyst (Cu-ZnO-Vo, cu-ZrO-Vo, cu-CeO-Vo and the like), namely the plasmon metal copper-metal oxide composite structure catalyst.
Wherein the alkali solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), etc., and the water-soluble metal salt is zinc chloride (ZnCl) 2 ) Zinc sulfate (ZnSO) 4 ) Zinc nitrate (Zn (NO) 3 ) 2 ) Zirconyl nitrate (ZrO (NO) 3 ) 2 ) Zirconyl chloride (ZrOCl) 2 ) Cerium nitrate (Ce (NO) 3 ) 2 ) Etc. the water-soluble copper salt is cupric chloride (CuCl) 2 ) Copper sulfate (CuSO) 4 ) Copper nitrate (Cu (NO) 3 ) 2 ) Etc.
The plasmon metallic copper-metal oxide composite structure catalyst (Cu-ZnO-Vo) is most preferably CuCl 2 And ZnCl 2 The molar ratio of (2): 100, i.e. Cu: zn molar ratio is 2:100, annealing for 2 hours in a vacuum atmosphere at 400 ℃, wherein the obtained plasmon metal copper-metal oxide composite structure catalyst has excellent catalytic activity on hydrogen production from formic acid: 10mg of the catalyst can catalyze the conversion rate of 10uL (265.217 umol) formic acid to be close to 100% in 5 minutes, the selectivity reaches 96.3%, the hydrogen generation rate of the reaction is more than 300 mmol/(g.h), and the catalyst can be recycled.
The invention relates to a method for catalyzing gaseous phase formic acid to prepare hydrogen under the room temperature visible light by using a copper-based plasmon photocatalyst, which comprises the steps of placing a plasmon metallic copper-metal oxide composite structure catalyst in a gaseous phase reactor, controlling the reaction at room temperature by a constant temperature water bath kettle, adding formic acid into the reactor by vaporization, and carrying out the reaction by irradiation of visible light (lambda >400 nm) from the upper part of the gaseous phase reactor, thereby obtaining the product hydrogen.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses soluble zinc salt ZnCl 2 The method is characterized in that hydrogen peroxide is used for processing a precursor to synthesize zinc oxide rich in oxygen vacancies, the catalyst is improved on the basis of the zinc oxide rich in vacancies, and the copper-modified zinc oxide catalyst is synthesized, namely, a plasmon metal copper-metal oxide composite structure catalyst. The catalyst material has good electron transfer performance and photoinduction performance, and can also realize the utilization of the SPR photo-thermal effect.
2. The invention adopts a coprecipitation method of water-soluble metal salt and alkali solution and a vacuum annealing method to prepare a catalyst, firstly adopts the coprecipitation method to synthesize metal hydroxide, and then uses 1M H 2 O 2 The aqueous solution is treated to precipitate and obtain metal peroxide, the dispersed solution is kept in an oil bath at 75 ℃ for 2 hours, then the precipitate is separated by suction filtration to obtain copper doped metal peroxide powder, and then the copper doped metal peroxide powder is annealed in vacuum at 400 ℃ for 2 hours to obtain the copper modified oxygen vacancy oxide catalyst. The catalyst has higher activity and selectivity under the action of visible light. The catalyst is used for catalyzing the hydrogen production reaction of formic acid by visible light, and still has good catalytic activity at room temperature (20 ℃), the conversion rate is nearly 100%, the selectivity reaches 96.3%, and the hydrogen production rate of the reaction is more than 300 mmol/(g.h). The catalyst has the advantages of simple preparation method, simple and easily obtained required raw materials and large-scale production.
Drawings
FIG. 1 is a powder X-ray diffraction chart of the products obtained in examples 1, 2, 3, 4, 5, compared with a zinc oxide standard card (JCPDS: 36-1451), to confirm that the products are zinc oxide.
FIG. 2 is a Mapping graph of the 2% Cu-ZnO-Vo product obtained in example 4, with zinc and copper elements, demonstrating that copper is doped into oxygen vacancy zinc oxide.
FIG. 3 is a High Resolution Transmission Electron Microscope (HRTEM) before and after the reaction of photocatalytic formic acid to produce hydrogen, which is obtained in example 4, and FIG. 3 (a) is a transmission electron microscope image before the reaction of 2% Cu-ZnO-Vo, and the lattice spacing of zinc oxide is measured
A (100) plane belonging to wurtzite ZnO; FIG. 3 (b) is the HRTEM of the 2% Cu-ZnO-Vo product after the reaction, and the copper nanoparticles can be clearly seen. It was confirmed that copper participated in the reaction as stable copper nanoparticles during the reaction of the product.
FIG. 4 is an electron paramagnetic resonance EPR graph of the 2% Cu-ZnO-Vo product obtained in example 4 before and after the photocatalytic reaction for producing hydrogen from formic acid, wherein the 2% Cu-ZnO-Vo has stronger EPR signal peaks at splitting factors g=1.961, g=2.002 and g=2.044, the signal peaks respectively correspond to Zn in the 2% Cu-ZnO-Vo capturing conduction electrons 2+ Oxygen vacancies and Cu 2+ The pre-reaction product is proved to contain oxygen vacancies and Cu 2+ The splitting factor of 2% Cu-ZnO-Vo, i.e. 2% Cu-ZnO-Vo-Used, after the reaction is only g=2.002, confirming that the copper species exist as zero-valent copper nanoparticles after the reaction.
Fig. 5 is a bar graph of photocatalytic formic acid hydrogen production performance obtained in examples 1, 2, 3, 4, 5, confirming the product Cu: the molar ratio of Zn is 2: the 100 th is the best in the photocatalytic hydrogen production performance of formic acid.
FIG. 6 is a bar graph of photocatalytic formic acid hydrogen production performance obtained by annealing the 2% Cu-ZnO-Vo product at 200℃to 600℃in example 4, demonstrating that the product is best among photocatalytic formic acid hydrogen production performance in vacuum annealing at 400 ℃.
FIG. 7 is a graph showing the cycle performance of the photocatalytic hydrogen production reaction of formic acid from the 2% Cu-ZnO-Vo product of example 4, which demonstrates that the product can be recycled no less than 30 times.
Detailed description of the preferred embodiments
The invention is illustrated in further detail by the following examples. The examples are not to be construed as limiting the invention.
Example 1
Process for preparing a catalyst
1.363g of zinc chloride (ZnCl) are weighed out 2 ) Dissolving in 25mL of aqueous solution, weighing 0.4g of sodium hydroxide (NaOH) and dissolving in 25mL of aqueous solution, adding NaOH solution into ZnCl 2 Stirring the solution for 2h at room temperature to fully react to generate Zn (OH) 2 Precipitating, filtering to separate precipitate, and washing with distilled water to remove impurities; dispersing the obtained precipitate in 1M, 100mL H 2 O 2 In the aqueous solution, the dispersed solution was kept in an oil bath at 75 ℃ for 2 hours, and then the precipitate was separated by suction filtration to obtain zinc peroxide powder. The obtained powder was subsequently annealed at 400 ℃ under vacuum for 2 hours, and the obtained catalyst sample was denoted ZnO-Vo.
Dehydrogenation process
10mg of the prepared ZnO-Vo catalyst is filled into a reactor, the reaction is controlled by a water bath kettle with the constant temperature of 20 ℃, then formic acid is gasified and added into the reactor, visible light with the wavelength of lambda being more than 400nm is irradiated from the upper part of a gas phase reactor for reaction, the product hydrogen is obtained, reaction gas is collected, the selectivity of the hydrogen is 83.3 percent, the conversion rate of formic acid is 9.1 percent after the reaction, and the hydrogen generation rate of the reaction is 30 mmol/(g.h).
Example 2
Process for preparing a catalyst
1.363g of zinc chloride (ZnCl) are weighed out 2 ) And 0.0034g copper chloride (CuCl) 2 ) Dissolving in 25mL of aqueous solution, weighing 0.4g of sodium hydroxide (NaOH) and dissolving in 25mL of aqueous solution, adding NaOH solution into ZnCl 2 、CuCl 2 Stirring the mixed solution for 2 hours at room temperature to fully react to generate metal hydroxide precipitate, filtering and separating the precipitate, and washing the precipitate with distilled water to remove impurities; dispersing the obtained precipitate in 1M, 100mL H 2 O 2 In the aqueous solution, the dispersed solution was kept in an oil bath at 75℃for 2 hours, and then the precipitate was separated by suction filtration to obtain copper-doped metal peroxide powder, and then the obtained Cu/ZnO was subjected to a vacuum filtration at 400 ℃ 2 The powder was annealed under vacuum for 2 hours and the catalyst sample obtained was expressed as 0.2% Cu-ZnO-Vo (molar ratio of Cu to Zn: 2:1000).
Dehydrogenation process
10mg of prepared 0.2% Cu-ZnO-Vo catalyst is filled into a gas phase reactor, reaction is controlled by a water bath kettle with the constant temperature of 20 ℃, then formic acid is gasified and added into the reactor, and visible light with the wavelength of lambda being more than 400nm is irradiated from the upper part of the gas phase reactor for reaction, so that the product hydrogen is obtained. The reaction gas was collected, and after the reaction, the selectivity for hydrogen was 94.76%, the conversion of formic acid was 26.3%, and the hydrogen generation rate of the reaction was 83.64 mmol/(g.h).
Example 3
Process for preparing a catalyst
1.363g of zinc chloride ZnCl is weighed 2 And 0.0171g of copper chloride CuCl 2 Dissolving in 25mL of aqueous solution, weighing 0.4g of sodium hydroxide NaOH, dissolving in 25mL of aqueous solution, adding NaOH solution into ZnCl 2 、CuCl 2 Stirring the mixed solution for 2 hours at room temperature to fully react to generate metal hydroxide precipitate, filtering and separating the precipitate, and washing the precipitate with distilled water to remove impurities; dispersing the obtained precipitate in 1M, 100mL H 2 O 2 In the aqueous solution, the dispersed solution was kept in an oil bath at 75℃for 2 hours, and then the precipitate was separated by suction filtration to obtain copper-doped metal peroxide powder, and then the obtained Cu/ZnO was subjected to a vacuum filtration at 400 ℃ 2 The powder was annealed under vacuum for 2 hours and the catalyst sample obtained was expressed as 1% Cu-ZnO-Vo (molar ratio of Cu to Zn 1:100).
Dehydrogenation process
10mg of the prepared 1% Cu-ZnO-Vo catalyst is filled into a reactor, the reaction is controlled by a water bath kettle with the constant temperature of 20 ℃, then formic acid is gasified and added into the reactor, and visible light with the wavelength of lambda being more than 400nm is irradiated from the upper part of a gas phase reactor for reaction, so that the product hydrogen is obtained. The reaction gas was collected, and after the reaction, the selectivity for hydrogen was 95.3%, the conversion of formic acid was 69.6%, and the hydrogen generation rate of the reaction was 221.5 mmol/(g.h).
Example 4
Process for preparing a catalyst
1.363g of zinc chloride ZnCl is weighed 2 And 0.0341g of copper chloride CuCl 2 Dissolving in 25mL of aqueous solution, weighing 0.4g of sodium hydroxide NaOH, dissolving in 25mL of aqueous solution, adding NaOH solution into ZnCl 2 、CuCl 2 Stirring the mixed solution for 2 hours at room temperature to fully react to generate metal hydroxide precipitate, filtering and separating the precipitate, and washing the precipitate with distilled water to remove impurities; dispersing the obtained precipitate in 1M, 100mL H 2 O 2 In aqueous solution, the dispersed solution was kept at 75 ℃ for 2 hours in an oil bath, then the precipitate was separated by suction filtration, copper doped with metal peroxide powder, and then Cu/ZnO was added at 400 ℃ 2 The powder was annealed under vacuum for 2 hours and the catalyst sample obtained was expressed as 2% Cu-ZnO-Vo (molar ratio of Cu to Zn: 2:100).
Dehydrogenation process
10mg of the prepared 2% Cu-ZnO-Vo catalyst is filled into a reactor, the reaction is controlled by a water bath kettle with the constant temperature of 20 ℃, then formic acid is gasified and added into the reactor, and visible light with the wavelength of lambda being more than 400nm is irradiated from the upper part of a gas phase reactor for reaction, so that the product hydrogen is obtained. The reaction gas was collected, and after the reaction, the selectivity of hydrogen was found to be 96.3%, the conversion of formic acid was found to be 97.2%, and the rate of hydrogen generation by the reaction was found to be 309.4 mmol/(g.h), which was at least 30 times recyclable.
Example 5
Process for preparing a catalyst
1.363g of zinc chloride ZnCl is weighed 2 And 0.08525g of copper chloride CuCl 2 Dissolving in 25mL of aqueous solution, weighing 0.4g of sodium hydroxide NaOH, dissolving in 25mL of aqueous solution, adding NaOH solution into ZnCl 2 、CuCl 2 Stirring the mixed solution for 2 hours at room temperature to fully react to generate metal hydroxide precipitate, filtering and separating the precipitate, and washing the precipitate with distilled water to remove impurities; dispersing the obtained precipitate in 1M, 100mL H 2 O 2 In the aqueous solution, the dispersed solution was kept in an oil bath at 75 ℃ for 2 hours, and then the precipitate was separated by suction filtration to obtain copper-doped metal peroxide powder, followed by subjecting Cu/ZnO to 400 DEG C 2 The powder was annealed at 400℃under vacuum for 2 hours, and the catalyst sample obtained showed 5% Cu-ZnO-Vo (molar ratio of Cu to Zn: 5:100).
Dehydrogenation process
10mg of the prepared 5% Cu-ZnO-Vo catalyst is filled into a reactor, the reaction is controlled by a water bath kettle with the constant temperature of 20 ℃, then formic acid is gasified and added into the reactor, and visible light with the wavelength of lambda being more than 400nm is irradiated from the upper part of a gas phase reactor for reaction, so that the product hydrogen is obtained. The reaction gas was collected, and after the reaction, the selectivity for hydrogen was 94.4%, the conversion of formic acid was 93.1%, and the hydrogen generation rate of the reaction was 296.25 mmol/(g.h), which was lower than the 2% Cu-ZnO-Vo catalyst prepared in example 4.
While the invention has been described in detail in connection with specific preferred embodiments thereof, it is not to be construed as limited thereto, but rather as a result of a simple deduction and substitution by a person having ordinary skill in the art to which the invention pertains without departing from the spirit of the invention, and it is to be considered that the invention resides in the scope of protection of the patent defined by the claims which issue.
Claims (5)
1. A plasmonic metal copper-metal oxide composite structure catalyst, characterized in that: is prepared by the following steps of,
(1) Adding an alkali solution into a mixed solution of water-soluble metal salt and water-soluble copper salt, wherein the concentration of alkali in the alkali solution is 2M, the sum of the concentration of metal salt and copper salt in the mixed solution of water-soluble metal salt and water-soluble copper salt is 2M, and the dosage mole ratio of the metal salt to the copper salt is 0.2-5: 100; stirring at room temperature to fully react to generate metal hydroxide precipitate, filtering to separate precipitate, and washing with distilled water to remove impurities;
(2) Dispersing the precipitate obtained in the step (1) in 1M H 2 O 2 In the aqueous solution, then keeping the aqueous solution for 1 to 4 hours in an oil bath at 70 to 90 ℃, and then separating the precipitate by suction filtration to obtain copper doped peroxide powder; annealing the obtained copper doped peroxide powder for 1 to 4 hours under the vacuum condition of 200 to 600 ℃ to obtain the copper doped oxygen vacancy oxide catalyst, namely the plasmon metal copper-metal oxide composite structure catalyst.
2. A plasmonic metallic copper-gold as defined in claim 1The catalyst belongs to an oxide composite structure and is characterized in that: the alkali is one or more of NaOH and KOH, and the water-soluble metal salt is ZnCl 2 、ZnSO 4 、Zn(NO 3 ) 2 、ZrO(NO 3 ) 2 、ZrOCl 2 、Ce(NO 3 ) 2 One or more of the following; the water-soluble copper salt is CuCl 2 、CuSO 4 、Cu(NO 3 ) 2 One or more of the following.
3. A plasmonic metal copper-metal oxide composite structure catalyst as defined in claim 2, wherein: the water-soluble metal salt is ZnCl 2 The water-soluble copper salt is CuCl 2 。
4. A plasmonic metal copper-metal oxide composite structure catalyst as claimed in claim 3, wherein: cuCl 2 And ZnCl 2 The molar ratio of (2): 100, annealing for 2 hours in a vacuum atmosphere at 400 ℃ to obtain the plasmon metal copper-metal oxide composite structure catalyst.
5. A method for preparing hydrogen by catalyzing gas phase formic acid under visible light at room temperature by using a catalyst with a plasmon metal copper-metal oxide composite structure is characterized by comprising the following steps of: the catalyst with the plasmon metal copper-metal oxide composite structure according to any one of claims 1 to 4 is placed in a gas phase reactor, the reaction is controlled at room temperature through a constant temperature water bath, then formic acid is gasified and added into the reactor, and the reaction is carried out by irradiation of visible light from the upper part of the gas phase reactor, so that the product hydrogen is obtained.
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