CN113083307B - Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof - Google Patents
Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113083307B CN113083307B CN202110372946.0A CN202110372946A CN113083307B CN 113083307 B CN113083307 B CN 113083307B CN 202110372946 A CN202110372946 A CN 202110372946A CN 113083307 B CN113083307 B CN 113083307B
- Authority
- CN
- China
- Prior art keywords
- hydrogen production
- photo
- formaldehyde
- assisted chemical
- chemical catalysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 292
- 239000001257 hydrogen Substances 0.000 title claims abstract description 100
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 72
- 239000000126 substance Substances 0.000 title claims abstract description 47
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910003336 CuNi Inorganic materials 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 15
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 15
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 15
- 239000011975 tartaric acid Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002114 nanocomposite Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 41
- 239000008098 formaldehyde solution Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910003081 TiO2−x Inorganic materials 0.000 abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 99
- 239000000243 solution Substances 0.000 description 65
- 150000002431 hydrogen Chemical class 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 229910052724 xenon Inorganic materials 0.000 description 13
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 13
- 102000020897 Formins Human genes 0.000 description 8
- 108091022623 Formins Proteins 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- 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
Landscapes
- 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 belongs to the technical field of nano composite catalyst materials, and particularly relates to a photo-assisted chemical catalysis formaldehyde hydrogen production catalyst, and a preparation method and application thereof. Dissolving copper nitrate trihydrate, nickel nitrate hexahydrate and tartaric acid in water, adding titanium dioxide, uniformly mixing, making hydrothermal reaction, cooling and filtering obtained mixed liquor, drying filter residue, placing the obtained solid in N2Heating to 700-900 ℃ under protection, roasting, and cooling to obtain CuNi @ C/TiO2‑xAnd (3) compounding a catalyst. The invention makes use of TiO2The photocatalytic performance of the catalyst improves the chemical catalytic hydrogen production rate of CuNi @ C on formaldehyde, and solves the problem of low hydrogen production efficiency of metal catalysis and photocatalytic formaldehyde hydrogen production.
Description
Technical Field
The invention belongs to the technical field of nano composite catalyst materials, and particularly relates to a photo-assisted chemical catalysis formaldehyde hydrogen production catalyst, and a preparation method and application thereof.
Background
The green energy sources comprise solar energy, tidal energy, wind energy, hydrogen energy and the like, wherein the hydrogen energy has good heat conductivity and high calorific value, is nontoxic, does not generate harmful substances during combustion, and is known as 'energy currency' in the 21 st century by utilizing the characteristics of multiple forms. At present, hydrogen sources include hydrocarbon reforming hydrogen production, biological hydrogen production, water electrolysis hydrogen production, chemical hydride catalytic water hydrogen production, metal catalytic formaldehyde hydrogen production and the like. Formaldehyde (HCHO) is a bulk industrial product, is the most main downstream product of methanol, can be converted from biomass, and is a hydrogen carrier which is cheap, easy to obtain, various in preparation mode and safe. The method can eliminate the pollution of formaldehyde to air and waste water while preparing hydrogen by using the formaldehyde, changes waste into valuable, meets the dual requirements of energy and clean environment, and accords with the concept of sustainable development.
The conventional HCHO hydrogen production catalyst is mainly noble metal catalysts such as Au, Pd, Ag, Rh and the like, the large-scale application of the noble metal catalysts is limited due to the defects of low abundance, high price and the like of the noble metal catalysts, and some non-noble metal catalysts such as nano-copper catalysts become research hotspots due to the advantages of good catalytic activity, low price and easy obtainment of raw materials and the like of the non-noble metal catalysts. However, the hydrogen production efficiency of hydrogen production by catalyzing formaldehyde with metal is still low at present, which influences the popularization and application of the method.
The metal oxide catalyst also plays an important role in catalyzing the reaction of producing hydrogen from formaldehyde. Titanium dioxide (TiO)2) The method has the advantages of high efficiency, low cost, stability and the like, and is used by people in the fields of solar cells, pollutant degradation, hydrogen production by photolysis of water and the like. But TiO 22The solar cell has a wider band gap, can only absorb ultraviolet light, and cannot effectively utilize solar energy; furthermore, TiO in photocatalytic processes2The generated photo-generated electrons and holes are easy to recombine, and the photocatalysis efficiency is greatly reduced.
How to improve the catalytic activity of the composite catalyst and solve the problem of low hydrogen production efficiency of catalyzing formaldehyde to prepare hydrogen is the problem to be solved at present.
Disclosure of Invention
According to one aspect of the invention, the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst is carbon-coated copper-nickel loaded titanium dioxide, and the general chemical composition formula of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst is CuNi @ C/TiO2-xX is TiO2The molar ratio of x to CuNi is more than or equal to 0.03125 and less than or equal to 0.125.
The composite catalyst provided by the invention mainly uses metal to catalyze formaldehyde to produce hydrogen, is mainly based on chemical catalysis, and is TiO2The amount of the metal compound is small as an auxiliary effect, but the metal compound also has photocatalytic performance, and the transmission efficiency of charges is improved by combining chemical catalysis and photocatalysis, so that the capability of catalyzing formaldehyde by metal is improved.
According to another aspect of the present invention there is provided the above mentioned photo-assisted chemocatalysisThe preparation method of the formaldehyde-to-hydrogen catalyst comprises the following steps: firstly, a hydrothermal method is adopted to prepare a carbon-coated copper-nickel precursor of composite titanium dioxide, and then a annealing method is adopted to obtain CuNi @ C/TiO2-xA nanocomposite material.
The invention prepares TiO by a hydrothermal method2Uniformly mixing the precursor in carbon-coated copper-nickel alloy nanoparticles to obtain a precursor, and enabling TiO to be2Loading the copper and the nickel together, and then annealing to obtain the product. The invention mainly uses metal copper nickel to catalyze formaldehyde, mainly uses chemical catalysis and uses photocatalysis as auxiliary, TiO2The dosage is small, and the auxiliary effect is achieved, so that the capability of catalyzing formaldehyde to prepare hydrogen by using the metal copper nickel is improved.
In some embodiments, the method of making comprises the steps of:
(1) dissolving copper nitrate trihydrate, nickel nitrate hexahydrate and tartaric acid in water to obtain a first mixed solution;
(2) putting titanium dioxide into the first mixed solution, and uniformly mixing to obtain a second mixed solution;
(3) carrying out hydrothermal reaction on the second mixed solution to obtain a suspension;
(4) cooling the suspension, filtering, washing the filter residue with absolute ethyl alcohol, and drying to obtain powder;
(5) and heating the powder to 700-900 ℃ under the protection of inert gas, roasting, and cooling to obtain the powder.
When gas is liquefied or solid is separated out from a liquid phase, the energy of the system can be greatly reduced due to the existence of condensation nuclei, and the stability is improved. According to the invention, titanium dioxide is insoluble in the first mixed solution, copper and nickel tend to be precipitated near the titanium dioxide or wrap the titanium dioxide in a hydrothermal reaction, and the precipitation of the copper and nickel depends on the titanium dioxide to form crystal growth, so that the stable and uniform compounding of the titanium dioxide and the copper and nickel precursor is ensured. Therefore, the uniformity and stability of the compounding can be improved.
In order to ensure that the anatase phase of the titanium dioxide is not transformed, the annealing temperature is not higher than 900 ℃, the preferred annealing temperature is 700-800 ℃, and the anatase phase of the titanium dioxide is slightly changed when the annealing temperature is 900 ℃ as can be seen by SEM.
In some embodiments, in step (1), the molar ratio of copper nitrate trihydrate, nickel nitrate hexahydrate and tartaric acid is 1 (1-4): 4.
In step (1), the molar ratio of copper nitrate trihydrate, nickel nitrate hexahydrate and tartaric acid is preferably 1:1: 4.
In some embodiments, in the step (2), the molar ratio of the added titanium dioxide to the copper nickel is 1 (8-32).
In some embodiments, in the step (3), the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 3-8 h.
In some embodiments, in the step (4), the drying temperature is 60-80 ℃ and is kept for 12-24 h.
In some embodiments, in step (5), the firing procedure is: heating from normal temperature to 700-900 ℃, wherein the heating rate is 2-3 ℃ per minute-1And heating to 700-900 ℃ and keeping for 1-3 h.
In some embodiments, in step (5), the inert gas is nitrogen (N)2)。
According to still another aspect of the invention, the application of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst in photo-assisted chemical catalysis formaldehyde hydrogen production is provided. The specific application method comprises the following steps: adding the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst into an alkaline formaldehyde solution, and carrying out a reaction of catalyzing formaldehyde to produce hydrogen under the illumination of ultraviolet light or sunlight; the alkaline formaldehyde solution is obtained by adding water to dilute a formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1 (4-19), and the solid-to-liquid ratio of the potassium hydroxide to a reaction solution is 31-124 g.L-1. The reaction solution herein refers to a solution obtained by diluting formalin solution with water.
The composite catalyst of the present application utilizes TiO2The photocatalytic performance of the composite material is used for improving the chemical catalysis hydrogen production rate of CuNi @ C on formaldehyde, optimizing the condition of the composite material for the photo-assisted chemical catalysis of the formaldehyde to produce the hydrogen, and solving the problems of metal catalysis and the hydrogen production of the photocatalytic formaldehyde to produce the hydrogenThe efficiency is low; wherein, the composite catalyst is mainly based on chemical catalysis, TiO2Plays the role of a photocatalysis auxiliary agent.
Drawings
FIG. 1 shows CuNi @ C/TiO prepared in examples 1-4 of the present invention2-xXRD pattern of the composite catalyst.
FIG. 2 shows CuNi @ C/TiO prepared in examples 1-4 of the present invention2-xSEM image of the composite catalyst.
FIG. 3 shows CuNi @ C/TiO prepared in example 8 of the present invention2-0.0625SEM image of the composite catalyst.
FIG. 4 is a graph showing a comparison of hydrogen production performance in examples 1 to 4 of application of the present invention.
FIG. 5 is a graph showing a comparison of hydrogen production performance in application example 3 and application examples 5 to 7 of the present invention.
FIG. 6 is a graph showing a comparison of hydrogen production performance in application example 3 and application examples 8 to 10 of the present invention.
FIG. 7 is a graph showing a comparison of hydrogen production performance in application example 3 and application examples 11 to 14 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available.
EXAMPLE 1 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 12.5mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 750 ℃, preserving heat for 2h at 750 ℃, and then cooling to obtain a product which is CuNi @ C/TiO2-0.03125。
Example 2 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 20mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 750 ℃, preserving heat for 2h at 750 ℃, and then cooling to obtain CuNi @ C/TiO2-0.05。
Example 3 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 25mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 750 ℃, preserving heat for 2h at 750 ℃, and then cooling to obtain CuNi @ C/TiO2-0.0625。
EXAMPLE 4 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 50mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 750 ℃, preserving heat for 2h at 750 ℃, and then cooling to obtain CuNi @ C/TiO2-0.125。
EXAMPLE 5 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 25mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 700 ℃, preserving heat for 2h at 700 ℃, and then cooling to obtain CuNi @ C/TiO2-0.0625。
EXAMPLE 6 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 25mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 800 ℃, preserving heat for 2h at 800 ℃, and then cooling to obtain CuNi @ C/TiO2-0.0625。
Example 7 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 25mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 850 ℃, keeping the temperature at 850 ℃ for 2h, and then cooling to obtain CuNi @ C/TiO2-0.0625。
EXAMPLE 8 preparation of composite catalyst
The preparation method of the composite catalyst of the embodiment comprises the following steps:
(1) dissolving 302mg of copper nitrate trihydrate, 363mg of nickel nitrate hexahydrate and 750mg of tartaric acid in deionized water to obtain a blue solution;
(2) adding 25mg of titanium dioxide into the blue solution obtained in the step (1), and carrying out ultrasonic treatment for 15min to obtain a mixed solution;
(3) transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 3 hours at 160 ℃ to obtain blue suspension;
(4) naturally cooling the blue suspension obtained in the step (3), filtering, washing filter residues with absolute ethyl alcohol for 3 times, and then placing the filter residues in a 70 ℃ drying oven to be dried for 24 hours to completely dry the filter residues to obtain white powder;
(5) placing the white powder obtained in the step (4) in a tube furnace in N2At 3 ℃ for min under protection-1Heating from room temperature to 900 ℃, preserving heat for 2h at 900 ℃, and then cooling to obtain CuNi @ C/TiO2-0.0625。
Application example 1
The CuNi @ C/TiO prepared in example 12-0.03125The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.03125Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:19, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Through detection, the hydrogen production performance of the application example is 97.19mmol g-1·h-1。
Application example 2
The CuNi @ C/TiO prepared in example 22-0.05The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.05Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:19, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Through detection, the hydrogen production performance of the application example is 105.09mmol g-1·h-1。
Application example 3
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:19, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Through detection, the hydrogen production performance of the application example is 122.85mmol g-1·h-1。
Application example 4
The CuNi @ C/TiO prepared in example 42-0.125The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.125Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:19, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
The detection proves that the hydrogen production performance of the application example is 98.49 mmol.g-1·h-1。
Application example 5
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Application example 6
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 4:17, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Application example 7
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:4, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Application example 8
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 31 g.L-1。
Application example 9
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 93 g.L-1。
Application example 10
The CuNi @ C/TiO prepared in example 32-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and adding the mixture into 300W of xenonPerforming a hydrogen production reaction by catalyzing formaldehyde under a lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 124 g.L-1。
Application example 11
The CuNi @ C/TiO prepared in example 52-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Application example 12
The CuNi @ C/TiO prepared in example 62-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Application example 13
The CuNi @ C/TiO prepared in example 72-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is prepared by diluting formalin (38 wt.%) with water, and adding potassium hydroxide, wherein the formalin solution (38 wt.%) is mixed with potassium hydroxideThe volume ratio of water is 1:9, and the solid-to-liquid ratio of the added amount of potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
Application example 14
The CuNi @ C/TiO prepared in example 82-0.0625The composite catalyst is used for photo-assisted chemical catalysis of formaldehyde to produce hydrogen, and the specific method comprises the following steps: 10mg of CuNi @ C/TiO are taken2-0.0625Adding the composite catalyst sample into 100mL of alkaline formaldehyde solution, and performing catalytic formaldehyde hydrogen production reaction under a 300W xenon lamp light source; the alkaline formaldehyde solution is obtained by adding water to dilute formalin solution (38 wt.%), and then adding potassium hydroxide, wherein the volume ratio of the formalin solution (38 wt.%) to the water is 1:9, and the solid-to-liquid ratio of the added potassium hydroxide (AR 90%) to the reaction solution is 62 g.L-1。
The analysis results in that:
1. for the CuNi @ C/TiO compounds prepared in examples 1-42-xXRD and SEM detection are carried out on the composite catalyst, the XRD detection result is shown in figure 1, and the SEM detection result is shown in figure 2.
As can be seen from FIG. 1, with TiO2Increased amount of CuNi @ C/TiO2-xThe crystal form of the composite catalyst is not changed, but the diffraction peak in XRD is gradually strengthened.
As can be seen from FIG. 2, with TiO2Increased amount of CuNi @ C/TiO2-xThe crystal form of the composite catalyst is not changed, but the CuNi @ C surface-loaded TiO2The number of particles became significantly larger.
2. For the CuNi @ C/TiO prepared in example 82-0.0625The composite catalyst was subjected to SEM examination, and the results are shown in fig. 3. It can be seen from fig. 3 that the anatase phase of titanium dioxide is slightly changed at an annealing temperature of 900 c.
3. The hydrogen production performance of application examples 1 to 4 were compared, and the results are shown in FIG. 4. As can be seen from FIG. 4, with TiO2The hydrogen production performance of the composite catalyst is enhanced when the dosage is increased, and when TiO is used2The hydrogen production performance of the composite catalyst is reduced on the contrary when the dosage is continuously increased. When TiO is present2When the dosage is 25mg, the dosage is CuNi @ C/TiO2-0.0625The hydrogen-producing performance of the catalyst is best,122.85mmol · g-1·h-1。
4. The results of comparison of hydrogen production performance of application example 3 and application examples 5 to 7 are shown in fig. 5. As can be seen from fig. 5, the hydrogen generation performance of the composite catalyst increases as the concentration of formaldehyde increases, but the hydrogen generation performance decreases as the concentration continues to increase. The hydrogen production performance of the composite catalyst is optimal when the volume ratio of formalin solution (38 wt.%) to water is 1: 9.
5. The results of comparison of hydrogen production performance of application example 3 and application examples 8 to 10 are shown in fig. 6. As can be seen from FIG. 6, the hydrogen production performance of the composite catalyst is enhanced with the increase of the added amount of the potassium hydroxide, and when the solid-to-liquid ratio of the added amount of the potassium hydroxide to the reaction solution exceeds 62 g.L-1When the catalyst is used, the influence of the increase of the addition amount of the potassium hydroxide on the hydrogen production performance of the composite catalyst is small.
6. The results of comparison of hydrogen production performance of application example 3 and application examples 11 to 14 are shown in FIG. 7. As can be seen from FIG. 7, with the increase of the annealing temperature, the hydrogen production performance of the composite catalyst does not greatly fluctuate, which indicates that the composite catalyst with good hydrogen production performance can be prepared at the annealing temperature of 700-900 ℃.
Claims (10)
1. The photo-assisted chemical catalysis formaldehyde hydrogen production catalyst is characterized in that the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst is carbon-coated copper-nickel loaded titanium dioxide, and the general chemical composition formula of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst is CuNi @ C/TiO2，TiO2The molar ratio of the CuNi to the CuNi is x, wherein x is more than or equal to 0.03125 and less than or equal to 0.125.
2. The method for preparing the catalyst for hydrogen production by formaldehyde through photo-assisted chemical catalysis as claimed in claim 1, wherein a carbon-coated copper-nickel precursor of composite titanium dioxide is prepared by a hydrothermal method, and then CuNi @ C/TiO is obtained by an annealing method2A nanocomposite material.
3. The preparation method of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst according to claim 2, which is characterized by comprising the following steps:
(1) dissolving copper nitrate trihydrate, nickel nitrate hexahydrate and tartaric acid in water to obtain a first mixed solution;
(2) putting titanium dioxide into the first mixed solution, and uniformly mixing to obtain a second mixed solution;
(3) carrying out hydrothermal reaction on the second mixed solution to obtain a suspension;
(4) cooling the suspension, filtering, washing the filter residue with absolute ethyl alcohol, and drying to obtain powder;
(5) and heating the powder to 700-900 ℃ under the protection of inert gas, roasting, and cooling to obtain the powder.
4. The preparation method of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst according to claim 3, wherein in the step (1), the molar ratio of the copper nitrate trihydrate, the nickel nitrate hexahydrate and the tartaric acid is 1 (1-4): 4.
5. The preparation method of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst according to claim 4, wherein in the step (1), the molar ratio of the copper nitrate trihydrate, the nickel nitrate hexahydrate and the tartaric acid is 1:1: 4.
6. The preparation method of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst according to claim 3, wherein in the step (2), the molar ratio of the added amount of the titanium dioxide to the copper and the nickel is 1 (8-32).
7. The preparation method of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst according to claim 3, characterized in that in the step (3), the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 3-8 h.
8. The preparation method of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst according to claim 3, wherein in the step (5), the roasting treatment procedure is as follows: heating the mixture from the normal temperature to 700-900 ℃,the heating rate is 2-3 ℃ per minute-1And heating to 700-900 ℃ and keeping for 1-3 h.
9. The use of the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst of claim 1 in photo-assisted chemical catalysis formaldehyde hydrogen production.
10. The application of claim 9, wherein the photo-assisted chemical catalysis formaldehyde hydrogen production catalyst of claim 1 is added into a basic formaldehyde solution, and the hydrogen production reaction is catalyzed by formaldehyde under the illumination of ultraviolet light or sunlight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110372946.0A CN113083307B (en) | 2021-04-07 | 2021-04-07 | Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110372946.0A CN113083307B (en) | 2021-04-07 | 2021-04-07 | Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113083307A CN113083307A (en) | 2021-07-09 |
| CN113083307B true CN113083307B (en) | 2022-03-25 |
Family
ID=76674961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110372946.0A Active CN113083307B (en) | 2021-04-07 | 2021-04-07 | Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113083307B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047064A (en) * | 2017-11-06 | 2018-05-18 | 中国科学院兰州化学物理研究所 | A kind of method that paranitroanisole catalytic hydrogenation prepares paraphenetidine |
| CN109499577A (en) * | 2018-11-13 | 2019-03-22 | 浙江大学 | The preparation of Cu-Ni base catalyst for inverse water gas reaction and application method |
| CN110624550A (en) * | 2019-09-11 | 2019-12-31 | 上海电力大学 | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof |
| CN111085212A (en) * | 2019-08-20 | 2020-05-01 | 中国科学院广州能源研究所 | Method for preparing 2-methylfuran by catalyzing hydrogenation of D-xylose |
-
2021
- 2021-04-07 CN CN202110372946.0A patent/CN113083307B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047064A (en) * | 2017-11-06 | 2018-05-18 | 中国科学院兰州化学物理研究所 | A kind of method that paranitroanisole catalytic hydrogenation prepares paraphenetidine |
| CN109499577A (en) * | 2018-11-13 | 2019-03-22 | 浙江大学 | The preparation of Cu-Ni base catalyst for inverse water gas reaction and application method |
| CN111085212A (en) * | 2019-08-20 | 2020-05-01 | 中国科学院广州能源研究所 | Method for preparing 2-methylfuran by catalyzing hydrogenation of D-xylose |
| CN110624550A (en) * | 2019-09-11 | 2019-12-31 | 上海电力大学 | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Hydrodeoxygenation of dibenzofuran to bicyclic hydrocarbons using";Murtala M. Ambursa等;《Fuel》;20160418;第767-776页 * |
| "The IV period transition metal modified carbon@TiO2 nanoflower with high photo-electrochemical water oxidation performance under solar irradiation";Yuanyuan Liu等;《Applied Surface Science》;20190706;第795-806页 * |
| "负载型金属纳米颗粒的光化学沉积可控合成及催化应用";乔培胜;《中国博士学位论文全文数据库》;20150925;第49-59页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113083307A (en) | 2021-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113289693B (en) | Ammonia decomposition catalyst and preparation method and application thereof | |
| CN108671907B (en) | Platinum/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN112473717B (en) | Nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst | |
| CN113042090B (en) | Nonmetallic photocatalyst with charge transfer chain and preparation method and application thereof | |
| CN107308967B (en) | Catalyst promoter for photocatalytic decomposition of formic acid to produce hydrogen, photocatalytic system and method for decomposing formic acid to produce hydrogen | |
| CN110624550A (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN110586183A (en) | Method for preparing TiO by using supercritical carbon dioxide2Method for preparing/COF catalytic material | |
| CN112517043A (en) | Nitrogen vacancy and hydroxyl synergistically modified graphite-phase carbon nitride photocatalyst, preparation method thereof and application thereof in photocatalytic hydrogen production | |
| CN114534783B (en) | Method for preparing single-atom Pt-embedded covalent organic framework photocatalyst and application thereof | |
| CN114177940B (en) | Preparation and application of monoatomic Cu anchored covalent organic framework material | |
| CN114100661A (en) | Catalyst for preparing hydrogen by decomposing molybdenum-based ammonia and preparation method thereof | |
| CN116078419B (en) | Carbon nitride of cobalt phosphide coated by core-shell amorphous cobalt phosphate | |
| CN111701592B (en) | Co/M II Preparation of Fe layered double hydroxide and ammonia borane hydrogen production | |
| CN113083307B (en) | Photo-assisted chemical catalysis formaldehyde hydrogen production catalyst and preparation method and application thereof | |
| CN109876813B (en) | Preparation method and application of copper-zinc composite catalyst | |
| CN115608375B (en) | Catalyst for ammonia borane hydrolysis hydrogen evolution and preparation method thereof | |
| CN113398971B (en) | Two-dimensional RuNi/g-C3N4Composite photocatalyst and preparation method and application thereof | |
| CN115228489A (en) | Columnar BPQDs/ZnIn 2 S 4 Binary heterostructure composite photocatalytic material and preparation method and application thereof | |
| CN113083325A (en) | Catalyst Ru for ammonia borane hydrolysis hydrogen production1-xCox/P25 and preparation method thereof | |
| CN116174000A (en) | Preparation method and application of low-defect perovskite type tantalum-based oxynitride photocatalyst | |
| CN116273135B (en) | Nitrogen-doped oxide supported metal catalyst and preparation method and application thereof | |
| CN114849761B (en) | Photocatalytic material and preparation method and application thereof | |
| CN114870852B (en) | Load type Ni/W-ZrO for autothermal reforming of acetic acid to produce hydrogen 2 Catalyst | |
| CN114289065B (en) | Preparation method and application of metal ion doped x-MOF-74 photocatalyst | |
| CN115582124B (en) | Copper-based catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |