CN111229239B - Zinc oxide/zinc germanate-copper nano composite material photocatalyst and preparation method and application thereof - Google Patents
Zinc oxide/zinc germanate-copper nano composite material photocatalyst and preparation method and application thereof Download PDFInfo
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- CN111229239B CN111229239B CN202010074548.6A CN202010074548A CN111229239B CN 111229239 B CN111229239 B CN 111229239B CN 202010074548 A CN202010074548 A CN 202010074548A CN 111229239 B CN111229239 B CN 111229239B
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- 239000011701 zinc Substances 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 52
- 239000011787 zinc oxide Substances 0.000 title claims description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 25
- 229910052725 zinc Inorganic materials 0.000 title claims description 22
- 229910052802 copper Inorganic materials 0.000 title claims description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004246 zinc acetate Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract 1
- 229910005833 GeO4 Inorganic materials 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000010953 base metal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/835—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 germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a nano composite material photocatalystThe preparation method and the application thereof in the aspect of hydrogen production by catalytic decomposition of water. The catalyst takes sodium hydroxide with a certain concentration as a solvent, adopts a one-step hydrothermal method to obtain photocatalysts with different proportions by regulating the molar ratio of zinc acetate to germanium oxide, selects a photocatalytic composite material with the best catalytic activity proportion, and soaks copper ions with different concentrations by a wet chemical method to finally obtain ZnO/Zn2GeO4-a Cu nanocomposite photocatalyst. The method is simple and controllable, the reaction condition is mild, and the obtained catalyst has good appearance, low cost and wide photoresponse range. The research on hydrogen production by photocatalytic decomposition of the catalyst has high catalytic activity and has a high application prospect in the field of photocatalysis.
Description
Technical Field
The invention belongs to the field of nano composite material preparation technology and photocatalysis, and particularly relates to a photocatalyst with a zinc oxide/zinc germanate-copper photocatalytic hydrogen production function; also relates to the preparation of the catalyst and the application thereof in the aspect of photocatalytic hydrogen production.
Background
Environmental pollution and energy shortage are major problems restricting the development of human society at present, and the development of new energy to replace the combustion of fossil fuels is imminent. Hydrogen is the most renewable energy source with high combustion heat value, cleanness and environmental protection, and the decomposition of hydrogen to produce water by utilizing the photocatalysis technology has been widely researched. The key point of the technology is to develop and research a novel, efficient and low-cost photocatalyst.
Zn2GeO4Is an important n-type metal oxide semiconductor photocatalyst, and the crystal is made of GeO4Tetrahedron and ZnO4Tetrahedral composition due to presence of severely distorted GeO in the structure4Tetrahedra, i.e. the centre of a Ge atom being offset from the centre of the surrounding O atoms, the GeO4The electric field generated by the tetrahedral dipole moment is beneficial to the separation of the photo-generated electrons and the holes, and the photocatalysis performance of the photo-generated electrons is improved. However, the wider band gap results in Zn2GeO4The hydrogen production method can only absorb ultraviolet light, has low photoelectron utilization rate, and generally utilizes ion doping, composite metal modification and other methods to regulate and control the band gap value, broaden the photoresponse range, reduce the recombination rate of electrons and holes and further improve the hydrogen production activity in order to solve the problem. ZnO has the characteristics of high oxidation-reduction in situ, large exciton binding energy, good chemical stability and the like, is a photocatalytic material with great potential, and is also one of photocatalytic materials with wider research and application.
In order to prepare the photocatalyst which has low cost, wide light absorption range and stability and high efficiency, zinc acetate is taken as the zinc salt, the zinc salt and germanium oxide with different proportions are dissolved in prepared sodium hydroxide solution, the solution is evenly mixed and dissolved and then transferred into a reaction kettle, the zinc oxide/zinc germanate composite photocatalyst is prepared by a one-step hydrothermal method, and finally the zinc oxide/zinc germanate-copper zinc base metal oxide nano photocatalyst is obtained by taking copper acetate as a copper source and adopting a wet chemical method. At present, the zinc oxide/zinc germanate-copper zinc base metal oxide nano photocatalyst prepared by the method and the research on the application of the catalyst in photocatalytic water decomposition and hydrogen evolution are not reported.
The invention firstly adopts a hydrothermal method, controls the proportion of zinc and germanium, and performs mild reaction under solvothermal conditions to obtain the zinc oxide/zinc germanate catalyst, and finally introduces copper atoms through a wet chemical method to obtain the zinc oxide/zinc germanate-copper zinc base metal oxide photocatalyst. The photocatalyst prepared by the method not only widens the light absorption range, but also effectively inhibits the recombination of photo-generated electrons and holes, and shows remarkably improved activity of photocatalytic decomposition of water to produce hydrogen in the photocatalytic process. Has important theoretical guidance and practical significance for solving the problem of energy crisis.
Disclosure of Invention
Aiming at the problems of unsatisfactory performance of water decomposition and hydrogen evolution by photocatalysis in the prior art and application requirements in the field, the invention provides a preparation method of a zinc-based metal oxide nano photocatalyst and application thereof in hydrogen production by photocatalytic water decomposition. The catalyst uses sodium hydroxide with a certain concentration as a solvent, adopts a one-step hydrothermal method to obtain photocatalytic composite materials with different proportions by regulating the molar ratio of zinc acetate to germanium oxide, selects the photocatalytic composite material with the best catalytic activity proportion, and soaks copper ions with different concentrations by a wet chemical method to finally obtain the ZnO/Zn2GeO4-a Cu nanocomposite photocatalyst.
Specifically, the method comprises the following steps:
1. preparation of zinc oxide/zinc germanate nano composite material photocatalyst
(1) Weighing 1-6 mmol of zinc acetate, dispersing into 20 mL of 0.5M sodium hydroxide solution, and magnetically stirring until the zinc acetate is fully dissolved to obtain a colorless transparent solution;
(2) weighing 1-6 mmol of germanium oxide dispersion solution into the solution (1), magnetically stirring until the germanium oxide dispersion solution is completely dissolved, and then continuing magnetically stirring for 1-60 min to obtain a milky white solution;
(3) transferring the stirred solution in the step (2) into a 50 mL high-pressure reaction kettle to react for 10-12 h at 100-200 ℃, centrifugally washing the product for several times by using absolute ethyl alcohol, and drying for 8 h at 50 ℃ to obtain white powder for later use;
2. preparation of zinc oxide/zinc germanate-copper nano composite material photocatalyst
(1) Dispersing 0-0.347 g of zinc oxide/zinc germanate and 0-0.009 g of copper acetate in a certain amount of absolute ethyl alcohol, carrying out ultrasonic treatment for 1-10 min, and then stirring at room temperature for 1-12 h;
(2) and (3) centrifugally washing the mixed solution for a plurality of times, drying at 50 ℃ for 6-8 h, and collecting the obtained light blue powder for later use.
The specific implementation mode is as follows:
the invention will be further illustrated by the following examples in order to provide a further understanding of the invention, which are not to be construed as limiting in any way.
Example 1
(a) Preparation of zinc oxide/zinc germanate nano composite material photocatalyst
(1) 3 mmol of zinc acetate is weighed and dispersed into 20 mL of 0.5M sodium hydroxide solution, and the mixture is magnetically stirred until the zinc acetate is fully dissolved to obtain colorless transparent solution;
(2) weighing 1 mmol of germanium oxide dispersion solution into the solution (1), magnetically stirring until the germanium oxide dispersion solution is completely dissolved, and then continuously magnetically stirring for 60 min to obtain a milky white solution;
(3) transferring the stirred solution in the step (2) into a 50 mL high-pressure reaction kettle to react for 12 h at 200 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 8 h at 50 ℃ to obtain white powder for later use;
(b) preparation of zinc oxide/zinc germanate-copper nano composite material photocatalyst
(1) Dispersing 0.347 g of zinc oxide/zinc germanate and 0.009 g of copper acetate in a certain amount of absolute ethanol, performing ultrasonic treatment for 10 min, and then stirring at room temperature for 12 h;
(2) centrifuging and washing the mixed solution for several times, and drying at 50 ℃ for 8 h to obtain light blue powder for later use;
example 2
(a) ZnO/Zn2GeO4Preparation of nanocomposite photocatalyst
Prepared according to the method and conditions of step (a) in example 1;
(b) ZnO/Zn2GeO4preparation of-Cu nanocomposite photocatalyst
Prepared according to the method and conditions of step (b) in example 1;
(c) photocatalytic water splitting hydrogen production
The photocatalytic activity evaluation system for the hydrogen production performance test of the composite material is used for testing, and the specific experimental steps are as follows:
adding 100 mL of 10% methanol aqueous solution and 50 mg of ZnO/Zn into a quartz reaction vessel2GeO4Adding a certain amount of potassium chloroplatinite (the Pt content is 0.5%) as a catalyst promoter → a reaction vessel access system to continue vacuumizing until no bubbles are blown out from the solution, turning off a vacuum pump, turning on a lamp (the lamp source is a 300W xenon lamp) → accessing hydrogen generated by the reaction to a gas chromatograph to start analysis and recording the peak area (the retention time is about 1 min). And calculating the hydrogen evolution quantity and the hydrogen evolution rate according to the peak area and the hydrogen production time.
Adding 100 mL of 10% methanol aqueous solution and 50 mg of ZnO/Zn into a quartz reaction vessel2GeO4Adding a certain amount of potassium chloroplatinite (the Pt content is 0.5%) into the/Cu composite material to serve as a cocatalyst → a reaction vessel access system continuously vacuumizing until no bubbles are emitted from the solution, turning off a vacuum pump, turning on a lamp (the lamp source is a 300W xenon lamp) → accessing hydrogen generated by the reaction to a gas chromatograph, starting analysis and recording the peak area (the retention time is about 1 min). And calculating the hydrogen evolution quantity and the hydrogen evolution rate according to the peak area and the hydrogen production time.
Claims (5)
1. A preparation method of a zinc oxide/zinc germanate-copper nanocomposite photocatalyst is characterized in that sodium hydroxide with a certain concentration is used as a solvent, the photocatalyst with different proportions is obtained by regulating and controlling the molar ratio of zinc acetate to germanium oxide by adopting a one-step hydrothermal method, and finally the zinc oxide/zinc germanate-copper nanocomposite photocatalyst is obtained by adopting a wet chemical method by taking copper acetate as a copper source;
the preparation method of the nano composite material photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(a) preparation of zinc oxide/zinc germanate nano composite material photocatalyst
(1) Weighing 1-6 mmol of zinc acetate, dispersing into 20 mL of 0.5M sodium hydroxide solution, and magnetically stirring until the zinc acetate is fully dissolved to obtain a colorless transparent solution;
(2) weighing 1-6 mmol of germanium oxide dispersion solution into the solution (1), magnetically stirring until the germanium oxide dispersion solution is completely dissolved, and then continuing magnetically stirring for 1-60 min to obtain a milky white solution;
(3) transferring the stirred solution in the step (2) into a 50 mL high-pressure reaction kettle to react for 12 h at 200 ℃, centrifugally washing the product for a plurality of times by using absolute ethyl alcohol, and drying for 8 h at 50 ℃ to obtain white powder for later use;
(b) preparation of zinc oxide/zinc germanate-copper nano composite material photocatalyst
(1) Dispersing 0-0.347 g of zinc oxide/zinc germanate and 0-0.009 g of copper acetate in a certain amount of absolute ethyl alcohol, carrying out ultrasonic treatment for 1-10 min, and then stirring at room temperature for 1-12 h;
(2) and (3) centrifugally washing the mixed solution for a plurality of times, drying at 50 ℃ for 8 h, and collecting the obtained light blue powder for later use.
2. The method according to claim 1, wherein Zn (ac) in the step (a)2·2H2The dosage of O is 3 mmol; GeO2Is 1 mmol.
3. The method according to claim 1, wherein the amount of zinc oxide/zinc germanate in step (b) is 0.347 g; the amount of copper acetate was 0.009 g; the ultrasonic dispersion time is 10 min; stirring for 12 h at room temperature; centrifugation was performed using three washes with absolute ethanol.
4. The application of the nanocomposite photocatalyst prepared by the preparation method according to claim 1 in the field of hydrogen production by photocatalytic water decomposition.
5. Use according to claim 4, characterized in that: the light source under the test condition is a 300W xenon lamp; the amount of catalyst was 0.05 g; the concentration of the sacrificial agent methanol was 10%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011225397A (en) * | 2010-04-20 | 2011-11-10 | Ohara Inc | Glass ceramic, and process for producing the same |
| CN109589985A (en) * | 2018-12-19 | 2019-04-09 | 荣吴迪 | The preparation method and its catalysis reduction carbon dioxide of dopen Nano zinc germanate |
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| JP2011225397A (en) * | 2010-04-20 | 2011-11-10 | Ohara Inc | Glass ceramic, and process for producing the same |
| CN109589985A (en) * | 2018-12-19 | 2019-04-09 | 荣吴迪 | The preparation method and its catalysis reduction carbon dioxide of dopen Nano zinc germanate |
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