CN114836787A - Preparation method of molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst - Google Patents
Preparation method of molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 26
- 239000011733 molybdenum Substances 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
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- 238000000034 method Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 20
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- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
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- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
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- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
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- 244000105624 Arachis hypogaea Species 0.000 claims description 7
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 7
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- 235000020232 peanut Nutrition 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
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- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 235000021374 legumes Nutrition 0.000 claims description 2
- 244000194101 Ginkgo biloba Species 0.000 claims 1
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- 244000068988 Glycine max Species 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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 preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst, which comprises the following steps: mixing the crushed biomass raw material powder rich in nitrogen and sulfur organic matters with a molybdenum-containing compound, and carrying out ball milling in an inert atmosphere; adding a template agent and a pore-forming agent into the mixture after the full ball milling, and further mixing and ball milling in an inert atmosphere; and (4) calcining the mixture obtained by ball milling in the step two at high temperature in an inert atmosphere, and cooling to obtain the hydrogen evolution electrocatalyst. The molybdenum-supported hydrogen evolution electrocatalyst with high catalytic activity is prepared by simple ball milling and high-temperature calcination methods, so that the resource utilization of biomass waste can be completed, and meanwhile, a high-performance non-noble metal hydrogen evolution electrocatalyst can be prepared. Compared with the prior MoS 2 The synthesis process does not need to use a complex hydrothermal reaction process with high energy consumption, only needs to be subjected to mixing, ball milling and pyrolysis with biomass, and has wide and combined raw material sourcesThe method is simple and convenient, the energy consumption is low, and the economical efficiency is improved.
Description
Technical Field
The invention relates to the technical field of hydrogen evolution electrocatalysts, in particular to a preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst.
Background
The biomass waste is easy to decay due to the fact that the biomass waste is rich in organic matters, so that V ℃ can be generated in the process of consumption treatment, and meanwhile, smoke dust and nitrogen oxide pollution can be caused in the process of incineration treatment, so that the recycling utilization of the biomass waste can improve the recycling rate of the waste and can relieve the environmental problems possibly caused in the process of treatment. Nitrogen and sulfur organic matters in the biomass can enter carbon lattices in the pyrolysis process, and electronic balance in a carbon structure is broken, so that the carbon material is endowed with better electrochemical properties.
Molybdenum-based compounds, because of their band structure, are similar to those of the platinum group metals and possess the potential to replace the platinum group metals as hydrogen evolution catalysts. In the prior art, a hydrothermal method is mostly adopted to prepare the carbon-based molybdenum compound composite carrier, so that the operation is complex, the energy consumption is high, and the prepared catalyst has the advantages of low specific surface area and porosity on the surface and low catalytic activity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst, aiming at improving the catalytic performance of the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst.
The technical scheme adopted by the invention is as follows:
a preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst comprises the following steps:
the method comprises the following steps: mixing the crushed biomass raw material powder rich in nitrogen and sulfur organic matters with a molybdenum-containing compound, and carrying out ball milling in an inert atmosphere;
step two: adding a template agent and a pore-forming agent into the mixture after the full ball milling, and further mixing and ball milling in an inert atmosphere;
step three: and (4) calcining the mixture obtained by ball milling in the step two at high temperature in an inert atmosphere, and cooling to obtain the hydrogen evolution electrocatalyst.
The further technical scheme is as follows:
the template agent and the pore-forming agent are the same zinc-containing compound.
The zinc-containing compound is ZnCl 2 、ZnO、ZnCO 3 One or more of them.
The high-temperature calcination adopts a two-stage heating process:
the first heating process is carried out from room temperature to 800-900 ℃, and the second heating process is carried out from 800-900 ℃ to 950-1100 ℃.
In the first heating process, the heating rate is 1-3 ℃/min, and the heating time is maintained for 2-5 h; in the second stage of heating process, the heating rate is 5-8 ℃/min, and the heating time is maintained for 1-2 h.
The mass ratio of the biomass raw material to the template agent and the pore-forming agent is 1: 1-1: 3.
The mass ratio of the biomass raw material to the molybdenum-containing compound is 1: 0.5-1: 2.
The molybdenum-containing compound is one or more of ammonium molybdate, sodium molybdate and phosphomolybdic acid.
The biomass material is one or more of ginkgo leaf, peanut shell and bean plant rhizome.
The invention has the following beneficial effects:
the method utilizes the biomass waste with low cost to prepare the molybdenum-supported hydrogen evolution electrocatalyst with high catalytic activity by simple ball milling and high-temperature calcination methods, can complete the resource utilization of the biomass waste, and can prepare the non-noble metal hydrogen evolution electrocatalyst with high performance. Compared with most MoS at present 2 The synthesis process does not need to use a complex hydrothermal reaction process with high energy consumption, only needs to be subjected to mixing, ball milling and pyrolysis with biomass, and has the advantages of wide raw material source, simple and convenient synthesis method, low energy consumption and improvement on economy.
According to the invention, the pore-forming agent and the template agent are introduced, so that the pore structure of the material is enriched, and the specific surface area and the porosity of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst are increased, thereby promoting the electron transmission of the material and improving the catalytic performance.
The invention adopts zinc-containing compound as template agent and pore-forming agent, which can avoid the loss of carbon component, prevent the formation of more metal carbide, and improve the generation rate and quality of the product.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a crystal structure diagram of a hydrogen evolution electrocatalyst A prepared in example 1 of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
The preparation method of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst comprises the following steps:
the method comprises the following steps: mixing the crushed biomass raw material powder rich in nitrogen and sulfur organic matters with a molybdenum-containing compound, and carrying out ball milling in an inert atmosphere;
step two: adding a template agent and a pore-forming agent into the mixture after the full ball milling, and further mixing and ball milling in an inert atmosphere;
step three: and (4) calcining the mixture obtained by ball milling in the step two at high temperature in an inert atmosphere, and cooling to obtain the hydrogen evolution electrocatalyst.
According to the preparation method of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst, the method of ball milling and high-temperature calcination is adopted, molybdenum is loaded on the carbon-based material derived from the waste biomass, in the high-temperature calcination process, the molybdenum and the biomass react and are loaded on the carbon-based material, and partial organic matter decomposition of the biomass promotes the formation of catalyst pores and the promotion of catalytic activity.
According to the preparation method, the pore-foaming agent and the template agent are introduced, the pore structure of the material is enriched, and the specific surface area and the porosity of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst can be effectively increased. The prepared catalyst can effectively promote the electron transmission of the material, and the catalytic performance is greatly improved.
Specifically, the template agent and the pore-forming agent are the same zinc-containing compound.
Preferably, the zinc-containing compound is ZnCl 2 、ZnO、ZnCO 3 One or more of them.
Specifically, the high-temperature calcination adopts a two-stage heating process:
the first heating process is carried out from room temperature to 800-900 ℃, and the second heating process is carried out from 800-900 ℃ to 950-1100 ℃.
Specifically, in the first stage of heating process, the heating rate is 1-3 ℃/min, and the heating time is maintained for 2-5 h; in the second stage of heating process, the heating rate is 5-8 ℃/min, and the heating time is maintained for 1-2 h.
The preparation method can fully exert the effect of the zinc-containing compound by regulating and controlling the temperature through two-stage heating. The zinc-containing compound can form Zn in the pyrolysis process, the Zn can be used as a template for carbon growth, namely, the effect of the template is exerted, and when the temperature exceeds 950 ℃, the Zn volatilizes and escapes to generate pores, namely, the effect of the pore-forming agent is exerted.
The zinc-containing compound of the present application serves as a templating agent and a porogen during pyrolysis to achieve two different effects. The zinc-containing compound can not cause the etching of biomass in the pyrolysis process, can avoid causing the loss of a large amount of carbon components, prevent more metal carbides from being formed, and ensure the quality of the final product.
Specifically, the mass ratio of the biomass raw material to the template and the pore-forming agent is 1: 1-1: 3.
Specifically, the mass ratio of the biomass raw material to the molybdenum-containing compound is 1: 0.5-1: 2.
Specifically, the molybdenum-containing compound is one or more of ammonium molybdate, sodium molybdate and phosphomolybdic acid.
Specifically, the biomass raw material is one or more of ginkgo leaves, peanut shells and legume roots.
Example 1:
the method comprises the following steps: crushing ginkgo leaves serving as a biomass raw material into 300 meshes, adopting ammonium molybdate serving as a molybdenum-containing compound, mixing the ginkgo leaves and the ammonium molybdate according to the mass ratio of 1: 0.5, carrying out ball milling in a nitrogen atmosphere, wherein the rotating speed of a ball mill is 600r/min, and the running time is 3 hours;
step two: by using ZnCl 2 Adding the mixture serving as a template agent and a pore-forming agent into the mixture obtained in the step one, and continuously performing ball milling in a nitrogen atmosphere to obtain a mixture precursor, wherein the ginkgo leaf and the ZnCl are 2 The mass ratio is 1: 1, the rotating speed of the ball mill is 1200r/min,running for 8 h;
step three: and (3) putting the mixture precursor obtained in the step two into a tube furnace, firstly heating to 800 ℃ in nitrogen, maintaining the temperature rise rate at 1 ℃/min for 5h, then continuously heating to 950 ℃, maintaining the temperature rise rate at 5 ℃/min for 1h, cooling, and collecting a product to obtain the hydrogen evolution electrocatalyst A, wherein the crystal structure of the hydrogen evolution electrocatalyst A is shown in figure 1.
From FIG. 1, it is understood that the crystal structure composition in catalyst A is Mo 2 C and MoS 2 Ammonium molybdate not only combines with carbon to form Mo 2 C crystal phase, and combined with sulfur-containing components in folium Ginkgo to form MoS 2 。
Example 2:
the method comprises the following steps: the method comprises the following steps of (1) crushing peanut shells into 500 meshes by taking the peanut shells as a biomass raw material, mixing the peanut shells and sodium molybdate according to the mass ratio of 1: 1, carrying out ball milling in a nitrogen atmosphere, wherein the rotating speed of a ball mill is 800r/min, and the running time is 4 hours;
step two: ZnO is used as a template agent and a pore-forming agent, added into the mixture obtained in the first step, and continuously subjected to ball milling in a nitrogen atmosphere to obtain a mixture precursor, wherein the mass ratio of the peanut shell to the ZnO is 1: 2, the rotating speed of the ball mill is 2400r/min, and the operation is carried out for 16 hours;
step three: and (3) putting the mixture precursor obtained in the step two into a tubular furnace, firstly heating to 850 ℃ in nitrogen, keeping the temperature rise rate at 2 ℃/min for 4h, then continuously heating to 1000 ℃, keeping the temperature rise rate at 6 ℃/min for 1.5h, cooling, and collecting a product to obtain the hydrogen evolution electrocatalyst B.
Example 3:
the method comprises the following steps: crushing soybean roots and stems serving as a biomass raw material into 600 meshes, adopting sodium molybdate serving as a molybdenum-containing compound, mixing the soybean roots and stems with the sodium molybdate according to the mass ratio of 1: 2, and carrying out ball milling in a nitrogen atmosphere at the ball mill rotation speed of 1000r/min for 6 h;
step two: by using ZnCO 3 Adding the mixture serving as a template agent and a pore-forming agent into the mixture obtained in the step one, and continuously performing ball milling in a nitrogen atmosphere to obtain a mixture precursor, wherein soybean rhizomes and ZnCO 2 The mass ratio is 1: 3, the rotating speed of the ball mill is 3600r/min, and the operation is carried out for 24 hours;
step three: and (3) putting the mixture precursor obtained in the step two into a tube furnace, firstly heating to 900 ℃ in nitrogen, keeping the temperature rise rate at 3 ℃/min for 2h, then continuously heating to 1100 ℃, keeping the temperature rise rate at 8 ℃/min for 2h, cooling, and collecting a product to obtain the hydrogen evolution electrocatalyst C.
Through electrochemical test and determination, the hydrogen evolution electro-catalyst A, the hydrogen evolution electro-catalyst B and the hydrogen evolution electro-catalyst C drive the hydrogen evolution current density to reach 10mAcm -2 The overpotential for the reaction is 198mV, 210mV and 206mV, so that the catalyst has good catalytic activity.
Those of ordinary skill in the art will understand that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst is characterized by comprising the following steps:
the method comprises the following steps: mixing the crushed biomass raw material powder rich in nitrogen and sulfur organic matters with a molybdenum-containing compound, and performing ball milling in an inert atmosphere;
step two: adding a template agent and a pore-forming agent into the mixture after the full ball milling, and further mixing and ball milling in an inert atmosphere;
step three: and (4) calcining the mixture obtained by ball milling in the step two at high temperature in an inert atmosphere, and cooling to obtain the hydrogen evolution electrocatalyst.
2. The preparation method of the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 1, wherein the template agent and the pore-forming agent are the same zinc-containing compound.
3. The method of claim 2, wherein the zinc-containing compound is ZnCl 2 、ZnO、ZnCO 3 One or more of them.
4. The preparation method of the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 1, wherein the high-temperature calcination employs a two-stage heating process:
the first heating process is carried out from room temperature to 800-900 ℃, and the second heating process is carried out from 800-900 ℃ to 950-1100 ℃.
5. The preparation method of the molybdenum-loaded biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 4, wherein in the first heating process, the temperature rise rate is 1-3 ℃/min, and the temperature is maintained for 2-5 h; in the second stage of heating process, the heating rate is 5-8 ℃/min, and the heating time is maintained for 1-2 h.
6. The preparation method of the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 1, wherein the mass ratio of the biomass raw material to the template agent and the pore-forming agent is 1: 1-1: 3.
7. The preparation method of the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 1, wherein the mass ratio of the biomass raw material to the molybdenum-containing compound is 1: 0.5-1: 2.
8. The method for preparing the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 1, wherein the molybdenum-containing compound is one or more of ammonium molybdate, sodium molybdate and phosphomolybdic acid.
9. The preparation method of the molybdenum-supported biomass-derived carbon-based hydrogen evolution electrocatalyst according to claim 1, wherein the biomass raw material is one or more of ginkgo leaves, peanut shells and legume rhizomes.
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