CN112191273A - High-entropy coordination polymer catalyst for oxygen production by electrolyzing water and preparation method and application thereof - Google Patents
High-entropy coordination polymer catalyst for oxygen production by electrolyzing water and preparation method and application thereof Download PDFInfo
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- CN112191273A CN112191273A CN202011084825.8A CN202011084825A CN112191273A CN 112191273 A CN112191273 A CN 112191273A CN 202011084825 A CN202011084825 A CN 202011084825A CN 112191273 A CN112191273 A CN 112191273A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 58
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 35
- 239000001301 oxygen Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 51
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 38
- 239000013110 organic ligand Substances 0.000 claims abstract description 34
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 31
- -1 transition metal salts Chemical class 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 229910021381 transition metal chloride Inorganic materials 0.000 claims abstract description 7
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- MGFJDEHFNMWYBD-OWOJBTEDSA-N 4-[(e)-2-pyridin-4-ylethenyl]pyridine Chemical group C=1C=NC=CC=1/C=C/C1=CC=NC=C1 MGFJDEHFNMWYBD-OWOJBTEDSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- XZYLSJPLCLKCMR-UHFFFAOYSA-N 1-(pyridin-4-ylmethyl)piperazine Chemical compound C=1C=NC=CC=1CN1CCNCC1 XZYLSJPLCLKCMR-UHFFFAOYSA-N 0.000 claims description 3
- MQSMIIJCRWDMDL-UHFFFAOYSA-N 3,6-dipyridin-4-yl-1,2,4,5-tetrazine Chemical compound C1=NC=CC(C=2N=NC(=NN=2)C=2C=CN=CC=2)=C1 MQSMIIJCRWDMDL-UHFFFAOYSA-N 0.000 claims description 3
- DQRKTVIJNCVZAX-UHFFFAOYSA-N 4-(2-pyridin-4-ylethyl)pyridine Chemical compound C=1C=NC=CC=1CCC1=CC=NC=C1 DQRKTVIJNCVZAX-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006255 coating slurry Substances 0.000 claims 1
- 239000010408 film Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910001960 metal nitrate Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- SNCZMWAFNIRUPT-UHFFFAOYSA-N [Zn].[Cu].[Ni].[Co].[Fe] Chemical compound [Zn].[Cu].[Ni].[Co].[Fe] SNCZMWAFNIRUPT-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
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- 230000033764 rhythmic process Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention provides a high-entropy coordination polymer catalyst for oxygen production by electrolyzing water, a preparation method and application thereof, wherein the catalyst is prepared by reacting reaction liquid A and reaction liquid B: the A reaction solution comprises a plurality of transition metal salt solutions; the transition metal salts are selected from transition metal chlorides and/or transition metal nitrates; the reaction solution B comprises a heteroatom-containing organic ligand solution; the volume ratio of the various transition metal salts to the solvent is (0.1-100) mmol, (50-1000) ml; the volume ratio of the substance containing the heteroatom organic ligand to the solvent is (0.1-100) mmol, (50-1000) ml. The organic ligand in the catalyst and various transition metal salts directly synthesize coordination polymers, and the coordination polymers are used as catalysts for decomposing water and separating oxygen, so that the catalysis overpotential is small, the current density is large, and the stability is good. The catalyst can bear the stable catalysis for a long time under the condition of high current density in electrolyte with higher concentration.
Description
Technical Field
The invention belongs to the technical field of catalysts for producing oxygen by electrolyzing water, and particularly relates to a high-entropy coordination polymer catalyst for producing oxygen by electrolyzing water as well as a preparation method and application thereof.
Background
With the rapid development of science and technology, fossil energy is difficult to meet the rapid development rhythm at present, and provides higher challenge to sustainable clean energy, so that a new solution is urgently needed to meet the current situation, and a novel energy conversion and storage mode is urgently needed to be developed to make up for the deficiency of energy supply and demand at present. At present, the hydrogen energy developed according to the prior art can meet the current demand condition, and hydrogen is produced by directly electrolyzing water by solar energy in the process of obtaining the hydrogen energy, so that the method has unique advantages and is expected to realize the large-scale application of the hydrogen energy. However, water oxidation during electrolysis of water is a bottleneck limiting the technology of electrolysis of water. Because four electrons are needed for the reaction to be transferred in the water decomposition process, and higher activation energy is needed from the thermodynamic analysis, a catalyst is needed to accelerate the reaction rate, and the current situation of high energy consumption is overcome.
According to the previous research, the catalyst used in the water electrolysis oxygen production process of the commercial electrolytic cell mainly uses noble metal oxides such as ruthenium, iridium and the like, and the oxide catalyst is directly coated on the surface of an electrode, so that the catalyst is particularly seriously consumed due to the falling of the catalyst caused by a large amount of bubbles in the catalytic reaction process, particularly in the reaction under the condition of high current density, and in addition, the storage amount of the noble metal is low, the price is high, and the hydrogen production cost of the electrolyzed water is increased. Recently, the oxygen production catalyst by water electrolysis is entrusted to the abundant non-noble metal catalyst and causes a wide research heat, and the catalyst structure according to the current report mainly comprises the following types: non-noble metal oxides/hydroxides and heteroatom doping, metal organic framework compounds, molecular catalysts, and the like. According to reports, the catalysts show certain catalytic activity and stability, and most of the reported catalysts have small potential in commercial application by looking at the harsh requirements on the application environment of the catalysts in industrial application and the reported methods for synthesizing the catalysts, stability of large current density and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a high-entropy coordination polymer catalyst for electrolyzing water to generate oxygen, and a preparation method and an application thereof, wherein the catalyst has high catalytic activity and good stability when used as a catalyst for decomposing water to generate oxygen.
The invention provides a high-entropy coordination polymer catalyst for oxygen production by electrolyzing water, which is prepared by the reaction of reaction liquid A and reaction liquid B:
the A reaction solution comprises a plurality of transition metal salt solutions; the transition metal salts are selected from transition metal chlorides and/or transition metal nitrates;
the reaction solution B comprises a heteroatom-containing organic ligand solution;
the volume ratio of the substances of the transition metal salts in the transition metal salt solution to the solvent is (0.1-100) mmol (50-1000) ml;
the volume ratio of the substance containing the heteroatom organic ligand in the solution containing the heteroatom organic ligand to the solvent is (0.1-100) mmol (50-1000) ml.
Preferably, the heteroatom-containing organic ligand is selected from one or more of pyrazine, pyrimidine, 4' -bipyridine, 1, 2-bis (4-pyridyl) ethene, 3, 6-bis-4-pyridyl-1, 2,4, 5-tetrazine, 1, 2-bis (4-pyridyl) ethane, 1- (4-pyridylmethyl) piperazine.
Preferably, the metal of the plurality of transition metal salts is selected from at least five of iron, cobalt, nickel, copper, zinc, tin, chromium, manganese, zirconium, and vanadium.
Preferably, the solvent in the reaction liquid A and the reaction liquid B is independently selected from one or more of methanol and ethanol.
Preferably, the volume ratio of the substances of the transition metal salts to the solvent is (5-10) mmol:50 ml;
the volume ratio of the substance containing the heteroatom organic ligand in the heteroatom organic ligand solution to the solvent is 10-14 mmol:50 ml.
The invention provides a preparation method of a high-entropy coordination polymer catalyst for oxygen production by electrolyzing water, which comprises the following steps:
and adding the reaction solution A into the reaction solution B at an addition rate of 0.01-10 mL/min for reaction, washing, and freeze-drying to obtain the high-entropy coordination polymer catalyst for oxygen production by water electrolysis.
Preferably, the reaction temperature is-5 ℃, and the reaction time is 0.5-5 h.
The invention provides an electrode containing a high-entropy coordination polymer, which comprises a conductive carrier and a film loaded on the conductive carrier;
the film is prepared by coating the slurry of the high-entropy coordination polymer catalyst or the high-entropy coordination polymer catalyst prepared by the preparation method in the technical scheme;
the conductive carrier is selected from one or more of nickel strips, cobalt strips, iron strips, copper foam, nickel foam, iron foam, gold foam, conductive carbon paper, conductive cloth, conductive felt and glassy carbon electrodes.
The invention provides a high-entropy coordination polymer catalyst for oxygen production by electrolyzing water, which is prepared by the reaction of reaction liquid A and reaction liquid B: the A reaction solution comprises a plurality of transition metal salt solutions; the transition metal salts are selected from transition metal chlorides and/or transition metal nitrates; the reaction solution B comprises a heteroatom-containing organic ligand solution; the volume ratio of the substances of the transition metal salts in the transition metal salt solution to the solvent is (0.1-100) mmol (50-1000) ml; the volume ratio of the substance containing the heteroatom organic ligand in the solution containing the heteroatom organic ligand to the solvent is (0.1-100) mmol (50-1000) ml. In the high-entropy coordination polymer catalyst provided by the invention, an organic ligand and various transition metal salts are directly synthesized into a coordination polymer which is used as a catalyst for decomposing water and separating oxygen, so that the high-entropy coordination polymer catalyst has the advantages of small catalytic overpotential, large current density and good stability. The catalyst can bear the stable catalysis for a long time under the condition of high current density in electrolyte with higher concentration. The experimental results show that: when oxygen evolution reaction is carried out, the current density is 10mA cm-2The corresponding overpotential is 193-207 mV; the current density is 100mA cm-2The corresponding overpotential is 230-247 mV; the current density is 500mA cm-2The corresponding overpotential is 259-283 mV.
Drawings
FIG. 1 is an X-ray diffraction pattern of high entropy coordination polymer # 1 prepared in example 1 of this invention;
FIG. 2 is a scanning electron micrograph of high entropy coordination polymer 1# prepared in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph of high entropy coordination polymer 1# prepared in example 1 of the present invention;
FIG. 4 is a graph showing the effect of high entropy coordination polymer No. 1 prepared in example 1 of the present invention in catalyzing the decomposition of water to produce oxygen;
FIG. 5 is a graph showing the effect of high entropy coordination polymer No. 2 prepared in example 2 of the present invention in catalyzing the decomposition of water to produce oxygen;
FIG. 6 is a graph showing the effect of high entropy coordination polymer # 3 catalyzing the decomposition of water to produce oxygen in accordance with example 3 of the present invention;
FIG. 7 is a graph showing the effect of high entropy coordination polymer No. 1 prepared in example 1 of the present invention on the stability of oxygen production by catalytic decomposition of water.
Detailed Description
The invention provides a high-entropy coordination polymer catalyst for oxygen production by electrolyzing water, which is prepared by the reaction of reaction liquid A and reaction liquid B:
the A reaction solution comprises a plurality of transition metal salt solutions; the transition metal salts are selected from transition metal chlorides and/or transition metal nitrates;
the reaction solution B comprises a heteroatom-containing organic ligand solution;
the volume ratio of the substances of the transition metal salts in the transition metal salt solution to the solvent is (0.1-100) mmol (50-1000) ml;
the volume ratio of the substance containing the heteroatom organic ligand in the solution containing the heteroatom organic ligand to the solvent is (0.1-100) mmol (50-1000) ml.
In the high-entropy coordination polymer catalyst provided by the invention, an organic ligand and various transition metal salts are directly synthesized into a coordination polymer which is used as a catalyst for decomposing water and separating oxygen, so that the high-entropy coordination polymer catalyst has the advantages of small catalytic overpotential, large current density and good stability.
The A reaction solution comprises a plurality of transition metal salt solutions; the plurality of transition metal salts is selected from a plurality of transition metal chlorides and/or a plurality of transition metal nitrates. In the present invention, the metal of the plurality of transition metal salts is selected from at least five of iron, cobalt, nickel, copper, zinc, tin, chromium, manganese, zirconium, and vanadium. The solvent in the transition metal salt solution is preferably selected from methanol and/or ethanol. In a specific embodiment, the plurality of transition metal salts are selected from one or more of iron cobalt nickel zinc chromium manganese zirconium metal nitrates, iron cobalt nickel tin vanadium metal nitrates, and iron cobalt nickel copper zinc metal nitrates. The volume ratio of the various transition metal salts to the solvent is (0.1-100) mmol, (50-1000) ml, preferably (5-10) mmol:50 ml; in specific embodiments, the ratio of the amount of the plurality of transition metal salt species to the volume of the solvent is 7mmol:50 mL; or 5mmol:50 mL.
In the invention, the B reaction solution comprises a heteroatom-containing organic ligand solution; the heteroatom-containing organic ligand is preferably selected from one or more of pyrazine, pyrimidine, 4' -bipyridine, 1, 2-bis (4-pyridyl) ethylene, 3, 6-bis-4-pyridyl-1, 2,4, 5-tetrazine, 1, 2-bis (4-pyridyl) ethane, 1- (4-pyridylmethyl) piperazine; in a particular embodiment, the heteroatom-containing organic ligand is selected from 1, 2-bis (4-pyridyl) ethylene. The solvent in the heteroatom-containing organic ligand solution is preferably selected from methanol and/or ethanol. The volume ratio of the substance containing the heteroatom organic ligand in the heteroatom organic ligand solution to the solvent is (0.1-100) mmol (50-1000) mL, preferably (10-14) mmol (50 mL). In a specific embodiment, the volume ratio of the substance containing the heteroatom organic ligand to the solvent is 10mmol:50 mL; or 14mmol:50 mL.
The invention provides a preparation method of a high-entropy coordination polymer catalyst for oxygen production by electrolyzing water, which comprises the following steps:
and adding the reaction solution A into the reaction solution B at an addition rate of 0.01-10 mL/min for reaction, washing, and freeze-drying to obtain the high-entropy coordination polymer catalyst for oxygen production by water electrolysis.
The method provided by the invention is simple, low in cost and simple in product structure, can be directly synthesized in a large scale, does not influence the catalytic performance, and is directly used by coating the catalyst on an electrode. The high-entropy coordination polymer catalyst prepared by the method has simple and convenient operation equipment and method and high conversion rate, is expected to replace the expensive and scarce noble metal catalysts such as ruthenium, iridium and the like at present, and is expected to realize large-scale application.
The method preferably comprises the step of stirring the reaction solution A and the reaction solution B in an ice bath for 20-40 min respectively for later use.
The invention preferably adopts a peristaltic pump to drop the A reaction liquid into the B reaction liquid. The dropping rate is 0.01-10 mL/min, preferably 2-3 mL/min.
The reaction temperature is preferably-5 ℃, and the reaction time is 0.5-5 h.
The invention provides an electrode containing a high-entropy coordination polymer, which comprises a conductive carrier and a film loaded on the conductive carrier;
the film is prepared by coating the slurry of the high-entropy coordination polymer catalyst or the high-entropy coordination polymer catalyst prepared by the preparation method in the technical scheme;
the conductive carrier is selected from one or more of nickel strips, cobalt strips, iron strips, copper foam, nickel foam, iron foam, gold foam, conductive carbon paper, conductive cloth, conductive felt and glassy carbon electrodes.
In the invention, the thickness of the film on the conductive carrier is 25-500 nm.
In order to further illustrate the present invention, the following examples are provided to describe the high entropy coordination polymer catalyst for the electrolysis of water to generate oxygen and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
1. Uniformly mixing the following raw materials in an equimolar ratio to prepare a reaction solution A:
7mmol of metal nitrate of Fe, Co, Ni, Zn, Cr, Mn and Zr
50mL of ethanol
Dissolving the following raw materials by mole to prepare a reaction solution B:
14mmol of 1, 2-bis (4-pyridyl) ethylene
50mL of ethanol
2. Firstly, stirring reaction solution A and reaction solution B in an ice domain for 20-40 min, and then dropwise adding the reaction solution A into the reaction solution B at the speed of 2-3 mL/min through a peristaltic pump, wherein the reaction temperature is-5 ℃, and the reaction time is 1 h. After reaction, respectively using ethanol, washing with deionized water for at least three times, drying in a freeze dryer after washing, and finally preparing the high-entropy coordination polymer catalyst powder. As can be seen from FIGS. 1 to 3, the synthesis method can effectively synthesize the coordination polymer with crystal form through X-ray diffraction pattern. Scanning electron micrographs and transmission electron micrographs show that a particular high-entropy coordination polymer is composed mainly of a nanofilm.
3. The high-entropy coordination polymer powder synthesized in example 1 is prepared into catalyst slurry, uniformly drop-coated on a foam nickel substrate, dried at low temperature, and directly used as a working electrode without other treatment.
Example 2
Uniformly mixing the following raw materials in an equimolar ratio to prepare a reaction solution A:
5mmol of metal nitrate of iron, cobalt, nickel, tin and vanadium
50mL of ethanol
Dissolving the following ligands in mol number to prepare a B reaction solution:
1, 2-bis (4-pyridyl) ethylene 10mmol
50mL of ethanol
2. The preparation method is the same as that of the embodiment 1;
3. the high-entropy coordination polymer powder synthesized in example 2 is prepared into catalyst slurry, uniformly dripped on a foam nickel substrate, dried at low temperature, and directly used as a working electrode without other treatment.
Example 3
1. Uniformly mixing the following raw materials in an equimolar ratio to prepare a reaction solution A:
iron-cobalt-nickel-copper-zinc metal nitrate 5mmol
50mL of ethanol
Dissolving the following ligands in mol number to prepare a B reaction solution:
1, 2-bis (4-pyridyl) ethylene 10mmol
50mL of ethanol
2. The preparation method is the same as that of the embodiment 1;
3. the high-entropy coordination polymer powder synthesized in example 3 is prepared into catalyst slurry, uniformly dripped on a foam nickel substrate, dried at low temperature, and directly used as a working electrode without other treatment.
As can be seen from FIGS. 1 to 3, the synthesis method can effectively synthesize the coordination polymer with crystal form through X-ray diffraction pattern. Scanning electron micrographs and transmission electron micrographs show that a particular high-entropy coordination polymer is composed mainly of a nanofilm.
In order to prove that the high-entropy coordination polymer has a high-efficiency electrocatalytic oxygen generation effect, foamed nickel coated with the catalysts of examples 1-3 is used as a working electrode, a carbon rod is used as a counter electrode, and an Hg/HgO electrode (1mol/L KOH) is used as a reference electrode, and after electrochemical activation, cyclic voltammetry is adopted to obtain 5mV s-1The scanning speed of (1) is in 1mol/L KOH aqueous solution to detect the oxygen evolution catalytic performance of the electrolyzed water, all detection experiments are carried out at room temperature, and the measured potential is according to ERHE＝EHg/HgOAnd the final measurement results are relative to the standard hydrogen electrode potential, wherein the over-potentials under different current densities are mainly determined by selecting the negative scanning potential in the cyclic voltammetry, and the influence of oxidation current factors in the positive scanning potential is eliminated. While the current density in a 1mol/L KOH electrolyte for the catalyst of example 1 was 100mA cm-2The stability test is carried out under the condition, resistance compensation is not carried out in the test process, the real voltage of the test is-1.57V, the catalyst can stably catalyze and separate oxygen and keep the voltage increase for more than 70h, and the catalyst is seen to have good stability.
The electrochemical performance test results are shown in fig. 4-7 and table 1:
TABLE 1 results of testing catalytic Properties of catalysts prepared in examples 1 to 3
As can be seen from FIGS. 5 to 7 and Table 1, the entropy-coordinated polymer catalyst prepared by the method of the present invention has a small catalytic overpotential, a large current density and a good stability when used as a water-splitting oxygen evolution catalyst. And the synthesis process is simple, the cost is low, and the method has a large-scale application prospect.
From the above examples, the present invention provides a high entropy coordination polymer catalyst for oxygen production by water electrolysis, which is prepared by the reaction of reaction solution A and reaction solution B: the A reaction solution comprises a plurality of transition metal salt solutions; the transition metal salts are selected from transition metal chlorides and/or transition metal nitrates; the reaction solution B comprises a heteroatom-containing organic ligand solution; the volume ratio of the substances of the transition metal salts in the transition metal salt solution to the solvent is (0.1-100) mmol (50-1000) ml; the volume ratio of the substance containing the heteroatom organic ligand in the solution containing the heteroatom organic ligand to the solvent is (0.1-100) mmol (50-1000) ml. In the high-entropy coordination polymer catalyst provided by the invention, an organic ligand and various transition metal salts are directly synthesized into a coordination polymer which is used as a catalyst for decomposing water and separating oxygen, so that the high-entropy coordination polymer catalyst has the advantages of small catalytic overpotential, large current density and good stability. The catalyst can bear the stable catalysis for a long time under the condition of high current density in electrolyte with higher concentration. The experimental results show that: when oxygen evolution reaction is carried out, the current density is 10mA cm-2The corresponding overpotential is 193-207 mV; the current density is 100mA cm-2The corresponding overpotential is 230-247 mV; the current density is 500mA cm-2The corresponding overpotential is 259-283 mV.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A high-entropy coordination polymer catalyst for preparing oxygen by electrolyzing water is prepared by the reaction of reaction liquid A and reaction liquid B:
the A reaction solution comprises a plurality of transition metal salt solutions; the transition metal salts are selected from transition metal chlorides and/or transition metal nitrates;
the reaction solution B comprises a heteroatom-containing organic ligand solution;
the volume ratio of the substances of the transition metal salts in the transition metal salt solution to the solvent is (0.1-100) mmol (50-1000) ml;
the volume ratio of the substance containing the heteroatom organic ligand in the solution containing the heteroatom organic ligand to the solvent is (0.1-100) mmol (50-1000) ml.
2. A high entropy coordination polymer catalyst according to claim 1, wherein said heteroatom containing organic ligand is selected from one or more of pyrazine, pyrimidine, 4' -bipyridine, 1, 2-bis (4-pyridyl) ethylene, 3, 6-bis-4-pyridyl-1, 2,4, 5-tetrazine, 1, 2-bis (4-pyridyl) ethane, 1- (4-pyridylmethyl) piperazine.
3. A high entropy coordination polymer catalyst according to claim 1, wherein the metal of said plurality of transition metal salts is selected from at least five of iron, cobalt, nickel, copper, zinc, tin, chromium, manganese, zirconium and vanadium.
4. A high entropy coordination polymer catalyst according to claim 1, wherein the solvent in reaction liquid a and reaction liquid B is independently selected from methanol and/or ethanol.
5. A high entropy coordination polymer catalyst according to claim 1, wherein the ratio of the amount of said plurality of transition metal salt species to the volume of solvent is (5-10) mmol:50 ml;
the volume ratio of the substance containing the heteroatom organic ligand in the heteroatom organic ligand solution to the solvent is (10-14) mmol:50 ml.
6. A preparation method of the high-entropy coordination polymer catalyst for oxygen production by electrolyzing water as claimed in any one of claims 1 to 4, comprising the following steps:
and adding the reaction solution A into the reaction solution B at a dropping rate of 0.01-10 mL/min for reaction, washing, and freeze-drying to obtain the high-entropy coordination polymer catalyst for oxygen production by water electrolysis.
7. The preparation method according to claim 6, wherein the reaction temperature is-5 to 5 ℃ and the reaction time is 0.5 to 5 hours.
8. An electrode containing a high-entropy coordination polymer comprises a conductive carrier and a thin film loaded on the conductive carrier;
the film is prepared by coating slurry of the high-entropy coordination polymer catalyst prepared by any one of claims 1 to 5 or the high-entropy coordination polymer catalyst prepared by the preparation method of any one of claims 6 to 7;
the conductive carrier is selected from one or more of nickel strips, cobalt strips, iron strips, copper foam, nickel foam, iron foam, gold foam, conductive carbon paper, conductive cloth, conductive felt and glassy carbon electrodes.
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