CN113862724B - Iron single-atom doped carbon material supported metal nanocluster composite catalyst and preparation method and application thereof - Google Patents
Iron single-atom doped carbon material supported metal nanocluster composite catalyst and preparation method and application thereof Download PDFInfo
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- CN113862724B CN113862724B CN202111149218.XA CN202111149218A CN113862724B CN 113862724 B CN113862724 B CN 113862724B CN 202111149218 A CN202111149218 A CN 202111149218A CN 113862724 B CN113862724 B CN 113862724B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 105
- 239000002184 metal Substances 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 53
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000007833 carbon precursor Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 13
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 108010024636 Glutathione Proteins 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 101150003085 Pdcl gene Proteins 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 229960003180 glutathione Drugs 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229940098773 bovine serum albumin Drugs 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 239000006260 foam Substances 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000010931 gold Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229920000128 polypyrrole Polymers 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012716 precipitator Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B11/097—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 comprising two or more noble metals or noble metal alloys
-
- 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 provides an iron single-atom doped carbon material supported metal nanocluster composite catalyst and a preparation method and application thereof. The preparation method comprises the following steps: obtaining a substrate material loaded with an iron-doped carbon precursor on a porous conductive carrier; and loading the metal nanoclusters on a substrate material, and then carrying out high-temperature pyrolysis to obtain the iron single-atom doped carbon material loaded metal nanocluster composite catalyst. The catalyst is a composite material comprising a porous conductive carrier, an iron single-atom doped carbon material and metal nanoclusters. The iron single-atom doped carbon material supported metal nanocluster composite catalyst is used for catalyzing at least one of an electrolytic water cathode hydrogen evolution reaction and an anode oxygen evolution reaction. The iron single-atom doped carbon material supported metal nanocluster composite catalyst provided by the invention has the advantages of high catalytic activity, good stability and simple synthesis method.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an iron single-atom doped carbon material supported metal nanocluster composite catalyst as well as a preparation method and application thereof.
Background
Hydrogen energy is used as an efficient and clean renewable energy source, and the hydrogen production technology gradually becomes a worldwide research hotspot. The water electrolysis hydrogen production is a clean, efficient, raw material-rich and sustainable new energy technology, and is an effective way for solving the current energy and environmental problems. However, the two half reactions involved in the water splitting reaction are difficult to carry out due to slow reaction kinetics, so that the industrialization of the water splitting hydrogen production technology is greatly limited. The overpotential of Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) can be reduced by coating the catalyst on the cathode and anode of the electrolytic cell, the voltage required by the electrolytic water is reduced, the electrolytic water efficiency is effectively improved, and the electrolytic water reaction is promoted. Therefore, the development of an efficient, stable and low-cost electrolyzed water catalyst has become one of the focus of current scientific research.
The full hydropower catalysts that have been reported are classified into noble metal catalysts and non-noble metal catalysts. At present, the most excellent noble metal catalyst performance is mainly Pt-based catalyst, such as Pt/NiO@Ni/NF and Pt@DNA-GC; the non-noble metal catalyst is mainly composed of transition metal and phosphorus, sulfur, boron, carbon, nitrogen, etc., such as Fe-N-C, niFe 2 O 4 @MOF-74, etc. The catalyst can effectively reduce the overpotential of the electrolytic water reaction, but the preparation process of the catalytic material is complicated, the condition is harsh, and the stability of the catalyst self-reaction still needs to be further improved.
Therefore, developing an electrolyzed water catalyst with simple and convenient preparation process, excellent catalytic performance and stable reaction process is still a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide an electrocatalytic full water-splitting catalyst with high catalytic activity, good stability and simple synthesis method and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing an iron single-atom doped carbon material supported metal nanocluster composite catalyst, which comprises:
obtaining a substrate material loaded with an iron-doped carbon precursor on a porous conductive carrier;
and loading the metal nanoclusters on a substrate material, and then carrying out high-temperature pyrolysis to obtain the iron single-atom doped carbon material loaded metal nanocluster composite catalyst.
According to the preparation method, the metal nanoclusters are loaded on a special substrate material (the substrate material with the iron-doped carbon precursor loaded on the porous conductive carrier is a self-supporting catalyst substrate containing iron and carbon elements at the same time), and the special catalyst material with the porous conductive carrier as the substrate and the metal nanoclusters loaded by the iron single-atom-doped carbon material as the loading components is obtained through high-temperature pyrolysis. The catalyst material can be effectively used as an electrocatalytic full water-splitting catalyst.
In the preparation method, after the metal nanoclusters are loaded on a special substrate material (the substrate material with the iron-doped carbon precursor loaded on the porous conductive carrier is a self-supporting catalyst substrate containing iron and carbon elements at the same time) and subjected to high-temperature pyrolysis, the iron-doped carbon precursor with the surface of the metal nanoclusters playing a role in stabilizing is carbonized, so that the metal nanoclusters can be highly dispersed in the carbon material, and the average particle size is about 3-6nm in a preferred embodiment, so that higher utilization efficiency of the metal elements is realized.
In the above-described production method, preferably, the metal nanoclusters include one or a combination of two or more of Au nanoclusters, pt nanoclusters, pd nanoclusters, ag nanoclusters, cu nanoclusters and the like.
In the above preparation method, preferably, the metal nanoclusters are prepared by the following method:
mixing a first solvent, metal salt, a stabilizer and a reducing agent, regulating the pH value to be slightly alkaline, and carrying out reduction reaction to obtain a mixed solution; adding a precipitator into the mixed solution to obtain a precipitate, namely the metal nanocluster;
more preferably, the stabilizer comprises one or a combination of more than two of glutathione, bovine serum albumin, polymethyl acrylate, polyacrylic acid and the like; further preferably, the stabilizer is glutathione;
more preferably, the reducing agent comprises one or more of hydrazine hydrate, sodium borohydride, citric acid and the like; further preferably, the reducing agent is hydrazine hydrate;
more preferably, the metal salt comprises Au 3+ Salts, pt 4+ Salt, pd 2+ Salt, ag + Salts and Cu 2+ One or a combination of two or more of salts and the like; more preferably, the metal salt comprises HAuCl 4 、H 2 PtCl 6 、Na 2 PdCl 4 、PdCl 2 、AgNO 3 、CH 3 COOAg、AgF、Ag 2 SO 4 、AgClO 4 、CuCl 2 、CuNO 3 、CuSO 4 And CH (CH) 3 One or a combination of two or more of COOCu and the like;
more preferably, the molar ratio of stabilizer, reducing agent to metal ion in the metal salt is from 5 to 30:1 to 20:1;
more preferably, the reduction reaction is carried out at 60-90 ℃ (e.g. at 80 ℃);
more preferably, the first solvent is water;
more preferably, the precipitant is isopropanol;
more preferably, the addition volume of the precipitant is 3 times or more the volume of the mixed solution;
in a specific embodiment, a proper amount of metal ion solution is taken to be dispersed in 5-10mL of water, stabilizer glutathione and reducer hydrazine hydrate are added, the mixture is fully and uniformly mixed, the pH is regulated to be slightly alkaline, and the mixture reacts for 4 hours at 80 ℃ to obtain a reduced mixed solution; adding a precipitator into the mixed solution, and centrifuging for 15min at 6500r/min after precipitation occurs to obtain precipitation, namely the metal nanocluster;
wherein the concentration of metal ions in the metal ion solution is preferably 1mmol/L to 50mmol/L, and more preferably 10mmol/L to 30mmol/L;
wherein the metal ion solution preferably comprises HAuCl 4 、H 2 PtCl 6 、Na 2 PdCl 4 、PdCl 2 、AgNO 3 、CH 3 COOAg、AgF、Ag 2 SO 4 、AgClO 4 、CuCl 2 、CuNO 3 、CuSO 4 And/or CH 3 COOCu aqueous solution.
In the above preparation method, preferably, the porous conductive carrier has a three-dimensional network structure; more preferably, the porous conductive carrier is selected from one or a combination of more than two of foam nickel, foam copper and graphene foam materials.
In the above preparation method, preferably, the iron monoatomic doped carbon material is further doped with nitrogen element; more preferably, the substrate material of the porous conductive carrier loaded with the iron-doped carbon precursor is a self-supporting catalyst substrate containing iron, nitrogen and carbon elements at the same time; further preferably, the iron-doped carbon precursor is selected from iron-doped polypyrrole.
In the above preparation method, preferably, obtaining the substrate material having the iron-doped carbon precursor supported on the porous conductive carrier includes:
mixing a second solvent, pyrrole monomer and ferric ion salt, and polymerizing the ferric ion salt serving as an initiator in a porous conductive carrier to obtain the substrate material;
more preferably, the ferric ion salt is FeCl 3 ；
More preferably, the molar ratio of the pyrrole monomer to the ferric ion is 5:1 to 20:1;
more preferably, the ratio of the usage amount of the pyrrole monomer to the porous conductive carrier is 0.01 g/1 cm 2 -0.5g:1cm 2 ；
More preferably, the second solvent is water;
more preferably, the porous conductive support is pre-treated to remove surface oxide layers and heteroatoms prior to use; further preferably, the porous conductive carrier is pretreated with hydrochloric acid and acetone before use to remove surface oxide layers and foreign ions;
more preferably, the polymerization reaction temperature is 10-60 ℃ (e.g., 30 ℃);
in the above preferred embodiment, the second solvent, the porous conductive carrier, the pyrrole monomer and the ferric ion salt are mixed, and the ferric ion salt is used as an initiator to perform polymerization reaction to obtain the base material, and the surface of the porous conductive carrier is coated with the iron-nitrogen double doped carbon precursor (iron doped polypyrrole), that is, the surface of the porous conductive carrier is coated with the material simultaneously containing iron, nitrogen and carbon elements. In the preparation mode of the substrate material with the iron-doped carbon precursor loaded on the porous conductive carrier, ferric ions are adopted as an initiator to initiate pyrrole polymerization, iron atoms are introduced into the carbon precursor, and finally, the doping of the iron atoms in the carbon layer is completed through the subsequent steps. In the subsequent pyrolysis process, polypyrrole on the surface of the foam nickel forms a composite carrier, and nitrogen element in the polypyrrole is doped into a carbon layer in the reaction process; fe in polypyrrole carbon layer 3+ The Fe-doped carbon material can form a coordination structure with nitrogen element, and exists in a carbon layer in a single-atom form to obtain a single-atom Fe-doped carbon material; the polypyrrole and the organic ligand on the nanocluster are carbonized at high temperature, so that the nanocluster and the carrier form a whole to obtain the active component iron single-atom doped carbon material loaded metal nanocluster composite material. The polymer iron doped polypyrrole with the stabilizing effect on the surface of the metal nanocluster is carbonized in the subsequent pyrolysis process, so that the metal nanocluster can be highly dispersed in a carbon material, the average particle size is about 3-6nm, and the higher utilization efficiency of metal elements is realized.
In a specific embodiment, 1-20 pieces of foam nickel pretreated by hydrochloric acid and acetone and a certain amount of pyrrole monomer are put into 50mL of deionized water, and a small amount of FeCl is added under the constant temperature condition of 30 DEG C 3 The solution is used as an initiator to react for 6 to 12 hours to prepare the foam nickel coated by the polypyrrole doped with iron to formA layer of material with iron, nitrogen and carbon elements at the same time; wherein each piece of foam nickel has an area of 2cm 2 The addition amount of pyrrole monomer is 0.5-10mL, feCl with concentration of 0.045g/mL-0.2g/mL 3 The addition amount of the solution is 1-10mL.
In the preparation method, the loading of the metal nanoclusters to the substrate material may be achieved by dipping; preferably, the loading of the metal nanoclusters onto the base material includes:
immersing the substrate material into the dispersion liquid of the metal nanoclusters for a period of time to realize loading of the metal nanoclusters into the substrate material; wherein, in the dispersion liquid of the metal nanoclusters, the concentration of the metal nanoclusters (based on the volume of the dispersion liquid of the metal nanoclusters) is 0.75mmol/L to 15mmol/L;
more preferably, the time of the impregnation is not less than 4 hours;
more preferably, the substrate material is immersed in the dispersion liquid of the metal nanoclusters for a period of time and then dried at 60 ℃ for 3 hours to realize loading of the metal nanoclusters to the substrate material;
in the above preferred embodiment, the content of the supported metal nanoclusters may be adjusted by changing the concentration of the metal nanocluster dispersion.
In the above preparation method, preferably, the pyrolysis is performed under a protective atmosphere; for example in an inert gas atmosphere.
In the above preparation method, preferably, the high temperature pyrolysis is at 300 to 600 ℃;
in the preferred technical scheme, the number of defective sites and the resistance of the carbon material can be regulated by changing the pyrolysis temperature (300 ℃ -600 ℃).
The invention also provides a metal nanocluster composite catalyst loaded with the iron single-atom doped carbon material, which is a composite material comprising a porous conductive carrier, the iron single-atom doped carbon material and the metal nanocluster.
The invention provides an iron single-atom doped carbon material supported metal nanocluster composite catalyst, which is a self-supporting multifunctional composite electrocatalytic full-water-dissolving catalyst.
In the above composite catalyst, preferably, the metal nanoclusters include one or a combination of two or more of Au nanoclusters, pt nanoclusters, pd nanoclusters, ag nanoclusters, cu nanoclusters, and the like.
In the above composite catalyst, preferably, the porous conductive support has a three-dimensional network structure; more preferably, the porous conductive carrier is nickel foam.
In the above composite catalyst, preferably, the iron monatomic doped carbon material is further doped with nitrogen element. The nitrogen atoms in the carbon material can modulate the electronic structure of the metal element, so that the hydrogen adsorption energy of the metal material is optimized, and meanwhile, the hetero atoms in the carbon material are good water adsorption sites; the carbon material wrapping the metal nanoclusters can also effectively prevent the agglomeration and poisoning of the metal nanoclusters, and effectively improve the electrocatalytic activity and stability of the material.
In the above composite catalyst, preferably, the metal nanoclusters have an average particle size of 3 to 6nm.
In the above composite catalyst, preferably, the single-atom-doped carbon-material-supported metal nanocluster composite catalyst is prepared by the preparation method of the single-atom-doped carbon-material-supported metal nanocluster composite catalyst.
The invention also provides application of the iron single-atom doped carbon material supported metal nanocluster composite catalyst in electrolytic water reaction, and the iron single-atom doped carbon material supported metal nanocluster composite catalyst is used for catalyzing at least one of electrolytic water cathodic hydrogen evolution reaction and anodic oxygen evolution reaction.
Compared with the prior art, the invention has the following advantages:
(1) According to the technical scheme provided by the invention, the metal nanoclusters are loaded on a special substrate material (the substrate material with the iron-doped carbon precursor loaded on the porous conductive carrier), and after high-temperature treatment, the iron-doped carbon precursor with the stabilizing effect on the surface of the metal nanoclusters is carbonized, so that the metal nanoclusters can be highly dispersed in the carbon material, and the higher utilization efficiency of metal elements is improved. The carbon material can also effectively prevent agglomeration and poisoning of the metal nanoclusters, and effectively improve the electrocatalytic activity and stability of the material. In a preferred embodiment, fe monoatoms are introduced into the carbon material by means of a simple initiator to initiate polymerization of the monomer, forming a composite catalyst with the metal nanoclusters, which significantly improves the catalytic activity of the material by the synergistic effect created between the Fe monoatoms and the metal nanoclusters.
(2) The technical scheme provided by the invention has the advantages of small environmental pollution, high metal utilization rate, excellent catalytic activity, good catalyst stability, simple method, low cost, easy operation and good repeatability, and is suitable for mass production.
(3) The catalyst material provided by the technical scheme of the invention has excellent electrocatalytic hydrogen evolution reaction activity and oxygen evolution reaction activity, and has excellent stability, thus being an electrocatalytic full water-splitting catalyst with excellent performance.
Drawings
FIG. 1 is a scanning electron microscope image of a composite catalyst carrying copper nanoclusters according to example 1.
Fig. 2 is a copper nanocluster transmission electron microscope image and a high resolution transmission electron microscope image in example 1.
FIG. 3 is a dark field image of an iron monoatomic and gold nanocluster spherical aberration correcting transmission electron microscope in example 2.
FIG. 4 is an electrocatalytic hydrogen evolution linear sweep voltammetry graph of example 2 with a catalyst provided.
FIG. 5 is an electrocatalytic oxygen evolution linear sweep voltammetry curve for example 2 with a catalyst provided.
FIG. 6 is a graph showing the results of electrocatalytic hydrogen evolution stability test of the catalyst provided in example 3.
FIG. 7 is a graph of the results of an electrocatalytic oxygen evolution stability test for the catalyst provided in example 2.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides an iron single-atom doped carbon material supported metal nanocluster composite catalyst, which is prepared by the following steps:
0.0328g of reduced glutathione is weighed and dissolved in 5mL of water as a stabilizer, and then 250 mu L of CuNO with the concentration of 50mmol/L is sequentially added 3 Stirring the solution and 35 mu L of hydrazine hydrate for 10min, and heating at 80 ℃ for 4h to obtain a mixed solution after reaction; washing the reacted mixed solution with isopropanol as a precipitator, centrifuging for 15min at 6500r/min, and collecting precipitates, wherein the collected precipitates are copper nanoclusters; dispersing the collected precipitate in 5mL of water, wherein the obtained solution is copper nanocluster dispersion;
performing ultrasonic treatment on the cut foam nickel sheet with the shape of 1cm multiplied by 2cm in a 0.5mol/L hydrochloric acid solution under the condition of 100Hz for 10min, washing with deionized water, performing ultrasonic treatment in an acetone solution under the condition of 100Hz for 5min, and washing with deionized water to obtain pretreated foam nickel with the surface oxide layer and impurity ions removed;
adding 35mL of deionized water into a 250mL three-neck flask, and then adding pretreated foam nickel and 2.7mL of pyrrole monomer with purity of 99% to obtain a mixed solution; stirring the mixed solution at a constant temperature of 30 ℃ in a water bath at a rotating speed of 10r/s, and when the temperature of the mixed solution reaches 30 ℃, adding FeCl 3 Solution (0.135 g FeCl) 3 ·6H 2 O is obtained by dissolving 5mL of deionized water) as a polymerization initiator, and the polymerization initiator is added into the mixed solution to initiate the pyrrole monomer to perform polymerization reaction on the surface of the foam nickel, so as to prepare a substrate material;
immersing the substrate material in copper nanocluster dispersion for more than 4 hours to load the metal nanoclusters on the substrate material, and then taking out the loaded substrate material to dry; roasting the dried product at 600 ℃ in an argon atmosphere to obtain the iron single-atom doped carbon material supported metal nanocluster composite catalyst (expressed by Cu-ppyFC/NF).
FIG. 1 is a scanning electron microscope image of a composite catalyst supporting copper nanoclusters. The carrier foam nickel of the catalyst can be found to have a three-dimensional network structure by scanning electron micrographs. Surface-grown poly (nickel foam)After carbonization, pyrrole is uniformly coated on the surface of foam nickel to form a continuous carbon layer, and the microstructure of the carbon layer is shown in figure 1. FIG. 2 is a transmission electron microscope image of a composite catalyst carrying copper nanoclusters, from which it can be seen that the carried copper nanoclusters are uniformly dispersed in a carbon layer, cu nanoclusters have a size of about 5nm and a uniform particle diameter, and an illustration in FIG. 2 is a high-resolution transmission electron microscope image of Cu nanoclusters, showing that the size of Cu nanoclusters is about 5.2nm and the lattice spacing of the nanoclusters isAs can be seen from fig. 1 and 2, the copper nanoclusters are supported on the iron-nitrogen co-doped carbon material generated by the carbonization of polypyrrole, and are fixed on the surface of the foam nickel by the iron-nitrogen co-doped carbon material.
Comparative example 1
The comparative example provides a composite catalyst, wherein the catalyst is prepared by the following method:
0.0153g of reduced glutathione was weighed and dissolved in 5mL of water as a stabilizer, and then 80. Mu.L of HAuCl with a concentration of 50mmol/L was added in sequence 4 Stirring the solution and 20 mu L of hydrazine hydrate for 10min, and heating at 80 ℃ for 4h to obtain a mixed solution after reaction; washing the reacted mixed solution with isopropanol as a precipitator, centrifuging for 15min at 6500r/min, and collecting precipitates, wherein the collected precipitates are gold nanoclusters; dispersing the collected precipitate in 5mL of water, wherein the obtained solution is gold nanocluster dispersion liquid (yellow solution);
performing ultrasonic treatment on the cut foam nickel sheet with the shape of 1cm multiplied by 2cm in a 0.5mol/L hydrochloric acid solution under the condition of 100Hz for 10min, washing with deionized water, performing ultrasonic treatment in an acetone solution under the condition of 100Hz for 5min, and washing with deionized water to obtain pretreated foam nickel with the surface oxide layer and impurity ions removed;
adding 35mL of deionized water into a 250mL three-neck flask, and then adding pretreated foam nickel and 2.7mL of pyrrole monomer with purity of 99% to obtain a mixed solution; stirring the mixed solution at a constant temperature water bath condition of 30 ℃ and a rotating speed of 10r/s, and adding ammonium persulfate as a polymerization initiator into the mixed solution when the temperature of the mixed solution reaches 30 ℃ to initiate the pyrrole monomer to perform polymerization reaction on the surface of the foam nickel to prepare a substrate material;
immersing the substrate material in gold nanocluster dispersion for more than 4 hours to load the metal nanoclusters on the substrate material, and then taking out the loaded substrate material to dry; the dried product was calcined at 600 c in an argon atmosphere to give a composite catalyst (denoted as non-iron initiated catalyst).
Comparative example 2
The comparative example provides a composite catalyst, wherein the catalyst is prepared by the following method:
0.0153g of reduced glutathione was weighed and dissolved in 5mL of water as a stabilizer, and then 80. Mu.L of HAuCl with a concentration of 50mmol/L was added in sequence 4 Stirring the solution and 20 mu L of hydrazine hydrate for 10min, and heating at 80 ℃ for 4h to obtain a mixed solution after reaction; washing the reacted mixed solution with isopropanol as a precipitator, centrifuging for 15min at 6500r/min, and collecting precipitates, wherein the collected precipitates are gold nanoclusters; dispersing the collected precipitate in 5mL of water, wherein the obtained solution is gold nanocluster dispersion liquid (yellow solution);
35mL of deionized water is added into a 250mL three-neck flask, and then 2.7mL of pyrrole monomer with purity of 99% is added to obtain a mixed solution; stirring the mixed solution at a constant temperature of 30 ℃ in a water bath at a rotating speed of 10r/s, and when the temperature of the mixed solution reaches 30 ℃, adding FeCl 3 Solution (0.425 g FeCl) 3 ·6H 2 O is obtained by dissolving 5mL of deionized water) as a polymerization initiator, and the mixture is added into the mixed solution to initiate the pyrrole monomer to carry out polymerization reaction, so as to prepare a carbon precursor material;
immersing the carbon precursor material in gold nanocluster dispersion liquid for more than 4 hours to load the metal nanoclusters on the carbon precursor material, and then taking out the loaded carbon precursor material to dry; the dried product was calcined at 600 c in an argon atmosphere to give a composite catalyst (expressed as a non-foam nickel catalyst).
Example 2
The embodiment provides an iron single-atom doped carbon material supported metal nanocluster composite catalyst, which is prepared by the following steps:
0.0153g of reduced glutathione was weighed and dissolved in 5mL of water as a stabilizer, and then 80. Mu.L of HAuCl with a concentration of 50mmol/L was added in sequence 4 Stirring the solution and 20 mu L of hydrazine hydrate for 10min, and heating at 80 ℃ for 4h to obtain a mixed solution after reaction; washing the reacted mixed solution with isopropanol as a precipitator, centrifuging for 15min at 6500r/min, and collecting precipitates, wherein the collected precipitates are gold nanoclusters; dispersing the collected precipitate in 5mL of water, wherein the obtained solution is gold nanocluster dispersion liquid (yellow solution);
performing ultrasonic treatment on the cut foam nickel sheet with the shape of 1cm multiplied by 2cm in a 0.5mol/L hydrochloric acid solution under the condition of 100Hz for 10min, washing with deionized water, performing ultrasonic treatment in an acetone solution under the condition of 100Hz for 5min, and washing with deionized water to obtain pretreated foam nickel with the surface oxide layer and impurity ions removed;
adding 35mL of deionized water into a 250mL three-neck flask, and then adding pretreated foam nickel and 2.7mL of pyrrole monomer with purity of 99% to obtain a mixed solution; stirring the mixed solution at a constant temperature of 30 ℃ in a water bath at a rotating speed of 10r/s, and when the temperature of the mixed solution reaches 30 ℃, adding FeCl 3 Solution (0.425 g FeCl) 3 ·6H 2 O is obtained by dissolving 5mL of deionized water) as a polymerization initiator, and the polymerization initiator is added into the mixed solution to initiate the pyrrole monomer to perform polymerization reaction on the surface of the foam nickel, so as to prepare a substrate material;
immersing the substrate material in gold nanocluster dispersion for more than 4 hours to load the metal nanoclusters on the substrate material, and then taking out the loaded substrate material to dry; roasting the dried product at 600 ℃ in an argon atmosphere to obtain the iron single-atom doped carbon material supported metal nanocluster composite catalyst (represented by Au-ppyFC/NF).
As shown in FIG. 3, under the spherical aberration transmission electron microscope, the Au nanoclusters are 2-4nm in size and uniform in particle size, and a large number of iron monoatoms are uniformly dispersed on the surface of the carbon material.
The iron single-atom doped carbon material supported metal nanocluster composite catalyst prepared in the embodiment is used as a sample to be tested for carrying out electrolytic water hydrogen evolution performance test:
when the electrolytic water hydrogen evolution reaction test is carried out, the model of an electrochemical workstation is Shanghai Chenhua CHI760e, the electrolyte solution is 1.0mol/L potassium hydroxide solution, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a graphite electrode, and the working electrode is a sample to be tested (1 cm multiplied by 2 cm). Each electrode was connected to an electrochemical workstation and extended into the electrolyte, the working electrode extending to a depth of 0.5cm into the liquid surface. The test was performed using a linear sweep voltammetry with an instrumental auto-compensation resistor, a sweep range of-0.9V to-1.5V, and a sweep rate of 5mV/s.
As a comparison, an electrolyzed water hydrogen evolution performance test of the catalyst provided in comparative example 1, the catalyst provided in comparative example 2, and a commercial 20% platinum carbon catalyst (microphone brand CAS number: 7440-06-4) under the same conditions was performed, and the results are shown in fig. 4. As can be seen from FIG. 4, the current reaches 10mA/cm 2 When the overpotential is needed, the hydrogen evolution overpotential of the iron single-atom doped carbon material supported metal nanocluster composite catalyst provided by the embodiment is 56.9mV; under the same conditions, a commercial 20% platinum carbon catalyst (microphone brand CAS number 7440-06-4) has a hydrogen evolution overpotential of 36mV; the results of the catalysts provided in comparative examples 1 and 2 under the same conditions that the hydrogen evolution performance of electrolyzed water is far lower than that of the catalyst provided in the example show that the iron single-atom doped carbon material supported metal nanocluster composite catalyst provided in the invention has excellent hydrogen evolution activity, and meanwhile, the introduction of carrier and metal Fe single atoms is an important factor for the excellent performance of the catalyst, which is indispensable.
The iron single-atom doped carbon material supported metal nanocluster composite catalyst provided by the embodiment is used as a sample to be tested for performing an electrolytic water oxygen evolution performance test:
when the electrolytic water oxygen evolution reaction test is carried out, the model of an electrochemical workstation is Shanghai Chenhua CHI760e, the electrolyte solution is 1.0mol/L potassium hydroxide solution, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a graphite electrode, and the working electrode is a sample to be tested (1 cm multiplied by 2 cm). Each electrode was connected to an electrochemical workstation and extended into the electrolyte, the working electrode extending to a depth of 0.5cm into the liquid surface. The test was performed using a linear sweep voltammetry with an instrumental auto-compensation resistor, a sweep range of 1V to 2V and a sweep rate of 5mV/s.
As shown in FIG. 5, it is clear from FIG. 5 that the current reaches 10mA/cm 2 When the overpotential is needed, the oxygen evolution overpotential of the iron single-atom doped carbon material supported metal nanocluster composite catalyst provided by the embodiment is 290mV, which shows that the iron single-atom doped carbon material supported metal nanocluster composite catalyst provided by the invention has excellent oxygen evolution activity.
Example 3
The embodiment provides an iron single-atom doped carbon material supported metal nanocluster composite catalyst, which is prepared by the following steps:
0.0164g of reduced glutathione was weighed as a stabilizer and dissolved in 5mL of water, followed by sequential addition of 150. Mu.L of PdCl at a concentration of 50mmol/L 2 Stirring the solution and 25 mu L of hydrazine hydrate for 10min, and heating at 80 ℃ for 4h to obtain a mixed solution after reaction; washing the reacted mixed solution with isopropanol as a precipitator, centrifuging for 15min at 6500r/min, and collecting the precipitate, wherein the collected precipitate is the palladium nanocluster; dispersing the collected precipitate in 5mL of water, wherein the obtained solution is palladium nanocluster dispersion;
performing ultrasonic treatment on the cut foam nickel sheet with the shape of 1cm multiplied by 2cm in a 0.5mol/L hydrochloric acid solution under the condition of 100Hz for 10min, washing with deionized water, performing ultrasonic treatment in an acetone solution under the condition of 100Hz for 5min, and washing with deionized water to obtain pretreated foam nickel with the surface oxide layer and impurity ions removed;
adding 35mL of deionized water into a 250mL three-neck flask, and then adding pretreated foam nickel and 2.7mL of pyrrole monomer with purity of 99% to obtain a mixed solution; stirring the mixed solution at a constant temperature of 30 ℃ in a water bath at a rotating speed of 10r/s, and when the temperature of the mixed solution reaches 30 ℃, adding FeCl 3 Solution (0.685 g FeCl) 3 ·6H 2 O is obtained by dissolving 5mL of deionized water) as a polymerization initiator, and the polymerization initiator is added into the mixed solution to initiate the pyrrole monomer to perform polymerization reaction on the surface of the foam nickel, so as to prepare a substrate material;
immersing the substrate material in palladium nanocluster dispersion for more than 4 hours to load metal nanoclusters on the substrate material, and then taking out the loaded substrate material to dry; roasting the dried product at 600 ℃ in an argon atmosphere to obtain the iron single-atom doped carbon material supported metal nanocluster composite catalyst (expressed by Pd-ppyFC/NF).
The iron single-atom doped carbon material supported metal nanocluster composite catalyst prepared in the embodiment is used as a sample to be tested for testing the hydrogen evolution stability of electrolyzed water:
when the electrolytic water hydrogen evolution reaction test is carried out, the model of an electrochemical workstation is Shanghai Chenhua CHI760e, the electrolyte solution is 1.0mol/L potassium hydroxide solution, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a graphite electrode, and the working electrode is a sample to be tested (1 cm multiplied by 2 cm). Each electrode was connected to an electrochemical workstation and extended into the electrolyte, the working electrode extending to a depth of 0.5cm into the liquid surface. The test was performed using a linear sweep voltammetry with an instrumental auto-compensation resistor, a sweep range of-0.9V to-1.5V, and a sweep rate of 5mV/s. The cyclic voltammetry carries out stability cycle, the scanning range is-0.9V to-1.0V, and the scanning rate is 50mV/s.
As shown in fig. 6, the activity was slightly attenuated after 5000 cycles of CV scan, indicating that the reaction stability was good.
The iron single-atom doped carbon material supported metal nanocluster composite catalyst provided by the embodiment is used as a sample to be tested for testing the oxygen evolution stability of electrolytic water:
when the electrolytic water oxygen evolution reaction test is carried out, the model of an electrochemical workstation is Shanghai Chenhua CHI760e, the electrolyte solution is 1.0mol/L potassium hydroxide solution, the reference electrode is a mercury/mercury oxide electrode, the counter electrode is a graphite electrode, and the working electrode is a sample to be tested (1 cm multiplied by 2 cm). Each electrode was connected to an electrochemical workstation and extended into the electrolyte, the working electrode extending to a depth of 0.5cm into the liquid surface. The test was performed using a linear sweep voltammetry with an instrumental auto-compensation resistor, a sweep range of 1V to 2V and a sweep rate of 5mV/s. The cyclic voltammetry was used for stability cycling, with a scan rate of 50mV/s, ranging from 1.45V to 1.55V.
As shown in fig. 7, it is clear from fig. 7 that the activity was less attenuated after 5000 cycles of CV scan, indicating that the reaction stability was good.
Claims (14)
1. A preparation method of an iron single-atom doped carbon material supported metal nanocluster composite catalyst comprises the following steps:
obtaining a substrate material loaded with an iron-doped carbon precursor on a porous conductive carrier;
loading the metal nanoclusters on a substrate material, and then carrying out high-temperature pyrolysis to obtain the iron single-atom doped carbon material loaded metal nanocluster composite catalyst;
wherein, the metal nanocluster comprises one or more than two of Au nanoclusters, pt nanoclusters, pd nanoclusters, ag nanoclusters and Cu nanoclusters;
wherein the pyrolysis is performed under a protective atmosphere;
wherein the temperature of the high-temperature pyrolysis is 300-600 ℃;
wherein, the obtaining the substrate material with the iron doped carbon precursor loaded on the porous conductive carrier comprises the following steps:
mixing a second solvent, pyrrole monomer and ferric ion salt, and polymerizing the ferric ion salt serving as an initiator on a porous conductive carrier to obtain the substrate material through reaction;
the ferric ion salt is FeCl 3 ；
The porous conductive carrier is foamed nickel;
the molar ratio of the pyrrole monomer to the ferric ion is 5:1-20:1;
the usage amount ratio of the pyrrole monomer to the porous conductive carrier is 0.01g:1cm 2 -0.5 g : 1cm 2 ；
The porous conductive carrier is pretreated before use to remove a surface oxide layer and foreign ions;
the reaction temperature of the polymerization is 10-60 ℃.
2. The preparation method of claim 1, wherein the metal nanoclusters are prepared by the following method:
mixing a first solvent, metal salt, a stabilizer and a reducing agent, regulating the pH value to be slightly alkaline, and carrying out reduction reaction to obtain a mixed solution; and adding a precipitant into the mixed solution to obtain a precipitate, namely the metal nanocluster.
3. The production method according to claim 2, wherein the stabilizer comprises one or a combination of two or more of glutathione, bovine serum albumin, polymethyl acrylate and polyacrylic acid.
4. The preparation method according to claim 2, wherein the reducing agent comprises one or a combination of two or more of hydrazine hydrate, sodium borohydride and citric acid.
5. The preparation method according to claim 2, wherein the metal salt comprises Au 3+ Salts, pt 4+ Salt, pd 2+ Salt, ag + Salts and Cu 2+ One or a combination of two or more salts.
6. The process according to claim 5, wherein the metal salt comprises HAuCl 4 、H 2 PtCl 6 、Na 2 PdCl 4 、PdCl 2 、AgNO 3 、CH 3 COOAg、AgF、Ag 2 SO 4 、AgClO 4 、CuCl 2 、CuNO 3 、CuSO 4 And CH (CH) 3 One or a combination of two or more of COOCu.
7. The process according to claim 5, wherein the molar ratio of the stabilizer, the reducing agent to the metal ions in the metal salt is 5-30:1-20:1.
8. The production method according to claim 2, wherein the reduction reaction is carried out at 60 to 90 ℃.
9. The preparation method according to claim 2, wherein the precipitant is isopropanol.
10. The method of any one of claims 1, 2-9, wherein the loading of the metal nanoclusters to the substrate material is accomplished by dipping.
11. The method of preparing of claim 10, wherein the loading the metal nanoclusters onto a base material includes:
immersing the substrate material into the dispersion liquid of the metal nanoclusters for a period of time to realize loading of the metal nanoclusters into the substrate material; wherein, in the dispersion liquid of the metal nanoclusters, the concentration of the metal nanoclusters is 0.75mmol/L to 15mmol/L based on the volume of the dispersion liquid of the metal nanoclusters.
12. The composite catalyst comprises a porous conductive carrier, an iron single-atom doped carbon material and a metal nano-cluster composite material;
wherein the metal nanoclusters comprise one or a combination of more than two of Au nanoclusters, pt nanoclusters, pd nanoclusters, ag nanoclusters and Cu nanoclusters;
wherein, the porous conductive carrier is foamed nickel;
wherein the iron monatomic doped carbon material is doped with nitrogen;
wherein the iron single-atom-doped carbon material supported metal nanocluster composite catalyst is prepared by the preparation method of the iron single-atom-doped carbon material supported metal nanocluster composite catalyst as claimed in any one of claims 1 to 11.
13. The catalyst of claim 12, wherein the metal nanoclusters have an average particle size of 3-6nm.
14. Use of the iron single-atom-doped carbon-material-supported metal nanocluster composite catalyst as claimed in claim 12 or 13 in an electrolytic water reaction, wherein the iron single-atom-doped carbon-material-supported metal nanocluster composite catalyst is used for catalyzing at least one of an electrolytic water cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction.
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