CN117737771A - Integral non-noble metal electrocatalyst and preparation method thereof - Google Patents
Integral non-noble metal electrocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN117737771A CN117737771A CN202311717570.8A CN202311717570A CN117737771A CN 117737771 A CN117737771 A CN 117737771A CN 202311717570 A CN202311717570 A CN 202311717570A CN 117737771 A CN117737771 A CN 117737771A
- Authority
- CN
- China
- Prior art keywords
- noble metal
- conductive substrate
- sodium
- complexing agent
- organic amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 45
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 10
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 10
- 229940038773 trisodium citrate Drugs 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 8
- 239000001433 sodium tartrate Substances 0.000 claims description 8
- 229960002167 sodium tartrate Drugs 0.000 claims description 8
- 235000011004 sodium tartrates Nutrition 0.000 claims description 8
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 6
- 229940102253 isopropanolamine Drugs 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019263 trisodium citrate Nutrition 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000176 sodium gluconate Substances 0.000 claims description 3
- 235000012207 sodium gluconate Nutrition 0.000 claims description 3
- 229940005574 sodium gluconate Drugs 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 claims description 3
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 36
- 230000000694 effects Effects 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract 2
- 238000004070 electrodeposition Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 101
- 239000006260 foam Substances 0.000 description 22
- 238000011010 flushing procedure Methods 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910002520 CoCu Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 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 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses an integral non-noble metal electrocatalyst and a preparation method thereof, and relates to the technical field of catalysts. Firstly, placing a pretreated conductive substrate in a reducing solution prepared from non-noble metal salt, sodium hypophosphite, organic amine and complexing agent for electrodeposition, and pre-depositing a layer of metal particles on the conductive substrate; and then carrying out constant temperature reaction in a reducing solution, and growing a compact film assembled by metal nano particles on a conductive substrate in situ by means of the self-catalysis of the metal particles, and forming a rough surface by means of the small-size effect of the nano particles, so that a large number of high-activity sites are fully exposed, and the activity and stability of the catalyst are improved. The method provided by the invention has the advantages of mild reaction conditions, low energy consumption and easiness in industrialization, and the obtained electrocatalyst has high activity and stability.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an integral non-noble metal electrocatalyst and a preparation method thereof.
Background
Noble metal catalysts (Pd, pt, au, ir, rh and Ru, etc.) are currently still the most advanced electrolytic water Hydrogen Evolution (HER) electrocatalysts, however, the high cost and scarcity of noble metal-based materials have limited their widespread use. Therefore, there is a need to develop low cost, high reserves of non-noble metal-based electrocatalysts. Transition metal (such as iron, cobalt, manganese, nickel, copper, molybdenum and the like) based electrocatalysts have the advantages of large reserves, low cost and the like, are widely paid attention to, and prepare series of transition metal oxides, nitrides, carbides, sulfides, phosphides and the like, but the preparation process of the transition metal compound electrocatalysts is loaded, and still can not meet the industrial requirements in the aspects of catalytic activity and stability.
The metal catalyst has excellent conductivity, is favorable for electron transfer, but has poor activity. Common HER metallic electrocatalysts can be classified as elemental metals, monoatoms of metals, alloys, complex catalysts, and the like. Literature Carbon,2020,163:178-185 uses nickel-based MOF as precursor to prepare Ni-based catalyst Ni@NC6-600 encapsulated by nitrogen doped multi-layer Carbon nanotubes, which requires 181mV overpotential in 1.0M KOH solution to drive 10mA cm -2 The catalyst has low hydrogen evolution activity of electrolyzed water and complex preparation process. Document Carbon,2021,185:96-104 prepares an electrocatalyst hybridized by Ni monoatoms and Ni nano particles on nitrogen-doped Carbon fibers by electrostatic spinning, pyrolysis and etching, and the Ni SA/NP-NCF-800 electrocatalyst is 10 mA.cm -2 The overpotential under the current density is 137.3mV (1 MKOH), and the defects of complex preparation method, poor catalyst activity and the like exist. Chinese patent CN202110959098.3 discloses a preparation method of an integral type NiCoP electrocatalyst, which takes metal salt, a reducing agent, a complexing agent, a buffering agent and deionized water as raw materials, and adopts chemical plating to prepare the integral type NiCoP electrocatalyst, but the activity is worse at 150 mA.cm due to larger particle size -2 The overpotential at current density is 420-460mV (1M KOH), and the stability is unknown. In summary, the catalytic performance of the metallic catalyst still needs to be further improved, but the preparation of the high-performance metallic catalyst still faces a great challenge. Therefore, there is a need to develop a novel transition metal-based electrocatalyst with high catalytic activity and catalytic stability and its preparationThe preparation method is novel.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an integral non-noble metal electrocatalyst and a preparation method thereof.
The invention is realized by adopting the following technical scheme:
the preparation method of the monolithic non-noble metal electrocatalyst comprises the following steps:
s1, preparing a reduction solution:
weighing non-noble metal salt and sodium hypophosphite with a molar ratio of 1:1-10, mixing and dissolving in water to obtain a mixed solution; then adding organic amine and complexing agent into the mixed solution, and uniformly mixing to obtain a reducing solution;
s2, pretreatment of conductive substrate
Soaking the conductive substrate in 1-3M hydrochloric acid solution for 5-15 minutes, then performing ultrasonic treatment in ethanol and/or deionized water for 5-10 minutes, and finally flushing with deionized water to neutrality; the cleaned conductive substrate is used as a working electrode, a graphite plate is used as a counter electrode, and the graphite plate is used as a counter electrode in a reducing solution with the concentration of 5-20mA.cm -2 And (3) depositing the self-catalytic metal nano-particle layer on the conductive substrate for 4-10 minutes to obtain the pretreated conductive substrate.
S3, soaking the pretreated conductive substrate in the reduction solution, reacting for 1-3 hours at 60-150 ℃, and reducing metal ions in the reduction solution into metal nano-particles by means of metal nano-particle self-catalysis; and after the reaction is finished, taking out the conductive substrate, washing the conductive substrate with deionized water and ethanol, and drying the conductive substrate to obtain the integral non-noble metal nanoparticle film electrocatalyst.
The non-noble metal salt is M 1 And M 2 Is a mixture of M 1 Is any one or two of Co and Ni chloride, sulfate and sulfamate, M 2 Is any one of Fe, cr, cu, la chloride, sulfate and sulfamate or sodium molybdate, sodium tungstate, sodium tantalate and sodium niobate; wherein M is 2 And M is as follows 1 Molar ratio of 0 to 0.5:1, preferably 0.05 to 0.3:1, more preferablyThe selection is 0.1 to 0.2:1.
the molar concentration of the organic amine in the reducing solution is 0.5 to 5mol/L, preferably 1 to 2mol/L.
The molar concentration of the complexing agent in the reducing solution is 0.01 to 0.5mol/L, preferably 0.05 to 0.2mol/L.
Preferably, the organic amine is one of n-butylamine, ethanolamine, isopropanolamine, diethylenetriamine and triethylenetetramine. More preferably, the organic amine is one of n-butylamine, ethanolamine and isopropanolamine. Still more preferably, the organic amine is n-butylamine or ethanolamine.
Preferably, the complexing agent is one of ammonia water, trisodium citrate, sodium tartrate, sodium gluconate and sodium aminotriacetate. More preferably, the complexing agent is one of ammonia water, trisodium citrate and sodium tartrate. Still preferably, the complexing agent is ammonia or trisodium citrate.
Preferably, the combination effect of n-butylamine and ammonia water, ethanolamine and trisodium citrate, isopropanolamine and sodium tartrate is better.
The conductive substrate nickel, nickel-based alloy and stainless steel foam, metal sheet or wire mesh are preferably nickel foam, nickel mesh and stainless steel mesh.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a dense and rough film electrocatalyst assembled by non-noble metal nano particles and in-situ grown on a conductive substrate and a preparation method thereof. The invention is to soak the pretreated conductive substrate in the reducing solution prepared by non-noble metal salt, sodium hypophosphite, organic amine and complexing agent, deposit a layer of self-catalyzed nano particles on the conductive substrate through electric reduction, then grow the compact film assembled by metal nano particles on the conductive substrate through constant temperature reduction in situ, and meanwhile, form a rough surface by virtue of the small-size effect of nano particles, so that a large number of high active sites are fully exposed, thereby improving the activity and stability of the catalyst. The method provided by the invention has the advantages of simple operation process, mild reaction conditions, short reaction time and low energy consumption, and solves the problems of complex preparation process, high cost and poor activity and stability of the existing electrolyzed water hydrogen evolution electrocatalyst.
Drawings
FIG. 1 is an XRD spectrum of the catalyst obtained in example 1;
FIG. 2 is an SEM photograph of the catalyst obtained in example 1;
FIG. 3 is an EDS-mapping photograph of the catalyst obtained in example 1;
FIG. 4 is a HRTEM photograph of the catalyst obtained in example 1;
FIG. 5 shows the polarization curve (a), tafel slope (b), electrochemical impedance (c) and capacitance (d) of the catalyst obtained in example 1 in 1M KOH solution;
FIG. 6 shows the results of a stability test of the catalyst obtained in example 1 in 1M KOH solution.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
A. 4.00g of nickel chloride hexahydrate, 0.30g of ferrous chloride tetrahydrate and 7.00g of sodium hypophosphite are weighed and mixed, 80mL of deionized water is added for dissolution, then 10.00mL of n-butylamine and 15.00mL of ammonia water (the mass concentration is 25%) are added, and the mixture is uniformly mixed to obtain a reducing solution.
B. 1 piece was 4X 5cm in size 2 Soaking the foam nickel in 3M hydrochloric acid solution for 10 minutes, taking out, performing ultrasonic treatment with deionized water for 5 minutes, and flushing with deionized water to neutrality; the treated foam nickel is used as a working electrode, a graphite plate is used as a counter electrode, and 10mA cm is used in a reducing solution -2 Current density deposition for 5 minutes.
C. And immersing electrodeposited foam nickel in the reduction solution, sealing completely, then placing into a constant-temperature water bath at 65 ℃ for reduction for 1h, and flushing 6 with deionized water and ethanol after the reaction is finished to obtain the integral NiFe metal nano particle film electrocatalyst.
The resulting catalyst was characterized and the results are shown in FIGS. 1-4.
Fig. 1 is an XRD spectrum of the catalyst, in which characteristic diffraction peaks belonging to metallic Ni appear, indicating successful reduction of metallic Ni nanoparticles, and Fe element doped in metallic Ni lattice.
Fig. 2 is an SEM photograph of the catalyst, and it can be seen that the nickel foam framework is completely covered by the film assembled from NiFe metal nanoparticles, with a rough and dense surface.
FIG. 3 is an EDS-mapping photograph of a catalyst, in which Ni, fe, P, O elements are uniformly distributed on a foam nickel substrate, showing that NiFe metal nanoparticles are uniformly distributed.
Fig. 4 is a HRTEM photograph of the catalyst, and a high resolution photograph shows that there are a large number of lattice fringes belonging to metallic Ni, indicating that metallic Ni nanoparticles were successfully reduced, and Fe was doped in the Ni lattice.
The prepared catalyst was subjected to electrochemical performance testing on a CHI660E electrochemical workstation, and to eliminate the influence of temperature on electrochemical performance, the testing was completed in a 25 ℃ constant temperature water bath with a standard three-electrode system, i.e., graphite rod and Hg/HgO electrode were counter electrode and reference electrode, respectively. The potential calibration was corrected by 90% IR, and the electrocatalytic activity was measured at 5 mV.s -1 A Linear Sweep Voltammogram (LSV) test was performed and the impedance and capacitance were tested, as shown in fig. 5.
As can be seen from the LSV curve of FIG. 5a, the catalyst has excellent HER activity, and only 100mV overpotential is needed to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts; it can be seen from FIG. 5b that the catalyst has a low Tafel slope (29.35 mV.dec -1 ) The method comprises the steps of carrying out a first treatment on the surface of the It can be seen from fig. 5c that the catalyst has a small electrochemical resistance (0.9Ω); as can be seen from FIG. 5d, the catalyst has a large electrochemically active area (28.33 mF.cm -2 )。
The stability of the catalytic material was evaluated by using a DC power supply, and the result is shown in FIG. 6, which shows that the current density remains at 300mA cm after 200 hours of operation at constant voltage -2 The catalyst is proved to have good alkaline HER stability.
Example 2
A. Weighing 2.00g of nickel sulfate, 0.20g of chromium sulfate and 3.50g of sodium hypophosphite, mixing, adding 90mL of deionized water, and carrying out ultrasonic dissolution to obtain a mixed solution; then 10.00mL of n-butylamine and 20.00mL of ammonia water (the mass concentration is 25%) are added, and the mixture is uniformly mixed to obtain a reducing solution.
B. 1 piece of the size was about 4X 5cm 2 Soaking nickel screen in 4M sulfuric acid solution for 15 min, respectively carrying out ultrasonic treatment with ethanol and deionized water for 10 min, and washing with deionized water to neutrality; the treated foam nickel is used as a working electrode, a graphite plate is used as a counter electrode, and 6mA cm is used in a reducing solution -2 Current density deposition for 5 minutes.
C. Immersing the electrodeposited nickel screen in a reducing solution, sealing completely, then placing the electrodeposited nickel screen in a constant-temperature water bath at 80 ℃ for reduction for 1h, and washing the electrodeposited nickel screen with deionized water and ethanol for 5 times after the reaction is finished to obtain the integral NiCr metal nanoparticle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 105mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
Example 3
A. Weighing 3.00g of nickel sulfamate and 4.50g of sodium hypophosphite, mixing, adding 80mL of deionized water, and carrying out ultrasonic mixing to obtain a mixed solution; then, 4.00g of trisodium citrate and 10.00mL of diethylenetriamine were added and mixed uniformly to obtain a reducing solution.
B. 1 piece of the size was about 4X 6cm 2 Soaking the nickel sheet in 1M hydrochloric acid solution for 10 minutes, respectively carrying out ultrasonic treatment on the nickel sheet by using ethanol and deionized water for 10 minutes, and flushing the nickel sheet to be neutral by using deionized water; the treated nickel sheet is used as a working electrode, a graphite plate is used as a counter electrode, and 15mA cm is used in a reducing solution -2 Current density deposition was carried out for 6 minutes.
C. And immersing the electrodeposited nickel sheet in a reducing solution, sealing completely, and then placing the electrodeposited nickel sheet in a constant-temperature water bath at 80 ℃ for reducing for 3 hours. And after the reaction is finished, washing the catalyst with deionized water and ethanol for 7 times to obtain the monolithic Ni metal nano particle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 119mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
Example 4
A. Weighing 2.80g of cobalt chloride, 0.24g of copper chloride and 4.90g of sodium hypophosphite, mixing, adding 80mL of deionized water, and carrying out ultrasonic mixing to obtain a mixed solution; then, 2.10g of sodium tartrate and 8.00mL of ethanolamine were added and mixed uniformly to obtain a reducing solution.
B. 1 piece of the size was about 4X 5cm 2 Soaking the stainless steel mesh in 4M sulfuric acid solution for 15 minutes, respectively carrying out ultrasonic treatment on the stainless steel mesh by using ethanol and deionized water for 10 minutes, and flushing the stainless steel mesh to be neutral by using deionized water; the treated stainless steel net is used as a working electrode, a graphite plate is used as a counter electrode, and the graphite plate is used as a counter electrode in a reducing solution of 20mA cm -2 Current density deposition was carried out for 6 minutes.
C. And immersing the electrodeposited stainless steel mesh in a reducing solution, sealing completely, then placing the solution in a constant-temperature water bath at 70 ℃ for reduction for 1.5 hours, and respectively flushing the solution with deionized water and ethanol for 4 times after the reaction is finished to obtain the integral CoCu metal nanoparticle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 112mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
Example 5
A. Weighing and mixing 4.50g of cobalt sulfamate, 0.20g of sodium tungstate and 2.65g of sodium hypophosphite, adding 100mL of deionized water, and carrying out ultrasonic mixing to obtain a mixed solution; then, 4.80g of sodium aminotriacetate and 10.00mL of triethylene tetramine are added and mixed uniformly to obtain a reducing solution.
B. 1 piece of the size was about 4X 4cm 2 Soaking the foam nickel in 5M hydrochloric acid solution for 15 minutes, respectively carrying out ultrasonic treatment on the foam nickel by using ethanol and deionized water for 10 minutes, and flushing the foam nickel to be neutral by using deionized water; the treated foam nickel is used as a working electrode, a graphite plate is used as a counter electrode, and 9mA cm is used in a reducing solution -2 Current density deposition was carried out for 10 minutes.
C. And immersing the electrodeposited foam nickel in a reducing solution, putting the electrodeposited foam nickel in a baking oven at 130 ℃ for reduction for 1h after sealing, and flushing the electrodeposited foam nickel with deionized water and ethanol for 5 times after the reaction is finished to obtain the integral CoW metal nanoparticle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 124mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
Example 6
A. Weighing 5.00g of cobalt sulfate, 0.80g of sodium molybdate and 4.50g of sodium hypophosphite, mixing, adding 80mL of deionized water, and carrying out ultrasonic mixing to obtain a mixed solution; then, 3.20g of sodium gluconate and 10.00mL of ethanolamine were added and mixed uniformly to obtain a reducing solution.
B. 1 piece of the size was about 4X 6cm 2 Soaking nickel screen in 4.5M sulfuric acid solution for 15 min, respectively carrying out ultrasonic treatment with ethanol and deionized water for 10 min, and washing with deionized water to neutrality; the treated nickel screen is used as a working electrode, a graphite plate is used as a counter electrode, and 8mA cm is used in a reducing solution -2 Current density deposition was carried out for 6 minutes.
C. And (3) putting the electrodeposited nickel screen into a reducing solution, sealing completely, putting into a constant-temperature water bath at 90 ℃ for reduction for 1h, and flushing with deionized water and ethanol for 6 times after the reaction is finished to obtain the integral CoMo metal nanoparticle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 118mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
Example 7
A. Weighing 6.00g of nickel chloride, 0.90g of lanthanum sulfate and 6.00g of sodium hypophosphite, mixing, adding 90mL of deionized water, and carrying out ultrasonic mixing to obtain a mixed solution; then, 4.00g of trisodium citrate and 10.00mL of n-butylamine were added and mixed uniformly to obtain a reducing solution.
B. 1 piece of the size was about 4X 6cm 2 Soaking the nickel sheet in 2M hydrochloric acid solution for 5 minutes, respectively carrying out ultrasonic treatment on the nickel sheet by ethanol and deionized water for 8 minutes, and flushing the nickel sheet to be neutral by deionized water; the treated nickel sheet is used as a working electrode, a graphite plate is used as a counter electrode, and the nickel sheet is used as a counter electrodeThe raw solution is 10 mA.cm -2 Current density deposition was carried out for 8 minutes.
C. And (3) placing the electrodeposited nickel sheet into a reducing solution, sealing completely, placing into a 140 ℃ oven for reduction for 1.5 hours, and flushing with deionized water and ethanol for 6 times after the reaction is finished to obtain the integral NiLa metal nano particle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 126mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
Example 8
A. Weighing 5.00g of cobalt chloride, 0.90g of sodium niobate and 2.00g of sodium hypophosphite, mixing, adding 100mL of deionized water, and carrying out ultrasonic mixing to obtain a mixed solution; then, 1.00g of sodium tartrate and 10.00mL of ethanolamine were added and mixed uniformly to obtain a reducing solution.
B. 1 piece of the size was about 4X 4cm 2 Soaking the foam nickel in 4M sulfuric acid solution for 10 minutes, respectively carrying out ultrasonic treatment on the foam nickel by using ethanol and deionized water for 10 minutes, and flushing the foam nickel to be neutral by using deionized water; the treated foam nickel is used as a working electrode, a graphite plate is used as a counter electrode, and 10mA cm is used in a reducing solution -2 Current density deposition for 5 minutes.
C. And (3) placing the electrodeposited foam nickel into a reducing solution, sealing the foam nickel completely, and placing the foam nickel into a 120 ℃ oven for reduction for 1h. And after the reaction is finished, washing the catalyst with deionized water and ethanol for 6 times to obtain the integral CoNb metal nanoparticle film electrocatalyst.
The prepared catalyst was tested for electrochemical performance on a CHI660E electrochemical workstation, which required only 112mV overpotential to drive 600mA cm -2 Is significantly better than commercial Pt/C electrocatalysts.
It should be noted that the above-mentioned embodiments are only a few specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, but other modifications are possible. All modifications directly or indirectly derived from the disclosure of the present invention will be considered to be within the scope of the present invention.
Claims (8)
1. The preparation method of the monolithic non-noble metal electrocatalyst is characterized by comprising the following steps of:
s1, preparing a reduction solution:
weighing non-noble metal salt and sodium hypophosphite with a molar ratio of 1:1-10, mixing and dissolving in water to obtain a mixed solution; then adding organic amine and complexing agent into the mixed solution, and uniformly mixing to obtain a reducing solution;
s2, pretreatment of conductive substrate
Sequentially adopting 1-3M hydrochloric acid solution, ethanol and deionized water to clean the conductive substrate, and cleaning the conductive substrate for later use;
the cleaned conductive substrate is used as a working electrode, a graphite plate is used as a counter electrode, and the graphite plate is used as a counter electrode in the reducing solution with the concentration of 5-20mA.cm -2 Depositing the self-catalytic metal nano-particle layer on the conductive substrate for 4-10 minutes to obtain a pretreated conductive substrate;
s3, soaking the pretreated conductive substrate in the reducing solution, and reacting for 1-3 hours at 60-150 ℃; and taking out the conductive substrate after the reaction is finished, and cleaning and drying to obtain the integral non-noble metal nanoparticle film electrocatalyst.
2. The method for preparing a monolithic non-noble metal electrocatalyst according to claim 1, wherein the non-noble metal salt is M 1 And M 2 Is a mixture of M 1 Is any one or two of Co and Ni chloride, sulfate and sulfamate, M 2 Is Fe, cr, cu, la chloride, sulfate, sulfamate or sodium molybdate, sodium tungstate, sodium tantalate or sodium niobate.
3. The method for preparing the monolithic non-noble metal electrocatalyst according to claim 2, wherein M 2 And M is as follows 1 Molar ratio of 0 to 0.5:1, preferably 0.05 to 0.3:1, more preferably 0.1 to 0.2:1.
4. the method for preparing monolithic non-noble metal electrocatalyst according to claim 1, wherein the molar concentration of the organic amine in the reducing solution is from 0.5 to 5mol/L, preferably from 1 to 2mol/L; the molar concentration of the complexing agent in the reducing solution is 0.01 to 0.5mol/L, preferably 0.05 to 0.2mol/L.
5. The method for preparing the monolithic non-noble metal electrocatalyst according to claim 1, wherein the organic amine is one of n-butylamine, ethanolamine, isopropanolamine, diethylenetriamine and triethylenetetramine; preferably, the organic amine is one of n-butylamine, ethanolamine and isopropanolamine; more preferably, the organic amine is n-butylamine or ethanolamine.
6. The method for preparing the monolithic non-noble metal electrocatalyst according to claim 1, wherein the complexing agent is one of aqueous ammonia, trisodium citrate, sodium tartrate, sodium gluconate, and sodium aminotriacetate; preferably, the complexing agent is one of ammonia water, trisodium citrate and sodium tartrate; more preferably, the complexing agent is aqueous ammonia or trisodium citrate.
7. The method for preparing a monolithic non-noble metal electrocatalyst according to claim 6, wherein when the organic amine is n-butylamine, the complexing agent is aqueous ammonia; when the organic amine is ethanolamine, the complexing agent is trisodium citrate; when the organic amine is isopropanolamine, the complexing agent is sodium tartrate.
8. A monolithic non-noble metal electrocatalyst, characterised in that it is prepared by a process according to claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311717570.8A CN117737771A (en) | 2023-12-14 | 2023-12-14 | Integral non-noble metal electrocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311717570.8A CN117737771A (en) | 2023-12-14 | 2023-12-14 | Integral non-noble metal electrocatalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117737771A true CN117737771A (en) | 2024-03-22 |
Family
ID=90260118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311717570.8A Pending CN117737771A (en) | 2023-12-14 | 2023-12-14 | Integral non-noble metal electrocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117737771A (en) |
-
2023
- 2023-12-14 CN CN202311717570.8A patent/CN117737771A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Interfacing Co3Mo with CoMoOx for synergistically boosting electrocatalytic hydrogen and oxygen evolution reactions | |
| Huo et al. | Synthesis of functional Ni2P/CC catalyst and the robust performances in hydrogen evolution reaction and nitrate reduction | |
| CN110280249B (en) | Preparation method of non-noble metal NiCoFe/NF electrocatalyst and oxygen precipitation application thereof | |
| CN110129815B (en) | Modified TM-LDH nano material, preparation method and application thereof | |
| CN112156788B (en) | Quaternary Ni-Fe-W-Mo alloy high-efficiency oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN112774704A (en) | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof | |
| CN113699552B (en) | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof | |
| CN112264047A (en) | Noble metal monoatomic catalyst for electrolyzing water to generate oxygen and preparation method and application thereof | |
| CN115142073A (en) | Preparation and application of FeCoNiCuMn nano high-entropy alloy electrocatalyst | |
| CN114959770A (en) | Preparation method and application of bimetallic ion doped carbon quantum dot catalyst | |
| CN115961305A (en) | (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof | |
| Wang et al. | Significantly enhanced oxygen evolution reaction performance by tuning surface states of Co through Cu modification in alloy structure | |
| Liu et al. | Ultra-thin carbon layer encapsulated NiCoP coralline-like catalysts for efficient overall water electrolysis | |
| Wen et al. | Reconstruction of FeNi layered dihydroxides by cobalt doping to improve the electrocatalytic activity of oxygen evolution reaction | |
| CN111774073B (en) | Ag nano particle loaded nickel sulfide nanosheet film structure material and preparation method and application thereof | |
| CN116062722B (en) | Catalyst and preparation method and application thereof | |
| CN110528024B (en) | Preparation method of ruthenium/molybdenum disulfide/reduced graphene oxide @ carbon fiber cloth catalytic electrode | |
| Guo et al. | Highly dispersed Rh prepared by the in-situ etching-growth strategy for energy-saving hydrogen evolution | |
| CN111686812B (en) | Ligand-activated transition metal layered dihydroxy compound, preparation method and application | |
| CN117737771A (en) | Integral non-noble metal electrocatalyst and preparation method thereof | |
| CN116200768A (en) | Preparation method and application of high-performance nickel-platinum catalytic material and application method | |
| CN114150345B (en) | Method for improving catalytic performance of NiCu alloy by electrochemical oxidation | |
| CN110453256B (en) | Polyhedral cobalt-iridium nanoparticle hydrogen evolution electrocatalyst, plating solution and preparation method thereof | |
| CN115161661A (en) | Composite catalyst material and preparation method and application thereof | |
| CN115323392B (en) | Preparation of efficient Co/NiCoP/CC heterogeneous nanoparticle hydrogen evolution reaction electrocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |