CN113694928A - Metal catalyst and preparation method and application thereof - Google Patents
Metal catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113694928A CN113694928A CN202010373979.2A CN202010373979A CN113694928A CN 113694928 A CN113694928 A CN 113694928A CN 202010373979 A CN202010373979 A CN 202010373979A CN 113694928 A CN113694928 A CN 113694928A
- Authority
- CN
- China
- Prior art keywords
- metal
- precursor
- catalyst
- spraying
- drying
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 170
- 239000002184 metal Substances 0.000 title claims abstract description 169
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000005507 spraying Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000013110 organic ligand Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000007750 plasma spraying Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- -1 vinyl siloxane Chemical class 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001848 post-transition metal Inorganic materials 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 238000010891 electric arc Methods 0.000 claims description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
- 238000010285 flame spraying Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 12
- 239000002923 metal particle Substances 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007921 spray Substances 0.000 description 10
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 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
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The application discloses a metal catalyst and a preparation method and application thereof, wherein the preparation method of the metal catalyst comprises the following steps: and spraying the mixture containing the metal precursor and the metal powder onto the conductive substrate at high temperature to obtain the metal catalyst. The method has simple steps, is not limited to specific metal and substrate materials, and has certain universality; the method is convenient for controlling the size of the final active metal particles on the conductive substrate, can prepare atomic-level dispersion, metal atom clusters and nano metal particles, and ensures high dispersibility of the active metal particles. When the metal catalyst prepared by the method is applied to the water electrolysis reaction, the energy conversion efficiency can be obviously improved, and the unit hydrogen production energy consumption is reduced.
Description
Technical Field
The invention relates to the field of electrolyzed water, in particular to a metal catalyst, a preparation method and application thereof in electrolyzed water.
Background
With the development of hydrogen energy industry, green economy and low-carbon requirements, hydrogen formally serves as an energy source or an energy source carrier to enter civil and industrial production. At present, industrial hydrogen production is still mainly from fossil resources, green and sustainable problems are not solved from the source, and environmental ecological problems such as atmospheric pollution, haze and the like cannot be solved. The hydrogen is produced by water electrolysis from renewable energy sources such as solar energy, and the like, so that the current energy supply and environmental problems are expected to be fundamentally solved.
At present, hydrogen is produced by water electrolysis, which is a method for producing hydrogen more conveniently and relatively efficiently. The current alkaline water electrolysis hydrogen production industry generally adopts transition metal-based catalysts (metal nickel, stainless steel and the like) as electrode materials. In order to realize certain hydrogen yield and energy utilization efficiency, the operation voltage of the industrial alkaline water electrolysis hydrogen production is usually as high as 2-2.2V and is far larger than the lowest value of the heat balance theory of 1.48V, so that the electrolysis efficiency is lower (59-70 percent), and the unit hydrogen production energy consumption is larger (5.0-6.6 kWh.Nm.Nm)-3). The main reasons are that the catalytic activity of the current commercial electrolytic water electrode is low, and the overpotential of the hydrogen and oxygen evolution reaction is too high. Therefore, it is desirable to make the best possible use ofThe working voltage of the electrolytic cell is reduced, and the working current is increased, so that the energy efficiency of the electrolytic cell is improved, and the energy consumption is reduced.
In view of the development of the current water electrolysis catalyst, the porous metal substrate is often used as an electrode skeleton to support the catalytic reaction active center due to the large specific surface area, the moderate pore structure and the sufficient mechanical strength. A new generation of electrocatalyst is constructed by introducing transition metal elements into the framework. For example, patents CN201810487534 and CN201510303542 introduce transition metal oxides and hydroxides to construct active centers, patents CN201510607936, CN201510295130, CN201610043831 and CN201510334080 introduce nitrides, sulfides, selenides, phosphides to construct active centers, and these water electrolysis catalysts show catalytic activity close to or equivalent to noble metals. However, the catalytic active centers in these materials are introduced and constructed in the form of larger nanoparticles, on the one hand, many catalytic active sites are wrapped inside the particles and cannot be effectively utilized; on the other hand, the cost of raw materials is increased.
Recent developments have shown that materials can exhibit specific catalytic water splitting activity superior to noble metals by rational construction of active center structures, reducing particle size to a few nanometers, sub-nanoclusters, and even atomic scale dispersion. Patent CN201811375698 discloses a preparation method of a composite material with ruthenium in atomic-level dispersion; firstly, a hydrotalcite material synthesized by a solution method is used as a carrier, then the carrier is treated in an alkaline solution containing ruthenium, and then the ruthenium catalyst dispersed on the hydrotalcite in atomic scale is obtained by treatment such as separation, vacuum drying and the like. CN201910517151 discloses a method for obtaining a monatomic material by processing a precursor in a plasma atmosphere in a specific reaction chamber under a certain vacuum degree.
At present, the preparation and research of materials with small size and high dispersion of catalytic active centers are advanced to a certain extent, but the preparation process conditions are harsh, the element types are limited, the catalyst powder needs to be formed secondarily and the like. The method cannot realize rapid, high-repeatability and industrial-grade amplification production in practical industrial application. Therefore, how to develop a preparation method of an electrode plate with universality, easy load adjustment, high active center dispersion and even atomic level dispersion, which is suitable for industrial mass and rapid production, becomes a problem to be solved at present.
Disclosure of Invention
According to a first aspect of the present application, a method for preparing a metal catalyst is provided, which has simple steps, is not limited to specific metals and substrate materials, and has a certain universality; the method is convenient for controlling the size of the final active metal particles on the conductive substrate, can prepare atomic-level dispersion, metal atom clusters and nano metal particles, and ensures high dispersibility of the active metal particles.
The preparation method of the metal catalyst comprises the following steps:
and spraying the mixture containing the metal precursor and the metal powder onto the conductive substrate at high temperature to obtain the metal catalyst.
Optionally, the metal precursor is a metal inorganic salt or a metal organic complex;
optionally, the metal inorganic salt is selected from at least one of potassium chloroplatinate, nickel nitrate, cobalt nitrate, chromium nitrate, ferric nitrate, sodium molybdate, sodium tungstate and stannous chloride.
The metal element in the metal precursor is a transition metal element and/or a post-transition metal element;
the transition metal element is at least one of platinum element, nickel element, cobalt element, chromium element, molybdenum element, tungsten element and iron element;
the post-transition metal element is at least one of tin element, lead element and bismuth element.
Optionally, the metal precursor is a metal organic complex;
the organic ligand in the metal organic complex is at least one selected from vinyl siloxane, sodium ethylene diamine tetracetate, ethylene diamine tetracetic acid, glycine, phthalic acid, triethylene diamine, N-dimethylformamide, acetic acid and glucose, and the vinyl siloxane is preferred.
Optionally, the metal precursor is a metal-organic complex, and the preparation method of the metal-organic complex includes:
and reacting the mixed solution containing the metal source and the organic ligand to obtain the metal precursor.
In one embodiment, the preparation method of the metal organic complex comprises the following steps:
and reacting the mixed solution containing the metal source, the organic ligand and the alkali source, washing and drying to obtain the metal precursor.
Wherein the alkali source is at least one selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate; the mixed solution also contains a solvent, and the solvent can be selected from conventional solvents such as water, ethanol, acetone, isopropanol and the like; the metal source is a compound containing a transition metal element and/or a post-transition metal element, and the metal source is preferably potassium chloroplatinate.
Optionally, the reaction temperature is 70-80 ℃, and the reaction time is 30-300 min; optionally, the molar ratio of the organic ligand to the metal source is 1-200: 1;
optionally, the metal powder is elemental metal powder and/or metal alloy powder;
the metal element in the metal powder is a transition metal element and/or a main group metal element;
the transition metal element is at least one of nickel element, iron element, cobalt element, manganese element, titanium element, copper element, zinc element, tungsten element and molybdenum element;
the main group metal element is at least one selected from aluminum element and indium element;
the metal powder is 20-600 meshes.
Optionally, the metal element in the metal precursor is different from the metal element of the metal powder.
Optionally, the mass of the metal precursor is 10 of the mass of the metal powder-4-5%, wherein the mass of the metal precursor is based on the mass of the catalytically active metal. Preferably, the mass of the metal precursor is 0.0001-0.4% of the mass of the metal powder, and more preferably, the mass of the metal precursor is 0.0001-0.4% of the mass of the metal powderSelecting 0.0001-0.02% to ensure atomic level dispersion.
Alternatively, the lower limit of the mass of the metal precursor to the mass percentage of the metal powder may be selected from 0.0001%, 0.0015%, 0.0020%, 0.0025%, 0.0030%, 0.0035%, 0.0040%, 0.0047%, 0.0050%, 0.0055%, 0.0060%, 0.0065%, 0.0070%, 0.0075%, 0.0077%, 0.031%, 0.11%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.20%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.30%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, or 0.37%, the upper limit may be selected from 0.0015%, 0.0020.0020%, 0030.0025%, 0.0030.0050%, 0.0050.0055%, 0.0070.19%, 0.19%, 0.15%, 0.30%, 0.1%, 0.30%, 0.0070.20%, 0.15%, 0.20%, 0.30%, 0.15%, 0.30%, 15%, 0.30%, 15%, 0.1%, 0., 0.33%, 0.34%, 0.35%, 0.36%, 0.37% or 0.4%.
Optionally, a binder is also included in the mixture; the binder is selected from at least one of perfluorinated sulfonic acid resin, carboxymethyl cellulose, dextrin, ethylene-acrylic acid copolymer, polyvinyl alcohol, polyurethane, polystyrene, polyoxyethylene-polyoxypropylene-polyoxyethylene, polyoxypropylene-polyoxyethylene-polyoxypropylene and polystyrene-polyoxyethylene;
preferably, the binder is selected from at least one of perfluorosulfonic acid resin, carboxymethyl cellulose, polyvinyl alcohol, and polyurethane.
Optionally, the binder is 0.05% to 10% by mass of the metal powder.
Optionally, the conductive substrate is a nickel substrate, a stainless steel substrate, a copper substrate or a titanium substrate;
the conductive substrate is in the shape of a plate, a sheet, a net or a foam.
Optionally, the high temperature spray is combustion flame spray, electric arc spray, supersonic spray or plasma spray.
Optionally, the powder feeding speed of the high-temperature spraying is 45-80 g/min, the spraying distance is 150-380 mm, and the horizontal moving speed of the spray gun is 10-600 mm/s.
Alternatively, the mixture containing the metal precursor, the binder and the metal powder is obtained by: adding a metal precursor into a solvent to obtain a mixed solution, adding a binder and metal powder into the mixed solution, and removing the solvent to obtain the mixture;
optionally, the molar concentration of the metal precursor in the mixed solution is 0.2-10 mmol.L in terms of metal mol-1(ii) a Preferably, the molar concentration of the metal precursor in the mixed solution is 0.2-5 mmol.L in terms of metal mol-1；
In one embodiment, the mixture containing the metal precursor, the binder, and the metal powder is obtained by:
dissolving a certain amount of metal precursor in a quantitative solvent, adding a quantitative binder and quantitative metal powder, stirring for a certain time, and drying to remove the solvent to obtain a mixture. Wherein the mixing mode can be selected from mechanical stirring and/or ball milling mixing;
optionally, the solvent removal specifically includes:
removing the solvent by cyclone drying or freeze drying;
the specific conditions of the cyclone drying include:
the inlet hot air temperature is 130-150 ℃, the drying pressure is normal pressure, the residence time of hot gas is 2-8 s, and the average residence time of materials is 15-60 min;
specific conditions for the freeze-drying include: the drying pressure is vacuum drying (<30Pa), the temperature of a cold trap is-40 to-70 ℃, and the drying time is 48 to 120 hours.
Optionally, after spraying the mixture of the metal precursor, the binder and the metal powder onto the conductive substrate at a high temperature, the method further includes:
and washing with an alkali or acid solution, wherein the molar concentration of the alkali or acid solution is 0.1-10M. The alkali solution can be sodium hydroxide solution, potassium hydroxide solution and the like; the acid solution may be a hydrochloric acid solution, a nitric acid solution, a sulfuric acid solution, or the like.
In one embodiment, the preparation method comprises the following steps:
(1) preparing a metal precursor I;
(2) mixing the prepared metal precursor I with metal powder and a binder, and drying to obtain a precursor II;
(3) and spraying the precursor II on a conductive substrate at a high temperature to obtain a precursor III, and washing and drying to obtain the metal catalyst. In this embodiment, the metal precursor I is the metal precursor, the precursor II is the mixture containing the metal precursor and the metal powder, and the precursor iii is the conductive substrate on which the precursor II is sprayed.
Preferably, (1) the metal element in the metal precursor is a transition metal element and/or a post-transition metal element; the transition metal element is at least one of platinum element, nickel element, cobalt element, chromium element, molybdenum element, iron element and tungsten element; the late transition metal element is at least one of tin element, lead element and bismuth element
Preferably, the metal precursor I in (1) includes metal organic complexes, metal nitrates, chlorides, sulfates, molybdates, compounds containing specific metal elements, and the like. The preparation method of the metal organic complex comprises the following steps: mixing organic ligand and metal salt in solution, removing solvent, washing and drying. The organic ligand can be vinylsiloxane, sodium ethylene diamine tetracetate, glycine, phthalic acid, triethylene diamine, N, N-dimethylformamide, acetic acid and glucose.
Preferably, the metal powder in (2) is an alloy powder or a mixed powder of one or more of nickel, iron, cobalt, manganese, titanium, aluminum, copper, zinc, indium, tungsten and molybdenum powder, and the size range is 20-600 meshes.
Preferably, the metal powder in (2) is a nickel aluminum alloy powder.
Preferably, the binder in (2) is at least one or more selected from perfluorosulfonic acid resin, carboxymethyl cellulose, dextrin, ethylene-acrylic acid copolymer, polyvinyl alcohol, polyurethane, polystyrene, polyoxyethylene-polyoxypropylene-polyoxyethylene, polyoxypropylene-polyoxyethylene-polyoxypropylene, and polystyrene-polyoxyethylene.
Preferably, the binder in (2) is perfluorosulfonic acid resin, carboxymethyl cellulose, polyvinyl alcohol, polyurethane.
Preferably, the mixing in (2) may be mechanical stirring, ball milling, and drying may be cyclone drying, freeze drying, etc.
Preferably, the drying in (2) is vacuum freeze drying, and the drying time is 2-5 days.
Preferably, the high-temperature spraying in (3) is one selected from the group consisting of combustion flame spraying, electric arc spraying, supersonic spraying and plasma spraying.
Preferably, (3) the conductive substrate is in the form of a plate, sheet, mesh, foam, or the like of nickel, titanium, copper, stainless steel, or the like.
Preferably, (3) the conductive substrate refers to nickel mesh, nickel sheet and foamed nickel.
Preferably, (3) the washing treatment means soaking the III in an alkaline solution for a certain time. Wherein the alkaline solution is an aqueous solution of sodium hydroxide and potassium hydroxide, and the concentration is 2-40 wt.%.
According to a second aspect of the present application, there is provided a metal catalyst prepared by the preparation method described in any one of the above.
According to a third aspect of the present application, there is provided the use of the metal catalyst prepared by any one of the above-mentioned preparation methods in alkaline electrolysis of water for hydrogen evolution and oxygen production reactions.
In the present application, the high-temperature spraying means that the spraying temperature is above 500 ℃.
The beneficial effects that this application can produce include:
(1) according to the invention, the metal precursor and the metal powder are combined to obtain the material to be sprayed, after high-temperature spraying, the metal powder forms the base layer, and metal or metal oxide particles formed by high-temperature decomposition of the metal precursor are dispersed and embedded in the base layer, so that effective dispersion is realized;
(2) the method is not limited to specific metal and substrate materials, and has certain universality;
(3) by adopting the method, the size of the final active metal particles on the conductive substrate can be conveniently controlled by controlling the amount of the metal precursor and the powder and the spraying process conditions, so that the active metal particles with atomic-level dispersion, metal atom clusters and nano metal particles can be obtained;
(4) the method for preparing the high-dispersion metal catalyst is convenient for large-scale production;
(5) the metal catalyst provided by the application has higher energy conversion efficiency when being applied to alkaline electrolysis water hydrogen evolution and oxygen generation reactions.
Drawings
FIG. 1 is a statistical distribution diagram of the particle size of the catalyst of example 1.
FIG. 2 is a statistical distribution diagram of the particle size of the catalyst of example 2.
FIG. 3 is a statistical distribution diagram of the particle size of the catalyst of example 3.
FIG. 4 is a statistical distribution diagram of the particle size of the catalyst of example 4.
FIG. 5 is a high resolution spherical aberration electron micrograph of the catalyst particles of example 5.
FIG. 6 is a plot of the hydrogen evolution reaction polarization for example 7 and a comparative example.
FIG. 7 is a graph showing the stability of hydrogen production in example 7.
FIG. 8 is a polarization diagram of oxygen evolution reaction for example 15 and a comparative example.
FIG. 9 is a graph showing the stability against oxygen evolution in example 15.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, all the raw materials described in this application are commercially available products.
Wherein the double head (vinylsiloxane) was purchased from model GEL-SIV9097.5-25G of mazell chemical technologies, inc;
perfluorosulfonic acid resin purchased from DuPont as model D520
Polyvinyl alcohol was purchased from M29057-1KG model of mazel chemical technologies, inc;
the metal salt, glycine, sodium ethylene diamine tetracetate, phthalic acid and organic solvent are all purchased from national chemical reagent company Limited and are all analytically pure. The nickel screen was purchased from Conway wire mesh products, Inc., Anping county, and had a 60 mesh specification.
The supersonic spraying system used was a JP8000 type supersonic flame spraying (HP/HVOF) system from plex surface technology, USA, and the specific process parameters for each example are shown in Table a.
The plasma spraying system used was model 7700 from plex surface technology, usa, and the specific process parameters for each example are shown in table a.
The particle size of the active metal particles in the catalyst was measured by a JEM-2100F transmission electron microscope.
Table a table of parameters of the spraying process of each example
The preparation of the highly dispersed metal catalyst and its use are further illustrated by the following examples:
example 1
40mL of potassium chloroplatinate isopropanol solution (120 mmol. L)-1) Mixing with double head (vinylsiloxane) (1g) and then adding NaHCO3(1g) And (3) obtaining a suspension emulsion, stirring the obtained suspension emulsion at 70-80 ℃ for 30min, and removing isopropanol to obtain a precursor I. The obtained precursor I, nickel-aluminum alloy powder (250g, 180 to 250 mesh, Ni: Al ═ 4:1, molar ratio), 3mL of 5 wt.% ethanol solution of perfluorosulfonic acid resin and 50mL of ethanol were mechanically stirred for 3 hours, and then freeze-dried at-60 ℃ for 72 hours to obtain precursor II. Loading precursor II on nickel net by supersonic spraying system to obtain III. And soaking the III in 10 wt.% potassium hydroxide solution for 12 hours to wash off alkali-soluble substances, washing with water, and drying to obtain the catalyst.
Example 2
The preparation was carried out in the same manner as in example 1, except that the potassium chloroplatinate concentration was 50 mmol. multidot.L-1And obtaining the catalyst.
Example 3
The preparation was carried out in the same manner as in example 1, except that the potassium chloroplatinate concentration was 36 mmol. multidot.L-1And obtaining the catalyst.
Example 4
The preparation was carried out in the same manner as in example 1, except that the potassium chloroplatinate concentration was 10.0 mmol. multidot.L-1And obtaining the catalyst.
Example 5
The preparation was carried out in the same manner as in example 1, except that the potassium chloroplatinate concentration was 0.5 mmol. multidot.L-1And obtaining the catalyst.
Table 1, examples 1-5 provide catalysts in which the average diameter of the platinum nano-ions
As shown in FIGS. 1 to 5, the particle size of the prepared platinum nanoparticles gradually decreased with the decreasing concentration of potassium chloroplatinate, especially at 0.5 mmol.L-1At the concentration, the prepared platinum nanoparticles are 0.35nm, and the particle size of the particles reaches 1-2 atomic radii, so that the particles are considered to be atomically dispersed, and the catalyst prepared at the concentration is equivalent to an atomically dispersed catalyst.
Example 6
250g of nickel-aluminum alloy powder (Ni: Al molar ratio 4:1) with a particle size of about 180 to 250 meshes was taken and added to 40mL of 120 mmol/L-1To the aqueous solution of potassium chloroplatinate, 1g of polyvinyl alcohol was added, mechanically stirred for 4 hours, and freeze-dried at-60 ℃ for 96 hours to obtain a mixture. The resulting mixture was introduced onto a nickel mesh support by means of supersonic spraying. Placing the obtained material intoThe catalyst was washed in 10 wt.% KOH for 20 hours, then washed with water and dried to yield the final catalyst.
Example 7
250g of nickel-aluminum alloy powder having a particle size of about 180 to 250 mesh (Ni: Al molar ratio 4:1) was added to 40mL of 0.5 mmol/L-1To the aqueous solution of potassium chloroplatinate, 1g of polyvinyl alcohol was added, mechanically stirred for 4 hours, and freeze-dried at-60 ℃ for 5 days to obtain a mixture. The resulting mixture was introduced onto a nickel mesh support by means of supersonic spraying. The resulting material was washed in 10 wt.% KOH for 20 hours, then washed with water and dried to yield the final catalyst.
Example 8
The same preparation as in example 6 was conducted except that the metal salt was cobalt nitrate and the concentration of the aqueous solution was 120 mmol. multidot.L-1And obtaining the catalyst.
Example 9
The same preparation as in example 7 was conducted except that the metal salt was cobalt nitrate and the concentration of the aqueous solution was 0.5 mmol.L-1And obtaining the catalyst.
Example 10
The preparation process was carried out in the same manner as in example 6 except that the metal salt was sodium molybdate and the concentration of the aqueous solution was 120 mmol. multidot.L-1And obtaining the catalyst.
Example 11
The same procedure as in example 7 was repeated, except that the metal salt was sodium molybdate and the aqueous solution thereof was 0.5 mmol. multidot.L-1And obtaining the catalyst.
Example 12
The same preparation as in example 6 was conducted except that the metal salt was chromium nitrate and the concentration of the aqueous solution was 120 mmol. multidot.L-1And obtaining the catalyst.
Example 13
The same preparation as in example 7 was conducted except that the metal salt was chromium nitrate and the concentration of the aqueous solution was 0.5 mmol.L-1And obtaining the catalyst.
Example 14
And embodiments thereof6 the preparation method is the same, the only difference is that the metal salt is ferric nitrate, the concentration of the aqueous solution is 120 mmol.L-1And obtaining the catalyst.
Example 15
The same procedure as in example 7 was repeated, except that the metal salt was ferric nitrate and the concentration of the aqueous solution was 0.5 mmol.L-1And obtaining the catalyst.
Example 16
The same preparation as in example 6 was conducted except that the metal salt was sodium tungstate and the aqueous solution thereof had a concentration of 120 mmol. multidot.L-1And obtaining the catalyst.
Example 17
The same preparation as in example 7 was conducted except that the metal salt was sodium tungstate and the aqueous solution thereof had a concentration of 0.5 mmol. multidot.L-1And obtaining the catalyst.
Example 18
The preparation method is the same as that of example 6, except that the metal salt is stannous chloride, and the concentration of the aqueous solution is 120 mmol.L-1And obtaining the catalyst.
Example 19
The preparation method is the same as that of example 7, except that the metal salt is stannous chloride, and the concentration of the aqueous solution is 0.5 mmol.L-1And obtaining the catalyst.
Table 2, examples 6-19 provide the average particle size of the metal nanoparticles in the catalysts
Table 2 shows that different metal precursors can be used to effectively prepare metal nanoparticles, especially when a low-concentration metal precursor is used, the prepared nanoparticles are the atomic-scale dispersion scale of the corresponding metal.
Example 20
The preparation method is the same as that of the embodiment 5, and the only difference is that the metal powder comprises 50g of 400-450-mesh cobalt powder, 100g of 180-250-mesh nickel powder and 50g of 180-250-mesh aluminum powder.
Example 21
The preparation method is the same as that of the embodiment 5, and the only difference is that the metal powder comprises the following components: 80g of 200-280-mesh titanium-aluminum alloy powder (the molar ratio of titanium to aluminum is 1:3) and 150g of 180-250-mesh nickel powder.
Example 22
The same preparation as in example 5 was carried out, the only difference being that the metal composition was: 250g of 180-250 mesh iron-aluminum alloy powder (iron: aluminum molar ratio is 3: 1).
TABLE 3 average particle size of platinum nanoparticles in catalysts provided in examples 20-22
As can be seen from Table 3, the platinum metal particles with the diameter of 0.34-0.37 nm can be prepared in an atomically dispersed manner under different metal nano-powder compositions.
Example 23
The same procedure as in example 5 was followed, except that the organic ligand used herein was sodium ethylenediaminetetraacetate, having a mass of 12 mg.
Example 24
The same procedure as in example 5 was followed, except that the organic ligand used herein was glycine having a mass of 15 mg.
Example 25
The same procedure as in example 5 was followed, except that the organic ligand used herein was phthalic acid and had a mass of 20 mg.
Table 4 particle size of platinum nano-metal particles prepared using different organic ligands
Example 26
The preparation method is the same as that of the embodiment 7, and the only difference is that the spraying method is changed into high-temperature plasma spraying to obtain the catalyst.
Example 27
The preparation method is the same as that of the embodiment 9, and the only difference is that the spraying method is changed into high-temperature plasma spraying to obtain the catalyst.
Example 28
The same preparation method as that of example 11 was used, except that the spraying method was changed to high-temperature plasma spraying to obtain a catalyst.
Example 29
The same preparation method as that of example 13 was used, except that the spraying method was changed to high-temperature plasma spraying to obtain a catalyst.
TABLE 5 Metal nanoparticle particle size of different metals under supersonic spray and high temperature plasma spray conditions
As can be seen from Table 5, the atomically dispersed nanoparticles can be prepared for different metals by both supersonic spray and high temperature plasma spray.
Comparative example 30
Comparative examples a commercial nickel catalyst, commercially available from hydrogen energy plant, inc.
Example 31
Evaluation of catalytic activity: the hydrogen or oxygen producing catalytic activity of the catalyst was measured by the CHI760D electrochemical workstation in a standard three electrode configuration. During measurement, the prepared catalyst is directly used as a working electrode, mercury/mercury oxide is used as a reference electrode, a nickel net is used as a counter electrode, a potassium hydroxide aqueous solution with the concentration of 30 wt.% is used as an electrolyte, the activity of a Hydrogen Evolution Reaction (HER) and/or an Oxygen Evolution Reaction (OER) is tested by linear sweep voltammetry or cyclic voltammetry at the sweep speed of 5mV/s, and the ohmic compensation is 90%.
The hydrogen production catalytic activity is typically represented by the catalyst provided in example 7, and as shown in fig. 6, the catalysts prepared in example 7 all have high hydrogen production catalytic activity by electrolysis, and the hydrogen production catalytic activity under the same conditions is much higher than that of the commercial catalyst in comparative example 30.
Example 32
Oxygen generating catalytic activity the catalyst provided in example 15 is representative, and as shown in fig. 8, the catalysts prepared in example 15 all have high electrolytic water generating catalytic activity, which is much higher than that of the commercial catalyst of comparative example 30 under the same conditions.
Example 33
Evaluation of catalytic stability: the hydrogen or oxygen production by electrolysis of water or catalytic stability of the catalysts provided in the examples and comparative examples was measured in a standard two-electrode configuration by the CHI760D workstation. The commercial catalyst of comparative example 30 was prepared as a counter electrode, the catalyst provided in each example was used as a hydrogen-evolving cathode, a 30 wt.% aqueous solution of potassium hydroxide was used as an electrolyte, and the working temperature was 80 ℃ at 400mA cm-2And the ohmic compensation proportion is 90 percent when the test is carried out under the current by constant current test.
Taking the catalyst provided in example 7 as a representative, as shown in fig. 7, the nickel-platinum catalyst prepared in example 7 has high stability of hydrogen production by electrolysis. Other embodiments also have higher stability of hydrogen produced by electrolysis.
Example 34
In the same manner as in example 33, the catalyst provided in each example was used as an oxygen evolution anode, and the commercial catalyst of comparative example 30 prepared was used as a counter electrode at 500mA cm-2And the ohmic compensation proportion is 90 percent when the test is carried out under the current by constant current test.
Taking the catalyst provided in example 15 as a representative, as shown in fig. 9, the nickel-iron catalyst prepared in example 15 has high oxygen stability for water electrolysis. Other embodiments also have higher oxygen stability of electrolyzed water.
Example 35
In the embodiment of the invention, the electrolysis efficiency is 1.48 per electrolysis voltage;
the unit hydrogen production energy consumption refers to the total electric energy consumed by the whole system when one cubic meter of hydrogen is produced by electrolysis.
The electrolytic efficiency and the specific hydrogen production energy consumption of the catalyst provided by each embodiment and comparative example of the invention are determined according to the method of GB32311-2015, and specific parameters are shown in Table 6.
TABLE 6 catalytic performances of catalysts obtained in examples and comparative examples
As can be seen from table 6, the catalyst provided by the present application has better electrolysis efficiency and low energy consumption per unit of hydrogen production.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of a metal catalyst is characterized by comprising the following steps:
and spraying the mixture containing the metal precursor and the metal powder onto the conductive substrate at high temperature to obtain the metal catalyst.
2. The production method according to claim 1, wherein the metal precursor is a metal inorganic salt or a metal organic complex;
the metal element in the metal precursor is a transition metal element and/or a post-transition metal element;
the transition metal element is at least one of platinum element, nickel element, cobalt element, chromium element, molybdenum element, tungsten element and iron element;
the post-transition metal element is at least one of tin element, lead element and bismuth element;
the metal inorganic salt is at least one of potassium chloroplatinate, nickel nitrate, cobalt nitrate, chromium nitrate, ferric nitrate, sodium molybdate, sodium tungstate and stannous chloride;
preferably, the metal precursor is a metal organic complex;
the organic ligand in the metal organic complex is at least one selected from vinyl siloxane, sodium ethylene diamine tetracetate, ethylene diamine tetraacetic acid, glycine, phthalic acid, triethylene diamine, N-dimethylformamide, acetic acid and glucose;
preferably, the method for preparing the metal precursor includes:
reacting a mixed solution containing a metal source and the organic ligand to obtain the metal precursor;
preferably, the metal powder is elemental metal powder and/or metal alloy powder;
the metal element in the metal powder is a transition metal element and/or a main group metal element;
the transition metal element is at least one of nickel element, iron element, cobalt element, manganese element, titanium element, copper element, zinc element, tungsten element and molybdenum element;
the main group metal element is at least one selected from aluminum element and indium element;
the metal powder is 20-600 meshes;
preferably, the metal element in the metal precursor is different from the metal element of the metal powder.
3. The production method according to claim 1, wherein the mass of the metal precursor is 10 mass of the metal powder-4-5%, wherein the mass of the metal precursor is based on the mass of the catalytically active metal.
4. The method of claim 1, wherein the mixture further comprises a binder; the binder is selected from at least one of perfluorinated sulfonic acid resin, carboxymethyl cellulose, dextrin, ethylene-acrylic acid copolymer, polyvinyl alcohol, polyurethane, polystyrene, polyoxyethylene-polyoxypropylene-polyoxyethylene, polyoxypropylene-polyoxyethylene-polyoxypropylene and polystyrene-polyoxyethylene;
preferably, the binder in the mixture is 0.05% to 10% by mass of the metal powder.
5. The production method according to claim 1, wherein the conductive substrate is a nickel substrate, a stainless steel substrate, a copper substrate, or a titanium substrate;
the conductive substrate is in a plate shape, a sheet shape, a net shape or a foam shape;
preferably, the high temperature spraying is at least one selected from the group consisting of combustion flame spraying, electric arc spraying, supersonic spraying, and plasma spraying.
6. The production method according to claim 1, wherein the mixture containing the metal precursor, the binder, and the metal powder is obtained by:
adding a metal precursor into a solvent to obtain a mixed solution, adding a binder and metal powder into the mixed solution, mixing, and removing the solvent to obtain the mixture;
preferably, the solvent for removing specifically includes:
removing the solvent by cyclone drying or freeze drying;
the specific conditions of the cyclone drying include:
the inlet hot air temperature is 130-150 ℃;
the drying pressure is normal pressure;
the residence time of hot gas is 2-8 s;
the average retention time of the materials is 15-60 min;
specific conditions for the freeze-drying include:
drying pressure <30 Pa;
the drying temperature is-40 to-70 ℃;
the drying time is 48-120 h.
7. The method of claim 1, further comprising, after the high temperature spraying of the mixture containing the metal precursor and the metal powder onto the conductive substrate:
and washing with an alkali or acid solution, wherein the molar concentration of the alkali or acid solution is 0.1-10M.
8. The method of claim 1, comprising the steps of:
preparing a metal precursor I;
mixing the prepared metal precursor I with metal powder and a binder, and drying to obtain a precursor II;
and spraying the precursor II on a conductive substrate at a high temperature to obtain a precursor III, and washing and drying to obtain the metal catalyst.
9. A metal catalyst produced by the production method according to any one of claims 1 to 8.
10. The application of the metal catalyst prepared by the preparation method of any one of claims 1 to 8 in alkaline electrolysis water hydrogen evolution and oxygen generation reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010373979.2A CN113694928B (en) | 2020-05-06 | 2020-05-06 | Metal catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010373979.2A CN113694928B (en) | 2020-05-06 | 2020-05-06 | Metal catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113694928A true CN113694928A (en) | 2021-11-26 |
| CN113694928B CN113694928B (en) | 2023-04-07 |
Family
ID=78645291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010373979.2A Active CN113694928B (en) | 2020-05-06 | 2020-05-06 | Metal catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113694928B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774967A (en) * | 2022-05-25 | 2022-07-22 | 江苏双良新能源装备有限公司 | Electrolytic water catalysis net and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463487A (en) * | 2007-12-17 | 2009-06-24 | 中国电子科技集团公司第十八研究所 | Preparation of proton exchange membrane electrode for electrolyzing water |
| CN105728063A (en) * | 2016-03-23 | 2016-07-06 | 新奥科技发展有限公司 | Preparation method of metal substrate catalyst |
| CN108359927A (en) * | 2018-05-04 | 2018-08-03 | 河北工业大学 | A kind of NiCr/Al2O3The preparation method of composite coating |
| CN110408950A (en) * | 2019-08-30 | 2019-11-05 | 南通大学 | A kind of electrolysis water cathode and preparation method thereof based on microcosmic blasting technology |
-
2020
- 2020-05-06 CN CN202010373979.2A patent/CN113694928B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463487A (en) * | 2007-12-17 | 2009-06-24 | 中国电子科技集团公司第十八研究所 | Preparation of proton exchange membrane electrode for electrolyzing water |
| CN105728063A (en) * | 2016-03-23 | 2016-07-06 | 新奥科技发展有限公司 | Preparation method of metal substrate catalyst |
| CN108359927A (en) * | 2018-05-04 | 2018-08-03 | 河北工业大学 | A kind of NiCr/Al2O3The preparation method of composite coating |
| CN110408950A (en) * | 2019-08-30 | 2019-11-05 | 南通大学 | A kind of electrolysis water cathode and preparation method thereof based on microcosmic blasting technology |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774967A (en) * | 2022-05-25 | 2022-07-22 | 江苏双良新能源装备有限公司 | Electrolytic water catalysis net and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113694928B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109847778B (en) | Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof | |
| CN110252335B (en) | Carbon-coated nickel-ruthenium nano material and preparation method and application thereof | |
| CN110479329B (en) | Preparation and application of phosphorus-doped cobalt telluride nano material | |
| CN111041517B (en) | Preparation method and application of two-dimensional bismuth alkene nanosheet | |
| CN112647095B (en) | Atomically dispersed bimetallic site anchored nitrogen-doped carbon material and preparation and application thereof | |
| WO2020118786A1 (en) | Platinum/phosphorus catalyst, preparation method therefor, and application thereof | |
| CN113026047B (en) | Method for synthesizing methanol by electrochemically catalyzing and converting carbon dioxide | |
| CN110681406B (en) | Nitrogen-phosphorus-doped carbon nanotube @ Mo/MoS2/MoP composite material and preparation method thereof | |
| CN113373471B (en) | For electrocatalytic reduction of CO2Preparation method and application of indium-based catalyst for preparing low-carbon alcohol | |
| CN113842936B (en) | Platinum-based monoatomic electrocatalytic material and preparation method and application thereof | |
| CN116139867B (en) | MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof | |
| CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
| CN110013855B (en) | High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof | |
| Yang et al. | A robust octahedral NiCoOxSy core-shell structure decorated with NiWO4 nanoparticles for enhanced electrocatalytic hydrogen evolution reaction | |
| Xie et al. | Ultrasmall Co-NiP embedded into lantern shaped composite achieved by coordination confinement phosphorization for overall water splitting | |
| Ji et al. | Bifunctional o-CoSe2/c-CoSe2/MoSe2 heterostructures for enhanced electrocatalytic and photoelectrochemical hydrogen evolution reaction | |
| CN109768293A (en) | Nanoscale tin nitrogen carbon material, preparation method and the application as oxygen reduction elctro-catalyst under alkaline condition | |
| CN113694928B (en) | Metal catalyst and preparation method and application thereof | |
| Wu et al. | Electronic structural engineering of bimetallic Bi-Cu alloying nanosheet for highly-efficient CO2 electroreduction and Zn-CO2 batteries | |
| CN110560094B (en) | Preparation method of 3D porous cobalt-tin-molybdenum trimetal catalyst | |
| CN110354870B (en) | Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst | |
| CN108842165B (en) | Solvothermal preparation of sulfur doped NiFe (CN)5NO electrolysis water oxygen evolution catalyst and application thereof | |
| CN115770621A (en) | Preparation method and application of bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst | |
| CN113200555A (en) | NiCo-PBA cross skeleton @ NiS2Preparation method and application of nano-framework material | |
| CN111697241A (en) | Nickel selenide composite material loaded with nickel iron tannate and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |