CN108671953A - A kind of transition metal nitride/carbon elctro-catalyst and its preparation and application - Google Patents
A kind of transition metal nitride/carbon elctro-catalyst and its preparation and application Download PDFInfo
- Publication number
- CN108671953A CN108671953A CN201810477132.1A CN201810477132A CN108671953A CN 108671953 A CN108671953 A CN 108671953A CN 201810477132 A CN201810477132 A CN 201810477132A CN 108671953 A CN108671953 A CN 108671953A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- catalyst
- elctro
- nitride
- carbon
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 75
- -1 transition metal nitride Chemical class 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 53
- 239000010949 copper Substances 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 238000004176 ammonification Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 230000000802 nitrating effect Effects 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 122
- 239000000243 solution Substances 0.000 claims description 88
- 229910052759 nickel Inorganic materials 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000006260 foam Substances 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 150000003624 transition metals Chemical class 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 30
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 150000004767 nitrides Chemical class 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000011065 in-situ storage Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 239000013110 organic ligand Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 40
- 239000002131 composite material Substances 0.000 description 33
- 238000001035 drying Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 15
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 230000009977 dual effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 241000555268 Dendroides Species 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- WYPNXPVMAIXNNH-UHFFFAOYSA-N [Mn].[Co]=S Chemical compound [Mn].[Co]=S WYPNXPVMAIXNNH-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- HJZMCWKYJQFMPG-UHFFFAOYSA-J cobalt(2+);manganese(2+);dicarbonate Chemical compound [Mn+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HJZMCWKYJQFMPG-UHFFFAOYSA-J 0.000 description 2
- NQFNBCXYXGZSPI-UHFFFAOYSA-L copper;diacetate;dihydrate Chemical group O.O.[Cu+2].CC([O-])=O.CC([O-])=O NQFNBCXYXGZSPI-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to electrochmical power source and electrochemical catalysis field, in particular to a kind of transition metal nitride/carbon elctro-catalysts, include the shell of substrate and clad substrates；The shell includes copper nitride, also includes carbon material or nitrating carbon material.The present invention also provides the preparation methods of the elctro-catalyst, are pre-formed the MOF of copper, are calcined with latter step ammonification, and the elctro-catalyst is made.Oxygen evolution and hydrogen precipitation process in alkaline environment present low overpotential, can be used as the catalyst material of alkaline high-efficient electrolytic water.
Description
Technical field
The present invention relates to electrochmical power source and electrochemical catalysis field, in particular to a kind of efficient transitional metal nitrides of alkalinity
The preparation method and applications of object/carbon elctro-catalyst.
Background technology
Electrolyzed alkaline water as a kind of novel energy storage apparatus, due to its have compared with high-energy-density, low cost, it is environmental-friendly,
Can machinery replace the advantages that, cause the attention of domestic and international researcher in recent years.Alkaline electrolysis water installations by catalyst anode,
Alkaline electrolyte and catalyst cathode three parts composition.During the reaction, oxygen evolution reaction (OER) occurs for anode, cloudy
Hydrogen evolution reaction (HER) then occurs for pole.OER processes are more complicated, it is considered that oxygen evolution reaction mainly has four electronics mistakes
Journey, i.e. OH-Directly it is oxidized to oxygen：4OH-→O2+2H2O+4e-, E0=1.23V；But it can be produced along with centre in reaction process
The generations such as object HO*, H*, O*, HOO*.HER processes are relatively simple：2H2O+2e-→2OH-+H2, E0=0V.Noble metal is recognized at present
For the electrolysis water catalyst for being best in alkaline electrolysis liquid system, there is stronger electro catalytic activity, but since it is expensive
And active the shortcomings of easily degenerating, limits its application in alkaline environment.Incline in the direction of current electrolysis water power catalyst research
To in base metal, non-precious metal catalyst is caused more and more gradually with the cost of its relative moderate and good catalytic activity
More people study.
Non-precious metal catalyst has very much, and wherein transition metal nitride, oxide sulfide are widely studied, and for
The research of the composite material of metallic compound and carbon material is very few.Once article reports (ACS Appl.Mater.Interfaces
2017,10,417-426) Ni and Co and its oxide and nickel foam, the material belong to a kind of loaded catalyst, Ni and Co with
And its oxide is supported in nickel foam, which has preferable oxygen evolution reaction catalytic activity.
For another example, the Chinese patent literature of Publication No. CN107855128A discloses a kind of system of cobalt sulfide manganese elctro-catalyst
Preparation Method, including following characteristics step：I, cobalt salt, manganese salt and urea are weighed, and the cobalt salt weighed, manganese salt and urea are dissolved in water
In, the uniformly mixed solution of stirring to obtain；Ii, it will be placed in reaction kettle together with the solution and carrier and carry out hydro-thermal reaction, obtained
To loaded cobalt carbonate manganese；Iii, by loaded cobalt carbonate manganese be placed in the aqueous solution of sulfur-bearing agent carry out vulcanization reaction to get
To loaded cobalt sulfide manganese.The invention only obtains single excellent liberation of hydrogen or analysis oxygen performance.
It to sum up analyzes, the existing technology relatively solved, catalyst material, which is primarily present only, has single liberation of hydrogen or analysis oxygen
Performance, and there is larger overpotential in hydrogen evolution reaction and oxygen evolution reaction.
Invention content
The technical issues of to solve the prior art, an object of the present disclosure is, provides a kind of transition metal nitride/carbon
Elctro-catalyst (present invention also abbreviation elctro-catalyst or catalyst), it is desirable to provide one kind having relatively low overpotential, has excellent
OER and HER dual catalytic performances transition metal nitride/carbon elctro-catalyst.
Second purpose of the invention is, provides a kind of preparation method of the transition metal nitride/carbon elctro-catalyst,
It is intended to that transition metal nitride/carbon elctro-catalyst that the original position successively coats is made.
Third purpose of the present invention is, provides a kind of application of the transition metal nitride/carbon elctro-catalyst.
A kind of transition metal nitride/carbon elctro-catalyst, includes the shell of substrate and clad substrates；
The shell includes copper nitride, also includes carbon material or nitrating carbon material.
Elctro-catalyst of the present invention has excellent electrocatalysis characteristic, especially by the shell of carbon dope copper nitride
The effect of material, the HER performances that can be unexpectedly obviously improved.
Include carbon material or nitrating carbon material in case material of the present invention.It that is to say, the case material
For the mixture of copper nitride and carbon material, or the mixture for copper nitride and nitrating carbon material.
Still more preferably, the case material is the mixture of copper nitride and nitrating carbon material.
Currently preferred transition metal nitride/carbon elctro-catalyst, is also compounded with folder between the substrate and shell
Central layer；
The material of the sandwich of layers is the nitride of transition metal；
The nitride of the transition metal is the nitride of at least one of iron, cobalt, nickel transition metal element.
Currently preferred elctro-catalyst, including the nitride intermediate layer of substrate compound successively, transition metal are (sandwich
Layer) and shell comprising copper nitride.Currently preferred elctro-catalyst is transition metal nitride/carbon electricity of successively In-situ reaction
Catalyst can get the catalyst with good electrocatalysis characteristic by the collaboration of material variety and the structure.The electricity
Catalyst stability in alkaline environment is good, and oxygen evolution process and hydrogen precipitation process show low overpotential, realizes
Elctro-catalyst is difficult to the dual catalytic performance realized in industry.
Currently preferred transition metal nitride/carbon elctro-catalyst has three-decker.Wherein, including copper nitride layer
Shell have certain hole.
Preferably, the nitride of the transition metal is cobalt nitride.The study found that using the preferred material conduct
Middle layer coordinates the sheathing material of copper nitride, can obviously cooperate with the performance for promoting catalyst.
Preferably, the transition metal nitride/carbon elctro-catalyst, the content of the nitride of transition metal is 80~
90wt%；The content of copper nitride is 20~67.5wt%；The content of carbon material or nitrating carbon material is 10~20wt%.
Further preferably, the mass ratio of composite metal nitride and N doping carbon materials is between 1: 4-1: 9.
Elctro-catalyst of the present invention, grain size are 0.5~5 μm.
The present invention also provides a kind of preparation method of the transition metal nitride/carbon elctro-catalyst,
Step (1)：The preparation of elctro-catalyst presoma：
Hydro-thermal reaction will be carried out comprising the solution A of substrate, copper source, organic ligand, had in the metal that substrate surface deposits copper
Machine frame compound obtains the elctro-catalyst presoma；
Step (2)：Ammonification is calcined
The elctro-catalyst presoma that step (1) obtains is calcined under containing ammonia atmosphere, the transition metal nitrogen is made
Compound/carbon elctro-catalyst.
Copper metal organic frame is innovatively made in the present invention in advance, then again by a step ammonification, is formed in situ described
The shell of carbon dope copper nitride；By the method for the invention, the elctro-catalyst haveing excellent performance can be made.
The substrate is one kind in nickel foam, foam copper, carbon paper, stainless steel substrates.
As preferred：The organic ligand is terephthalic acid (TPA), and 2- amino terephthalic acid (TPA)s, 2-methylimidazole, how is Isosorbide-5-Nitrae
Dioctyl phthalate, at least one of benzenetricarboxylic acid.
Preferably, the copper source is Cu2+Salt；Further preferably copper nitrate, copper chloride, in copper acetate at least
It is a kind of.
Copper source and the molar ratio of organic ligand are 2: 1~1: 5.
In solution A, the molar concentration of organic ligand is 0.01~2M.
Preferably, the solvent in solution A is n,N dimethylformamide.
Solution A carry out hydro-thermal reaction condition be：Temperature is 100~160 DEG C, preferably 120~130 DEG C；Time is preferred
For 12~for 24 hours.
A kind of preferred method, in step (1), substrate is pre-processed, before carrying out the hydro-thermal reaction in its table
Face in-situ deposition transition metal hydroxide precipitation；
It is in the step of its surface in situ deposition transition metal hydroxide precipitation：Will include transition metal source, substrate and
The solution B of precipitating reagent carries out hydro-thermal reaction.
Surface deposition is had substrate (pretreated substrate), the copper of transition metal hydroxide by preparation method of the present invention
Source, ligand solution carry out hydro-thermal reaction, in the metal organic frame of the transition metal hydroxide copper-depositing on surface of substrate
Object is closed, elctro-catalyst presoma is made；Through a step ammonification after, the elctro-catalyst is made.It, can by the preferred method
With the elctro-catalyst of obtained substrate, sandwich of layers, shell successively compound multilayered structure, the elctro-catalyst is by means of the structure
And material characteristic, it can express out excellent dual electro-catalysis effect.
Preferred preparation method：Specifically include following steps：
Step (a)：Pretreatment：
Hydro-thermal reaction will be carried out comprising the solution B of transition metal source, substrate and precipitating reagent, being made has in substrate surface deposition
The presoma 1 of transition metal hydroxide；
Step (b)：The preparation of elctro-catalyst presoma：
Hydro-thermal reaction will be carried out comprising the solution C of presoma 1, copper source, ligand, being made has in the surface of presoma 1 deposition
The presoma 2 (that is to say elctro-catalyst presoma) of the metal organic framework compound of copper；
Step (c)：Presoma 2 is calcined under containing ammonia atmosphere, the transition metal nitride/carbon electro-catalysis is made
Agent.
In the preparation method of preferred option b, the hydroxide precipitation of transition metal is formed in situ in substrate surface in advance
Layer, then the innovative hydroxide layer surface in situ in the transition metal deposits the metal organic frame chemical combination of copper again
Nitride layer；It is calcined again by a step ammonification, you can the electricity for obtaining the successively composite construction being made of dissimilar metal nitride is urged
Agent.The method of the present invention avoids the cumbersome preparation method of the carbon materials such as existing carbon nanotube, and operation is just clean, environmental-friendly, easily
It is synthesized in amplification, it is often more important that, it has been made and active elctro-catalyst is precipitated with excellent oxygen evolution and hydrogen.
Preferably, the transition metal source is the compound for including at least one of iron, cobalt, nickel transition elements.
Further preferably, the transition metal source is the water soluble salt of the water soluble salt of iron, the water soluble salt of cobalt, nickel
At least one of.
The water soluble salt of each transition metal is, for example, chlorate, acetate, nitrate of each transition metal element etc..
Most preferably, the transition metal source is at least one of cobalt nitrate, cobalt chloride, cobalt acetate.The study found that phase
Than that unexpectedly can form dendroid pattern using cobalt source in other transition metal sources in substrate surface, contribute to follow-up
The In-situ reaction of material contributes to the catalytic performance for further promoting elctro-catalyst.
Preferably, the molar ratio of copper source and transition metal source is 10: 1~1: 3.
The precipitating reagent is one kind in urea, ammonium fluoride, urotropine；Further preferred urea.It is preferred that
Urea effect it is more excellent.
Preferably, the substrate is one kind in nickel foam, foam copper, carbon paper, stainless steel substrates；Further preferably
Nickel foam.
Solvent in solution B is water.
Preferably, in solution B, the molar concentration of transition metal source is 0.001-0.2M.Under the preferred concentration, have
Help control pattern, obtains the uniform material of pattern, help further to promote catalytic performance.
Preferably, in solution B, the molar concentration of precipitating reagent is 0.03-2M.
Preferably, transition metal source, the molar ratio of precipitating reagent are 1: 1~1: 40.
Preferably, the hydro-thermal reaction of solution B carries out in pressure vessel.
Preferably, solution B hydrothermal reaction condition is：Temperature is 100~160 DEG C；Time is preferably 4~12h；Further
Preferably 6~12h.
After solution B hydro-thermal reaction, the presoma 1 is obtained through being separated by solid-liquid separation, washing.
In the present invention, the step of passing through innovation (1), in one layer of metal MOF material of surface recombination of presoma 1, the material
There can be special pattern according to the difference of ligand, it may have certain porosity also contains organic carbon in material, passes through institute
Calcining under the ammonia atmosphere stated, can be by the metal organic framework compound of the hydroxide of transition metal and copper together nitrogen
Change, the nitride layer of respective metal is formed in situ, moreover, the organic frame of copper contains carbon, can shape under the calcining
At nitrogen-doped carbon material, in the shell of the compound nitrogen-doped carbon/copper nitride of surface in situ of middle layer.The material shows excellent
Different electric property.
In solution C after hydro-thermal reaction, it is separated by solid-liquid separation, it is washed, dry that the elctro-catalyst presoma is made.
Calcination process carries out under the atmosphere containing ammonia.
The atmosphere containing ammonia is, for example, ammonia atmosphere, or has the mixing of ammonia atmosphere and other protective atmospheres
Atmosphere；The protective atmosphere is, for example, nitrogen, inert atmosphere etc..
As preferred：The temperature of calcining is 300~600 DEG C.
The heating rate of calcination process is, for example, 1~10 DEG C/min.
Calcination time is preferably 1~3h.
A kind of preparation method of preferred elctro-catalyst of the present invention, is as follows：
Urea is added into the aqueous solution of cobalt source for step (A), stirs to clear solution is completely dissolved into, addition cleans up
Nickel foam, be packaged in pressure-resistant reaction kettle, hydro-thermal reaction, reaction time 4-12h, after reaction carried out at 100-160 DEG C
Product water and alcohol respectively washing several times, after filtering drying obtain hydroxide and nickel foam composite precursor (presoma 1)；
Organic ligand is dissolved in DMF by step (B), is stirred to clear solution is completely dissolved into, by 1 He of above-mentioned presoma
Copper source is added, and is packaged in 100mL reaction kettles, and setting reaction temperature is 100-160 DEG C, reaction time 12-24h, after reaction
Product water and alcohol respectively washing several times, after filtering dry (such as being dried at 45~50 DEG C) obtain metal organic frame@
Hydroxide and nickel foam composite precursor (elctro-catalyst presoma), are impregnated in the ethanol solution of argon gas saturation and are protected
It deposits；The elctro-catalyst presoma dried in (B) is placed in tube furnace by step (C), and setting heating rate is 1-10 DEG C/min, is protected
Temperature is 300-600 DEG C, leads to protection of ammonia, soaking time 1-3h, and natural cooling obtains the elctro-catalyst.
Currently preferred elctro-catalyst preparation method, before using cobalt source that dendroid is made with urea mixed solution hydro-thermal
It drives body and is carried on froth foam nickel surface (step (A)), then secondary growth in situ copper-MOF (step (B)), finally by a step
The heterojunction structure of copper nitride, cobalt nitride and foam nickel base, wherein transition metal nitrogen can be obtained in calcining under ammonia atmosphere
Compound homoepitaxial is in foam nickel surface, and between 80-90wt%, N adulterates carbon materials for wherein transition metal nitride content control
Content is expected between 10-20wt%, and overall dimensions are between 0.5-5 μm.
The present invention also includes using transition metal nitride/carbon elctro-catalyst made from the preparation method.
The present invention also provides a kind of applications of transition metal nitride/carbon elctro-catalyst, are used as catalyst, are catalyzed OER
And/or HER reactions.
Catalyst of the present invention, has the function of dual catalytic, compared to mix multiple functions catalyst physical
The catalytic performance of material, the successively compound material in original position of the present invention is more excellent.
Preferably, in the application, by the catalyst for water electrolysis for be catalyzed alkaline aqueous solution electrolytic hydrogen production and/or
Produce oxygen.
The principle of the invention is as follows：
1, in the present invention, by the one step ammonification of form of the organic frame compound of copper, the shell of carbon dope copper nitride is made
Material has an excellent effect also doped with part N in the material in terms of electrolysis water catalysis, in terms of especially again HER, effect
It is prominent；
2, surface is further studied, first passes through hydro-thermal reaction in advance, it is in situ in substrate surface carrying transition metal hydroxide
(presoma 1), after its surface coat one layer of metal organic frame, low temperature ammoniated processing, at the same time, under ammonia atmosphere,
The hydroxide of transition metal and metal organic frame ammonification become the nitride of respective metal, in subsequent metal organic frame
Organic carbon is carbonized under ammonia atmosphere and generates nitrogen-doped carbon with ammonification, and products therefrom is different metal nitride and substrate
Hetero-junctions catalyst.Transition metal nitride has splendid stability, and mistake with N doped porous carbon materials in alkaline solution
Crossing metal nitride has preferable electric conductivity, so its ohmic polarization is also smaller, is conducive to the power-performance for improving battery.It is logical
It crosses and is preferably provided with the sandwich of layers in substrate and the shell, the especially transition metal element of sandwich of layers is cobalt when institute
The special dendroid pattern presented, can further cooperate with case material, assign the elctro-catalyst good dual catalytic effect
Fruit.
The beneficial effects of the invention are as follows：
Elctro-catalyst of the present invention has lower overpotential, and catalytic performance is excellent, and dual with OER and HER
Function.
Metal nitride is uniformly grown in substrate surface in catalyst material prepared by the present invention.When transition metal source is adopted
When with cobalt source, can also the hydroxide of branch stratiform pattern unexpectedly be formed in substrate surface, compared to other transition gold
Category source has lower oxygen evolution and hydrogen Evolution overpotential, catalytic performance more excellent.
Elctro-catalyst of the present invention shows high-efficient electrolytic water efficiency under alkaline environment, and the material is in highly basic body
System is lower to have splendid stability, is the preferred of high-efficient electrolytic water electrode catalyst.
Description of the drawings
Fig. 1 is the X-ray diffraction of catalyst (Cu, Co, Ni nitride/foam nickel composite catalyst) prepared by embodiment 2
(XRD) collection of illustrative plates.
Fig. 2 is the SEM figures of catalyst prepared by Examples 1 and 2；
Wherein, 2a is that the SEM of 1 non-ammoniated treatment of embodiment schemes, and 2b is that the SEM of 1 ammoniated treatment of embodiment schemes；2c is to implement
The SEM of 2 non-ammoniated treatment of example schemes, and 2d is that the SEM of 2 ammoniated treatment of embodiment schemes.
Fig. 2 a are clear that the formation that sheet Cu-MOF is grown in foam nickel surface, after 400 degrees Celsius of ammonifications
Copper nitride is with particulate load foam nickel surface (Fig. 2 b) again.The surface that Fig. 2 c can see dendroid cobalt hydroxide covers one again
The cubical copper MOF of layer, after 400 degrees Celsius of ammonifications, copper MOF is combined together (Fig. 2 d) at particle and dendroid cobalt nitride.
The composite catalyst and commercialization RuO that Fig. 3 is embodiment 1, prepared by embodiment 22In the oxygen-saturated KOH solutions of 0.1M
Oxygen evolution reaction linear sweep voltammetry curve, sweep speed be 5mV s-1。
Fig. 4 is embodiment 1, the composite catalyst of the preparation of embodiment 2 and commercialization Pt/C in the oxygen-saturated KOH solutions of 0.1M
Hydrogen evolution reaction linear sweep voltammetry curve, sweep speed be 5mV s-1。
Specific implementation mode
Method for preparing catalyst is precipitated disclosure sets forth a kind of alkaline electrolysis water battery oxygen evolution, hydrogen and its answers
With the catalyst is a kind of copper, cobalt, nickel nitride and nickel foam hetero-junctions catalyst, metal nitride content control therein
Between 80-90%, nitrogen-doped carbon content is between 10-20%, and overall dimensions are between 0.5-5 μm.Specific embodiment is to this
Invention is further described, but these embodiments do not constitute any limitation of the invention.
Embodiment, which uses, is grown directly upon the online catalyst material of nickel foam as working electrode, with traditional three electrode bodies
System, 0.1M KOH solutions are electrolyte, HER the and OER performances of test material.
Embodiment 1
The shell is directly formed in substrate surface, it is specific as follows：
0.2mmol Gerhardites are dissolved in 40mL n,N-Dimethylformamide (DMF) and form reaction solution A, it will
1mmol 2- amino terephthalic acid (TPA)s are dissolved in formation reaction solution B in 15mL DMF, reaction solution A are added in reaction solution B, magnetic force stirs
It after mixing 15 minutes, is transferred in polytetrafluoroethyllining lining, a piece of nickel foam cleaned up is then added, is positioned over not after sealing
It is reacted 24 hours in rust steel autoclave and at 120 DEG C, cooled to room temperature (25 DEG C).Product is passed through into absolute ethyl alcohol
Copper metal organic frame and nickel foam composite precursor are obtained with drying at after each three times washings of water 60 DEG C；Above-mentioned copper metal is had
Machine frame is placed in nickel foam composite precursor in tube furnace, and under ammonia atmosphere, setting heating rate is 5 DEG C/min, heat preservation
Temperature is 400 DEG C, soaking time 2h, and natural cooling obtains copper, nickel nitride and nickel foam composite heterogenous junction catalyst.This
It is 420mV (10mA cm to invent oxygen evolution overpotential of the obtained composite catalyst in the KOH solution that 0.1M oxygen is saturated-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be -26mV (10mA cm-2).The material shows excellent
HER performances.
Embodiment 2
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing
(presoma 1)；0.5mmol Gerhardites are dissolved in formation reaction solution A in 15mL DMF, by 1mmol 2- amino to benzene
Dioctyl phthalate is dissolved in formation reaction solution B in 15mL DMF, and reaction solution A is added in reaction solution B, and magnetic agitation is after 15 minutes, transfer
It is then above-mentioned that cobalt hydroxide and foam nickel clad (presoma 1) is prepared into polytetrafluoroethyllining lining, it is placed after sealing
It is reacted 24 hours in stainless steel autoclave and at 120 DEG C, cooled to room temperature (25 DEG C).By product by anhydrous
60 DEG C of drying after each three times washings of second alcohol and water；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting rises
Warm speed is 5 DEG C/min, and holding temperature is 400 DEG C, soaking time 2h, natural cooling, obtains copper, cobalt, nickel nitride and bubble
Foam nickel composite heterogenous junction catalyst.Oxygen analysis of the composite catalyst that the present invention obtains in the KOH solution that 0.1M oxygen is saturated
It is 116mV (10mA cm to go out overpotential-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be 32mV (10mA
cm-2)。
Embodiment 3
It is compared with embodiment 2, the main distinction is, change calcination temperature is 500 DEG C, specific as follows：
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing；
0.5mmol Gerhardites are dissolved in formation reaction solution A in 15mL DMF, 1mmol 2- amino terephthalic acid (TPA)s are dissolved
Reaction solution B is formed in 15mL DMF, reaction solution A is added in reaction solution B, magnetic agitation is transferred to polytetrafluoroethyl-ne after 15 minutes
It is then above-mentioned that cobalt hydroxide and foam nickel clad is prepared in alkene liner, stainless steel autoclave is positioned over after sealing
In and react 24 hours at 120 DEG C, cooled to room temperature (25 DEG C).By product by each three times washings of absolute ethyl alcohol and water
60 DEG C of drying afterwards；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting heating rate is 5 DEG C/min, is protected
Temperature is 500 DEG C, soaking time 2h, natural cooling, obtains copper, cobalt, nickel nitride and nickel foam composite heterogenous junction and is catalyzed
Agent.Oxygen evolution overpotential of the composite catalyst that the present invention obtains in the KOH solution that 0.1M oxygen is saturated is 132mV
(10mA cm-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be 68mV (10mA cm-2)。
Embodiment 4
It is compared with embodiment 2, the main distinction is, change calcination temperature is 300 DEG C, specific as follows：
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing；
0.5mmol Gerhardites are dissolved in formation reaction solution A in 15mL DMF, 1mmol 2- amino terephthalic acid (TPA)s are dissolved
Reaction solution B is formed in 15mL DMF, reaction solution A is added in reaction solution B, magnetic agitation is transferred to polytetrafluoroethyl-ne after 15 minutes
It is then above-mentioned that cobalt hydroxide and foam nickel clad is prepared in alkene liner, stainless steel autoclave is positioned over after sealing
In and react 24 hours at 120 DEG C, cooled to room temperature (25 DEG C).By product by each three times washings of absolute ethyl alcohol and water
60 DEG C of drying afterwards；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting heating rate is 5 DEG C/min, is protected
Temperature is 300 DEG C, soaking time 2h, natural cooling, obtains copper, cobalt, nickel nitride and nickel foam composite heterogenous junction and is catalyzed
Agent.Oxygen evolution overpotential of the composite catalyst that the present invention obtains in the KOH solution that 0.1M oxygen is saturated is 240mV
(10mA cm-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be 125mV (10mA cm-2)。
Embodiment 5
It is compared with embodiment 2, the main distinction is, replacement copper source is Copper dichloride dihydrate, specific as follows：
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing；
0.5mmol Copper dichloride dihydrates are dissolved in formation reaction solution A in 15mL DMF, 1mmol 2- amino terephthalic acid (TPA)s are dissolved
Reaction solution B is formed in 15mL DMF, reaction solution A is added in reaction solution B, magnetic agitation is transferred to polytetrafluoroethyl-ne after 15 minutes
It is then above-mentioned that cobalt hydroxide and foam nickel clad is prepared in alkene liner, stainless steel autoclave is positioned over after sealing
In and react 24 hours at 120 DEG C, cooled to room temperature (25 DEG C).By product by each three times washings of absolute ethyl alcohol and water
60 DEG C of drying afterwards；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting heating rate is 5 DEG C/min, is protected
Temperature is 400 DEG C, soaking time 2h, natural cooling, obtains copper, cobalt, nickel nitride and nickel foam composite heterogenous junction and is catalyzed
Agent.Oxygen evolution overpotential of the composite catalyst that the present invention obtains in the KOH solution that 0.1M oxygen is saturated is 165mV
(10mA cm-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be 76mV (10mA cm-2)。
Embodiment 6
It is compared with embodiment 2, the main distinction is, replacement copper source is copper acetate dihydrate, specific as follows：
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing；
0.5mmol copper acetate dihydrates are dissolved in formation reaction solution A in 15mL DMF, 1mmol 2- amino terephthalic acid (TPA)s are dissolved
Reaction solution B is formed in 15mL DMF, reaction solution A is added in reaction solution B, magnetic agitation is transferred to polytetrafluoroethyl-ne after 15 minutes
It is then above-mentioned that cobalt hydroxide and foam nickel clad is prepared in alkene liner, stainless steel autoclave is positioned over after sealing
In and react 24 hours at 120 DEG C, cooled to room temperature (25 DEG C).By product by each three times washings of absolute ethyl alcohol and water
60 DEG C of drying afterwards；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting heating rate is 5 DEG C/min, is protected
Temperature is 400 DEG C, soaking time 2h, natural cooling, obtains copper, cobalt, nickel nitride and nickel foam composite heterogenous junction and is catalyzed
Agent.Oxygen evolution overpotential of the composite catalyst that the present invention obtains in the KOH solution that 0.1M oxygen is saturated is 198mV
(10mA cm-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be 98mV (10mA cm-2)。
Embodiment 7
It is compared with embodiment 2, the main distinction is, replacement organic ligand is terephthalic acid (TPA), specific as follows：
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing；
0.5mmol Gerhardites are dissolved in formation reaction solution A in 15mL DMF, 1mmol terephthalic acid (TPA)s are dissolved in 15mL
Reaction solution B is formed in DMF, reaction solution A is added in reaction solution B, magnetic agitation is transferred to polytetrafluoroethyllining lining after 15 minutes
In, then it is above-mentioned cobalt hydroxide and foam nickel clad is prepared, be positioned over after sealing in stainless steel autoclave and
It is reacted 24 hours at 120 DEG C, cooled to room temperature (25 DEG C).By product 60 DEG C after each three times washings of absolute ethyl alcohol and water
Drying；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting heating rate is 5 DEG C/min, holding temperature
It it is 400 DEG C, soaking time 2h, natural cooling obtains copper, cobalt, nickel nitride and nickel foam composite heterogenous junction catalyst.This hair
Oxygen evolution overpotential of the bright obtained composite catalyst in the KOH solution that 0.1M oxygen is saturated is 210mV (10mA cm-2),
Hydrogen Evolution overpotential in the KOH solution of 0.1M argon gas saturation is 162mV (10mA cm-2)。
Embodiment 8
It is compared with embodiment 2, the main distinction is, replacement organic ligand is Isosorbide-5-Nitrae naphthalenedicarboxylic acid, specific as follows：
The urea of 3mmol is added into the cobalt chloride solution of the 1mM of 80ml, stirs to clear solution is completely dissolved into, adds
Enter a piece of clear clean nickel foam, be packaged in reaction kettle, setting reaction temperature is 120 DEG C, reaction time 10h, reaction
Respectively several times, drying obtains cobalt hydroxide and nickel foam composite precursor to product water and alcohol afterwards at 60 DEG C after filtering for washing；
0.5mmol Gerhardites are dissolved in formation reaction solution A in 15mL DMF, 1mmol Isosorbide-5-Nitrae naphthalenedicarboxylic acids are dissolved in
Reaction solution B is formed in 15mL DMF, reaction solution A is added in reaction solution B, magnetic agitation is transferred to polytetrafluoroethylene (PTFE) after 15 minutes
It is then above-mentioned that cobalt hydroxide and foam nickel clad is prepared in liner, it is positioned over after sealing in stainless steel autoclave
And it is reacted 24 hours at 120 DEG C, cooled to room temperature (25 DEG C).By product after each three times washings of absolute ethyl alcohol and water
60 DEG C of drying；The product of above-mentioned drying is placed in tube furnace, under ammonia atmosphere, setting heating rate is 5 DEG C/min, heat preservation
Temperature is 400 DEG C, soaking time 2h, and natural cooling obtains copper, cobalt, nickel nitride and nickel foam composite heterogenous junction catalyst.
Oxygen evolution overpotential of the composite catalyst that the present invention obtains in the KOH solution that 0.1M oxygen is saturated is 157mV (10mA
cm-2), 0.1M argon gas saturation KOH solution in hydrogen Evolution overpotential be 66mV (10mA cm-2)。
By assembled three-electrode system in above-described embodiment under room temperature (25 DEG C), with 10mAcm-2Current density survey
HER the and OER performances of catalyst are tried, the results are shown in Table 1：
Table 1
By above-described embodiment it is found that there is catalyst material of the present invention outstanding oxygen evolution and hydrogen precipitation to urge
Change activity, the chemical property of electrolyzed alkaline water can be improved.
Claims (10)
1. a kind of transition metal nitride/carbon elctro-catalyst, it is characterised in that：Shell including substrate and clad substrates；
The shell includes copper nitride, also includes carbon material or nitrating carbon material.
2. transition metal nitride as described in claim 1/carbon elctro-catalyst, it is characterised in that：The substrate and shell
Between be also compounded with sandwich of layers；
The material of the sandwich of layers is the nitride of transition metal；
The nitride of the transition metal is the nitride of at least one of iron, cobalt, nickel transition metal element.
3. transition metal nitride as claimed in claim 2/carbon elctro-catalyst, it is characterised in that：The nitride of transition metal
Content be 80~90wt%；The content of copper nitride is 20~67.5wt%；The content of carbon material or nitrating carbon material is 10
~20wt%.
4. a kind of preparation method of claims 1 to 3 any one of them transition metal nitride/carbon elctro-catalyst, feature
It is：Include the following steps：
Step (1)：The preparation of elctro-catalyst presoma：
Hydro-thermal reaction will be carried out comprising the solution A of substrate, copper source, organic ligand, has machine frame in the metal that substrate surface deposits copper
Frame compound obtains the elctro-catalyst presoma；
Step (2)：Ammonification is calcined
The elctro-catalyst presoma that step (1) obtains is calcined under containing ammonia atmosphere, the obtained transition metal nitride/
Carbon elctro-catalyst.
5. the preparation method of transition metal nitride as claimed in claim 4/carbon elctro-catalyst, it is characterised in that：Described
Organic ligand is terephthalic acid (TPA), 2- amino terephthalic acid (TPA)s, 2-methylimidazole, Isosorbide-5-Nitrae how dioctyl phthalate, in benzenetricarboxylic acid extremely
Few one kind；
Copper source and the molar ratio of organic ligand are 2：1~1：5；
In solution A, the molar concentration of organic ligand is 0.01~2M；
Preferably, the substrate is one kind in nickel foam, foam copper, carbon paper, stainless steel substrates.
6. the preparation method of transition metal nitride/carbon elctro-catalyst as described in claim 4 or 5, it is characterised in that：Step
(1) in, substrate is pre-processed before carrying out the hydro-thermal reaction, and transition metal hydroxide is deposited in its surface in situ
Precipitation；
It is in the step of its surface in situ deposition transition metal hydroxide precipitation：To include transition metal source, substrate and precipitation
The solution B of agent carries out hydro-thermal reaction.
7. the preparation method of transition metal nitride as claimed in claim 6/carbon elctro-catalyst, it is characterised in that：Described
Transition metal source is the compound for including at least one of iron, cobalt, nickel transition elements；The preferably water soluble salt of iron, cobalt
At least one of the water soluble salt of water soluble salt, nickel；It is still more preferably cobalt nitrate, chlorination for the transition metal source
At least one of cobalt, cobalt acetate；
The precipitating reagent is one kind in urea, ammonium fluoride, urotropine.
8. the preparation method of transition metal nitride as claimed in claim 7/carbon elctro-catalyst, it is characterised in that：Solution B
In, the molar concentration of transition metal source is 0.001-0.2M；The molar concentration of precipitating reagent is 0.03-2M；
Transition metal source, precipitating reagent molar ratio are 1：1~1：40；
The molar ratio of copper source and transition metal source is 10：1~1：3.
9. the preparation method of transition metal nitride as claimed in claim 5/carbon elctro-catalyst, it is characterised in that：Hydro-thermal is anti-
The temperature answered is 100-160 DEG C；
The temperature of calcining is 300~600 DEG C；Calcination time is preferably 1~3h.
10. a kind of Claims 1 to 4 any one of them transition metal nitride/carbon elctro-catalyst or claim 5~9 times
The application of transition metal nitride made from one preparation method/carbon elctro-catalyst, it is characterised in that：As catalyst, urge
Change OER and/or HER reactions；
It is preferred for being catalyzed alkaline aqueous solution electrolytic hydrogen production and/or produces oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477132.1A CN108671953B (en) | 2018-05-17 | 2018-05-17 | Transition metal nitride/carbon electrocatalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477132.1A CN108671953B (en) | 2018-05-17 | 2018-05-17 | Transition metal nitride/carbon electrocatalyst and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108671953A true CN108671953A (en) | 2018-10-19 |
| CN108671953B CN108671953B (en) | 2019-12-24 |
Family
ID=63806799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810477132.1A Active CN108671953B (en) | 2018-05-17 | 2018-05-17 | Transition metal nitride/carbon electrocatalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108671953B (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772408A (en) * | 2019-02-01 | 2019-05-21 | 浙江大学 | A kind of carbon elctro-catalyst and its preparation method and application that nickel-is nitrogen co-doped |
| CN109926083A (en) * | 2019-03-25 | 2019-06-25 | 湖北大学 | A kind of bimetallic Fe-Co nitride elctro-catalyst and the preparation method and application thereof |
| CN110508314A (en) * | 2019-09-06 | 2019-11-29 | 温州涂屋信息科技有限公司 | A kind of Co2N-Ni3N loads graphene oxide-carbon cloth and analyses its preparation method of oxygen material |
| CN110635141A (en) * | 2019-09-11 | 2019-12-31 | 华南理工大学 | Non-noble metal hydrazine oxidation catalyst based on synergistic modification and preparation method thereof |
| CN110655654A (en) * | 2019-09-18 | 2020-01-07 | 常州大学 | Preparation of two-dimensional layered cobalt-based metal organic framework (Co-MOF) electrode material and research on oxygen evolution performance |
| CN110721728A (en) * | 2019-11-12 | 2020-01-24 | 南京工程学院 | Supported bifunctional catalytic composite material and preparation method thereof |
| CN110787806A (en) * | 2019-08-28 | 2020-02-14 | 浙江工业大学 | Preparation method of full-hydrolysis catalyst with heterojunction structure |
| CN111203254A (en) * | 2020-01-13 | 2020-05-29 | 陕西科技大学 | Co-N high-activity species modified vanadium sulfide hydrogen-producing electrocatalyst and preparation method and application thereof |
| CN111206271A (en) * | 2020-02-14 | 2020-05-29 | 山西大学 | Preparation method, product and application of self-supporting metal doped iron nitride electrode |
| CN111229227A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Cobalt catalyst and preparation and application thereof |
| CN111822024A (en) * | 2019-04-18 | 2020-10-27 | 湖北大学 | Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof |
| CN113173574A (en) * | 2021-04-25 | 2021-07-27 | 哈尔滨工业大学（威海） | Two-dimensional carbon material loaded with transition metal oxide or sulfide, and method and application thereof |
| CN113307246A (en) * | 2021-06-10 | 2021-08-27 | 浙江大学 | Carbon-loaded transition metal/transition metal nitride composite material and preparation method thereof |
| CN113659153A (en) * | 2021-07-13 | 2021-11-16 | 江苏大学 | Preparation method of bifunctional transition metal nitride heterojunction electrocatalyst for oxygen reduction/oxygen precipitation reaction |
| CN113842940A (en) * | 2021-09-27 | 2021-12-28 | 太原理工大学 | Catalyst for preparing methanol by low-temperature conversion of low-concentration coal bed gas and method for preparing methanol |
| CN113981469A (en) * | 2021-11-04 | 2022-01-28 | 武汉工程大学 | Organic ligand modified transition metal layered hydroxide electrocatalytic material and preparation method and application thereof |
| CN114392757A (en) * | 2022-01-21 | 2022-04-26 | 海南大学 | Preparation method and application of transition metal compound catalyst |
| CN114672822A (en) * | 2022-04-11 | 2022-06-28 | 华南理工大学 | Anti-perovskite phase nitride three-dimensional self-supporting electrode material for preparing ammonia by nitrate reduction and preparation method and application thereof |
| CN115990493A (en) * | 2022-12-28 | 2023-04-21 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
| CN116334663A (en) * | 2023-05-29 | 2023-06-27 | 中石油深圳新能源研究院有限公司 | Method and device for preparing amorphous transition metal nitride electrocatalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006134602A (en) * | 2004-11-02 | 2006-05-25 | Bridgestone Corp | Catalyst structure and film-electrode junction for solid polymer fuel cell using the same |
| CN101427406A (en) * | 2006-02-17 | 2009-05-06 | 孟山都技术公司 | Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts |
| CN105552393A (en) * | 2016-01-22 | 2016-05-04 | 中南大学 | Bi-functional catalyst for alkaline water system metal/air battery and preparation method thereof |
-
2018
- 2018-05-17 CN CN201810477132.1A patent/CN108671953B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006134602A (en) * | 2004-11-02 | 2006-05-25 | Bridgestone Corp | Catalyst structure and film-electrode junction for solid polymer fuel cell using the same |
| CN101427406A (en) * | 2006-02-17 | 2009-05-06 | 孟山都技术公司 | Transition metal-containing catalysts and processes for their preparation and use as fuel cell catalysts |
| CN105552393A (en) * | 2016-01-22 | 2016-05-04 | 中南大学 | Bi-functional catalyst for alkaline water system metal/air battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| C.-Y.SU等: "Carbon nanotube-supported Cu3N nanocrystals as a highly active catalyst for oxygen reduction reaction", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 肖剑荣等: "氮化铜薄膜的研究", 《材料导报：综述篇》 * |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229227A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Cobalt catalyst and preparation and application thereof |
| CN109772408A (en) * | 2019-02-01 | 2019-05-21 | 浙江大学 | A kind of carbon elctro-catalyst and its preparation method and application that nickel-is nitrogen co-doped |
| CN109926083B (en) * | 2019-03-25 | 2022-02-08 | 湖北大学 | Bimetallic Fe-Co nitride electrocatalyst and preparation method and application thereof |
| CN109926083A (en) * | 2019-03-25 | 2019-06-25 | 湖北大学 | A kind of bimetallic Fe-Co nitride elctro-catalyst and the preparation method and application thereof |
| CN111822024A (en) * | 2019-04-18 | 2020-10-27 | 湖北大学 | Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof |
| CN111822024B (en) * | 2019-04-18 | 2023-04-18 | 湖北大学 | Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof |
| CN110787806A (en) * | 2019-08-28 | 2020-02-14 | 浙江工业大学 | Preparation method of full-hydrolysis catalyst with heterojunction structure |
| CN110787806B (en) * | 2019-08-28 | 2022-10-28 | 浙江工业大学 | Preparation method of full-hydrolysis catalyst with heterojunction structure |
| CN110508314A (en) * | 2019-09-06 | 2019-11-29 | 温州涂屋信息科技有限公司 | A kind of Co2N-Ni3N loads graphene oxide-carbon cloth and analyses its preparation method of oxygen material |
| CN110635141A (en) * | 2019-09-11 | 2019-12-31 | 华南理工大学 | Non-noble metal hydrazine oxidation catalyst based on synergistic modification and preparation method thereof |
| CN110655654A (en) * | 2019-09-18 | 2020-01-07 | 常州大学 | Preparation of two-dimensional layered cobalt-based metal organic framework (Co-MOF) electrode material and research on oxygen evolution performance |
| CN110721728A (en) * | 2019-11-12 | 2020-01-24 | 南京工程学院 | Supported bifunctional catalytic composite material and preparation method thereof |
| CN110721728B (en) * | 2019-11-12 | 2022-03-25 | 南京工程学院 | Supported bifunctional catalytic composite material and preparation method thereof |
| CN111203254B (en) * | 2020-01-13 | 2023-01-31 | 陕西科技大学 | Co-N high-activity species modified vanadium sulfide hydrogen-producing electrocatalyst and preparation method and application thereof |
| CN111203254A (en) * | 2020-01-13 | 2020-05-29 | 陕西科技大学 | Co-N high-activity species modified vanadium sulfide hydrogen-producing electrocatalyst and preparation method and application thereof |
| CN111206271A (en) * | 2020-02-14 | 2020-05-29 | 山西大学 | Preparation method, product and application of self-supporting metal doped iron nitride electrode |
| CN113173574A (en) * | 2021-04-25 | 2021-07-27 | 哈尔滨工业大学（威海） | Two-dimensional carbon material loaded with transition metal oxide or sulfide, and method and application thereof |
| CN113307246A (en) * | 2021-06-10 | 2021-08-27 | 浙江大学 | Carbon-loaded transition metal/transition metal nitride composite material and preparation method thereof |
| CN113659153A (en) * | 2021-07-13 | 2021-11-16 | 江苏大学 | Preparation method of bifunctional transition metal nitride heterojunction electrocatalyst for oxygen reduction/oxygen precipitation reaction |
| CN113659153B (en) * | 2021-07-13 | 2023-07-18 | 江苏大学 | Preparation method of oxygen reduction/oxygen precipitation reaction difunctional transition metal nitride heterojunction electrocatalyst |
| CN113842940A (en) * | 2021-09-27 | 2021-12-28 | 太原理工大学 | Catalyst for preparing methanol by low-temperature conversion of low-concentration coal bed gas and method for preparing methanol |
| CN113981469A (en) * | 2021-11-04 | 2022-01-28 | 武汉工程大学 | Organic ligand modified transition metal layered hydroxide electrocatalytic material and preparation method and application thereof |
| CN114392757A (en) * | 2022-01-21 | 2022-04-26 | 海南大学 | Preparation method and application of transition metal compound catalyst |
| CN114672822A (en) * | 2022-04-11 | 2022-06-28 | 华南理工大学 | Anti-perovskite phase nitride three-dimensional self-supporting electrode material for preparing ammonia by nitrate reduction and preparation method and application thereof |
| CN114672822B (en) * | 2022-04-11 | 2023-05-23 | 华南理工大学 | Anti-perovskite-phase nitride three-dimensional self-supporting electrode material for preparing ammonia by nitrate reduction, and preparation method and application thereof |
| CN115990493A (en) * | 2022-12-28 | 2023-04-21 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
| CN115990493B (en) * | 2022-12-28 | 2024-06-07 | 电子科技大学 | Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial |
| CN116334663A (en) * | 2023-05-29 | 2023-06-27 | 中石油深圳新能源研究院有限公司 | Method and device for preparing amorphous transition metal nitride electrocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108671953B (en) | 2019-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108671953A (en) | A kind of transition metal nitride/carbon elctro-catalyst and its preparation and application | |
| Zhang et al. | Recent advances in cobalt-based electrocatalysts for hydrogen and oxygen evolution reactions | |
| Wang et al. | Efficient oxygen evolution reaction from iron-molybdenum nitride/molybdenum oxide heterostructured composites | |
| CN107376958B (en) | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof | |
| Fang et al. | Nickel promoted cobalt disulfide nanowire array supported on carbon cloth: an efficient and stable bifunctional electrocatalyst for full water splitting | |
| Rinawati et al. | Designing a spontaneously deriving NiFe-LDH from bimetallic MOF-74 as an electrocatalyst for oxygen evolution reaction in alkaline solution | |
| Cheng et al. | Facile synthesis of porous (Co, Mn) 3 O 4 nanowires free-standing on a Ni foam and their catalytic performance for H 2 O 2 electroreduction | |
| CN111659401B (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| CN104549242B (en) | Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst | |
| CN110743603B (en) | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof | |
| CN112774704A (en) | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof | |
| CN106111171A (en) | A kind of preparation method of the phosphatization cobalt of carbon-coating parcel | |
| CN108923051A (en) | A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application | |
| Wang et al. | Efficient electrocatalytic conversion of N 2 to NH 3 on NiWO 4 under ambient conditions | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| CN108067248A (en) | The PtNi alloy catalysts of three-dimensional manometer stick structure and its preparation and application | |
| CN110280271B (en) | Preparation method of OER composite electrocatalyst | |
| CN110075853A (en) | Water CoZn-LDHs-ZIF@C sandwich and preparation method, application are decomposed in a kind of electro-catalysis entirely | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN113105645B (en) | Preparation method, product and application of nickel-based metal organic framework compound | |
| Yu et al. | Bimetallic sulfide particles incorporated in Fe/Co-based metal–organic framework ultrathin nanosheets toward boosted electrocatalysis of the oxygen evolution reaction | |
| CN113463128B (en) | Water splitting catalyst and its prepn and application | |
| CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
| Ghosh et al. | Bifunctional catalytic activity of solvothermally synthesized CeO2 nanosphere/NiO nanoflake nanocomposites | |
| Chebrolu et al. | Overview of emerging catalytic materials for electrochemical green ammonia synthesis and process |
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 |