CN106732613A - A kind of preparation method of novel nano carbon material and its electro-catalysis hydrogen manufacturing application - Google Patents
A kind of preparation method of novel nano carbon material and its electro-catalysis hydrogen manufacturing application Download PDFInfo
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- CN106732613A CN106732613A CN201710018538.9A CN201710018538A CN106732613A CN 106732613 A CN106732613 A CN 106732613A CN 201710018538 A CN201710018538 A CN 201710018538A CN 106732613 A CN106732613 A CN 106732613A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 62
- 239000001257 hydrogen Substances 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 230000004044 response Effects 0.000 claims abstract description 13
- 238000004502 linear sweep voltammetry Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 64
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052697 platinum Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052753 mercury Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229940078494 nickel acetate Drugs 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229940075397 calomel Drugs 0.000 claims description 6
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 claims description 6
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- VWFLTHZUCYHIEC-UHFFFAOYSA-N cobalt sulfamic acid Chemical compound [Co].S(N)(O)(=O)=O VWFLTHZUCYHIEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 claims description 2
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 2
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 239000013176 zeolitic imidazolate framework-12 Substances 0.000 claims description 2
- 239000013159 zeolitic imidazolate framework-69 Substances 0.000 claims description 2
- 239000013173 zeolitic imidazolate framework-9 Substances 0.000 claims description 2
- 239000013166 zeolitic imidazolate framework-65 Substances 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical class [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000013249 bimetallic zeolitic imidazolate framework Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction 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
- 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
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
Preparation method and its electro-catalysis hydrogen manufacturing application the present invention relates to a kind of novel nano carbon material.Including following preparation method：（1）, at a certain temperature, in monometallic ZIFs skeleton structures introduce second or various metals synthesis bimetallic or various metals base ZIFs materials；（2）, under higher than the ZIFs material organic ligand decomposition temperatures material is carried out being carbonized under an inert atmosphere obtaining the carbon material；（3）, carbon material modified in electrode surface, carry out linear sweep voltammetry response in certain PH and certain density electrolyte solution；（4）, in certain PH and certain density electrolyte solution carry out AC impedance；（5）, be circulated in alkaline solution volt-ampere response linear scanning volt-ampere response again；Beneficial effect is：Metal salt starting materials wide ranges, it is cost-effective, prepared beneficial to industrial production；The method is in terms of the nano-carbon material for preparing, the application of extension ZIFs materials and electro-catalysis field have great importance and be widely applied prospect.
Description
Technical field
The present invention relates to the preparation and application of a kind of carbon nanomaterial, more particularly to a kind of preparation of novel nano carbon material
Method and its electro-catalysis hydrogen manufacturing application.
Background technology
Since 20th century global human social development speed is surprising, as population increases and people's living standard is carried
Height, the mankind also constantly increase the demand of the energy.People result in the heavy dependence of traditional non-renewable fossil energy
The serious problem of environmental pollution that current social development is faced, therefore the various cleanings of research and probe, regenerative resource is increasingly
Paid much attention to by countries in the world.Hydrogen Energy as secondary energy sources not only have cleanliness without any pollution, efficiently, can store, good luck is defeated,
Beyond the advantages of aboundresources, and combustion product only has water, does not pollute the environment, and all will using safety, thus countries in the world
Hydrogen is studied as following optimal energy carrier.Current mature hydrogen production process has fossil fuel hydrogen manufacturing, electrolysis
Water hydrogen manufacturing, biological hydrogen production, solar hydrogen making etc..Wherein water electrolysis hydrogen production technology is turned using the electric energy produced by regenerative resource
It is changed into the most promising technology of Hydrogen Energy, high with product purity, electrolytic efficiency is high, the advantages of pollution-free.Make in production at present
Electrode is mainly platinum carbon class material, but because platinum is a kind of less noble metal of abundance ratio, cause it is expensive and
It is rare, it is difficult to realize industrialization.Therefore developing low-cost, free of contamination new electro-catalysis hydrogen manufacturing material is extremely urgent.Carbon bag
The one kind of bimetallic or polymetallic carbon material as metal carbon material is covered, electricity can be played in the electrolyte solution of different PH
The effective catalyst effect of Xie Shui, based on the relevant report of polymetallic carbon material electrolytic hydrogen production catalyst, many Metal Substrate carbon materials
The factors such as size, pattern, the specific surface of material can influence its catalytic performance.Therefore by appropriate synthetic method, obtain not
With the carbon coating bimetallic or polymetallic nano-carbon material of pattern, carbon coating bimetallic or polymetallic carbon material can be improved
Electro-catalysis hydrogen manufacturing performance.
The preparation method prepared at present about hydrogen manufacturing alloy catalyst has following several, such as electrodeposition process（H.A.
Sang, H.Y. Park, I. Choi. Int. J. Hydrogen. Energy., 2013, 38(31), 13493-
13501.）, thermal decomposition method（L.P.R. Profeti, D. Profeti, P. Olivi. Int. J. Hydrogen.
Energy., 2009, 349(6), 2747-2757.）, electroless plating method（F.J. Pérez-Alonso, C. Adán, S.
Rojas. Int. J. Hydrogen. Energy., 2015, 40(1), 51-61.）With Mechanical Method alloy（J.Y. Huot,
M.L. Trudeau, R. Schulz. J. Electrochem. Soc., 1991, 138(5), 1316-1321.）.Zeolite
Imidazole skeleton structural material（ZIFs）As the branch of MOFs, matched somebody with somebody by tetrahedron central ion and organic glyoxaline ligand bridging
The nitrogen heterocyclic ring metal-organic framework materials that position is formed（MOFs）.ZIFs materials are except the stable hole knot with routine MOFs materials
Structure, homogeneous pore size distribution, outside larger specific surface area characteristic, due to the strong interaction between imidazoles chain and metal ion, should
Class material also has heat endurance and chemical stability higher, as in gas storage and separation, chemical sensitisation, catalysis and film
Preferred material in terms of the researchs such as separation, and show good application prospect.Therefore using the porous of ZIFs materials, big
The features such as specific surface area, controllable skeleton structure and high density and scattered metal position, with reference to metal position is carried out proportioning and
The method of species regulation and control, second or various metals for adulterating appropriate in original monometallic skeleton structure, synthesis keeps former
The bimetallic or many Metal Substrate ZIFs materials of the monometallic ZIFs structures come；Make it using bimetallic or many Metal Substrate ZIFs as preceding
Drive body and prepare bimetallic or many metal carbon materials with high surface and loose structure as a kind of effectively preparation method.
The content of the invention
A kind of drawbacks described above that the purpose of the present invention exists aiming at prior art, there is provided system of novel nano carbon material
Preparation Method and its electro-catalysis hydrogen manufacturing application, be by with the zeolite imidazole skeleton structural material containing two kinds of metals or various metals
Presoma, is carbonized to bimetallic or many Metal Substrate ZIFs materials at a certain temperature, controllable synthesis different-shape, size
Carbon coating bimetallic or polymetallic carbon material, and be applied to electrolytic hydrogen production reaction, the material shows catalysis high and lives
Property, high stability has very big application potential in electro-catalysis field.
A kind of preparation method of novel nano carbon material that the present invention is mentioned, including following preparation method：
（1）, at a certain temperature, in monometallic ZIFs skeleton structures introduce second or various metals synthesis bimetallic or many
Plant Metal Substrate ZIFs materials；
（2）, material carried out being carbonized under an inert atmosphere under higher than the ZIFs material organic ligand decomposition temperatures obtains described
The carbon coating bimetallic or polymetallic carbon material of nano-scale；
The specified temp be selected from it is following any one：Room temperature, frozen water mixing bath（4℃）, use liquid nitrogen snap frozen；
The monometallic ZIFs materials be selected from it is following any one：ZIF-9（Co(bIm)2）, ZIF-12（Co(bIm)2）, ZIF-
65（Co(nIm)2）, ZIF-67（Co(mIm)2）, ZIF-69（Zn(nIm)2）, ZIF-90（Zn(Ica)2）, ZIF-90（Zn
(cBIm)2）, HKUST-1（Cu(BTC)2）；Second or various metals be selected from it is following any one or more：Nickel acetate, sulfuric acid
Nickel, nickel sulfamic acid, nickel borate, sulfamic acid cobalt, copper carbonate, ammonium molybdate, iron chloride.
Preferably, to the decomposition temperature scope of bimetallic or many Metal Substrate ZIFs materials between 600-900 DEG C.
Preferably, the inert atmosphere is selected from following any one gas：Argon gas, nitrogen, neon, helium, Krypton.
A kind of preparation method of novel nano carbon material that the present invention is mentioned, including preparation method in detail below：
（a）Zeolite imidazole skeleton structural material NixCo1-xThe synthetic method of-ZIFs is as follows：Under frozen water mixing bath, by 1.3686
Part 2-methylimidazole and 1.6868 parts of triethylamines are dissolved in 15 portions of frozen water mixed liquors, and 0.4152 part of cobalt acetate and nickel acetate are molten
In 15ml frozen water mixed liquors, two solution are stirred into 30 min on the magnetic stirring apparatus of 800 r/min respectively, it is then molten by two
Liquid mixes 10 min, and gained precipitation is washed with water and is centrifuged, reject supernatant；Repeated washing centrifugally operated 5 times, 60 DEG C
Dry 10 h；Wherein the addition of cobalt acetate and nickel acetate is taken by the mol ratio of raw material metal, and the nano-carbon material for obtaining is produced
Product are named as NixCo1-x- ZIFs, wherein x refer to the mole of Ni, and 1-x refers to the mole of Co；
（b）The synthetic method of the bimetallic carbon material of nano-carbon coated：The Ni that will be obtainedxCo1-x- ZIFs inserts clean quartz
In boat, by quartz boat square in tube furnace, argon gas 20min is passed through to drive the air in tube furnace and ensures to be argon gas atmosphere,
Carbonization heating is carried out by temperature programming, 4 DEG C/min of programming rate is set from room temperature to 800 DEG C, reach target temperature
When stop heating up keep temperature 4h after naturally cool to room temperature, the black sample for obtaining is named as NixCo1-x@N-Cs800。
A kind of electro-catalysis hydrogen manufacturing application of novel nano carbon material that the present invention is mentioned, comprises the following steps：By by newly
Type nano-carbon material is modified in working electrode surface, and linear volt-ampere response, the LSV obtained by observation are tested in certain PH solution
The height of the potential corresponding to curve corner judges the power of electro-catalysis hydrogen manufacturing performance；
The working electrode is graphite electrode, carbon paste electrode, Ti electrode, glass-carbon electrode, gold electrode, zinc electrode or platinum electrode；Institute
Comparison electrode is stated for platinum electrode, platinum post electrode, gauze platinum electrode, platinum plate electrode or coated graphite rod electrrode；The reference electrode is full
With calomel electrode, silver silver chloride electrode, Mercurous sulfate electrode or mercury oxidation mercury electrode；
The solution of certain PH is the KOH of PH=0 ~ 14, NaOH or aqueous sulfuric acid；
The concentration of the novel nano carbon material of described modified electrode is the nafion- ethanol solutions of 4.5 ~ 6 mg/ml
（Vnafion/VEthanol=1:1）, modification liquor capacity is 5 ~ 10 μ L；
The scanning voltage scope of the electrochemistry linear volt-ampere response is 0 ~ -1.6 V；The sweep speed is 5 mV/s, 10
MV/s, 20 mV/s.
Preferably, comprise the following steps：Modified in working electrode surface by by novel nano carbon material, in certain PH and
In certain density electrolyte solution AC impedance is tested under a certain constant potential；
The working electrode is graphite electrode, carbon paste electrode, Ti electrode, glass-carbon electrode, gold electrode, zinc electrode or platinum electrode；Institute
Comparison electrode is stated for platinum electrode, platinum post electrode, gauze platinum electrode, platinum plate electrode or coated graphite rod electrrode；The reference electrode is full
With calomel electrode, silver silver chloride electrode, Mercurous sulfate electrode or mercury oxidation mercury electrode；
The solution of certain PH is the KOH of PH=0 ~ 14, NaOH or aqueous sulfuric acid
The certain density solution is the KOH of 0.1 ~ 3 M, NaOH, aqueous sulfuric acid or PBS；
The constant voltage scope of the electrochemical AC impedance response is between -0.02 ~ -0.2 V.
The electro-catalysis hydrogen manufacturing application of the novel nano carbon material that the present invention is mentioned, comprises the following steps：By by carbon coating
Bimetallic or polymetallic carbon material are modified in working electrode surface, one in certain PH and certain density electrolyte solution
Determine test loop volt-ampere test between current potential；
The working electrode is graphite electrode, carbon paste electrode, Ti electrode, glass-carbon electrode, gold electrode, zinc electrode or platinum electrode；Institute
Comparison electrode is stated for platinum electrode, platinum post electrode, gauze platinum electrode, platinum plate electrode or coated graphite rod electrrode；The reference electrode is full
With calomel electrode, silver silver chloride electrode, Mercurous sulfate electrode or mercury oxidation mercury electrode；
The solution of certain PH is the KOH of PH=0 ~ 14, NaOH or aqueous sulfuric acid
The certain density solution is the KOH of 0.1 ~ 3 M, NaOH, aqueous sulfuric acid or PBS；
The stability of the modified electrode is surveyed and uses cyclic voltammetry, and scanning voltage scope is between -0.2 ~ 0.2 V；It is described
The scanning number of turns is 500 ~ 10000；The scanning voltage scope of linear volt-ampere response is 0 ~ -1.6 V；The sweep speed is 5
MV/s, 10 mV/s, 20 mV/s.
A kind of electro-catalysis hydrogen manufacturing application of novel nano carbon material that the present invention is mentioned, including step in detail below：
It is working electrode to use glass-carbon electrode, and carbon-point is to electrode, saturated calomel electrode reference electrode；With W0.5 gold on polishing cloth
Hard rock abrasive pastes polish glass-carbon electrode, ethanol and deionized water 5 min of ultrasound are then used respectively, in air drying；Then claim
Take 45 mg samples and 80 μ L nafion solution, 5 wt%, by its ultrasonic disperse in 1 mL ethanol solutions, ultrasonically treated 40
Min, makes sample form uniform slurries；Take 10 μ L slurries uniformly to drop in GCE surfaces and be dried at room temperature for, obtain modification electricity
Pole；Unmodified and modification electrode is respectively placed in the 0.1 M KOH aqueous solution, linear sweep voltammetry response, scanning speed is carried out
It is 10 mV/s to spend, the V of scanning voltage 0 ~ -1.6.
The beneficial effects of the invention are as follows：1st, the material needed for synthesizing is cheap and easy to get, green, pollution-free；2nd, method is easy,
Reaction speed is fast, saves the time；3rd, yield is high, metal salt starting materials wide ranges used, cost-effective, prepare 4 beneficial to industrial production,
Size, morphology controllable synthesis to carbon coating bimetallic or polymetallic nano-carbon material, is conducive to carbon coating bimetallic or many
The nano-carbon material of metal is more effectively applied in terms of electro-catalysis.The method is preparing various carbon coating bimetallics or many metals
Nano-carbon material aspect, extension ZIFs materials application aspect and electro-catalysis field have great importance and widely should
Use prospect.
Brief description of the drawings
Fig. 1 is Ni prepared by the present inventionxCo1-xFirst width SEM schematic diagram of-ZIFs nano materials；
Fig. 2 is Ni prepared by the present inventionxCo1-xSecond width SEM schematic diagram of-ZIFs nano materials；
Fig. 3 is Ni prepared by the present inventionxCo1-xFirst width X-ray diffracting spectrum of the powder of@N-Cs nano materials；
Fig. 4 is Ni prepared by the present inventionxCo1-xSecond width X-ray diffracting spectrum of the powder of@N-Cs nano materials；
Fig. 5 is Ni prepared by the present inventionxCo1-xFirst width powder infrared chromatography of@N-Cs nano materials；
Fig. 6 is Ni prepared by the present inventionxCo1-xSecond width powder infrared chromatography of@N-Cs nano materials；
Fig. 7 is Ni prepared by the present inventionxCo1-xFirst width powder projection electron microscope photo figure of@N-Cs nano materials；
Fig. 8 is Ni prepared by the present inventionxCo1-xSecond width powder projection electron microscope photo figure of@N-Cs nano materials；
Fig. 9 is that monometallic carbon material, bimetallic carbon material, Pt-C modified electrodes and the unmodified electrode of carbon coating of the invention exist
Linear volt-ampere LSV curve synoptic diagrams are tested in alkaline solution；
Figure 10 is that carbon material modified electrode of the invention encloses cyclic voltammetry later in alkaline solution in scanning 500 ~ 2000
In test the linear volt-ampere LSV curve synoptic diagrams for obtaining；
Figure 11 is that monometallic carbon material modified electrode of the invention encloses cyclic voltammetry later in alkali in scanning 500 ~ 2000
The linear volt-ampere LSV curve synoptic diagrams for obtaining are tested in property solution.
Specific embodiment
Technical characterstic of the invention is illustrated with reference to specific experiment scheme and accompanying drawing, but the invention is not limited in this.
Test method described in example below, unless otherwise specified, is conventional method；The instrument and material, unless otherwise specified,
Commercially obtain.
The preparation method of the novel nano carbon material that the present invention is mentioned, comprises the following steps：
A, zeolite imidazole skeleton structural material NixCo1-xThe synthetic method of-ZIFs is as follows：Under frozen water mixing bath, by 1.3686 g
2-methylimidazole and 1.6868 g triethylamines are dissolved in 15 ml frozen water mixed liquors, and 0.4152 g cobalt acetates and nickel acetate are dissolved in
In 15ml frozen water mixed liquors, two solution are stirred into 30 min on the magnetic stirring apparatus of 800 r/min respectively, then by two solution
10 min are mixed, gained precipitation is washed with water and is centrifuged, reject supernatant.Repeated washing centrifugally operated 5 times, 60 DEG C of bakings
Dry 10 h.Wherein the addition of cobalt acetate and nickel acetate is taken by the mol ratio of raw material metal, and the product for obtaining is named as
NixCo1-x-ZIFs（X refers to the mole of Ni, and 1-x refers to the mole of Co）.SEM signs are carried out to sample, as illustrated, can see
It is the subsphaeroidal particle of the nm of average grain diameter 135 or so to go out synthesized Ni-Co-ZIFs materials.
, nano-carbon coated bimetallic carbon material synthetic method：The Ni that will be obtainedxCo1-x- ZIFs inserts clean stone
Ying Zhouli, by quartz boat square in tube furnace, is passed through argon gas 20min and is ensured as argon gas gas with driveing the air in tube furnace
Atmosphere, carbonization heating is carried out by temperature programming, sets 4 DEG C/min of programming rate from room temperature to 800 DEG C, reaches target temperature
Stop naturally cooling to room temperature after intensification keeps the temperature 4h when spending, the black sample for obtaining is named as NixCo1-x@N-Cs800。
XRD signs are carried out to sample, as shown in the figure, it can be seen that resulting product and Co C standard x RD spectrograms（R. Qiang, Y.
Du, D. Chen, J. Alloy Compd., 2016, 681, 384-393）With Ni@C standard x RD spectrograms（Wang J.,
Gao D., Wang G., J. Mater. Chem. A., 2014, 2(47), 20067-20074）It coincide, shows second
Metal is successfully entered in the lattice of organic framework material material, and shows the structure of high-crystallinity and similar pure sample product.Take
Sample segment, infared spectrum analysis (FT-IR) is carried out to it, it can be seen that all samples are in 1056 cm after high-temperature calcination-1At wavelength
The C-N stretching vibration peaks for belonging to ZIF parts disappear, and show that monometallic/bimetallic ZIF skeleton structures are caved in.And it was observed that belong to
The broad absorption band characteristic peak of carbon.This result and the document reported（M. Sevilla, P. Valle-Vigón, A.B.
Fuertes, J. Adv. Funct. Mater., 2011, 21(14), 2781-2787）Match.Sample segment is taken, it is right
It carries out TEM signs, it can be seen that the bimetallic carbon material of gained carbon coating is the particle of average grain diameter 5-15 nm or so, and protects
Ni is heldxCo1-xThe subsphaeroidal pattern of-ZIFs materials, and significantly find out the carbon-coating for being enclosed in surface of metal particles.
A kind of electro-catalysis hydrogen manufacturing application of novel nano carbon material that the present invention is mentioned, including step in detail below：
Electro-catalysis hydrogen-making reaction procedure：It is working electrode to use glass-carbon electrode, and carbon-point is to electrode, saturated calomel electrode reference electricity
Pole.Glass-carbon electrode is polished with W0.5 diamond pastes on polishing cloth, ethanol and deionized water ultrasound 5 are then used respectively
Min, in air drying.Then 45 mg samples and 80 μ L nafion solution (5 wt%) are weighed, by its ultrasonic disperse in 1
In mL ethanol solutions, ultrasonically treated 40 min makes sample form uniform slurries.Take 10 μ L slurries and uniformly drop in GCE surfaces simultaneously
It is dried at room temperature for, obtains modified electrode.Unmodified and modification electrode is respectively placed in the 0.1 M KOH aqueous solution, is carried out
Linear sweep voltammetry is responded, and sweep speed is 10 mV/s, the V of scanning voltage 0 ~ -1.6.Can from the polarization curve for obtaining
Go out, bare glassy carbon electrode does not have significant change, show that bare glassy carbon electrode does not have catalysis activity.And other the three electrode performances of modification
Go out relatively good electro-catalysis hydrogen manufacturing effect.Pt-C, Ni0.4Co0.6@N-Cs800With Co@N-Cs800The glass-carbon electrode of modification is in electric current
Density is 10 mA cm-2When corresponding voltage be respectively 40,68,95 mV (vs RHE).The electrode of noble metal platinum carbon modification is still
So there is highest electro catalytic activity.And then the glass-carbon electrode of the bimetallic carbon material modification of carbon coating shows to compare monometallic
Carbon material electro-catalysis hydrogen production activity higher.After forming alloy due to nickel cobalt, cobalt atom surface d electronics more than needed is former with reactive hydrogen
Bonding power reduction between son, and monometallic weakens the bond energy between metallic atom M-H, and then effectively improve reactive hydrogen
Desorption ability, improves producing hydrogen, catalyzing performance.Therefore, the bimetallic carbon material of the carbon coating can be as the electricity for preparing new energy
Solution water catalyst for preparing hydrogen.
The present invention carries out stability test process to the glass-carbon electrode of the mono-/bis-metal carbon material modification of carbon coating：Sweeping
Voltage -0.1 ~ 0.2 V is retouched, under the operating condition of the mV/s of sweep speed 50, the glass carbon of the bimetallic carbon material modification of carbon coating
Electrode is circulated volt-ampere test in the 1 M KOH aqueous solution, and the scanning number of turns is 500 ~ 2000.Often scan through the circulation of 500 circles
Once linear volt-ampere test is surveyed after volt-ampere test, and obtains the LSV curves after long-time electrolytic etching.Be can be seen that by comparing
The LSV curves obtained after scanning first lap and after the 2000th circle almost overlap.Do not degenerate significantly.Illustrate the list of carbon coating/
The glass-carbon electrode material of bimetallic carbon material modification shows stability higher under conditions of continuous electrolysis.
To sum up, the present invention centered on bimetallic ion ion zeolite imidazole skeleton structural material ZIFs as predecessor,
Calcined under uniform temperature and inert gas atmosphere by by it, obtained the bimetallic carbon material of carbon coating of nano-scale,
The uniformity for confirming its structure and reference material is analyzed by powder x-ray diffraction, by SEM and transmission electricity
Sub- microscope characterizes its size and pattern, and crystallinity is high.The bimetallic carbon material of the nano-carbon coated that will be obtained is modified in electricity
Pole surface, electricity is carried out in alkaline solution and urges hydrogen manufacturing performance test to show high catalytic activity and high stability, therefore this material
There is significant application value in electro-catalysis hydrogen preparation field.
The above, is only part preferred embodiment of the invention, and any those of ordinary skill in the art may profit
Equivalent technical scheme is changed or is revised as with the technical scheme of above-mentioned elaboration.Therefore, according to technology of the invention
Any simple modification or substitute equivalents that scheme is carried out, belong to the greatest extent the scope of protection of present invention.
Claims (8)
1. a kind of preparation method of novel nano carbon material, it is characterized in that including following preparation method：
（1）, at a certain temperature, in monometallic ZIFs skeleton structures introduce second or various metals synthesis bimetallic or many
Plant Metal Substrate ZIFs materials；
（2）, material carried out being carbonized under an inert atmosphere under higher than the ZIFs material organic ligand decomposition temperatures obtains described
The carbon coating bimetallic or polymetallic carbon material of nano-scale；
The specified temp be selected from it is following any one：Room temperature, frozen water mixing bath（4℃）, use liquid nitrogen snap frozen；
The monometallic ZIFs materials be selected from it is following any one：ZIF-9（Co(bIm)2）, ZIF-12（Co(bIm)2）, ZIF-65
（Co(nIm)2）, ZIF-67（Co(mIm)2）, ZIF-69（Zn(nIm)2）, ZIF-90（Zn(Ica)2）, ZIF-90（Zn
(cBIm)2）, HKUST-1（Cu(BTC)2）；Second or various metals be selected from it is following any one or more：Nickel acetate, sulfuric acid
Nickel, nickel sulfamic acid, nickel borate, sulfamic acid cobalt, copper carbonate, ammonium molybdate, iron chloride.
2. the preparation method of novel nano carbon material according to claim 1, it is characterized in that：To bimetallic or many Metal Substrates
The decomposition temperature scope of ZIFs materials is between 600-900 DEG C.
3. the preparation method of novel nano carbon material according to claim 1, it is characterized in that：The inert atmosphere is selected from down
State any one gas：Argon gas, nitrogen, neon, helium, Krypton.
4. the preparation method of novel nano carbon material according to claim 1, it is characterized in that including the side of preparation in detail below
Method：
（a）Zeolite imidazole skeleton structural material NixCo1-xThe synthetic method of-ZIFs is as follows：Under frozen water mixing bath, by 1.3686 parts
2-methylimidazole and 1.6868 parts of triethylamines are dissolved in 15 portions of frozen water mixed liquors, and 0.4152 part of cobalt acetate and nickel acetate are dissolved in
In 15ml frozen water mixed liquors, two solution are stirred into 30 min on the magnetic stirring apparatus of 800 r/min respectively, then by two solution
10 min are mixed, gained precipitation is washed with water and is centrifuged, reject supernatant；Repeated washing centrifugally operated 5 times, 60 DEG C of bakings
Dry 10 h；Wherein the addition of cobalt acetate and nickel acetate is taken by the mol ratio of raw material metal, the nano-carbon material product for obtaining
It is named as NixCo1-x- ZIFs, wherein x refer to the mole of Ni, and 1-x refers to the mole of Co；
（b）The synthetic method of the bimetallic carbon material of nano-carbon coated：The Ni that will be obtainedxCo1-x- ZIFs inserts clean quartz boat
In, by quartz boat square in tube furnace, argon gas 20min is passed through to drive the air in tube furnace and ensures to be argon gas atmosphere, lead to
Crossing temperature programming carries out carbonization heating, 4 DEG C/min of programming rate is set from room temperature to 800 DEG C, when reaching target temperature
Stop naturally cooling to room temperature after intensification keeps temperature 4h, the black sample for obtaining is named as NixCo1-x@N-Cs800。
5. the electro-catalysis hydrogen manufacturing application of a kind of novel nano carbon material as any one of claim 1-4, it is characterized in that：
Comprise the following steps：Modified in working electrode surface by by novel nano carbon material, linear volt is tested in certain PH solution
Peace response, observes the height of the potential corresponding to resulting LSV curves corner to judge the power of electro-catalysis hydrogen manufacturing performance；
The working electrode is graphite electrode, carbon paste electrode, Ti electrode, glass-carbon electrode, gold electrode, zinc electrode or platinum electrode；Institute
Comparison electrode is stated for platinum electrode, platinum post electrode, gauze platinum electrode, platinum plate electrode or coated graphite rod electrrode；The reference electrode is full
With calomel electrode, silver silver chloride electrode, Mercurous sulfate electrode or mercury oxidation mercury electrode；
The solution of certain PH is the KOH of PH=0 ~ 14, NaOH or aqueous sulfuric acid；
The concentration of the novel nano carbon material of described modified electrode is the nafion- ethanol solutions of 4.5 ~ 6 mg/ml
（Vnafion/VEthanol=1:1）, modification liquor capacity is 5 ~ 10 μ L；
The scanning voltage scope of the electrochemistry linear volt-ampere response is 0 ~ -1.6 V；The sweep speed is 5 mV/s, 10
MV/s, 20 mV/s.
6. the electro-catalysis hydrogen manufacturing application of a kind of novel nano carbon material as any one of claim 1-4, it is characterized in that：
Comprise the following steps：Modified in working electrode surface by by novel nano carbon material, in certain PH and certain density electrolysis
In liquor AC impedance is tested under a certain constant potential；
The working electrode is graphite electrode, carbon paste electrode, Ti electrode, glass-carbon electrode, gold electrode, zinc electrode or platinum electrode；Institute
Comparison electrode is stated for platinum electrode, platinum post electrode, gauze platinum electrode, platinum plate electrode or coated graphite rod electrrode；The reference electrode is full
With calomel electrode, silver silver chloride electrode, Mercurous sulfate electrode or mercury oxidation mercury electrode；
The solution of certain PH is the KOH of PH=0 ~ 14, NaOH or aqueous sulfuric acid
The certain density solution is the KOH of 0.1 ~ 3 M, NaOH, aqueous sulfuric acid or PBS；
The constant voltage scope of the electrochemical AC impedance response is between -0.02 ~ -0.2 V.
7. the electro-catalysis hydrogen manufacturing application of a kind of novel nano carbon material as any one of claim 1-4, it is characterized in that：
Comprise the following steps：Modified in working electrode surface by by carbon coating bimetallic or polymetallic carbon material, in certain PH and
The test loop volt-ampere test between certain potentials in certain density electrolyte solution；
The working electrode is graphite electrode, carbon paste electrode, Ti electrode, glass-carbon electrode, gold electrode, zinc electrode or platinum electrode；Institute
Comparison electrode is stated for platinum electrode, platinum post electrode, gauze platinum electrode, platinum plate electrode or coated graphite rod electrrode；The reference electrode is full
With calomel electrode, silver silver chloride electrode, Mercurous sulfate electrode or mercury oxidation mercury electrode；
The solution of certain PH is the KOH of PH=0 ~ 14, NaOH or aqueous sulfuric acid
The certain density solution is the KOH of 0.1 ~ 3 M, NaOH, aqueous sulfuric acid or PBS；
The stability of the modified electrode is surveyed and uses cyclic voltammetry, and scanning voltage scope is between -0.2 ~ 0.2 V；It is described
The scanning number of turns is 500 ~ 10000；The scanning voltage scope of linear volt-ampere response is 0 ~ -1.6 V；The sweep speed is 5
MV/s, 10 mV/s, 20 mV/s.
8. the electro-catalysis hydrogen manufacturing application of a kind of novel nano carbon material as any one of claim 1-4, it is characterized in that：
Including step in detail below：
It is working electrode to use glass-carbon electrode, and carbon-point is to electrode, saturated calomel electrode reference electrode；With W0.5 gold on polishing cloth
Hard rock abrasive pastes polish glass-carbon electrode, ethanol and deionized water 5 min of ultrasound are then used respectively, in air drying；Then claim
Take 45 mg samples and 80 μ L nafion solution, 5 wt%, by its ultrasonic disperse in 1 mL ethanol solutions, ultrasonically treated 40
Min, makes sample form uniform slurries；Take 10 μ L slurries uniformly to drop in GCE surfaces and be dried at room temperature for, obtain modification electricity
Pole；Unmodified and modification electrode is respectively placed in the 0.1 M KOH aqueous solution, linear sweep voltammetry response, scanning speed is carried out
It is 10 mV/s to spend, the V of scanning voltage 0 ~ -1.6.
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