CN110252348A - A kind of preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas - Google Patents
A kind of preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 24
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 50
- 238000004140 cleaning Methods 0.000 claims abstract description 23
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 19
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 19
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- -1 thio ammonium molybdate Chemical compound 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 239000006260 foam Substances 0.000 claims description 22
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000012163 sequencing technique Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 7
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 239000013598 vector Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- KXQZVEBGRVKTOK-UHFFFAOYSA-N cobalt;formamide Chemical compound [Co].NC=O KXQZVEBGRVKTOK-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- SWLTWQONANDENH-UHFFFAOYSA-L C(=O)N.[Co](Cl)Cl Chemical compound C(=O)N.[Co](Cl)Cl SWLTWQONANDENH-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910003185 MoSx Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/06—Washing
-
- 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
- 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
Abstract
The present invention relates to a kind of preparation methods of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, it is impregnated including being respectively placed in electrode holder in the four thio ammonium molybdate solution and transition metal salt solution of 0.05~0.2mol/L, electrode holder is placed in air after the completion and is stood, the electrode holder cleaning completed will be stood, it is dry, it can be applied in the reaction process of electrolysis water, method of the invention has loaded transition metal molybdenum sulphur gel catalyst on electrode holder in situ, the catalyst is uniformly distributed in the surface of electrode, and the multistage micro nano structure for having " accordion ", for amorphous phase, there is a large amount of unsaturated sites and defect in internal and surface, it can be efficient, stable electrocatalytic hydrogen evolution, electro-catalysis produces oxygen；Super thin gas is super hydrophilic to make it still maintain well stable catalysis characteristics when working under industrial high current density；And this method operating process is simple, reproducible, controllability is good, and the requirement carried out under normal temperature and pressure to equipment is low, and low energy consumption, is suitable for heavy industrialization application.
Description
Technical field
The present invention relates to a kind of preparation method of elctro-catalyst more particularly to a kind of transition metal molybdenum sulphur gel elctro-catalysts
Preparation method, belong to electro-catalysis technical field.
Background technique
In recent years, running down due to the consumption of fossil energy and environment, hydrogen is held as a kind of clean and effective
The continuous energy is widely studied.Electrolysis water is the approach for preparing hydrogen of current most simple and effective, and the H that electrolysis water obtains2
And O2Purity is high, but unfortunately the cost of electrolysis water is too high, the catalyst of especially traditional electrocatalytic decomposition water is main
It is made of noble metal and its oxide, significantly limits the industrial application of electrolysis water.Therefore seek to have high catalytic activity,
The catalyst of inexpensive feature has become the mainstream of current electrolysis water area research.
Transition metal (TM) sulfide of nanostructure is considered as most being hopeful that noble metal is replaced to be applied to practical industry
A kind of material, more and more researchers, which demonstrate nano molybdenum disulfide material, can be used as the efficient electric of electrochemistry liberation of hydrogen
Catalyst.The verified unsaturated coordination center of research is the active site crystallized on molybdenum disulfide.However, blocky molybdenum disulfide
Catalytic performance and thermodynamic stability it is general because its active marginal position density is low.In addition, MoS2Electric conductivity compared with
Difference also counteracts the fast transfer of electronics during HER.There is the TMS of greater activity by combiningxConstruction unit with have compared with
High stability MoSxConstruction unit, compact and stable CoMoS can be formedxGel amorphous structure, design low cost, can
Substitute the nanocatalyst of noble metal.There are a large amount of unsaturated sites and lack in this unbodied material internal and surface
It falls into, the far super crystalline state molybdenum disulfide of quantity, it is preferably to be used as efficient elctro-catalyst.
Super thin vapor interface can leave electrode surface with Accelerative mass transfer process to enhance bubble, therefore design a kind of Chao Shuqi circle
Face will be helpful to improve the gross efficiency for being similar to this gas evolution type reaction of electrolysis water.Under industrial high current density, electrode
Surface can generate a large amount of bubbles to influence mass transport process, transition metal molybdenum sulphur gel be it is a kind of be made of metal sulfide,
Inside, which has, is intertwined the gel rubber material of duct and structural disorder, with general sulfide comparatively, they have it is big
Specific surface area and high porosity can be applied to catalytic field as a kind of different-phase catalyst, and can be by transition metal molybdenum sulphur
Gel in situ is supported on different carriers the high-efficient electrode material constructed and have super thin gas performance, and then close in industrial high current
The lower work of degree will not influence its catalytic performance.But the preparation method of the transition metal molybdenum sulphur gel of existing report is using height
What temperature or the high pressure method that even high temperature and pressure uses simultaneously were prepared, the requirement to equipment is high, and energy consumption is also high, and technique is multiple
It is miscellaneous, and the pattern of gained transition metal molybdenum sulphur gel and electrocatalysis characteristic are also unsatisfactory.
Summary of the invention
The present invention provides a kind of super for the upper existing deficiency of existing transition metal molybdenum sulphur gel and preparation method thereof
The preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of hydrophilic super thin gas.
The technical scheme to solve the above technical problems is that
A kind of preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) raw material preparation: using organic amine as solvent, respectively prepare 0.05~0.2mol/L four thio ammonium molybdate solution and
Transition metal salt solution is spare, and electrode holder is cut out, is cleaned, and the electrode holder is nickel foam, foam copper, foamed iron or carbon
Any one in paper；
2) electrode holder impregnation: is respectively placed in Yu Changwen in four thio ammonium molybdate solution and transition metal salt solution
It is impregnated under normal pressure, control dip time is 30min~4h, and electrode holder is placed in sky after the completion without sequencing by dipping process
It is stood in gas；
3) it cleans, is dry: will stand spare after the electrode holder completed cleans, is dry.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the transition metal salt is one of cobalt salt, nickel salt, molysite or a variety of mixtures.
Further, the organic amine be formamide, in n,N-Dimethylformamide any one or both mixture.
Further, the step of electrode holder described in step 1) cleans are as follows: electrode holder is first placed on to organic solvent, acid
It is cleaned in solution and pure water, it is ultrasonic simultaneously during cleaning.
Further, dip time described in step 2) is 50~70min.
Further, the time of standing described in step 2) is 45~75min.
The reaction occurred in dipping process is as follows:
Co2++[MoS4]2-→CoMoS4
Ni2++[MoS4]2-→NiMoS4
Fe3++[MoS4]2-→F2[MoS4]3
The beneficial effects of the present invention are:
1) method of the invention has loaded transition metal molybdenum sulphur gel catalyst in situ on electrode holder, and the catalyst is equal
The even surface for being distributed in electrode, and have the multi-stage micro-nano structure of " accordion ", it is amorphous phase, internal and surface exists
A large amount of unsaturated sites and defect, electrocatalytic hydrogen evolution that can be efficient, stable, electro-catalysis produce oxygen；
2) method operating process of the invention is simple, reproducible, and controllability is good, carries out wanting equipment under normal temperature and pressure
Ask low, low energy consumption, is suitable for heavy industrialization application.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of empty vectors nickel foam；
Scanning electron microscope (SEM) photo of 1 gained cobalt doped molybdenum sulphur gel of Fig. 2 embodiment；
Fig. 3 is transmission electron microscope (TEM) photo of 1 gained cobalt doped molybdenum sulphur gel of embodiment；
Fig. 4 is the XRD spectrum of 1 gained cobalt doped molybdenum sulphur gel of embodiment；
Fig. 5 is scanning electron microscope (SEM) photo of 2 gained nickel doping molybdenum sulphur gel of embodiment；
Fig. 6 is the enlarged photograph of Fig. 5；
Fig. 7 is the underwater adhesion strength test chart of the carrier of 2 gained nickel-loaded doping molybdenum sulphur gel of embodiment；
Fig. 8 is the underwater adhesion strength test chart of 2 empty vectors of embodiment；
Fig. 9 is scanning electron microscope (SEM) photo of 3 gained Fe2O3 doping molybdenum sulphur gel of embodiment；
Figure 10 is the enlarged photograph of Fig. 9；
Figure 11 is Raman (Raman) map of 4 gained cobalt doped molybdenum sulphur gel of embodiment；
Figure 12 is scanning electron microscope (SEM) photo of 5 gained cobalt doped molybdenum sulphur gel of embodiment；
Figure 13 blank nickel foam, Examples 1 to 3 resulting product catalytic performance test data；
Figure 14 is 4 products obtained therefrom of embodiment in current density 500mA/cm2When electrolysis water stability data；
Figure 15 is the catalytic performance test data of blank foam copper, 6 products obtained therefrom of embodiment；
A is that CoMoSx loads foam copper；B is blank foam copper；
Figure 16 is bare carbon paper, the catalytic performance test data of 7 products obtained therefrom of embodiment.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
A kind of preparation method of the cobalt doped molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) commercial foam nickel is cut into strip, is put in ultrasound removal surface and oil contaminant in acetone, clear water cleaning is placed on
The oxide on ultrasound removal surface finally uses second using the cleaning of a large amount of deionized waters and ultrasound in the hydrochloric acid solution of 1mol/L
It is spare after normal-temperature vacuum is two hours dry after alcohol wetting.
2) the cobalt chloride formamide of the four thio ammonium molybdate formamide solution and 0.2mol/L that prepare 0.2mol/L respectively is molten
Liquid.Carrier after cleaning is placed in four thio ammonium molybdate solution after impregnating one hour, taking-up, which is placed in cobalt chloride solution, impregnates
One hour, after the cobalt chloride solution in bottle is all sucked out, the carrier of gel was loaded in standing (aging) one hour in empty bottle.
It being cleaned with ethanol water, replaces solvent, the carrier electrode of the load gel finally obtained is dried in vacuo 2 hours at room temperature,
Spare, the pattern of products obtained therefrom, crystalline state are as shown in figures 1-4.
Embodiment 2:
A kind of preparation method of the nickel doping molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) commercial foam nickel is cut into strip, is put in ultrasound removal surface and oil contaminant in ethyl alcohol, clear water cleaning is placed on
The oxide on ultrasound removal surface finally uses second using the cleaning of a large amount of deionized waters and ultrasound in the hydrochloric acid solution of 1mol/L
It is spare after being dried in vacuo two hours after alcohol wetting.
2) the nickel chloride formamide of the four thio ammonium molybdate formamide solution and 0.2mol/L that prepare 0.2mol/L respectively is molten
Liquid.Carrier after cleaning is placed in four thio ammonium molybdate solution after impregnating one hour, taking-up, which is placed in nickel chloride solution, impregnates
One hour, after the nickel chloride solution in bottle is all sucked out, the carrier of gel was loaded in standing (aging) one hour in empty bottle.
It being cleaned with ethanol water, replaces solvent, the carrier electrode of the load gel finally obtained is dried in vacuo 2 hours at room temperature,
Spare, the pattern of products obtained therefrom is as shown in Figure 5,6.
Fig. 7,8 are respectively the supported catalyst of embodiment 2 and the adhesion strength test chart of the underwater minute bubbles of blank nickel foam.It crosses
Journey 1 is that elctro-catalyst moves closer to air bubble, and process 2 is that elctro-catalyst is contacted with minute bubbles, and process 3 is elctro-catalyst surface
It is gradually distance from minute bubbles.As seen from Figure 7, NiMoSxThere is no apparent adhesion strength, and in blank nickel foam minute bubbles adherency
Power is 30.3 μ N, can significantly be found out by Fig. 8, stingy to be soaked when minute bubbles are left on blank foamed nickel electrode material surface
Raw apparent deformation, NiMoSxWhen leaving bubble, minute bubbles do not deform.It is clear that TMMoSx/ NF electrode has super
Dredge gas, zero adherency characteristic, such as this property makes catalyst such as HER gas evolution type react when, generation it is stingy
Bubble can be detached from from electrode surface rapidly, and Accelerative mass transfer is to accelerate reaction rate.This advantage is more applicable for industrial high current
It works under density.This characteristic can be attributed to the fact that the micron and nanometer composite structure of electrode surface, so that minute bubbles and elctro-catalyst surface
There is high contact angle.
Embodiment 3:
A kind of preparation method of the Fe2O3 doping molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) commercial foam nickel is cut into strip, is put in ultrasound removal surface and oil contaminant, clear water in isopropanol and cleans postposition
The oxide on ultrasound removal surface is finally used using the cleaning of a large amount of deionized waters and ultrasound in the hydrochloric acid solution of 1mol/L
It is spare after being dried in vacuo two hours after ethanol wet.
2) chlorination of the four thio ammonium molybdate N,N-dimethylformamide solution and 0.2mol/L of 0.2mol/L is prepared respectively
Armor amide solution.Carrier after cleaning is placed in four thio ammonium molybdate solution after impregnating one hour, taking-up is placed in iron chloride
After impregnating one hour, one hour in solution, after the ferric chloride solution in bottle is all sucked out, the carrier of gel is loaded in empty bottle
Interior standing (aging) one hour.It cleaned with ethanol water, replace solvent, the carrier electrode of the load gel finally obtained is in room
Temperature lower vacuum drying 2 hours, spare, the pattern of products obtained therefrom was as shown in Figures 9 and 10.
Embodiment 4:
A kind of preparation method of the cobalt doped molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) commercial foam copper is cut into strip, is put in ultrasound removal surface and oil contaminant in ethyl alcohol, clear water cleaning is placed on
The oxide on ultrasound removal surface finally uses second using the cleaning of a large amount of deionized waters and ultrasound in the hydrochloric acid solution of 1mol/L
It is spare after being dried in vacuo two hours after alcohol wetting.
2) chlorination of the four thio ammonium molybdate N,N-dimethylformamide solution and 0.2mol/L of 0.2mol/L is prepared respectively
Cobalt formamide solution.Carrier after cleaning is placed in four thio ammonium molybdate solution after impregnating one hour, taking-up is placed in cobalt chloride
After impregnating one hour, one hour in solution, after the cobalt chloride solution in bottle is all sucked out, the carrier of gel is loaded in empty bottle
Interior standing (aging) one hour.It cleaned with ethanol water, replace solvent, the carrier electrode of the load gel finally obtained is in room
Temperature lower vacuum drying 2 hours, spare, the Raman spectrogram of products obtained therefrom was as shown in figure 11.
Embodiment 5:
A kind of preparation method of the cobalt doped molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) commercial foam nickel is cut into strip, is put in ultrasound removal surface and oil contaminant in acetone, clear water cleaning is placed on
The oxide on ultrasound removal surface finally uses second using the cleaning of a large amount of deionized waters and ultrasound in the hydrochloric acid solution of 1mol/L
It is spare after being dried in vacuo two hours after alcohol wetting.
2) the nickel chloride formamide of the four thio ammonium molybdate formamide solution and 0.2mol/L that prepare 0.2mol/L respectively is molten
Liquid.Carrier after cleaning is placed in four thio ammonium molybdate solution after impregnating one hour, taking-up, which is placed in nickel chloride solution, impregnates
After one hour, one hour, after the nickel chloride solution in bottle is all sucked out, the carrier for loading gel is (old in standing in empty bottle
Change) one hour.It cleaned with ethanol water, replace solvent, the carrier electrode vacuum at room temperature of the load gel finally obtained
2 hours dry, spare, the pattern of products obtained therefrom is as shown in figure 12.
Embodiment 6:
A kind of preparation method of the cobalt doped molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) commercial foam copper is cut into strip, is put in ultrasound removal surface and oil contaminant in ethyl alcohol, clear water cleaning is placed on
The oxide on ultrasound removal surface is finally used using the cleaning of a large amount of deionized waters and ultrasound in certain density hydrochloric acid solution
It is spare after being dried in vacuo two hours after ethanol wet.
2) the four thio ammonium molybdate formamide solution of 0.1mol/L and cobalt chloride N, the N- diformazan of 0.1mol/L are prepared respectively
Base formamide solution.Carrier after cleaning is placed in four thio ammonium molybdate solution after impregnating 30min, taking-up is placed on cobalt chloride
50min is impregnated in solution, after the cobalt chloride solution in bottle is all sucked out after, load the carrier of gel in standing in empty bottle
75min.It cleaned with ethanol water, replace solvent, the carrier electrode of the load gel finally obtained is dried in vacuo 2 at room temperature
Hour, it is spare.
Embodiment 7:
A kind of preparation method of the cobalt doped molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) carbon paper is cut into strip, is put in ultrasound removal surface and oil contaminant in ethyl alcohol, clear water cleaning is placed on certain dense
The oxide on ultrasound removal surface is finally moistened using ethyl alcohol using the cleaning of a large amount of deionized waters and ultrasound in the hydrochloric acid solution of degree
It is spare after vacuum drying two hours after wet.
2) the four thio ammonium molybdate N,N-dimethylformamide solution of 0.05mol/L and the chlorine of 0.05mol/L are prepared respectively
Change cobalt formamide solution.Carrier after cleaning is placed in four thio ammonium molybdate solution and impregnates 70min, taking-up is placed on cobalt chloride
Impregnated 4 hours in solution, after the cobalt chloride solution in bottle is all sucked out after, load the carrier of gel in standing in empty bottle
(aging) one hour.It cleaned with ethanol water, replace solvent, the carrier electrode of the load gel finally obtained is true at room temperature
Sky is 2 hours dry, spare.
Catalytic performance test:
The resulting elctro-catalyst of above-described embodiment 1~3 and its corresponding empty vectors electrocatalytic hydrogen evolution reaction has been subjected to
Catalytic performance test, respectively using empty vectors or the resulting electrode of Examples 1 to 3 as working electrode, wherein Hg/HgO electrode
Or Ag/AgCl electrode, as reference electrode, graphite rod is used as to electrode
Cyclic voltammetric (CV) test
Before electro-chemical test, lead to Ar 30 minutes into electrolyte solution first to remove oxygen in solution.Then three electricity of connection
Polar body system, Hg/HgO electrode is reference electrode, and in 1mol/L KOH solution, working electrode scan round 20 is enclosed, to activate electricity
The potential range of pole, cyclic voltammetry curve is set as -0.9V~-1.5V, sweeps fast 50mV/s, after volt-ampere curve to be recycled is stablized,
It can carry out next step test.
The test of linear sweep voltammetry (LSV) method
Potential range is set as -0.9V~-1.5V, sweeps fast 5mV/s, by -0.9V, until -1.5V terminates.All originals
Beginning data are compensated through iR and are post-processed.
As a result as shown in figure 13, CoMoSx/NF、NiMoSx/NF、FeMoSx/ NF and blank foam nickel electrode are in alkaline solution
HER performance test in (KOH of 1mol/L).Current density is -10mA/cm2When, CoMoSxThe overpotential of/NF electrode is minimum,
For 114mV, in comparison, NiMoSx/ NF overpotential is 130mV, FeMoSx/ NF needs to reach 128mV, and blank nickel foam is then
Need 283mV.Illustrate that the transition metal sulfur family gel prepared to us has good electrocatalytic hydrogen evolution performance.
Embodiment 6, the resulting elctro-catalyst of embodiment 7 and its corresponding carrier electrocatalytic hydrogen evolution reaction has been subjected to separately
Catalytic performance test using empty vectors or implements 6,7 resulting electrodes as working electrode respectively, wherein Hg/HgO electrode or Ag/
AgCl electrode is used as reference electrode, graphite rod to electrode.It is as above to repeat step, first carries out cyclic voltammetry and carries out again linearly
Voltammetry scanning.
As a result as shown in Figure 15, Figure 16, CoMoSx/CF、CoMoSx/ carbon paper, blank foam copper and bare carbon paper are molten in alkalinity
HER performance test in liquid (1mol/L KOH).Current density is -10mA/cm2When, the foam of Supported Co doping molybdenum sulphur gel
Copper is 166mV, the carbon paper of Supported Co doping molybdenum sulphur gel is 206mV, and blank foam copper, carbon paper without performance, illustrate us substantially
The transition metal molybdenum sulphur gel of preparation has good electrocatalytic hydrogen evolution performance on not having to carrier.
The stability test of catalyst:
It is decomposed in water test entirely in electrochemistry, the electrode of preparation makees cathode and anode respectively, in two electrode systems, alkaline electro
It is tested in solution matter (1mol/L KOH).Before test, half an hour Ar deoxygenation is first led in electrolyte solution, then utilizes circulation
Voltammetry sweeps fast 50mV/s, 50 circle of scanning, with activated electrode.Using linear sweep voltammetry, test scope 1.2V~2.2V,
Sweep fast 5mV/s.Current density is set later, carries out stability test.
As a result as shown in figure 14, in industrial high current density 500mA/cm2When, in 50 hours, catalyst performance is able to maintain
Well, illustrate that catalyst electrode prepared by the present invention is still with good stability under industrial high current density, be suitable for
Industrial-scale produces hydrogen.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas, includes the following steps:
1) raw material preparation: using organic amine as solvent, four thio ammonium molybdate solution and the transition of 0.05~0.2mol/L are prepared respectively
Metal salt solution is spare, and electrode holder is cut out, is cleaned, and the electrode holder is in nickel foam, foam copper, foamed iron or carbon paper
Any one；
2) impregnation: electrode holder is respectively placed in four thio ammonium molybdate solution and transition metal salt solution in normal temperature and pressure
Lower dipping, control dip time are 30min~4h, and electrode holder is placed in air by dipping process after the completion without sequencing
It stands；
3) it cleans, is dry: will stand spare after the electrode holder completed cleans, is dry.
2. preparation method according to claim 1, which is characterized in that the transition metal salt is cobalt salt, in nickel salt, molysite
One or more mixtures.
3. preparation method according to claim 1 or 2, which is characterized in that the organic amine is formamide, N, N- dimethyl
In formamide any one or both mixture.
4. preparation method according to claim 3, which is characterized in that the step of electrode holder described in step 1) cleans
Are as follows: electrode holder is first placed in organic solvent, acid solution and pure water and is cleaned, it is ultrasonic simultaneously during cleaning.
5. according to claim 1, preparation method described in any one of 2,4, which is characterized in that dip time described in step 2)
For 50~70min.
6. according to claim 1, preparation method described in any one of 2,4, which is characterized in that standing described in step 2) when
Between be 45~75min.
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