CN106669739A - Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof - Google Patents
Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof Download PDFInfo
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- CN106669739A CN106669739A CN201611257663.7A CN201611257663A CN106669739A CN 106669739 A CN106669739 A CN 106669739A CN 201611257663 A CN201611257663 A CN 201611257663A CN 106669739 A CN106669739 A CN 106669739A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 98
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 68
- -1 Transition metal sulfide Chemical class 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 52
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 32
- 230000001052 transient effect Effects 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000009713 electroplating Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 15
- 238000002604 ultrasonography Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 229910052960 marcasite Inorganic materials 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011978 dissolution method Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000083 pulse voltammetry Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004365 square wave voltammetry Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- 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 invention provides a transition metal sulfide/carbon nanotube composite material. A preparation method of the transition metal sulfide/carbon nanotube composite material comprises the following steps: adding carbon nanotubes to a solvent, forming a suspension by ultrasonic treatment; dropping the suspension on the surface of a pretreated glassy carbon electrode; naturally airing to form a uniform thin layer of carbon nanotubes, to obtain a carbon nanotube-modified glassy carbon electrode; adding thiourea and transition metal salt to deionized water; adjusting pH to 0-13 to obtain an electroplating solution; placing the carbon nanotube-modified glassy carbon electrode in the electroplating solution for electroplating to obtain the glassy carbon electrode covered with a transition metal sulfide/carbon nanotube composite material; washing with water and drying naturally; scraping the transition metal sulfide/carbon nanotube composite material from the surface of the glassy carbon electrode. The preparation method provided by the invention is simple in operation and easy in mass production; the prepared composite material has great advantages in catalytic oxygen evolution and energy conversion, and can be used as a catalyst for photo and electro-catalytic oxygen evolution reaction.
Description
(1) technical field
It is more particularly to a kind of synchronously to be deposited and dissolution method by electrochemistry the invention belongs to nano composite material research field
Porous transient metal sulfide/the carbon nano tube compound material of the high-hydrophilic of preparation, and its ground as the application of elctro-catalyst
Study carefully；Transient metal sulfide/the carbon nano tube compound material is designated as MS2/ CNT, wherein, M=Co, Ni, Fe or three are appointing
The mixture of meaning ratio.
(2) background technology
Traditional fossil energy is faced with the major crisis of resource exhaustion, and fossil as a kind of non-renewable energy
The use of the energy, a series of environmental problem brought has greatest relation with the burning of such energy.Therefore, actively open
The regenerative resource for sending out cleaning is extremely urgent.Because fuel cell has cleaning, renewable, high conversion efficiency, range of application
The concern of scientific research scholar is enjoyed the advantages of wide.However, the slow dynamics of fuel cell, particularly anode oxygen evolution reaction pole
The earth hinders the large-scale industrialized production of fuel cell.In order to solve the slow power of anode of fuel cell oxygen evolution reaction
Knowledge is inscribed, and scientists have developed oxygen and separate out catalyst.It is based on noble ruthenium or iridium that the oxygen for being considered as best separates out catalyst
And its catalyst of oxide.Noble ruthenium or iridium and its oxide shortage of resources, expensive etc. cause fuel cell cost
High, service life is short, it is impossible to which realization is commercially produced.
Therefore, substantial amounts of effort at present is concentrated mainly on the Non-precious Metal Catalysts of exploitation a kind of efficiently, stabilization and low cost
Agent.In these catalyst, sulfide is a kind of transient metal sulfide of the semi-metal of earth rich reserves, and is possessed
The same catalytic performance of noble metal.Therefore, sulfide shows alternative RuO2With IrO2Huge potential value.However, in order to
Obtain preferable oxygen and separate out performance, it is necessary to which the inherent physicochemical properties to sulfide are optimized, mainly include three aspects：
(1) electric conductivity and diffusion of sulfide are strengthened；(2) number and the enhancing for increasing the avtive spot of sulfide are inherent living
Property；(3) wetability at interface must be improved.For OER (oxygen evolution reaction), the improvement of the wetting behavior of sulfide can increase
The contact point of electrolyte-electrode, promotes electro transfer, the electro catalytic activity of reinforcing material.Therefore, wherein thirdly having to
Meet.
The development of elctro-catalyst is separated out on sulfide base oxygen recently, the following aspects is concentrated mainly on：(1) sulfide
Coupling conductive carbon material；(2) a kind of nano-scale structure is developed, increases the exposure of avtive spot；(3) by other transition of adulterating
Metal, design edge active site, promotes the intrinsic activity of sulfide.Although these methods improve the oxygen analysis of sulfide really
Go out performance, but the catalytic efficiency of most of sulfide base elctro-catalysts reported, do not reach and be comparable to RuO2Or IrO2
Level.The above-mentioned strategy process of comprehensive analysis, it is concluded that the main cause of limitation sulfide base elctro-catalyst process
It is probably because research above only optimizes or two in the middle of above-mentioned three specific requirements, the researchs of few correlations
The target of report is to direct at the hydrophilic improvement of sulfide.
In order to be able to realize that it is used on a large scale, it is necessary to research and develop easy and lower-cost preparation method to be lived
Property oxygen evolution reaction catalyst higher, so as to lift the actual application prospect of oxygen evolution reaction catalyst.
(3) content of the invention
It is an object of the invention to provide a kind of porous by the electrochemistry high-hydrophilic that synchronously prepared by deposition and dissolution method
Transient metal sulfide/carbon nano tube compound material, and carry out performance study as elctro-catalyst.It is many obtained in the inventive method
Hole composite material pore size is controllable, edge active position is more, activity is high, active component and carrier are preferable compound, and hydrophily is compared with business
The cobalt sulfide of industry is high, and the composite has shown the advantage for being easy to produce oxygen on a large scale in terms of oxygen precipitation is catalyzed.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of transient metal sulfide/carbon nano tube compound material, its preparation method is：
(1) carbon nano tube modified glass-carbon electrode is prepared：
CNT (CNTs) is added in solvent, ultrasonic (16~40KHz, 1~5h) forms suspension, by the suspension
Be added dropwise in pretreated glassy carbon electrode surface (usual dripping quantity be 50~200 μ L/cm2), dry to form uniform carbon naturally
Nanotube thin layer, obtains carbon nano tube modified glass-carbon electrode；
Described solvent is ethanol, water or ethanol/water volume ratio 1：1~5 mixed liquor；
The volumetric usage of the solvent is calculated as 0.1~1mL/mg (particularly preferred 1mL/mg) with the quality of CNT；
Described CNT be single wall, many walls, array or hetero atom (such as N, S) doping CNT in one kind or
The mixture of two or more arbitrary proportions；
The preprocess method of the glass-carbon electrode is the method for conventional treatment electrode, i.e.,：Glass-carbon electrode is thrown successively
Light, washing, the pretreatment in 16~32KHz ultrasounds, 10~60s；
(2) electroplate liquid is prepared：
In deionized water add thiocarbamide, transition metal salt, regulation pH be 0~13 (preferably 0~8, with 5wt%~
20wt% ammoniacal liquor or 5wt%~20wt% hydrochloric acid are adjusted), obtain electroplate liquid；
Described transition metal salt is one or more arbitrary proportions in the soluble inorganic salt of Co, Ni, Fe
The mixture of one or more arbitrary proportions in mixture, such as cobalt chloride, nickel chloride, iron chloride；
Described the thiocarbamide final concentration of 0.1~10mol/L in electroplate liquid, preferably 0.3~0.9mol/L, particularly preferably
0.6mol/L；
Described the transition metal salt final concentration of 0.1~10mmol/L in electroplate liquid, preferably 2~6mmol/L, especially
It is preferred that 4mmol/L；
(3) transient metal sulfide/carbon nano tube compound material is prepared：
The carbon nano tube modified glass-carbon electrode of step (1) gained is placed in step (2) gained electroplate liquid, in scanning current potential
For -2.0~1.0V (preferably -1.2~0.5V), sweep speed are that 1~100mV/s (preferably 10~80mV/s), operation temperature are
Implement plating under conditions of 18~35 DEG C, plating time is 1~200min (preferably 10~60min), obtains being covered with transition metal
The glass-carbon electrode of sulfide/carbon nano tube compound material, by the glass-carbon electrode cleaned with water and under normal temperature (20~30 DEG C) from
After so drying, (using blade) scrapes transient metal sulfide/carbon nano tube compound material from glassy carbon electrode surface, obtains final product final
Product；
The implementation electric plating method can be selected from：Cyclic voltammetry, linear voltammetry, chronoamperometry, timing voltage
Method, pulse voltammetry or square wave voltammetry.
Porous transient metal sulfide/the carbon nano tube compound material of high-hydrophilic obtained in the inventive method can be represented
It is MS2/ CNTs, wherein, M=Co, Ni, Fe or three are with the mixture of arbitrary proportion.
The aperture of the porous transient metal sulfide/carbon nano tube compound material of high-hydrophilic obtained in the inventive method is big
Small controllable (being realized by the regulation and control to electroplating time), and particle diameter is in the range of 10~200nm.
Porous transient metal sulfide/the carbon nano tube compound material of high-hydrophilic obtained in the inventive method can be used as
Light, electrocatalytic oxidation evolution reaction catalyst.For example, with 0.1M KOH solutions as electrolyte, in three-electrode system, to load
The electrode of transient metal sulfide/carbon nano tube compound material of the present invention is working electrode, carries out electro-catalysis water decomposition oxygen
Evolution reaction.
The beneficial effects of the present invention are：
(1) during the substrate selected by is the CNTs (single wall, many walls, array or Heteroatom doping etc.) with preferable electric conductivity
One or more；
(2) the composite pore size for preparing is controllable, and particle diameter is from 10nm to 200nm；
(3) the edge active position of the composite for preparing is a lot, good hydrophilic property；
(4) composite material interface for preparing is combined very well, is advantageously implemented between the high efficiency of transmission of electronics and material
Cooperative effect, preferably plays activity.
In sum, on the one hand, synchronously deposition is high with dissolution method preparation hydrophilic by electrochemistry for one kind that the present invention is provided
The method of the porous transient metal sulfide/carbon nano tube compound material of property, it is simple to operate, HTHP is not related to, at room temperature
Can complete, it is easy to mass produce；On the other hand, controlled by suitable condition, CNTs can be combined with other sulfide,
Obtained composite has very big advantage in terms of catalysis oxygen is separated out with energy conversion, in oxygen evolution reaction is catalyzed, system
The overpotential of the composite for obtaining is relatively low, and current density is larger, also, the composite can also be wide by adjusting forbidden band
Degree, so as to improve its application value in photocatalytic water splitting produces oxygen and opto-electronic conversion.
(4) illustrate
Fig. 1：Electro-deposition of the present invention prepares the stream of the porous transient metal sulfide/carbon nano tube compound material of high-hydrophilic
Journey schematic diagram；
Fig. 2：The scanning electron microscopy of the porous cobalt sulfide/carbon nano tube compound material of high-hydrophilic obtained in embodiment 2
Mirror picture (A)；Transmission electron micrograph (B, illustration is the SEAD of the composite)；Scanning-tunnelling electronic display
Micro mirror picture and corresponding Elemental redistribution collection of illustrative plates (C)；(D amplifies 200000 to the transmission electron micrograph of different amplification
Times, E amplifies 200000 times, and F amplifies 250000 times)；
Fig. 3：The line of the porous cobalt sulfide/carbon nano tube compound material of high-hydrophilic obtained in embodiment 2 and CNT
Property volt-ampere curve figure；
Fig. 4：Porous cobalt sulfide/the carbon nano tube compound material of high-hydrophilic obtained in embodiment 2 and material in comparative example
Performance comparision figure.
Fig. 5：The porous cobalt sulfide of high-hydrophilic obtained in embodiment 2/carbon nano tube compound material stability experiment figure；
Fig. 6：Porous cobalt sulfide/the carbon nano tube compound material of high-hydrophilic obtained in embodiment 2 connects with various materials
Feeler compares figure：(a) bare glassy carbon electrode；(b) original carbon nanotubes；C () is commercialized cobalt sulfide/CNT；(d) embodiment 2
Porous cobalt sulfide/the carbon nano tube compound material of prepared high-hydrophilic.
(5) specific embodiment
The present invention is further detailed below by specific embodiment, but protection scope of the present invention and is not only limited
In this.
Embodiment 1：Prepare the porous iron sulfide of high-hydrophilic/carbon nano tube compound material (FeS2/CNTs)
(1) pretreatment of electrode：Glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is thrown successively
Light, washing, the pretreatment of 16KHz ultrasounds 10s；
(2) carbon nano tube modified glass-carbon electrode is prepared：Array carbon nano tube (1mg) is added to ethanol and water volume ratio 1：
In 1 mixed liquor (1mL), suspension is formed in 16KHz ultrasounds 1h, the suspension is added dropwise in the glass pre-processed through step (1)
Carbon electrodes, dry to form uniform CNT thin layer (thin layer is for about the amount of 40 μ g CNTs) naturally, obtain carbon
Nanometer tube modified glass-carbon electrode；
(3) electroplate liquid is prepared：Presoma thiocarbamide (9.1344g, 0.3mol/L), chlorine are added in deionized water (400mL)
Change iron (0.1590g, 2mmol/L), be 0 with ammoniacal liquor and salt acid for adjusting pH, obtain electroplate liquid；
(4) the porous transient metal sulfide/carbon nano tube compound material of high-hydrophilic is prepared：Step (2) is obtained
Carbon nano tube modified glass-carbon electrode is placed in the electroplate liquid that step (3) is obtained, and is 0.5~-2V, sweep speed in scanning current potential
It is 10mV/s, to implement plating using cyclic voltammetry under conditions of 18 DEG C, plating time is 10min to operation temperature, is covered
There is the porous iron sulfide of high-hydrophilic/carbon nano tube compound material (FeS2/ CNTs) glass-carbon electrode, by the glass-carbon electrode water
After cleaning, without composite is scraped from electrode surface, electro-chemical test is directly carried out.
(5) electro-chemical test：In three-electrode system, (the porous iron sulfide/carbon of high-hydrophilic that is covered with prepared by step (4) is received
Mitron composite (FeS2/ CNTs) electrode as working electrode, silver/silver chloride electrode is used as reference electrode, platinum plate electrode
As auxiliary electrode) in, measure (FeS2/ CNTs) linear sweep voltammetry curve.Test electrolyte solution used is 0.1M
KOH solution.
Embodiment 2：Prepare the porous cobalt sulfide of high-hydrophilic/carbon nano tube compound material (CoS2/CNTs)
(1) pretreatment of electrode：Glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is thrown successively
Light, washing, the pretreatment of 20KHz ultrasounds 60s；
(2) carbon nano tube modified glass-carbon electrode is prepared：Array carbon nano tube (1mg) is added to ethanol and water volume ratio 1：
In 4 mixed liquor (1mL), suspension is formed in 40KHz ultrasounds 2h, the suspension is added dropwise in the glass pre-processed through step (1)
Carbon electrodes, dry to form uniform CNT thin layer (thin layer is for about the amount of 40 μ g CNTs) naturally, obtain carbon
Nanometer tube modified glass-carbon electrode；
(3) electroplate liquid is prepared：Presoma thiocarbamide (18.2688g, 0.6mol/L), chlorine are added in deionized water (400mL)
Change cobalt (0.3807g, 4mmol/L), be 6.0 with ammoniacal liquor and salt acid for adjusting pH, obtain electroplate liquid；
(4) the porous transient metal sulfide/carbon nano tube compound material of high-hydrophilic is prepared：Step (2) is obtained
Carbon nano tube modified glass-carbon electrode is placed in the electroplate liquid that step (3) is obtained, and is 0.5~-1.2V, scanning speed in scanning current potential
It is 50mV/s to spend, and to implement plating using cyclic voltammetry under conditions of 25 DEG C, plating time is 60min to operation temperature, is obtained
It is covered with the porous cobalt sulfide of high-hydrophilic/carbon nano tube compound material (CoS2/ CNTs) glass-carbon electrode, by the glass-carbon electrode use
After water cleaning, without composite is scraped from electrode surface, electro-chemical test is directly carried out.
(5) electro-chemical test：In three-electrode system, (the porous cobalt sulfide/carbon of high-hydrophilic that is covered with prepared by step (4) is received
Mitron composite (CoS2/ CNTs) electrode as working electrode, silver/silver chloride electrode is used as reference electrode, platinum plate electrode
As auxiliary electrode) in, measure CoS2The linear sweep voltammetry curve of/CNTs.Test electrolyte solution used is 0.1M's
KOH solution.Fig. 3 is its linear volt-ampere curve figure, in contrast to pure nano-carbon tube it can be found that take-off potential is smaller and electric current more
It is big, it can be seen that CoS obtained in the present embodiment2/ CNTs is precipitated with excellent catalysis activity for oxygen.
By the strong cobalt sulfide of obtained layered porous and hydrophily/carbon nano tube compound material (CoS2/ CNTs) from electrode
Surface scrapes to be tested, and Fig. 2 is scanning electron microscope diagram piece, TEM, the scanning tunneling microscope of the composite
Picture and corresponding distribution diagram of element spectrogram, it can be found that flake porous thing is uniformly covered on CNT, and aperture
Less than 50nm；Fig. 5 is the stability of the composite, it can be found that composite has good stability；Fig. 6 is described
The contact angle experiments figure of composite, illustrates that the hydrophily of composite has and significantly improves.
Embodiment 3：Prepare the porous nickel sulfide of high-hydrophilic/carbon nano tube compound material (NiS2/CNTs)
(1) pretreatment of electrode：Glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is thrown successively
Light, washing, the pretreatment of 32KHz ultrasounds 30s；
(2) carbon nano tube modified glass-carbon electrode is prepared：Array carbon nano tube (1mg) is added to ethanol and water volume ratio 1：
In 5 mixed liquor (1mL), suspension is formed in 28KHz ultrasounds 5h, the suspension is added dropwise in the glass pre-processed through step (1)
Carbon electrodes, dry to form uniform CNT thin layer (thin layer is for about the amount of 40 μ g CNTs) naturally, obtain carbon
Nanometer tube modified glass-carbon electrode；
(3) electroplate liquid is prepared：Presoma thiocarbamide (27.4032g, 0.9mol/L), chlorine are added in deionized water (400mL)
Change nickel (0.5705g, 8mmol/L), be 8.0 with ammoniacal liquor and salt acid for adjusting pH, obtain electroplate liquid；
(4) the porous transient metal sulfide/carbon nano tube compound material of high-hydrophilic is prepared：Step (2) is obtained
Carbon nano tube modified glass-carbon electrode is placed in the electroplate liquid that step (3) is obtained, and is 1~-1.2V, sweep speed in scanning current potential
It is 80mV/s, to implement plating using cyclic voltammetry under conditions of 35 DEG C, plating time is 35min to operation temperature, is covered
There is the porous nickel sulfide of high-hydrophilic/carbon nano tube compound material (NiS2/ CNTs) glass-carbon electrode, by the glass-carbon electrode water
After cleaning, composite is scraped from glassy carbon electrode surface, obtain final products.
Comparative example
(1) pretreatment of electrode：Glass-carbon electrode is taken, is polished successively, washed, the pretreatment of 40KHz ultrasounds 60s；
(2) electroplate liquid is prepared：Presoma thiocarbamide (18.2688g), cobalt chloride are added in deionized water (400mL)
(0.3807g), is 6.0 with ammoniacal liquor and salt acid for adjusting pH, obtains electroplate liquid；
(3) the porous transient metal sulfide of high-hydrophilic is prepared：The glass-carbon electrode pre-processed by step (1) is placed in
It is 0.5~-1.2V in scanning current potential in the electroplate liquid that step (2) is obtained, sweep speed is 50mV/s, and operation temperature is 25 DEG C
Under conditions of using cyclic voltammetry implement plating, plating time is 60min, obtains being covered with the glass-carbon electrode of cobalt sulfide, by this
After glass-carbon electrode is cleaned with water, electro-chemical test is directly carried out.
(4) electro-chemical test：Three-electrode system (step (3) prepare be covered with the glass-carbon electrode of cobalt sulfide as work
Electrode, used as reference electrode, platinum plate electrode is used as auxiliary electrode for silver/silver chloride electrode) in, measurement is layered porous and hydrophily is strong
Cobalt sulfide linear sweep voltammetry curve.Test electrolyte solution used is the KOH solution of 0.1M.
Cobalt sulfide/carbon nano tube compound material that the high-hydrophilic of the electrodeposition process of embodiment 2 preparation is porous is electric with comparative example
The linear sweep voltammetry curve of cobalt sulfide prepared by sedimentation is as shown in figure 4, as shown in Figure 4, high-hydrophilic of the present invention is porous
Cobalt sulfide/carbon nano tube compound material shows smaller take-off potential and bigger current density, therefore, the present invention is compound
Material is precipitated with excellent catalysis activity for oxygen.
Composite process obtained in the inventive method is synchronously related to two processes of electrochemical deposition and dissolving, and it is right to realize
The in-stiu coating of material, will not cause the material activity to reduce because the external world is ultrasonically treated, Stability Analysis of Structures and hydrophily is strong, show good
Good photoelectrocatalysis produces oxygen performance, stability and durability, is that photoelectrocatalysis produces the development exploration of oxygen and goes out a novelty and effective
Approach.
Claims (10)
1. a kind of transient metal sulfide/carbon nano tube compound material, it is characterised in that described transient metal sulfide/carbon
Nanometer tube composite materials are prepared as follows obtaining：
(1) carbon nano tube modified glass-carbon electrode is prepared：
CNT is added in solvent, suspension is ultrasonically formed, the suspension is added dropwise in pretreated glass-carbon electrode table
Face, dries to form uniform CNT thin layer naturally, obtains carbon nano tube modified glass-carbon electrode；
Described solvent is ethanol, water or ethanol/water volume ratio 1：1~5 mixed liquor；
(2) electroplate liquid is prepared：
Thiocarbamide, transition metal salt are added in deionized water, and regulation pH is 0~13, obtains electroplate liquid；
Described transition metal salt is the mixing of one or more arbitrary proportions in the soluble inorganic salt of Co, Ni, Fe
Thing；
Final concentration of 0.1~10mol/L of the described thiocarbamide in electroplate liquid；
Final concentration of 0.1~10mmol/L of the described transition metal salt in electroplate liquid；
(3) transient metal sulfide/carbon nano tube compound material is prepared：
Step (1) the carbon nano tube modified glass-carbon electrode of gained is placed in step (2) gained electroplate liquid, scanning current potential for-
2.0~1.0V, sweep speed are 1~100mV/s, operation temperature is implementation plating under conditions of 18~35 DEG C, and plating time is 1
~200min, obtains being covered with the glass-carbon electrode of transient metal sulfide/carbon nano tube compound material, and the glass-carbon electrode is clear with water
Wash and at normal temperatures spontaneously dry after, transient metal sulfide/carbon nano tube compound material is scraped from glassy carbon electrode surface, i.e.,
Obtain final products.
2. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (1),
The volumetric usage of the solvent is calculated as 0.1~1mL/mg with the quality of CNT.
3. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (1),
Described CNT is one or more any ratios in the CNT of single wall, many walls, array or Heteroatom doping
The mixture of example.
4. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (2),
It is 0~8 with ammoniacal liquor or salt acid for adjusting pH.
5. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (2),
Described transition metal salt is the mixture of one or more arbitrary proportions in cobalt chloride, nickel chloride, iron chloride.
6. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (2),
Final concentration of 0.3~0.9mol/L of the described thiocarbamide in electroplate liquid, the end of described transition metal salt in electroplate liquid is dense
It is 2~6mmol/L to spend.
7. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (3),
Described scanning current potential is -1.2~0.5V.
8. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (3),
Described sweep speed is 10~80mV/s.
9. transient metal sulfide/carbon nano tube compound material as claimed in claim 1, it is characterised in that in step (3),
Described plating time is 10~60min.
10. transient metal sulfide/carbon nano tube compound material as claimed in claim 1 is urged as electrocatalytic oxidation evolution reaction
The application of agent.
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