CN105624756A - High-activity molybdenum sulfide film electrocatalyst and preparation method thereof - Google Patents
High-activity molybdenum sulfide film electrocatalyst and preparation method thereof Download PDFInfo
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- CN105624756A CN105624756A CN201511005390.2A CN201511005390A CN105624756A CN 105624756 A CN105624756 A CN 105624756A CN 201511005390 A CN201511005390 A CN 201511005390A CN 105624756 A CN105624756 A CN 105624756A
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- molybdenum sulfide
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010411 electrocatalyst Substances 0.000 title abstract description 7
- 230000000694 effects Effects 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 31
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010409 thin film Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000010408 film Substances 0.000 claims description 12
- 230000009257 reactivity Effects 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- -1 thio molybdenum Chemical compound 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 claims description 2
- 241000282326 Felis catus Species 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 101710116850 Molybdenum cofactor sulfurase 2 Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
Abstract
The invention relates to a molybdenum sulfide film electrocatalyst and a preparation method thereof. The molybdenum sulfide film electrocatalyst has the advantages of simplicity, convenience, high efficiency, greenness and high catalytic activity, and is based on a conductive substrate. The preparation method comprises the following steps of dissolving molybdate or tetrathiomolybdate and thioacetamide at room temperature to form an aqueous solution; adjusting pH value, and adding a surfactant by stirring to form a stable liquid crystal template system; depositing a molybdenum sulfide film on the conductive substrate by an electrodeposition technology; and performing water washing, ethanol washing and vacuum drying on an obtained material to finally obtain a black film material. According to the molybdenum sulfide film electrocatalyst and the preparation method thereof disclosed by the invention, by adjusting the concentration of a reactant and the pH value, and changing the precipitation potential range and deposition number of turns, the size of a product can be controlled, and a molybdenum sulfide film material with higher purity is prepared; and the molybdenum sulfide film electrocatalyst and the preparation method thereof disclosed by the invention have important significance for controllable synthesis of the molybdenum sulfide film material under the condition of room temperature and application of the molybdenum sulfide film material.
Description
Technical field
The invention belongs to field of material technology, it relates to a kind of high reactivity moly-sulfide thin-film electro Catalysts and its preparation method.
Background technology
Hydrogen Energy is one of following most clean energy having prospect, extensive cleaning hydrogen producing technology needs the eelctro-catalyst of high reactivity to reduce overpotential and production cost, the most efficient catalyst for preparing hydrogen is platinum based noble metal catalyzer at present, and the price of its costliness and limited reserves greatly limit the application of its industrialization. Therefore, the alternative catalysts of developing low-cost, high reactivity becomes the research focus within the scope of the world. One of material that moly-sulfide enriches as earth reserves, cost is low and has certain electro catalytic activity, it is considered to have very big potentiality replacement platinum based noble metal and carries out catalyzing manufacturing of hydrogen, but the semi-conductor of moly-sulfide essence and two-dimensional layered structure limit the raising of its catalytic activity.
Up to now, the synthesis of moly-sulfide mainly high temperature dipping calcining, Hydrothermal Synthesis technology, but products therefrom is the two-dimensional material of a kind of similar Graphene, obtained moly-sulfide very easily produces phenomenons such as reuniting, particle is grown up, moly-sulfide arris position as catalytic active site is capped usually, seriously have impact on the raising of its catalytic performance. In addition, whether high-temperature calcination or Hydrothermal Synthesis, all needs to design comparatively harsh reaction conditions, long reaction time, and preparation process is complicated.
Although also there being electrochemical reduction to prepare the patent report of moly-sulfide, such as Chinese patent " electrochemical reducing process for preparing nanometer MOS 2 particle ", publication number CN1986893A, but its target product prepared still is molybdenum sulfide particle, very easily reunite, cannot be applied in the reaction of efficient electrocatalytic decomposition water. Chinese patent " preparation method of a kind of molybdenum disulfide film material ", publication number CN103205724A, its preparation technology is also comparatively complicated, and it is not thin-film material, it is difficult to carry out large-scale industrial production. Chinese patent " MoO3/MoS2 laminated film is as the organic solar batteries of anode interface layer and its preparation method ", application number 201310107834.8, although having prepared film oxidation molybdenum/moly-sulfide matrix material, but its preparation condition is harsh, and step is complicated. The shortcoming of these preparation methods above-mentioned and deficiency limit raising and the large-scale industrial production of moly-sulfide thin-film material catalytic performance. And at room temperature, adopt electro-deposition techniques, and utilize liquid crystal templated system, there is not been reported so far to synthesize the method for the moly-sulfide thin-film material with similar platinum based catalyst activity.
Summary of the invention
It is an object of the invention under mild conditions, the novel method of a kind of simplicity, efficient, green syt film material molybdenum sulfide is provided, by utilizing electro-deposition techniques, in liquid crystal templated system, synthesize the moly-sulfide film with similar platinum based catalyst activity, and realize the shape looks of thin-film material, the controlledly synthesis of size by control deposition current, concentration of electrolyte, substrate etc., raising and heavy industrialization application to moly-sulfide thin-film material electro catalytic activity are significant.
The technical scheme that the present invention is complete comprises:
The preparation method of a kind of high reactivity moly-sulfide thin-film electro catalyzer, it is characterised in that, comprise the steps:
(1) adopt molybdate or Thiomolybdate and thioacetamide to be raw material, dissolve and form solution;
(2) the PH value of above-mentioned solution is regulated;
(3) through regulating, the solution after PH adds tensio-active agent in above-mentioned steps (2), form the liquid crystal system with rock steady structure;
(4) use conductive glass or other conductive substrates, adopt electro-deposition techniques to be deposited in conductive substrates by moly-sulfide to form thin-film material under certain condition, obtain described high reactivity moly-sulfide thin-film electro catalyzer.
Adopting alkaline matter and/or acidic substance to regulate PH value, the PH value of reaction system is 6-12.
The alkaline matter added is the one in ammoniacal liquor, sodium hydroxide, potassium hydroxide or any two kinds.
In order to stabilizing liquid crystal system, ice-water bath or oil bath is adopted to regulate the temperature of reaction of whole system to be 20-35 DEG C; Reaction carries out under whipped state, and leads to into nitrogen to remove dissolved oxygen; And comprise after reaction terminates gained film left standstill, wash, ethanol is washed, vacuum-drying means process step.
Described molybdate is ammonium molybdate, Sodium orthomolybdate and other soluble compound or polyacid structure containing molybdate, and it forms solution mode for adopting solid particulate or the aqueous solution to add deionized water.
Described Thiomolybdate is four thio molybdenum acid sodiums, four thio ammonium molybdate, or its mixture, and it forms solution mode is adopt the solution of the aqueous solution or organic solvent dissolution to add deionized water.
When adopting molybdate and thioacetyl ammonium to be raw material, PH value is regulated to be 8-12; When adopting Thiomolybdate and thioacetyl ammonium to be raw material, PH value is regulated to be 8-10.
Described tensio-active agent is hydrophilic nonionogenic tenside or other cats products.
Described tensio-active agent is hydrophilic nonionogenic tenside is Brij56 or Brij58.
Different according to strength of solution, it is raw material according to molybdate and thioacetyl ammonium, need to be 8-12 by ammoniacal liquor regulating and controlling PH value; If adding Thiomolybdate is raw material, need regulating and controlling PH value for 8-10. Reaction system can add acidic substance when necessary and regulate PH again, and after adding acidic substance, reacting system PH value is 6-8.
High reactivity moly-sulfide thin-film electro catalyzer prepared by aforesaid method.
A kind of method that the present invention provides gentleness, simplicity, fast room temperature synthesize the moly-sulfide thin-film material based on different conductive substrates. Compared with traditional method, the present invention has following outstanding advantage: 1, react solvent for use be easy to get, inexpensive, green non-pollution; 2, reaction conditions is simple, reaction can carry out fast, save energy, save time; 3, product rate height, molybdate wide scope of material used, save cost; 4, by adding alkaline matter, condition pH value, equal regular, the stability height of gained moly-sulfide thin-film material shape looks; 5, it is possible to by conditions such as the concentration of adjustable liquid crystal display system, pH, it is achieved to the controlledly synthesis of thin-film material size, shape looks, size controlled range is wide, is beneficial to the application of this material in different catalyzed reaction and other field. The method extends the synthetic method of moly-sulfide, to the research formation mechanism study of moly-sulfide thin-film material, industrialization scale operation and expand its application in catalytic field and have important directive significance.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of moly-sulfide film prepared by embodiment 1;
Fig. 2 is scanning electron microscope (SEM) figure (amplifying 1000 times) of moly-sulfide film prepared by embodiment 2;
Fig. 3 is scanning electron microscope (SEM) photograph (SEM) figure (amplifying 5000 times) of moly-sulfide film prepared by embodiment 2;
Fig. 4 is electrocatalysis hydrogen manufacturing polarization curve (LSV) of moly-sulfide thin-film material prepared by embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described. But the present invention is not limited thereto, below test method described in embodiment, if no special instructions, be ordinary method; Described instrument and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1:
In aqueous systems, in the substrate of galvanic deposit conductive glass, the synthetic method of moly-sulfide thin-film material is as follows: under room temperature, ammonium molybdate is dissolved in 20ml water, its concentration is made to be 0.02M, adding ammoniacal liquor regulates its PH to be 9-10, add thioacetyl ammonium while stirring, make its concentration be 0.05M, stir 30 minutes, lead to the oxygen of nitrogen to remove in the aqueous solution during the course. Adopting cyclic voltammetry to carry out galvanic deposit, scanning potential range, from-0.2V-(-1.5V), sweeps speed for 100mVs-1, and the deposition number of turns is 50 circles. The sample obtained repeats each 3 times of washing, washing with alcohol operation, 60 degrees Celsius of vacuum-drying 12 hours. Sample is carried out SEM sign, as shown in the figure, it can be seen that being obtained film and have smooth two dimensional structure, sample is pure. Gained sample carries out electrocatalysis hydrogen manufacturing test, and gained result and document report are similar.
Embodiment 2:
The synthesis of galvanic deposit moly-sulfide thin-film material in conductive glass substrate in liquid crystal templated system: under room temperature, ammonium molybdate is dissolved in 20ml water, its concentration is made to be 0.02M, adding ammoniacal liquor regulates its PH to be 9-10, add thioacetyl ammonium while stirring so that it is concentration is 0.05M, whipping process adds the aqueous solution of surfactant B rij56, it is stirred to the stabilizing solution system obtaining homogeneous phase always, leads to the oxygen of nitrogen to remove in the aqueous solution during the course. Adopting cyclic voltammetry to carry out galvanic deposit, scanning potential range, from-0.5V-(-1.8V), sweeps speed for 50mVs-1, and the deposition number of turns is 20 circles. The sample obtained repeats each 3 times of washing, washing with alcohol operation, 60 degrees Celsius of vacuum-drying 12 hours. Sample is carried out SEM sign, as shown in the figure, it can be seen that obtained film and there is bulge-structure, it is made up of the circular protrusions of an equal size on the surface, overall in regular arrangement (such as Fig. 2). Under high magnification SEM tests, it can be seen that the circular protrusions structure on the surface of thin-film material, diameter is about 100-200nm (such as Fig. 3). Gained sample carries out electrocatalysis hydrogen manufacturing test, gained result be better than document report, close to the catalytic performance (Fig. 4) of Pt/C catalyzer.
To sum up, the present invention is at room temperature by adopting liquid crystal templated system, synthesize the moly-sulfide thin-film material with special construction and excellent catalytic activity, confirmed singularity and the size size of its structure by SEM test, electrocatalysis hydrogen manufacturing property detection shows that this material has catalytic performance that can be close with Pt/C catalyzer. The method is succinct, efficient, green, for the suitability for industrialized production of high reactivity moly-sulfide thin-film electro catalyzing manufacturing of hydrogen catalyzer provides novel thinking, has important guidance effect to expanding the application of moly-sulfide thin-film material in other catalytic fields.
Claims (10)
1. the preparation method of a high reactivity moly-sulfide thin-film electro catalyzer, it is characterised in that, comprise the steps:
(1) adopt molybdate or Thiomolybdate and thioacetamide to be raw material, dissolve and form solution;
(2) the PH value of above-mentioned solution is regulated;
(3) through regulating, the solution after PH adds tensio-active agent in above-mentioned steps (2), form the liquid crystal system with rock steady structure;
(4) use conductive substrates, adopt electro-deposition techniques to be deposited in conductive substrates by moly-sulfide to form thin-film material, obtain described high reactivity moly-sulfide thin-film electro catalyzer.
2. the method for claim 1, it is characterised in that, in described step (2), adopt alkaline matter and/or acidic substance to regulate PH value, the PH value of reaction system is 6-12.
3. method as claimed in claim 2, it is characterised in that, the alkaline matter added is the one in ammoniacal liquor, sodium hydroxide, potassium hydroxide or any two kinds.
4. the method for claim 1, it is characterised in that, in order to stabilizing liquid crystal system, adopt ice-water bath or oil bath to regulate the temperature of reaction of whole system to be 20-35 DEG C; Reaction carries out under whipped state, and leads to into nitrogen to remove dissolved oxygen; And comprise after reaction terminates gained film left standstill, wash, ethanol is washed, vacuum-drying means process step.
5. method as described in claim 1 or 4, it is characterised in that, described molybdate is ammonium molybdate, Sodium orthomolybdate and other soluble compound or polyacid structure containing molybdate, and it forms solution mode for adopting solid particulate or the aqueous solution to add deionized water.
6. method as described in claim 1 or 4, it is characterised in that, described Thiomolybdate is four thio molybdenum acid sodiums, four thio ammonium molybdate, or its mixture, and it forms solution mode is adopt the solution of the aqueous solution or organic solvent dissolution to add deionized water.
7. method as described in claim 1 or 4, it is characterised in that, when adopting molybdate and thioacetyl ammonium to be raw material, regulate PH value to be 8-12; When adopting Thiomolybdate and thioacetyl ammonium to be raw material, PH value is regulated to be 8-10.
8. the method for claim 1, it is characterised in that, described tensio-active agent is hydrophilic nonionogenic tenside or other cats products.
9. method as claimed in claim 8, it is characterised in that, described tensio-active agent is hydrophilic nonionogenic tenside is Brij56 or Brij58.
10. the high reactivity moly-sulfide thin-film electro catalyzer prepared by method according to the arbitrary item of claim 1-9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040264A (en) * | 2016-06-23 | 2016-10-26 | 中国石油大学(华东) | Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material |
| CN108569678A (en) * | 2017-03-13 | 2018-09-25 | 中国科学技术大学 | A kind of Transition-metal dichalcogenide and its preparation method and application |
| CN108642541A (en) * | 2018-04-11 | 2018-10-12 | 哈尔滨工程大学 | The preparation method of titanium doped molybdenum disulfide film with ultraviolet absorption peak |
| CN112030184A (en) * | 2020-07-27 | 2020-12-04 | 南京航空航天大学 | Amorphous molybdenum sulfide film modified silicon photoelectric cathode and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU960319A1 (en) * | 1981-04-13 | 1982-09-23 | Тюменский индустриальный институт им.Ленинского комсомола | Method for producing composite coatings |
| CN1614101A (en) * | 2004-09-30 | 2005-05-11 | 东南大学 | Molybdenum disulfide electrodepositing method and liquid for micromachinery surface |
| CN1986893A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Electrochemical reducing process for preparing nanometer MOS2 particle |
| CN1994895A (en) * | 2006-12-20 | 2007-07-11 | 浙江大学 | Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere |
| CN103613137A (en) * | 2013-11-08 | 2014-03-05 | 电子科技大学 | Hydrothermal synthesis method of molybdenum disulfide nano flowers |
| CN104198532A (en) * | 2014-09-05 | 2014-12-10 | 中国石油大学(华东) | Molybdenum disulfide thin film device with ammonia sensitive effect as well as preparation method and application thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU960319A1 (en) * | 1981-04-13 | 1982-09-23 | Тюменский индустриальный институт им.Ленинского комсомола | Method for producing composite coatings |
| CN1614101A (en) * | 2004-09-30 | 2005-05-11 | 东南大学 | Molybdenum disulfide electrodepositing method and liquid for micromachinery surface |
| CN1986893A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Electrochemical reducing process for preparing nanometer MOS2 particle |
| CN1994895A (en) * | 2006-12-20 | 2007-07-11 | 浙江大学 | Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere |
| CN103613137A (en) * | 2013-11-08 | 2014-03-05 | 电子科技大学 | Hydrothermal synthesis method of molybdenum disulfide nano flowers |
| CN104198532A (en) * | 2014-09-05 | 2014-12-10 | 中国石油大学(华东) | Molybdenum disulfide thin film device with ammonia sensitive effect as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张嘉芮: "脉冲电沉积制备二硫化钼薄膜及其电催化性能研究", 《重庆大学硕士学位论文》 * |
| 曾颖峰 等: "表面活性剂对制备纳米MoS2颗粒的影响", 《石油学报（石油化工）》 * |
| 赵兴蕾 等: "二硫化钼微球的制备及表征", 《青岛科技大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040264A (en) * | 2016-06-23 | 2016-10-26 | 中国石油大学(华东) | Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material |
| CN108569678A (en) * | 2017-03-13 | 2018-09-25 | 中国科学技术大学 | A kind of Transition-metal dichalcogenide and its preparation method and application |
| CN108569678B (en) * | 2017-03-13 | 2020-03-31 | 中国科学技术大学 | Transition metal chalcogenide and preparation method and application thereof |
| CN108642541A (en) * | 2018-04-11 | 2018-10-12 | 哈尔滨工程大学 | The preparation method of titanium doped molybdenum disulfide film with ultraviolet absorption peak |
| CN112030184A (en) * | 2020-07-27 | 2020-12-04 | 南京航空航天大学 | Amorphous molybdenum sulfide film modified silicon photoelectric cathode and preparation method thereof |
| CN112030184B (en) * | 2020-07-27 | 2021-11-23 | 南京航空航天大学 | Amorphous molybdenum sulfide film modified silicon photoelectric cathode and preparation method thereof |
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