CN111701597B - Multi-metal-doped molybdenum disulfide material and preparation method and application thereof - Google Patents

Multi-metal-doped molybdenum disulfide material and preparation method and application thereof Download PDF

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CN111701597B
CN111701597B CN202010429647.1A CN202010429647A CN111701597B CN 111701597 B CN111701597 B CN 111701597B CN 202010429647 A CN202010429647 A CN 202010429647A CN 111701597 B CN111701597 B CN 111701597B
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metal
intercalation
molybdenum
molybdenum oxide
cobalt
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CN111701597A (en
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宫勇吉
杨伟伟
陈乾
江华宁
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Beijing zhongruitai New Material Co.,Ltd.
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Beihang University
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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
    • B01J27/047—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
    • B01J37/20—Sulfiding
    • 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
    • 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 discloses a multi-metal-doped molybdenum disulfide material, and a preparation method and application thereof. The multi-metal-doped molybdenum disulfide material is a material formed by taking molybdenum trioxide as a substrate, inserting atoms of various metals between van der Waals layers of the molybdenum trioxide and then carrying out a vulcanization reaction; the plurality of metals includes a first metal and a second metal; the ratio of the total mole number of the metals to the mole number of the molybdenum disulfide is (0.04-0.15): 1; the first metal and the second metal are selected from one of tin, iron, cobalt, nickel, gold, silver, platinum and palladium, and the first metal and the second metal are different. The multi-metal-doped molybdenum disulfide material provided by the invention has a very high application prospect in the field of electrocatalytic hydrogen production, and particularly has a better application performance in an acidic medium. The multi-metal-doped molybdenum disulfide material has better durability, stable performance after more than ten thousand cycles, lower electrical impedance and good conductivity reflected by the impedance.

Description

Multi-metal-doped molybdenum disulfide material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a multi-metal-doped molybdenum disulfide material and a preparation method and application thereof.
Background
The hydrogen is a clean and renewable novel fuel, and has important significance for replacing the traditional fossil fuel and realizing the upgrading of industrial technology. The combustion value of hydrogen energy is extremely high, and the combustion product is only H2O, does not generate any pollutant and greenhouse gas such as CO2. More importantly, the utility modelThe hydrogen energy can be obtained directly through the electrolytic water hydrogen evolution reaction, and the raw materials are rich. The overpotential of the hydrogen evolution reaction is high, platinum noble metals are generally needed to be used as catalysts to reduce the overpotential, and the noble metal catalysts are expensive and lack resources, so that the wide application of hydrogen production by water electrolysis in industry is limited.
Among the numerous non-platinum hydrogen evolution electrocatalysts, the most studied in recent years are transition metal chalcogenide electrocatalysts such as molybdenum, tungsten sulfides and selenides, MoS2The catalyst system is very interesting because it is cheap and easy to obtain and has high catalytic efficiency. MoS2Has a layered structure, a Mo atomic layer is sandwiched between two S atomic layers to form a sandwich structure, and three crystal forms (1T-MoS) of 1T, 2H and 3R exist2Being metastable, metallic, 2H-MoS2Being a stable phase, semiconducting, 3R-MoS2Also metastable). In general, the local conductivity and charge density of the semiconductor can be effectively adjusted after the substitutional doping modification. Likewise, doping to MoS2Heteroatoms in the matrix can be held at basal planes by changing their local charge density or creating sulfur vacancies. Compared with a phase engineering method, the heteroatom doping strategy can obtain a stable product, and the 1T phase MoS2Are metastable. However, many common heteroatom introduction methods, such as plasma doping techniques, high temperature synthesis, electrochemical deposition, or hydrothermal conversion methods, typically introduce only MoS doped with metal atoms2. One disadvantage of these synthetic methods is that the heteroatoms tend to form clusters or tend to enrich the edges or form separate phases of various chemical compositions rather than to obtain a homogeneous doped phase.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a multi-metal-doped molybdenum disulfide material, and a preparation method and application thereof.
The invention provides a multi-metal doped molybdenum disulfide material, which is a material formed by taking molybdenum trioxide as a substrate, inserting atoms of various metals between van der Waals layers of the molybdenum trioxide and then carrying out a vulcanization reaction;
the plurality of metals includes a first metal and a second metal; the molar ratio of the total molar ratio of the plurality of metals to the molybdenum disulfide (calculated as molybdenum) is (0.04-0.15): 1;
the first metal and the second metal are respectively and independently selected from one of tin, iron, cobalt, nickel, gold, silver, platinum and palladium, and the first metal and the second metal are not the same.
The multi-metal-doped molybdenum disulfide material provided by the invention is characterized in that preferably, the first metal is one of cobalt or palladium, the second metal is the other of cobalt or palladium, and the molar ratio of cobalt to palladium is (5-17): (3-13);
or, the first metal is one of iron or platinum, the second metal is the other of iron or platinum, and the molar ratio of the iron to the platinum is (5-17): (0.5-5).
The multi-metal-doped molybdenum disulfide material of the invention, wherein preferably, the plurality of metals further comprises a first metal, a second metal and a third metal, each of the first metal, the second metal and the third metal is selected from one of cobalt, palladium or iron, and the first metal, the second metal and the third metal are different from each other; wherein, the ratio of cobalt: palladium: the molar ratio of iron is (5-17): (3-13): (5-17).
The multi-metal-doped molybdenum disulfide material provided by the invention has the advantages that the lattice spacing of the multi-metal-doped molybdenum disulfide material is preferably 0.600-0.900 nm (including 0.600nm and 0.900nm), the specific surface area is 10-100 m2/g。
The multi-metal doped molybdenum disulfide material of the present invention preferably has the first metal being one of cobalt or palladium and the second metal being the other of cobalt or palladium, and satisfies at least one of the following characteristics:
(a) the multi-metal doped molybdenum disulfide material has a current density of-10 mA cm-2The overpotential of the current is 40-55 mV;
(b) the tafel slope is 30-50 mV dec at a scan rate of 10mV/s-1；
(c) Current density at-200 mA cm after cyclic voltammetry cycling for 10,000 times-2Time overpotentialThe increase is only 0.5-4 mV.
The multi-metal-doped molybdenum disulfide material disclosed by the invention is preferably 1-20nm thick.
The multi-metal doped molybdenum disulfide material is preferably prepared by the following method:
first metal intercalation:
dispersing the molybdenum trioxide nanobelt and a first metal salt and/or a first metal complex in a solvent, and reacting in a closed container at 50-140 ℃ to obtain a molybdenum oxide material with a first metal intercalation; the first metal salt or first metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation is dispersed in a solvent, a second metal salt and/or a second metal complex are/is added, and the molybdenum oxide material with the two metal intercalation is obtained through reaction at 50-140 ℃ in a closed container; the second metal salt or second metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) vulcanization:
and vulcanizing the two metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain two metal doped molybdenum disulfide.
According to the multi-metal-doped molybdenum disulfide material, preferably, in the steps of the first metal intercalation and the second metal intercalation, the reaction is carried out for 0.5-6 h at 50-140 ℃ in a closed container;
and/or the presence of a gas in the gas,
in the vulcanization step: and (4) vulcanizing for 1-3 h.
The multi-metal doped molybdenum disulfide material of the present invention is preferably,
regarding the step of first metal intercalation:
the first metal is cobalt; first metal intercalation: and dispersing the molybdenum trioxide nanobelt and the carbonyl complex of cobalt in an acetone solution, and reacting for 2-3 h at 80-110 ℃ in a closed container to obtain the molybdenum oxide material with the cobalt intercalation.
Or
The first metal is palladium; first metal intercalation: mixing the molybdenum trioxide nanobelt with ammonium tetrachloropalladate [ (NH)4)2PdCl6]And ascorbic acid (C)6H8O6) Dispersing in deionized water, and reacting in a closed container at 80-110 ℃ for 0.5-4 h to obtain the molybdenum oxide material with palladium intercalation.
Or
The first metal is nickel; first metal intercalation: mixing molybdenum trioxide nanobelt with [ Ni (NO)3)2·H2O]And sodium borohydride (NaBH)4) Dispersing in absolute ethyl alcohol, and reacting in a closed container at 50-100 ℃ for 0.5-3h to obtain the nickel intercalated molybdenum oxide material.
Or
The first metal is platinum; first metal intercalation: mixing molybdenum trioxide nanobelt with [ (NH)4)2PtCl6]And glucose (C)6H12O6) Dispersing in absolute methanol, and reacting in a closed container at 80-140 ℃ for 1-6 h to obtain a platinum intercalated molybdenum oxide material;
or
The first metal is iron; first metal intercalation: mixing molybdenum trioxide nanobelt with nonacarbonyl di-iron [ Fe ]2(CO)9]Dispersing in acetone, and reacting in a closed container at 80-110 ℃ for 2-4 h to obtain an iron intercalated molybdenum oxide material;
or
Regarding the step of second metal intercalation:
the second metal is cobalt; and (3) second metal intercalation: and dispersing the molybdenum oxide material with the first metal intercalation and the carbonyl complex of cobalt in an acetone solution, and reacting for 2-3 h at 80-110 ℃ in a closed container to obtain the molybdenum oxide material with the cobalt intercalation.
Or
The second metal is palladium; and (3) second metal intercalation: the molybdenum oxide material with the first metal intercalation and ammonium tetrachloropalladate [ (NH)4)2PdCl6]And ascorbic acid (C)6H8O6) Dispersing in deionized water, sealingAnd reacting for 0.5-4 h at 80-110 ℃ in the container to obtain the molybdenum oxide material with the palladium intercalation.
Or
The second metal is nickel; and (3) second metal intercalation: intercalating said first metal intercalated molybdenum oxide material with [ Ni (NO)3)2·H2O]And sodium borohydride (NaBH)4) Dispersing in absolute ethyl alcohol, and reacting in a closed container at 50-100 ℃ for 0.5-3h to obtain the nickel intercalated molybdenum oxide material.
Or
The second metal is platinum; and (3) second metal intercalation: intercalating said first metal with an [ (NH) molybdenum oxide material4)2PtCl6]And glucose (C)6H12O6) Dispersing in absolute methanol, and reacting in a closed container at 80-140 ℃ for 1-6 h to obtain a platinum intercalated molybdenum oxide material;
or
The second metal is iron; and (3) second metal intercalation: the molybdenum oxide material with the first metal intercalation and the nonacarbonyl diiron [ Fe ]2(CO)9]Dispersing in acetone, and reacting in a closed container at 80-110 ℃ for 2-4 h to obtain the iron intercalated molybdenum oxide material.
According to the multi-metal doped molybdenum disulfide material, preferably, the lattice spacing of the molybdenum trioxide nanobelts is between 0.200 and 0.450nm (including 0.200nm and 0.450 nm);
more preferably, the ratio of the lattice spacing between the molybdenum trioxide nanoribbons and the multi-metal doped molybdenum disulfide material is 37: (75-85).
The multi-metal doped molybdenum disulfide material is preferably prepared by the following method:
reacting molybdenum powder with an oxidant at 160-200 ℃ for 8-10 h, then cooling at the temperature of not higher than 0 ℃ for 20-24 h, and drying to obtain the molybdenum powder;
the oxidant can be freely selected from conventional oxidants in the field, and a more preferable technical scheme is provided as follows, wherein the oxidant is selected from one or more of hydrogen peroxide, nitric acid (the mass concentration of the nitric acid is preferably 10-15 wt%), and the like.
According to the multi-metal doped molybdenum disulfide material, the thickness of the molybdenum trioxide nanobelt is preferably less than 20 nm.
In the multi-metal-doped molybdenum disulfide material of the present invention, preferably, the sulfur source includes one or more of sulfur, hydrogen sulfide gas, and the like. More preferably sulfur.
The multi-metal doped molybdenum disulfide material of the present invention preferably further comprises, between the step of intercalation of the second metal and the step of sulfurization:
and (3) intercalation of a third metal:
dispersing the molybdenum oxide material with the second metal intercalation in a solvent, adding a third metal salt and/or a third metal complex, and reacting in a closed container at 50-140 ℃ to obtain molybdenum oxide materials with three metal intercalation; the third metal salt or third metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and the step of vulcanizing is replaced by:
and sulfurizing the three metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain the three metal doped molybdenum disulfide.
In a second aspect, the present invention provides a method of making any one of the above multi-metal doped molybdenum disulfide materials.
According to the method for preparing the multi-metal doped molybdenum disulfide material, the molar number of the molybdenum trioxide nanobelts is preferably equal to that of the molybdenum trioxide nanobelts calculated on the basis of the first metal and the second metal
The ratio of the sum of the mole numbers of the first metal salt and/or the first metal complex and the second metal salt and/or the second metal complex is 1 (0.1-0.5).
According to the method for preparing the multi-metal-doped molybdenum disulfide material, the solvent is preferably one or more selected from acetone, ethanol, isopropanol, deionized water and methanol; wherein the solvents used in the first metal intercalation, the second metal intercalation or the third metal intercalation may be the same or different.
In the method for preparing the multi-metal-doped molybdenum disulfide material, the inert gas is preferably argon; the hydrogen gas accounts for 5-10% of the volume of the mixed gas of the inert gas and the hydrogen gas.
In a third aspect, the invention provides the use of any one of the above multi-metal doped molybdenum disulfide materials as a catalyst in an electrocatalytic hydrogen evolution reaction.
According to the application of the invention, preferably, the multi-metal doped molybdenum disulfide material is applied to an acid medium; the pH value of the acidic medium is not more than 1.
The multi-metal-doped molybdenum disulfide material provided by the invention has a very high application prospect in the field of electrocatalytic hydrogen production. The multi-metal doped molybdenum disulfide material provided by the invention has electrocatalytic activity close to that of a commercial catalyst Pt-C, and particularly has better application performance in an acidic medium. The material has better durability, stable performance after more than ten thousand cycles, lower electrical impedance and reflecting good conductivity of the material.
Drawings
FIG. 1 is MoO3HRTEM image of (A);
FIG. 2 shows Co-Pd-MoS2HRTEM image of (A);
FIG. 3 shows Co-Pd-MoS2HRTEM image of (A);
FIG. 4 shows Co-Pd-MoS2A TEM image of (B);
FIG. 5 shows MoO3,Co-MoO3And Co-Pd-MoO3XRD spectrum of (1);
FIG. 6 shows MoS2,Co-MoS2And Co-Pd-MoS2XRD spectrum of (1);
FIG. 7 shows MoS2,Co-MoS2And Co-Pd-MoS2(ii) a raman spectrum of;
FIG. 8 shows MoS2,Co-MoS2And Co-Pd-MoS2XPS spectra of (a);
FIG. 9-1 is a polarization curve of the materials of examples 1-5;
FIG. 9-2 is a polarization curve for the materials of example 1 and comparative examples 1-6;
FIG. 10 shows Co-Pd-MoS2And overpotential of the material of comparative examples 1 to 6;
FIG. 11 shows MoS2、Co-MoS2、Pd-MoS2Pt/C and Co-Pd-MoS2The tafel slope curve of (a);
FIG. 12 shows Co-Pd-MoS2CV cycle performance curve of (a);
FIG. 13 shows Co-Pd-MoS2Current time cycle curve of (d);
FIG. 14 shows Co-Pd-MoS2Doping MoS with other metal elements2And (5) comparing the performances of the materials.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a multi-metal doped molybdenum disulfide material, which is a material formed by taking molybdenum trioxide as a substrate, inserting atoms of various metals between van der Waals layers of the molybdenum trioxide and then carrying out a vulcanization reaction;
the plurality of metals includes a first metal and a second metal; the molar ratio of the total molar ratio of the plurality of metals to the molybdenum disulfide (calculated as molybdenum) is (0.04-0.15): 1;
the first metal and the second metal are respectively and independently selected from one of tin, iron, cobalt, nickel, gold, silver, platinum and palladium, and the first metal and the second metal are not the same.
In the invention, a plurality of metal atoms are intercalated between Van der Waals layers of molybdenum trioxide, then molybdenum trioxide in the molybdenum trioxide material after the intercalation of the plurality of metal atoms is vulcanized into molybdenum disulfide through a vulcanization reaction, and the intercalated metal atoms replace molybdenum atoms and enter a molybdenum disulfide lattice; thereby forming a composite material in which the plurality of metals are inserted between crystal lattices of molybdenum disulfide, rather than being merely supported on the surface of molybdenum disulfide.
The multi-metal-doped molybdenum disulfide material provided by the invention is characterized in that preferably, the first metal is one of cobalt or palladium, the second metal is the other of cobalt or palladium, and the molar ratio of cobalt to palladium is (5-17): (3 to 13)
Or, the first metal is one of iron or platinum, the second metal is the other of iron or platinum, and the molar ratio of the iron to the platinum is (5-17): (0.5-5).
More preferably, the first metal is one of cobalt or palladium and the second metal is the other of cobalt or palladium.
Through verification, the stability of the multi-metal doped molybdenum disulfide material can be effectively improved by doping cobalt and palladium, and the multi-metal doped molybdenum disulfide material has a smaller overpotential.
The multi-metal doped molybdenum disulfide material of the invention, wherein preferably, the plurality of metals may further include a first metal, a second metal and a third metal, each of the first metal, the second metal and the third metal is selected from one of cobalt, palladium or iron, and the first metal, the second metal and the third metal are different from each other; wherein, the ratio of cobalt: palladium: the molar ratio of iron is (5-17): (3-13): (5-17).
Through the intensive research of the inventor, the advantages of using the bimetal are better than those of using three metals, particularly cobalt-palladium bimetal, by balancing the cost and the effect.
The multi-metal-doped molybdenum disulfide material provided by the invention has the advantages that the lattice spacing of the multi-metal-doped molybdenum disulfide material is preferably 0.600-0.900 nm (including 0.600nm and 0.900nm), the specific surface area is preferably 10-100 m2/g。
The multi-metal doped molybdenum disulfide material of the present invention preferably has the first metal being one of cobalt or palladium and the second metal being the other of cobalt or palladium, and satisfies at least one of the following characteristics:
(a) the multi-metal doped molybdenum disulfide material is current-tightThe degree is-10 mA cm-2The overpotential of the current is 40-55 mV;
(b) at a scanning rate of 10mV/s and a Tafel slope of 30-50 mV dec-1；
(c) Current density at-200 mA cm after cyclic voltammetry cycling for 10,000 times-2The overpotential is increased by only 0.5-4 mV.
The three characteristics (a) to (c) may satisfy only one of the characteristics, or satisfy 2 to 3 of the characteristics, and all of the characteristics are within the protection scope of the present invention. Preferably, one or more of the above (a) to (c) is tested under the condition that the pH value is not more than 1.
The thickness of the multi-metal doped molybdenum disulfide material is preferably 1-20 nm.
The method of inserting atoms of various metals between van der waals layers of molybdenum trioxide based on molybdenum trioxide according to the present invention can employ the following technical means:
first metal intercalation:
dispersing the molybdenum trioxide nanobelt and a first metal salt and/or a first metal complex in a solvent, and reacting in a closed container at 50-140 ℃ to obtain a molybdenum oxide material with a first metal intercalation; the first metal salt or first metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation is dispersed in a solvent, a second metal salt and/or a second metal complex are/is added, and the molybdenum oxide material with the two metal intercalation is obtained through reaction at 50-140 ℃ in a closed container; the second metal salt or second metal complex is provided in the form of a chloride, nitrate, carbonyl complex, or the like.
More specifically, the multi-metal doped molybdenum disulfide material of the present invention is preferably prepared by the following method:
first metal intercalation:
dispersing the molybdenum trioxide nanobelt and a first metal salt and/or a first metal complex in a solvent, and reacting in a closed container at 50-140 ℃ to obtain a molybdenum oxide material with a first metal intercalation; the first metal salt or first metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation is dispersed in a solvent, a second metal salt and/or a second metal complex are/is added, and the molybdenum oxide material with the two metal intercalation is obtained through reaction at 50-140 ℃ in a closed container; the second metal salt or second metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) vulcanization:
and vulcanizing the two metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain two metal doped molybdenum disulfide.
By adopting the specific preparation method, the molybdenum disulfide doped with two metals can be obtained with high yield, and the two metals can be more uniformly inserted into the crystal lattice of the molybdenum disulfide. The first metal or the second metal is provided in the form of chloride, nitrate, carbonyl complex, etc., so that the reaction can be ensured and the reaction efficiency can be improved.
The multi-metal doped molybdenum disulfide material of the present invention preferably further comprises, between the step of doping the second metal and the step of sulfurizing:
and (3) intercalation of a third metal:
dispersing the molybdenum oxide material with the second metal intercalation in a solvent, adding a third metal salt and/or a third metal complex, and reacting in a closed container at 50-140 ℃ to obtain molybdenum oxide materials with three metal intercalation; the third metal salt or third metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and the step of vulcanizing is replaced by:
and sulfurizing the three metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain the three metal doped molybdenum disulfide.
In the multi-metal-doped molybdenum disulfide material, preferably, in the steps of doping the first metal and doping the second metal (or doping the third metal), the reaction is carried out for 0.5 to 6 hours at 50 to 140 ℃ in a closed container;
and/or the presence of a gas in the gas,
in the vulcanization step: and (4) vulcanizing for 1-3 h.
In the multi-metal-doped molybdenum disulfide material of the present invention, the step of doping the first metal, doping the second metal, or doping the third metal may further include: and (3) carrying out reaction in a closed container at 50-140 ℃ to obtain (one/two/three) metal intercalated molybdenum oxide material, and then carrying out ultrasonic treatment to remove surface particles.
In the multi-metal-doped molybdenum disulfide material of the invention, in the step of doping the first metal, doping the second metal or doping the third metal, the reaction raw material may further include a reducing agent. The reducing agent may be any one conventionally used in the art, and preferably may be sodium borohydride, ascorbic acid, glucose, or the like. The reducing agent may be adjusted in a manner conventional in the art, and preferred solutions are given here:
the molar ratio of the reducing agent to the molybdenum trioxide is (2-6): (10-30); and/or the molar ratio of the reducing agent to the plurality of metals is (2-6): (1-3).
According to the multi-metal doped molybdenum disulfide material, the mass ratio of the two metal intercalated molybdenum oxide materials to sulfur is preferably 3: (5-20); more preferably 3 (10-20); most preferably 3: 15;
or, the mass ratio of the three metal intercalated molybdenum oxide materials to the sulfur is 3: (5-20); more preferably 3 (10-20).
In the present invention, if the metal is cobalt, it is preferably provided in the form of a carbonyl complex; if the metal is palladium, preferably ammonium tetrachloropalladate [ (NH)4)2PdCl6]Is provided in the form of (1); if the metal is nickel, preferably nickel nitrate [ Ni (NO)3)2]Is provided in the form of (1); if the metal is iron, preferably nonacarbonyldiiron [ Fe ]2(CO)9](ii) a Such as metalAs platinum, preference is given to using ammonium hexachloroplatinate [ (NH)4)2PtCl6]Is provided in the form of (1). In this regard, it will be understood by those skilled in the art that the metal exemplified above may be any one of the first metal, the second metal, and the third metal.
The multi-metal doped molybdenum disulfide material of the present invention preferably comprises, with respect to the step of doping the first metal:
the first metal is cobalt;
first metal intercalation:
and dispersing the molybdenum trioxide nanobelt and the carbonyl complex of cobalt in an acetone solution, and reacting for 2-3 h at 80-110 ℃ in a closed container to obtain the molybdenum oxide material with the cobalt intercalation.
Or
The first metal is palladium;
first metal intercalation:
mixing the molybdenum trioxide nanobelt with ammonium tetrachloropalladate [ (NH)4)2PdCl6]And ascorbic acid (C)6H8O6) Dispersing in deionized water, and reacting in a closed container at 80-110 ℃ for 0.5-4 h to obtain the molybdenum oxide material with palladium intercalation.
Or
The first metal is nickel;
first metal intercalation:
mixing molybdenum trioxide nanobelt with [ Ni (NO)3)2·H2O]And sodium borohydride (NaBH)4) Dispersing in absolute ethyl alcohol, and reacting in a closed container at 50-100 ℃ for 0.5-3h to obtain the nickel intercalated molybdenum oxide material.
Or
The first metal is platinum;
first metal intercalation:
mixing molybdenum trioxide nanobelt with [ (NH)4)2PtCl6]And glucose (C)6H12O6) Dispersing in absolute methanol, and reacting in a closed container at 80-140 ℃ for 1-6 h to obtain a platinum intercalated molybdenum oxide material;
or
The first metal is iron;
first metal intercalation:
mixing molybdenum trioxide nanobelt with nonacarbonyl di-iron [ Fe ]2(CO)9]Dispersing in acetone, and reacting in a closed container at 80-110 ℃ for 2-4 h to obtain the iron intercalated molybdenum oxide material.
Regarding the step of second metal intercalation:
the second metal is cobalt;
and (3) second metal intercalation:
and dispersing the molybdenum oxide material with the first metal intercalation and the carbonyl complex of cobalt in an acetone solution, and reacting for 2-3 h at 80-110 ℃ in a closed container to obtain the molybdenum oxide material with the cobalt intercalation.
Or
The second metal is palladium;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation and ammonium tetrachloropalladate [ (NH)4)2PdCl6]And ascorbic acid (C)6H8O6) Dispersing in deionized water, and reacting in a closed container at 80-110 ℃ for 0.5-4 h to obtain the molybdenum oxide material with palladium intercalation.
Or
The second metal is nickel;
and (3) second metal intercalation:
intercalating said first metal intercalated molybdenum oxide material with [ Ni (NO)3)2·H2O]And sodium borohydride (NaBH)4) Dispersing in absolute ethyl alcohol, and reacting in a closed container at 50-100 ℃ for 0.5-3h to obtain the nickel intercalated molybdenum oxide material.
Or
The second metal is platinum;
and (3) second metal intercalation:
intercalating said first metal with an [ (NH) molybdenum oxide material4)2PtCl6]And glucose (C)6H12O6) Dispersing in absolute methanol, and reacting in a closed container at 80-140 ℃ for 1-6 h to obtain a platinum intercalated molybdenum oxide material;
or
The second metal is iron;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation and the nonacarbonyl diiron [ Fe ]2(CO)9]Dispersing in acetone, and reacting in a closed container at 80-110 ℃ for 2-4 h to obtain the iron intercalated molybdenum oxide material.
Procedure for vulcanization:
and vulcanizing the two metal intercalated molybdenum oxide materials or the three metal intercalated molybdenum oxide materials in a tube furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain two metal doped molybdenum disulfide or three metal intercalated molybdenum disulfide.
According to the multi-metal doped molybdenum disulfide material, preferably, the lattice spacing of the molybdenum trioxide nanobelts is between 0.200 and 0.450nm (including 0.200nm and 0.450 nm);
more preferably, the ratio of the lattice spacing between the molybdenum trioxide nanoribbons and the multi-metal doped molybdenum disulfide material is 37: (75-85). Under the proportion range, the HER performance of the obtained multi-metal doped molybdenum disulfide material is obviously improved.
The multi-metal doped molybdenum disulfide material is preferably prepared by the following method:
reacting molybdenum powder with an oxidant at 160-200 ℃ for 8-10 h, then cooling at 0 ℃ for 20-24 h, and drying to obtain the molybdenum powder;
the oxidant can be freely selected from conventional oxidants in the field, and a more preferable technical scheme is provided as follows, wherein the oxidant is selected from one or more of hydrogen peroxide, nitric acid (the mass concentration of the nitric acid is preferably 10-15 wt%), and the like.
According to the multi-metal doped molybdenum disulfide material, the thickness of the molybdenum trioxide nanobelt is preferably less than 20 nm. By using the molybdenum trioxide nanobelt with a specific thickness, the multi-metal doped molybdenum disulfide material with better performance can be obtained.
In the multi-metal-doped molybdenum disulfide material of the present invention, preferably, the sulfur source includes one or more of sulfur, hydrogen sulfide gas, and the like. More preferably sulfur.
The sulfur (sulfur powder) is used as a reaction raw material, so that the cost is low and the reaction is efficient.
In a second aspect, the present invention provides a method of making any one of the above multi-metal doped molybdenum disulfide materials.
The method comprises the following steps:
first metal intercalation:
dispersing the molybdenum trioxide nanobelt and a first metal salt and/or a first metal complex in a solvent, and reacting in a closed container at 50-140 ℃ to obtain a molybdenum oxide material with a first metal intercalation; the first metal salt or first metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation is dispersed in a solvent, a second metal salt and/or a second metal complex are/is added, and the molybdenum oxide material with the two metal intercalation is obtained through reaction at 50-140 ℃ in a closed container; the second metal salt or second metal complex is provided in the form of chloride, nitrate, carbonyl complex, or the like;
and (3) vulcanization:
and vulcanizing the two metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain two metal doped molybdenum disulfide.
According to the method for preparing the multi-metal doped molybdenum disulfide material, the ratio of the number of moles of the molybdenum trioxide nanobelts to the sum of the number of moles of the first metal and the second metal is preferably 1 (0.1-0.5) based on the first metal and the second metal. The specific molar ratio is adopted for preparation, which is beneficial to obtaining more intercalated molybdenum oxide materials.
According to the method for preparing the multi-metal-doped molybdenum disulfide material, the solvent is preferably one or more selected from acetone, ethanol, isopropanol, deionized water and methanol; wherein, the solvent used in the first metal doping, the second metal doping or the third metal doping may be the same or different.
According to the method for preparing the multi-metal doped molybdenum disulfide material, the inventor finds that the adopted gas is a mixed atmosphere of inert gas and hydrogen instead of pure inert gas, so that molybdenum trioxide is more favorably converted into disulfide, and intercalated metal atoms are favorably substituted for molybdenum atoms for doping. Preferably, the inert gas is argon; more preferably, the hydrogen gas accounts for 5-10% of the mixed gas of the inert gas and the hydrogen gas by volume. Within this range, the conversion of molybdenum trioxide is high and the doping of metal atoms is high.
According to the method for preparing the multi-metal doped molybdenum disulfide material, the molar volume ratio of the molybdenum trioxide nanobelts to the solvent is preferably (0.05-0.2 mmol): 15 mL.
In a third aspect, the invention provides the use of any one of the above multi-metal doped molybdenum disulfide materials in an electrocatalytic hydrogen evolution reaction.
According to the application of the invention, preferably, the multi-metal doped molybdenum disulfide material is applied to an acid medium; the pH value of the acidic medium is not more than 1.
Example 1
This example provides a Co-Pd-MoS2A material. The preparation method comprises the following steps:
(1) preparation of molybdenum trioxide nanobelts
Adding 0.2g of molybdenum powder into a 100mL hydrothermal reaction kettle, adding 20mL of deionized water, stirring for 10min, adding 10mL of hydrogen peroxide, stirring for 30min, transferring into an oven for reaction at 160 ℃ for 10h, then cooling the mixed solution at the low temperature of 0 ℃ for 24h, and respectively cleaning the obtained solution with deionized water and ethanol for three times for later use to obtain the molybdenum trioxide nanobelt with the thickness of about 10 nm.
The lattice spacing of the molybdenum trioxide nanobelts is 0.370nm by HRTEM scanning, as shown in figure 1.
(2)Co-Pd-MoS2Preparation of the material:
drying molybdenum trioxide nanobelts (1mmol) in the presence of a catalystDispersed acoustically in acetone solution (15 mL). Then, 0.1mmol of Co2(CO)8Was added to the above solution and stirred at 85 ℃ for 3h under Ar gas (99.99%). After mixing, MoO3The color of the solution gradually changed from white to dark indigo. Thereafter, the suspended solution was filtered and separately treated with 0.5M H2SO4Washing the solution with acetone for 2 times to obtain Co-MoO3。
Mixing Co-MoO3Ultrasonically dispersed in an acetone solution (5mL), and then 0.1mmol of ammonium tetrachloropalladate [ (NH)4)2PdCl6]And 0.2mmol ascorbic acid (C)6H8O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4The solution and acetone are respectively washed for 2 times to obtain Co-Pd-MoO3。
2g of Co-Pd-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Co-Pd-MoS2A material.
The characterization information is as follows:
FIG. 1 is MoO3HRTEM picture of the material with interplanar spacing of 0.370nm, corresponding to MoO3The (001) plane of (1).
FIG. 2 shows Co-Pd-MoO3HRTEM picture of the material with interplanar spacing of 0.391nm relative to pure phase MoO3，Co-Pd-MoO3The interplanar spacing of the crystal is increased by 0.021nm, and the increase of the interlayer spacing further verifies that the bimetal of cobalt and palladium is inserted into MoO3Between the van der waals layers.
FIG. 3 shows Co-Pd-MoS2HRTEM image of material, relative to standard MoS2Interlayer spacing of (002) plane of (Co-Pd-MoS)2The interlayer spacing of the catalyst is increased to 0.790 and 0.814nm, and the increase of the interlayer spacing is beneficial to improving Co-Pd-MoS2The electrocatalytic hydrogen evolution reaction capability.
FIG. 4 shows Co-Pd-MoS2TEM image of material, synthetic Co-Pd-MoS2Is in a shape of a nano-belt, the width is about 400-600nm, and the length is several micrometers.
FIG. 5 shows MoO3、Co-MoO3And Co-Pd-MoO3The XRD spectrum of the material shows that the product has diffraction peaks at 12.780 degrees, 23.339 degrees, 25.699 degrees, 25.879 degrees and 27.339 degrees, which correspond to (020), (110), (040), (120) and (021) crystal faces of PDF card numbers 35-0609. Furthermore, MoO relative to standard3,Co-MoO3And Co-Pd-MoO3The (020) peak of (A) is significantly shifted to the left, indicating that the interlayer spacing in the (020) direction is significantly increased and Co and Pd are intercalated into MoO3This is the same conclusion as HRTEM.
FIG. 6 shows MoS2、Co-MoS2And Co-Pd-MoS2The XRD spectrum of the material corresponds to PDF card numbers 37-1492.
FIG. 7 shows MoS2、Co-MoS2And Co-Pd-MoS2Raman spectrum with Raman shifts of 381.2 and 406.6cm-1Here, is the standard MoS2A characteristic raman peak. Co-MoS2And Co-Pd-MoS2The characteristic peak of the metal oxide is shifted to the left, which proves that Co single metal and Co/Pd double metal are doped.
FIG. 8 shows MoS2、Co-MoS2And Co-Pd-MoS2X-ray photoelectron spectroscopy (XPS), Co-MoS2And Co-Pd-MoS2The peaks of Co and Co/Pd are respectively shown, which indicates that Co and Co/Pd are successfully doped into MoS2Within the crystal lattice of (a).
Example 2
This example provides an Fe-Pd-MoS2A material. Compared with example 1, the difference is that:
(2)Fe-Pd-MoS2preparation of the material:
dried molybdenum trioxide nanoribbons (1mmol) were ultrasonically dispersed in acetone solution (15 mL). Then, 0.1mmol of nonacarbonyl diiron [ Fe ]2(CO)9]Was added to the above solution and stirred at 85 ℃ for 3h under Ar gas (99.99%). After mixing, MoO3The color of the solution gradually changed from white to dark indigo. Thereafter, the suspended solution was filtered and separately treated with 0.5M H2SO4Washing the solution with acetone for 2 times to obtain Fe-MoO3。
Fe-MoO3Ultrasonically dispersed in a deionized water solution (5mL), and then 0.1mmol ammonium tetrachloropalladate [ (NH)4)2PdCl6]And 0.2mmol ascorbic acid (C)6H8O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4Washing the solution and acetone for 2 times respectively to obtain Fe-Pd-MoO3。
2g of Fe-Pd-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Fe-Pd-MoS2A material.
Example 3
This example provides a Fe-Pt-MoS2A material. Compared with example 1, the difference is that:
(2)Fe-Pt-MoS2preparation of the material:
dried molybdenum trioxide nanoribbons (1mmol) were ultrasonically dispersed in acetone solution (15 mL). Then, 0.1mmol of nonacarbonyl diiron [ Fe ]2(CO)9]Was added to the above solution and stirred at 85 ℃ for 3h under Ar gas (99.99%). After mixing, MoO3The color of the solution gradually changed from white to dark indigo. Thereafter, the suspended solution was filtered and separately treated with 0.5M H2SO4Washing the solution with acetone for 2 times to obtain Fe-MoO3。
Mixing Fe-MoO3Ultrasonic dispersion in acetone solution (5mL), then 0.05mmol ammonium hexachloroplatinate [ (NH)4)2PtCl6]And 0.1mmol of glucose (C)6H12O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4Washing the solution and acetone for 2 times respectively to obtain Fe-Pt-MoO3。
2g of Fe-Pd-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2 hours to obtain Fe-Pt-MoS2A material.
Example 4
This example provides a Pd-Pt-MoS2A material. Compared with example 1, the difference is that:
(2)Pd-Pt-MoS2preparation of the material:
ultrasonically dispersing dried molybdenum trioxide nanobelts (1mmol) in deionized water solution (15mL), and then, adding 0.1mmol ammonium tetrachloropalladate [ (NH)4)2PdCl6]And 0.2mmol ascorbic acid (C)6H8O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4Washing the solution with acetone for 2 times to obtain Pd-MoO3。
Pd-MoO3Ultrasonic dispersion in an anhydrous methanol solution (5mL) was performed, and then 0.05mmol of ammonium hexachloroplatinate [ (NH)4)2PtCl6]And 0.1mmol of glucose (C)6H12O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4The solution and acetone are respectively washed for 2 times to obtain Pd-Pt-MoO3。
2g of Fe-Pd-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Pd-PtFe-Pt-MoS2A material.
Example 5
This example provides a Co-Pt-MoO3A material. Compared with example 1, the difference is that:
(2)Co-Pt-MoS2preparation of the material:
dried molybdenum trioxide nanoribbons (1mmol) were ultrasonically dispersed in acetone solution (15 mL). Then, 0.1mmol of Co2(CO)8Was added to the above solution and stirred at 85 ℃ for 3h under Ar gas (99.99%). After mixing, MoO3The color of the solution gradually changed from white to dark indigo. Thereafter, the suspended solution was filtered and separately treated with 0.5M H2SO4Washing the solution with acetone for 2 times to obtain Co-MoO3。
Mixing Co-MoO3Ultrasonic dispersion in an anhydrous methanol solution (5mL) was performed, and then 0.05mmol of ammonium hexachloroplatinate [ (NH)4)2PtCl6]And 0.1mmol of glucose (C)6H12O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4The solution and acetone are respectively washed for 2 times to obtain Co-Pt-MoO3。
2g of Co-Pt-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Co-Pt-MoS2A material.
Example 6
This example provides a Co-Fe-Pd-MoO3A material. Compared with example 1, the difference is that:
(2)Co-Fe-Pd-MoS2preparation of the material:
dried molybdenum trioxide nanoribbons (1mmol) were ultrasonically dispersed in acetone solution (15 mL). Then, 0.1mmol of Co2(CO)8Was added to the above solution and stirred at 85 ℃ for 3h under Ar gas (99.99%). After mixing, MoO3The color of the solution gradually changed from white to dark indigo. Thereafter, the suspended solution was filtered and separately treated with 0.5M H2SO4Washing the solution with acetone for 2 times to obtain Co-MoO3。
Mixing Co-MoO3Ultrasonically dispersed in a deionized water solution (5mL), and then 0.1mmol ammonium tetrachloropalladate [ (NH)4)2PdCl6]And 0.2mmol ascorbic acid (C)6H8O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4Washing the solution with acetone for 2 times to obtain Co-Pd-MoO3。
Mixing Co-Pd-MoO3Ultrasonically dispersed in an acetone solution (5mL), and then, the nonacarbonyl diiron [ Fe ]2(CO)9]Adding into the above solution under Ar gas (99.99%)Stirring for 3h at 85 ℃; thereafter, the suspended solution was filtered with 0.5M H each2SO4The solution and acetone are respectively washed for 2 times to obtain Co-Fe-Pd-MoO3。
2g of Co-Fe-Pd-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Co-Fe-Pd-MoS2A material.
Comparative example 1
This comparative example provides a MoS2The preparation method of the material comprises the following steps:
2g of the molybdenum trioxide nanoribbons prepared in example 1 were placed in argon and hydrogen (w% H)25%) was added 50g of sulfur and heated at 450 ℃ for 2h to obtain MoS2A material.
The MoS2XRD of the material is shown in FIG. 6, and only has characteristic peaks of (002), (100), (101) and (110); the Raman spectrum is shown in FIG. 7, with peaks at 381.2 and 406.6 corresponding to MoS2Characteristic peak of (2).
Comparative example 2
This comparative example provides a Co-MoS2The preparation method of the material comprises the following steps:
dried molybdenum trioxide nanoribbons (1mmol) were ultrasonically dispersed in acetone solution (15 mL). Then, 0.1mmol of Co2(CO)8Was added to the above solution and stirred at 85 ℃ for 3h under Ar gas (99.99%). After mixing, MoO3The color of the solution gradually changed from white to dark indigo. Thereafter, the suspended solution was filtered and separately treated with 0.5M H2SO4Washing the solution with acetone for 2 times to obtain Co-MoO3。
2g of Co-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Co-MoS2A material.
The Co-MoS2XRD of the material is shown in FIG. 6, and only has characteristic peaks of (002), (100), (101) and (110); the Raman spectrum is shown in FIG. 7, peaks at 376.6 and 403.5, corresponding to the standard MoS2A Raman peak; XPS spectrum as shown in FIG. 8, Co-MoS2The peak of Co appears, which indicates that Co is successfully doped into MoS2Within the crystal lattice of (a).
Comparative example 3
This comparative example provides a Pd-MoS2The preparation method of the material comprises the following steps:
dried molybdenum trioxide nanobelts (1mmol) were ultrasonically dispersed in acetone solution (5mL), and then 0.1mmol ammonium tetrachloropalladate [ (NH)4)2PdCl6]And 0.2mmol ascorbic acid (C)6H8O6) Adding into the above solution, and stirring at 85 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4Washing the solution with acetone for 2 times to obtain Pd-MoO3。
2g of Pd-MoO3Under argon and hydrogen (w% H)25%) was added 30g of sulfur and heated at 450 ℃ for 2h to obtain Pd-MoS2A material.
Comparative example 4
This comparative example provides a Pt-MoS2The preparation method of the material comprises the following steps:
dried molybdenum trioxide nanobelts (1mmol) were ultrasonically dispersed in an anhydrous methanol solution (5mL), and then 0.05mmol ammonium hexachloroplatinate [ (NH)4)2PtCl6]And 0.1mmol of glucose (C)6H12O6) Adding into the above solution, and stirring at 120 deg.C for 3h under Ar gas (99.99%); thereafter, the suspended solution was filtered with 0.5M H each2SO4Washing the solution with acetone for 2 times to obtain Pt-MoO3。
2g of Pt-MoO3Under argon and hydrogen (w% H)25%) was added 28g of sulfur and heated at 450 ℃ for 2h to obtain Pt-MoS2A material.
Comparative example 5
This comparative example provides a 5% Pd/C catalyst, type: alfa 000776; the purchase route is as follows: beijing YinuoKai Tech Co.
Comparative example 6
This comparative example provides a 5% Pt/C catalyst, type: alfa 195230100; the purchase route is as follows: beijing YinuoKai Tech Co.
Examples of the experiments
Subject: the catalyst materials provided in examples 1-5 and comparative examples 1-6.
The experimental method comprises the following steps: electrochemical measurement: standard three-electrode configuration on CHI 760E electrochemical workstation, at Ar2Saturated H2SO4Electrocatalytic HER activity was measured in solution (0.5M).
The working electrode was a catalyst coated glassy carbon electrode (3 mm diameter).
Graphite rods and Ag/AgCl (saturated KCl solution) were used as counter and reference electrodes, respectively.
All measured potentials are referred to as the Reverse Hydrogen Electrode (RHE) by the following equation:
E(RHE)＝E(Ag+/AgCl)+0.204V+0.0591V pH(1)
all catalysts (MoS)2，Co-MoS2，Pd-MoS2，Co-Pd-MoS2) The solutions were prepared by uniformly dispersing the corresponding 4mg catalyst and 5 μ L of 5 wt% Nafion solution in 1mL water/ethanol (4: 1 v/v). The catalyst loading on the glassy carbon electrode was calculated to be about 0.281mg/cm2。
At 25 ℃ in 10mV s-1The Linear Sweep Voltammetry (LSV) curve and Tafel slope (Tafel) curve were recorded.
By heating at 25 ℃ at 50mV s-1The durability test was performed by repeating a potential sweep from 0.104 to-0.296 (vs RHE) for 10,000CV cycles.
At H2Saturated 0.5M H2SO4A chronoamperometric characterization at 49.3mA (vs. RHE) overpotential for 32h was performed in the solution.
Electrochemical Impedance Spectroscopy (EIS) measurements A perturbation test of 5mV was performed on an Autolab PGSTAT 302N potentiostat (Metrohm Autolab, the Netherlands) at a frequency range of 0.01-100,000 Hz and a potential of-0.200V (vs. RHE).
The experimental results are as follows:
the polarization curves are shown in fig. 9-1 and 9-2. FromAs can be seen from FIG. 9-1, the multi-metal-doped molybdenum disulfide materials of examples 1-4 provided by the present invention all have excellent HER performance, Co-Pd-MoS2The electrocatalytic hydrogen evolution reaction activity is obviously superior to that of other bimetal doped MoS2. As can be seen from FIG. 9-2, Co-Pd-MoS2The material has a similar polarization curve with the existing platinum catalyst Pt/C; the Co-Pd-MoS of the invention is comparable to the materials of comparative examples 1 to 52The performance advantage of the material is obvious.
The specific data are as follows: Co-Pd-MoS of example 12When the current density of the material reaches 10mA/cm2The time-required overpotential (eta)10) 49.3 mV; example 2 materials when Current Density of 10mA/cm2The time-required overpotential (eta)10) 186 mV; example 3 materials when Current Density of 10mA/cm2The time-required overpotential (eta)10) Is 115 mV; example 4 materials when Current Density of 10mA/cm2The time-required overpotential (eta)10) Is 136 mV; comparative example 1 material when the current density reached 10mA/cm2The time-required overpotential (eta)10) 437.3 mV; comparative example 2 Material when Current Density reached 10mA/cm2The time-required overpotential (eta)10) 397.4 mV; comparative example 3 material when the current density reached 10mA/cm2The time-required overpotential (eta)10) 212.7 mV; comparative example 4 Material when Current Density reached 10mA/cm2The time-required overpotential (eta)10) 266.5 mV; comparative example 5 Material when Current Density reached 10mA/cm2The time-required overpotential (eta)10) Is 86 mV; comparative example 6 Material when Current Density reached 10mA/cm2The time-required overpotential (eta)10) Is 34 mV.
The overpotential is shown in fig. 10. Thus, the Co-Pd-MoS provided by the invention2The overpotential of the material is 10mA cm-2The overpotential during the process is only 49.3mV, which is far higher than that of comparative examples 1-5 and is close to that of comparative example 6.
The tafel slope curve is shown in fig. 11. Thus, the Co-Pd-MoS provided by the invention2The Tafel slope curve of the material was similar to that of comparative example 6 and was only 43.2mV dec-1And is far lower than that of comparative examples 1 to 5. In the hydrogen evolution reaction, the lower the tafel slope of the catalyst, the higher the catalytic current was demonstrated with the same increase in overpotential.
CV cycle performance is shown in fig. 12. As can be seen from the figure, the Co-Pd-MoS was observed even when the cycles were 10000 times2The polarization curve of the material is not greatly changed, and the overpotential is increased by only 2.9mV, so that the Co-Pd-MoS of the invention2The material has excellent durability and cycle performance.
The current time cycle performance is shown in fig. 13. This is seen. Co-Pd-MoS of the invention2The material still keeps stable current density after being cycled for more than 30 hours (32 hours), and shows excellent cycling performance.
The overall performance ratio is shown in fig. 14. It can be seen that the Co-Pd-MoS of the present invention2The catalytic performance of the electrocatalyst is obviously superior to that of MoS doped with other metal atoms2Material in which other metal elements are doped with MoS2Documents are derived from s.z.yang et al, adv.mater.2018,30,1803477, j.ding et al, nat.commun.2017,8,14430, z.y.luo et al, nat.commun.2018,9,2120, j.xu, et al, angelw.chem.int.edit.2016, 55,6612, s.j.ding et al, angelw.chem.int.ed.2019, 10,09698, y.shi et al, j.am.chem.soc.2017,139, 15479; the above documents are incorporated herein by reference in their entirety.
As can be seen from FIG. 14, the Co-Pd-MoS provided by the present invention2The material has excellent performance in the field of electrocatalysis, and is far superior to the similar research in the prior art.
The multi-metal-doped molybdenum disulfide material provided by the invention has a very high application prospect in the field of electrocatalytic hydrogen production, and particularly has a better application performance in an acidic medium. The multi-metal-doped molybdenum disulfide material has better durability, stable performance after more than ten thousand cycles, lower electrical impedance and good conductivity reflected by the impedance.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (13)

1. The application of the multi-metal-doped molybdenum disulfide material as a catalyst in an electrocatalytic hydrogen evolution reaction is characterized in that the multi-metal-doped molybdenum disulfide material is a material which is formed by taking molybdenum trioxide as a substrate, inserting atoms of various metals between van der Waals layers of the molybdenum trioxide and then carrying out a sulfurization reaction;
the plurality of metals includes a first metal and a second metal; the molar ratio of the total of the plurality of metals to the molybdenum disulfide is (0.04-0.15): 1;
the first metal and the second metal are respectively and independently selected from one of tin, iron, cobalt, nickel, gold, silver, platinum and palladium, and the first metal and the second metal are not the same.
2. The use according to claim 1, wherein the first metal is one of cobalt or palladium, the second metal is the other of cobalt or palladium, and the molar ratio of cobalt to palladium is (5-17): (3-13);
or, the first metal is one of iron or platinum, the second metal is the other of iron or platinum, and the molar ratio of the iron to the platinum is (5-17): (0.5-5).
3. The use according to claim 1 or 2, wherein the plurality of metals further comprises a first metal, a second metal and a third metal, each of the first metal, the second metal and the third metal is selected from one of cobalt, palladium or iron, and the first metal, the second metal and the third metal are different from each other; wherein, the ratio of cobalt: palladium: the molar ratio of iron is (5-17): (3-13): (5-17).
4. The use according to claim 1, wherein the multi-metal doped molybdenum disulfide material has a lattice spacing of 0.600 to 0.900nm and a specific surface area of 10 to 100m2/g。
5. The use of claim 4, wherein the first metal is one of cobalt or palladium, the second metal is the other of cobalt or palladium, and at least one of the following characteristics is satisfied:
(a) the multi-metal doped molybdenum disulfide material has a current density of-10 mA cm-2The overpotential of the current is 40-55 mV;
(b) the tafel slope at a scan rate of 10mV/s is 30-50 mV dec-1；
(c) Current density at-200 mA cm after cyclic voltammetry cycling for 10,000 times-2The overpotential is increased by only 0.5-4 mV.
6. Use according to claim 1 or 2, wherein the multi-metal doped molybdenum disulfide material is prepared by:
first metal intercalation:
dispersing the molybdenum trioxide nanobelt and a first metal salt and/or a first metal complex in a solvent, and reacting in a closed container at 50-140 ℃ to obtain a molybdenum oxide material with a first metal intercalation; the first metal salt or first metal complex is provided in the form of a chloride, nitrate, carbonyl complex;
and (3) second metal intercalation:
the molybdenum oxide material with the first metal intercalation is dispersed in a solvent, a second metal salt and/or a second metal complex are/is added, and the molybdenum oxide material with the two metal intercalation is obtained through reaction at 50-140 ℃ in a closed container; the second metal salt or second metal complex is provided in the form of a chloride, nitrate, carbonyl complex;
and (3) vulcanization:
and vulcanizing the two metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain the two metal intercalated molybdenum disulfide.
7. The use according to claim 6, wherein in the step of the first metal intercalation and the step of the second metal intercalation, the reaction is carried out for 0.5 to 6 hours at 50 to 140 ℃ in a closed container; and/or, in the vulcanization step: and (4) vulcanizing for 1-3 h.
8. Use according to claim 6, wherein the first metal is cobalt; first metal intercalation: dispersing a molybdenum trioxide nanobelt and a carbonyl complex of cobalt in an acetone solution, and reacting for 2-3 h at 80-110 ℃ in a closed container to obtain a molybdenum oxide material with a cobalt intercalation layer;
or
The first metal is palladium; first metal intercalation: mixing the molybdenum trioxide nanobelt with ammonium tetrachloropalladate [ (NH)4)2PdCl6]And ascorbic acid (C)6H8O6) Dispersing in deionized water, and reacting in a closed container at 80-110 ℃ for 0.5-4 h to obtain a molybdenum oxide material with palladium intercalation;
or
The first metal is nickel; first metal intercalation: mixing molybdenum trioxide nanobelt with [ Ni (NO)3)2·H2O]And sodium borohydride (NaBH)4) Dispersing in absolute ethyl alcohol, and reacting in a closed container at 50-100 deg.C for 0.5-3h to obtain nickel intercalated molybdenum oxide material;
or
The first metal is platinum; first metal intercalation: mixing molybdenum trioxide nanobelt with [ (NH)4)2PtCl6]And glucose (C)6H12O6) Dispersing in absolute methanol, and reacting in a closed container at 80-140 ℃ for 1-6 h to obtain a platinum intercalated molybdenum oxide material;
or
The first metal is iron; first metal intercalation: mixing molybdenum trioxide nanobelt with nonacarbonyl di-iron [ Fe ]2(CO)9]Dispersing in acetone, and reacting in a closed container at 80-110 ℃ for 2-4 h to obtain an iron intercalated molybdenum oxide material;
or:
the second metal is cobalt; and (3) second metal intercalation: dispersing the molybdenum oxide material with the first metal intercalation and a carbonyl complex of cobalt in an acetone solution, and reacting for 2-3 h at 80-110 ℃ in a closed container to obtain a molybdenum oxide material with the cobalt intercalation;
or
The second metal is palladium; and (3) second metal intercalation: the molybdenum oxide material with the first metal intercalation and ammonium tetrachloropalladate [ (NH)4)2PdCl6]And ascorbic acid (C)6H8O6) Dispersing in deionized water, and reacting in a closed container at 80-110 ℃ for 0.5-4 h to obtain a molybdenum oxide material with palladium intercalation;
or
The second metal is nickel; and (3) second metal intercalation: intercalating said first metal intercalated molybdenum oxide material with [ Ni (NO)3)2·H2O]And sodium borohydride (NaBH)4) Dispersing in absolute ethyl alcohol, and reacting in a closed container at 50-100 ℃ for 0.5-3h to obtain a nickel intercalated molybdenum oxide material;
or
The second metal is platinum; and (3) second metal intercalation: intercalating said first metal with an [ (NH) molybdenum oxide material4)2PtCl6]And glucose (C)6H12O6) Dispersing in absolute methanol, and reacting in a closed container at 80-140 ℃ for 1-6 h to obtain a platinum intercalated molybdenum oxide material;
or
The second metal is iron; and (3) second metal intercalation: the molybdenum oxide material with the first metal intercalation and the nonacarbonyl diiron [ Fe ]2(CO)9]Dispersing in acetone, and reacting in a closed container at 80-110 ℃ for 2-4 h to obtain the iron intercalated molybdenum oxide material.
9. The use of claim 6, wherein the sulfur source comprises one or both of sulfur, hydrogen sulfide gas.
10. Use according to claim 9, wherein the sulphur source is sulphur.
11. The use of claim 6, further comprising, between the step of intercalating the second metal and the step of sulfiding:
and (3) intercalation of a third metal:
dispersing the molybdenum oxide material with the second metal intercalation in a solvent, adding a third metal salt and/or a third metal complex, and reacting in a closed container at 50-140 ℃ to obtain molybdenum oxide materials with three metal intercalation; the third metal salt or the third metal complex is provided in the form of chloride, nitrate, carbonyl complex;
and the step of vulcanizing is replaced by:
and sulfurizing the three metal intercalated molybdenum oxide materials in a tubular furnace by using a sulfur source at 300-600 ℃ under the mixed atmosphere of inert gas and hydrogen to obtain the three metal doped molybdenum disulfide.
12. The use according to claim 1, wherein the method of preparing the multi-metal doped molybdenum disulfide material comprises:
the ratio of the mole number of the molybdenum trioxide nano-belt to the sum of the mole number of the first metal salt and/or the first metal complex and the mole number of the second metal salt and/or the second metal complex is 1 (0.1-0.5) calculated by the first metal and the second metal.
13. The use according to claim 1; the multi-metal doped molybdenum disulfide material is applied to an acid medium; the pH value of the acidic medium is not more than 1.
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