CN116121801A - Preparation method and application of non-noble metal polyatomic co-doped molybdenum disulfide - Google Patents
Preparation method and application of non-noble metal polyatomic co-doped molybdenum disulfide Download PDFInfo
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Abstract
The invention discloses a preparation method of non-noble metal polyatomic co-doped molybdenum disulfide, which comprises the steps of firstly uniformly mixing precursor solutions doped with a plurality of metal atoms with a molybdenum source solution, then reacting with a sulfur-containing compound at a certain temperature, finally carrying out solution treatment, and carrying out suction filtration and drying to obtain a target product. The material prepared by the method has a definite structure, a single crystalline phase and no metal atom clusters or non-molybdenum disulfide. The kind and the content of the mixed non-noble metal hetero atoms are easy to regulate and control. Experiments prove that the material has excellent electrocatalytic hydrogen evolution reaction performance and has the potential of replacing noble metal catalysts. The method is a universal method for preparing the non-noble metal polyatomic co-doped molybdenum disulfide, and has the characteristics of simple operation and easy regulation and control.
Description
Technical Field
The invention belongs to the technical field of two-dimensional nano material preparation, and particularly relates to a preparation method and application of non-noble metal polyatomic co-doped molybdenum disulfide.
Background
In recent years, two-dimensional (2D) materials have received widespread attention in the catalytic and other fields due to their unique structural and electronic properties (Y.Wang, D.H.Deng, X.H.Bao et al, chem.rev.,119,1806-1854 (2019)). Transition Metal Sulfides (TMDs) are one of the representative two-dimensional materials, which have a two-dimensional structure similar to graphene, and TMDs can be applied directly as a catalyst in many reaction processes (L.Tang, D.H.Deng, X.H.Bao et al Confinement Catalysis with 2D Materials for Energy Conversion.Adv.Mater.31,1901996 (2019)). On this basis, the electronic structure and catalytic activity of TMDs can also be regulated and controlled by methods such as TMDs manufacturing defects (J.F. Xie, yi Xie et al, adv. Mater.25,5807-5813 (2013)), compounding (X.Y.Meng, D.H.Deng, X.H.Bao et al, nano Energy 61,611-616 (2019)), doping (S.Z.Yang, W.Zhou et al, adv. Mater.30,1803477 (2018), J.Deng, D.H.Deng, X.H.Bao et al, energy & Environmental Science 8,1594-1601 (2015)), and the like. In addition, the existence form of TMDs can have a larger influence on catalytic activity, compared with bulk materials, ultrathin two-dimensional materials can expose more atomic surfaces under the same quality condition (J.Deng, D.H.Deng, X.H.Bao et al, RSC Advances,4,34733-34738 (2014)), so that the specific surface area is greatly improved, and more choices are provided for better optimization and design of high-activity catalysts.
There is literature that molybdenum disulfide (MoS 2 ) There is excellent activity of noble-like metals for electrocatalytic Hydrogen Evolution Reactions (HER) (Thomas f., ib Chorkendorff et al., science 317,100 (2007)), but only in terms of MoS 2 The few unsaturated S atoms at the edge were used for simulation calculations and to demonstrate that they have potentially high HER activity, but most of them are inert S atoms with in-plane saturation, theoretical calculations and experimental results indicate MoS 2 The thermodynamically stable (002) basal plane is preferentially exposed (J.F.Xie, yi Xie et al, adv. Mater.25,5807-5813 (2013)), which greatly limits MoS 2 Use in HER reactions. The doping aims to change the local electronic structure by doping the hetero atoms into molybdenum disulfide, so that the number of coordinated unsaturated sulfur atoms is greatly increased, and the hydrogen evolution activity of the self-body hydrogen-evolution catalyst is improved. However, the current doping strategies are mostly monoatomic or noble metal precursorsThe sub-doping has limited regulation and control on the activity of molybdenum sulfide, and the noble metal has high cost, so that the wide application of the doping strategy is greatly limited. Therefore, the non-noble metal polyatomic co-doped molybdenum disulfide becomes a potential efficient activity regulation strategy. However, in the process of simultaneously doping multiple atoms, the original molybdenum disulfide sandwich structure (S-Mo-S) is ensured not to be damaged and the agglomeration among multiple hetero atoms is avoided to form a new phase, so that the preparation of the non-noble metal multi-atom co-doped molybdenum disulfide has quite a challenge.
Disclosure of Invention
Based on the background technology, the invention aims to provide a preparation method of non-noble metal polyatomic co-doped molybdenum disulfide. The method is characterized in that a plurality of elements are co-doped into molybdenum disulfide by an in-situ doping method, and the doped molybdenum disulfide prepared by the method has excellent activity on electrocatalytic hydrogen evolution reaction. The method has the advantages that the doped atoms contain two or more than two atoms, and the method is non-noble metal polyatomic co-doping. The method is simple and convenient to operate and has wide application range. The material has wide application prospect in the fields of electrocatalysis, energy chemistry and the like through doping regulation and control.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in one aspect, the invention provides a polyatomic co-doped molybdenum disulfide, wherein two or more atoms are simultaneously doped with molybdenum disulfide, and the atoms are non-noble metal atoms.
Based on the technical scheme, further, the non-noble metal is titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and cadmium; the atom doped molybdenum disulfide is in a tubular, linear, spherical, flaky, three-dimensional foam-like or flower-like structure.
The invention also provides a preparation method of the non-noble metal polyatomic co-doped molybdenum disulfide, which comprises the following steps:
(1) Adding a molybdenum source into a solvent to obtain solution A, adding a doped non-noble metal atom precursor and a chelating agent into the solvent, and stirring at 15-90 ℃ for 0.5-24h to obtain solution B;
(2) Adding the solution A obtained in the step (1) into the solution B, uniformly mixing, mixing with a sulfur source under the protection of inert gas, sealing in a high-pressure reaction kettle, heating to 100-600 ℃, and keeping for 1-24h;
(3) And (3) treating the product obtained in the step (2) in a solution for 1-16h, washing, suction filtering and drying to obtain the non-noble metal polyatomic co-doped molybdenum disulfide.
Based on the above technical scheme, in the step (1), the molybdenum source is at least one of sodium molybdate, molybdenum chloride, molybdenum trioxide, ammonium molybdate, potassium molybdate, molybdenum tetrathiomolybdate phosphate, molybdenum acetate, molybdenum oxalate, molybdenum acetylacetonate and molybdenum phosphide; the sulfur source is at least one of sulfur powder, thiourea, thioacetamide, carbon disulfide, sodium sulfide, potassium sulfide, ammonium tetrathiomolybdate, butanethiol, dimethyl sulfoxide and potassium thiocyanate; the chelating agent is at least one of ethylenediamine tetraacetic acid, aminotriacetic acid, tartaric acid, gluconic acid, sodium citrate, citric acid monohydrate, ammonium citrate and hydroxyethyl ethylenediamine triacetic acid.
Based on the technical scheme, further, the molar ratio of molybdenum atoms to non-noble metal atoms in the molybdenum source is 10:0.1-20; the mole ratio of any two atoms in the doped non-noble metal atoms is 1:20-20:1; the molar ratio of any one of the non-noble metal atoms to the chelating agent is 0.1-10; in the step (2), the molar ratio of molybdenum atoms in the molybdenum source to sulfur atoms in the sulfur source is 1:500-10:1.
Based on the technical scheme, in the step (1), chelating agent is added into the non-noble metal atom precursor solution for ultrasonic dispersion; in the step (2), in the mixing process, the molybdenum source aqueous solution and the non-noble metal atom precursor solution are mixed and placed in an ultrasonic water bath for dispersion, and the ultrasonic dispersion time of each section is 0.5-6h.
Based on the above technical scheme, in the step (1), the solvent is at least one of water, methanol, formic acid, toluene and cyclohexane.
Based on the above technical solution, in the step (2), the inert gas is at least one of helium, nitrogen, argon, and neon; the temperature rising rate is 0.5-40 ℃/min.
Based on the above technical scheme, in the step (3), the solution is at least one of sodium hydroxide solution, potassium hydroxide solution, toluene solution, ethanol solution and hydrochloric acid solution; wherein the concentration of the sodium hydroxide solution, the potassium hydroxide solution, the ethanol solution and the hydrochloric acid solution is 5-50wt% and the concentration of the toluene solution is 20-70wt%; washing in ultrapure water and ethanol until the solution is neutral; the drying temperature is 25-150deg.C, and the drying time is 4-24h.
In addition, the invention also provides application of the non-noble metal polyatomic co-doped molybdenum disulfide or the non-noble metal polyatomic co-doped molybdenum disulfide obtained by the preparation method in electrocatalytic hydrogen evolution reaction.
The invention has the following beneficial effects:
1. the prepared non-noble metal multi-atom co-doped molybdenum disulfide material has a definite structure, a single crystalline phase, and the doped atoms are uniformly distributed in the material without forming independent metal clusters or metal particles.
2. The prepared non-noble metal polyatomic co-doped molybdenum disulfide material is rich in applicable metal heteroatom types, and the proportion of each component can be regulated and controlled in a large range.
3. The chelating agent added in the prepared non-noble metal polyatomic co-doped molybdenum disulfide can remarkably improve the hydrogen production performance of the non-noble metal polyatomic co-doped molybdenum disulfide on water electrolysis in an acidic environment.
4. The prepared non-noble metal polyatomic co-doped molybdenum disulfide has the advantages of simple preparation process, easy regulation and control, easy amplified preparation, wide sources of precursors required for preparation, good catalytic stability of the prepared material and good industrial application prospect.
Drawings
FIG. 1a is a Transmission Electron Microscope (TEM) image of a sample of comparative example 1, and FIG. 1b is a partial enlarged view;
FIG. 2a is a Transmission Electron Microscope (TEM) image of the sample of example 1, and FIG. 2b is a partial enlarged view;
FIG. 3 is an X-ray diffraction (XRD) pattern of the samples of examples 1, 2 and 4, comparative example 1;
FIG. 4 is a graph showing the electrocatalytic hydrogen evolution activity under acidic conditions for example 1, comparative example 1 and comparative example 2.
Detailed Description
The following describes the whole material preparation process in detail by means of specific examples, while the examples only give some of the conditions for achieving material preparation and do not necessarily require that these conditions be met in order to achieve this object, and the scope of the claims of the present invention is not limited by the examples.
Comparative example 1
(1) Dissolving 0.9g of ammonium molybdate in 20mL of water, uniformly dispersing by ultrasonic, and sealing with 10mL of carbon disulfide into a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Drying the sample obtained in the step (3) in an oven at 80 ℃ to obtain a few-layer molybdenum disulfide (FL-MoS) 2 )。
Comparative example 2
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.1417g of ferric nitrate nonahydrate and 0.0972g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; then 3mL of the solution A is slowly added into the solution B, stirred for 10min, and then sealed with 10mL of carbon disulfide to a 60mL high-pressure reaction kettle under the protection of argon;
(2) The autoclave in (1) was left at 400℃for 4 hours.
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 The mixture was treated with sodium hydroxide solution at 60℃for 3 hours, then washed with ultrapure water and ethanol and suction filtered.
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying, thus obtaining the Fe-Co Co-doped molybdenum disulfide (8 Fe8 Co-MoS) 2 )。
Comparative example 3
(1) Dissolving 0.9g of ammonium molybdate and 0.3226g of cobalt nitrate hexahydrate in 20mL of water, performing ultrasonic dispersion to obtain solution A, adding 0.2169g of ferrocene into 10mL of carbon disulfide, and stirring for 0.5h to obtain solution B; a, B liquid is mixed under the protection of argon and sealed into a 60mL high-pressure reaction kettle;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (8 Fe8 Co-MoS) 2 Ferrocene).
Comparative example 4
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 10mL of distilled water in a 20mL sample bottle, adding 0.4709g of ferric nitrate nonahydrate and 0.2372g of copper nitrate 2.5 water, and stirring for 0.5h to obtain solution B; slowly adding the solution A into the solution B, stirring for 10min, and sealing with 10mL of carbon disulfide into a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Cu co-doped molybdenum disulfide (8 Fe8 Cu-MoS) 2 )。
Comparative example 5
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 10mL of distilled water in a 20mL sample bottle, adding 0.4709g of ferric nitrate nonahydrate and 0.3234g of nickel nitrate hexahydrate, and stirring for 0.5h to obtain solution B; slowly adding the solution A into the solution B, stirring for 10min, and sealing with 10mL of carbon disulfide into a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Ni co-doped molybdenum disulfide (8 Fe8 Ni-MoS) 2 )。
Comparative example 6
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 10mL of distilled water in a 20mL sample bottle, adding 0.3234g of nickel nitrate hexahydrate and 0.3226g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; slowly adding the solution A into the solution B, stirring for 10min, and sealing with 10mL of carbon disulfide into a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain nickel-cobalt Co-doped molybdenum disulfide (8 Ni8 Co-MoS) 2 )。
Example 1
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.2450g of citric acid monohydrate, stirring to dissolve, adding 0.1417g of ferric nitrate nonahydrate and 0.0972g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; taking 3mL of the solution A, slowly adding the solution A into the solution B, stirring for 10min, and sealing the solution A and 10mL of carbon disulfide into a 60mL high-pressure reaction kettle under the protection of argon
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 The mixture was treated with sodium hydroxide solution at 60℃for 3 hours. Then washed with ultrapure water and ethanol and suction filtered.
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (8 Fe8 Co-MoS) 2 -CA)。
Fig. 2 is a Transmission Electron Microscope (TEM) image of co-doped molybdenum disulfide prepared in example 1, and as can be seen from fig. 2, the sample has a two-dimensional layered structure, and a uniform surface and rich edges are exposed, and no other clusters or impurity phases are present. FIG. 3 is an X-ray diffraction spectrum of a sample, showing that the obtained sample is composed of 2H-phase molybdenum sulfide, diffraction peaks related to doped metals do not appear in a certain doping atom concentration range, further proving that no agglomeration phenomenon exists among various doping elements, and showing that the doping elements do not form a new independent crystal phase structure, and the result is consistent with TEM results.
Example 2
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.490g of citric acid monohydrate, stirring to dissolve, adding 0.1417g of ferric nitrate nonahydrate and 0.0972g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; then 3mL of the solution A is slowly added into the solution B, stirred for 10min, and then sealed with 10mL of carbon disulfide to a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (8 Fe8 Co-MoS) 2 -2CA)。
Example 3
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.980g of citric acid monohydrate, stirring to dissolve, adding 0.1417g of ferric nitrate nonahydrate and 0.0972g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; then 3mL of the solution A is slowly added into the solution B, stirred for 10min, and then sealed with 10mL of carbon disulfide to a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (8 Fe8 Co-MoS) 2 -4CA)。
Example 4
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.2450g of citric acid monohydrate, stirring to dissolve, adding 0.2834 g of ferric nitrate nonahydrate and 0.1944g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; then 3mL of the solution A is slowly added into the solution B, stirred for 10min, and then sealed with 10mL of carbon disulfide to a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (16 Fe16 Co-MoS) 2 -CA)。
Example 5
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.2450g of citric acid monohydrate, stirring to dissolve, adding 0.0707g of ferric nitrate nonahydrate and 0.0972g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; then 3mL of the solution A is slowly added into the solution B, stirred for 10min, and then sealed with 10mL of carbon disulfide to a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (4 Fe8 Co-MoS) 2 -CA)。
Example 6
(1) Dissolving 0.9g of ammonium molybdate in 10mL of water, performing ultrasonic dispersion to obtain solution A, taking 17mL of distilled water in a 20mL sample bottle, adding 0.2450g of citric acid monohydrate, stirring to dissolve, adding 0.1417g of ferric nitrate nonahydrate and 0.0486g of cobalt nitrate hexahydrate, and stirring for 0.5h to obtain solution B; then 3mL of the solution A is slowly added into the solution B, stirred for 10min, and then sealed with 10mL of carbon disulfide to a 60mL high-pressure reaction kettle under the protection of argon;
(2) Placing the autoclave in the step (1) at 400 ℃ for 4 hours;
(3) The sample obtained in (2) was subjected to a reaction at 6mol L -1 Treating with 60 deg.c sodium hydroxide solution for 3 hr, washing with ultrapure water and ethanol, and suction filtering;
(4) Placing the sample obtained in the step (3) in an oven at 80 ℃ for drying to obtain the Fe-Co Co-doped molybdenum disulfide (8 Fe4 Co-MoS) 2 -CA)。
Example 7
The iron-cobalt co-doped molybdenum disulfide material with citric acid obtained in example 1, the few-layer molybdenum disulfide material in comparative example 1 and the iron-cobalt co-doped molybdenum disulfide material without citric acid obtained in comparative example 2 are used as catalysts for electrocatalytic hydrogen evolution reaction, and the influence of the presence or absence of citric acid and the presence or absence of molybdenum disulfide doped with non-noble metal atoms on electrocatalytic hydrogen evolution activity is examined.
1. According to the electrocatalytic hydrogen evolution performance evaluation method, a three-electrode system is adopted to carry out linear volt-ampere experiment, a reference electrode is an Ag/AgCl electrode, a counter electrode is a carbon rod electrode, and electrolyte is 0.5mol L saturated by argon gas -1 The glassy carbon electrode with the diameter of 5mm is selected as a working electrode. The catalyst electrode was prepared as follows:
1mL of ethanol solution was added to 4mg of the sample, followed by addition of 20. Mu.L of 5wt% Nafion solution, and ultrasonic dispersion was carried out until a slurry was formed. Then 25 mu L of the slurry is taken out on the surface of the glassy carbon electrode and dried for standby.
2. Test conditions: at 25℃the rotating disk electrode was used at a rotation rate of 1600rpm, at 2mV s -1 Is performed at a linear scan rate of (c).
3. Test results: under the condition that citric acid exists, the Fe-Co co-doped molybdenum disulfide shows excellent electrocatalytic activity in an acidic medium, and compared with the Fe-Co-doped molybdenum disulfide without citric acid, the Fe-Co-doped molybdenum disulfide has obviously improved hydrogen evolution performance. The hydrogen evolution activity sequence is as follows: iron-cobalt co-doped molybdenum disulfide-citric acid > iron-cobalt co-doped molybdenum disulfide > few-layer molybdenum disulfide.
By the preparation method, doping of larger atomic weight in molybdenum sulfide crystal lattices is successfully realized within a certain concentration range, and the hydrogen evolution performance of the few-layer molybdenum sulfide is improved. The electron microscope shows that the obtained samples are of a two-dimensional lamellar structure, uniform surfaces and rich edges are exposed, and no other clusters or impurity phases appear. The X-ray diffraction spectrum shows that the obtained sample is composed of 2H-phase molybdenum sulfide, diffraction peaks related to doped metal do not appear in a certain doping atom concentration range, no agglomeration phenomenon among various doping elements is further proved, and the fact that the doping elements do not form a new independent crystal phase structure is proved, and the result is consistent with a TEM result.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. An atomic doped molybdenum disulfide is characterized in that two or more atoms are doped with molybdenum disulfide at the same time, wherein the atoms are non-noble metal atoms.
2. The atom doped molybdenum disulfide of claim 1 wherein the non-noble metal is titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium; the atom doped molybdenum disulfide is in a tubular, linear, spherical, flaky, three-dimensional foam-like or flower-like structure.
3. A method of preparing the atomic-doped molybdenum disulfide of any one of claims 1-2, comprising the steps of:
(1) Adding a molybdenum source into a solvent to obtain solution A, adding a doped non-noble metal atom precursor and a chelating agent into the solvent, and stirring at 15-90 ℃ for 0.5-24h to obtain solution B;
(2) Adding the solution A obtained in the step (1) into the solution B, uniformly mixing, mixing with a sulfur source under the protection of inert gas, sealing in a high-pressure reaction kettle, heating to 100-600 ℃, and keeping for 1-24h;
(3) And (3) treating the product obtained in the step (2) in a solution for 1-16h, washing, suction filtering and drying to obtain the non-noble metal polyatomic co-doped molybdenum disulfide.
4. The method for preparing the atom-doped molybdenum disulfide according to claim 3, wherein the molybdenum source is at least one of sodium molybdate, molybdenum chloride, molybdenum trioxide, ammonium molybdate, potassium molybdate, molybdenum tetrathiomolybdate phosphate, molybdenum acetate, molybdenum oxalate, molybdenum acetylacetonate, and molybdenum phosphide;
the sulfur source is at least one of sulfur powder, thiourea, thioacetamide, carbon disulfide, sodium sulfide, potassium sulfide, ammonium tetrathiomolybdate, butanethiol, dimethyl sulfoxide and potassium thiocyanate;
the chelating agent is at least one of ethylenediamine tetraacetic acid, aminotriacetic acid, tartaric acid, gluconic acid, sodium citrate, citric acid monohydrate, ammonium citrate and hydroxyethyl ethylenediamine triacetic acid.
5. The method of producing an atom-doped molybdenum disulfide as claimed in claim 3, wherein the molar ratio of molybdenum atoms to non-noble metal atoms in the molybdenum source is 10:0.1-20; the mole ratio of any two atoms in the doped non-noble metal atoms is 1:20-20:1;
the molar ratio of molybdenum atoms in the molybdenum source to sulfur atoms in the sulfur source is 1:500-10:1;
the molar ratio of any one of the non-noble metal atoms to the chelating agent is 0.1-10.
6. The method for preparing the atomic doped molybdenum disulfide according to claim 3, wherein in the step (1), a chelating agent is added into the atomic precursor solution doped with the non-noble metal for ultrasonic dispersion, and in the step (2), in the mixing process, an aqueous solution of a molybdenum source and the atomic precursor solution of the non-noble metal are mixed and placed into an ultrasonic water bath for dispersion, and the ultrasonic dispersion time of each section is 0.5-6h.
7. The method of claim 3, wherein in the step (1), the solvent is at least one of water, methanol, formic acid, toluene, and cyclohexane.
8. The method of claim 3, wherein in the step (2), the inert gas is at least one of helium, nitrogen, argon, and neon; the temperature rising rate is 0.5-40 ℃/min.
9. The method for preparing atomic doped molybdenum disulfide according to claim 3, wherein in the step (3), the solution is at least one of sodium hydroxide solution, potassium hydroxide solution, toluene solution, ethanol solution, and hydrochloric acid solution, wherein the concentration of the sodium hydroxide solution, potassium hydroxide solution, ethanol solution, and hydrochloric acid solution is 5-50wt%, and the concentration of the toluene solution is 20-70wt%; washing in ultrapure water and ethanol until the solution is neutral; the drying temperature is 25-150deg.C, and the drying time is 4-24h.
10. Use of an atomic doped molybdenum disulphide according to any of claims 1 to 2 or obtained by a method according to any of claims 3 to 9 in an electrocatalytic hydrogen evolution reaction.
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