CN111111705B - Method for synthesizing transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt - Google Patents
Method for synthesizing transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt Download PDFInfo
- Publication number
- CN111111705B CN111111705B CN202010098520.6A CN202010098520A CN111111705B CN 111111705 B CN111111705 B CN 111111705B CN 202010098520 A CN202010098520 A CN 202010098520A CN 111111705 B CN111111705 B CN 111111705B
- Authority
- CN
- China
- Prior art keywords
- transition metal
- metal sulfide
- thiocyanate
- hydrogen evolution
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing a transition metal sulfide hydrogen evolution catalyst by low-temperature molten salt. And (2) uniformly mixing thiocyanate and a transition gold source to obtain a precursor, then loading the precursor into a container, heating the precursor in a muffle furnace for reaction, and washing the reactant with water after the reaction is finished to obtain the transition metal sulfide. The unreacted thiocyanate is recrystallized and recycled, so that the production cost is reduced. The raw materials related by the invention have low price, the synthesis temperature is low, harsh conditions such as high pressure, inert atmosphere and the like are not needed, and the equipment requirement is simple. The thiocyanate serves as a molten salt as a reaction medium and provides a sulfur source for the formation of sulfides, so that an external sulfur source is not needed in the material synthesis. The invention obviously simplifies the preparation process flow of the transition metal sulfide hydrogen evolution catalyst, improves the preparation efficiency of the transition metal sulfide material and is beneficial to industrial production and application.
Description
Technical Field
The invention belongs to the field of catalyst materials, and relates to a method for synthesizing a transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt.
Background
With the rapid development of global economy, the demand for energy from humans is increasing. Fossil fuels with limited reserves are the main energy support at present, and cause a huge energy crisis for sustainable development. Meanwhile, excessive dependence on fossil energy also brings about serious environmental problems. The replacement of traditional fossil energy with clean energy has significant potential applications. The hydrogen is a high-efficiency energy carrier, and the combustion product of the hydrogen is only water, has extremely high heat value and cannot cause pollution to the environment. Therefore, green and environmentally friendly hydrogen energy sources are receiving much attention. The production of hydrogen is the basis for the large-scale application of hydrogen energy. At present, the industry mainly depends on fossil fuel to produce hydrogen, which is a non-sustainable hydrogen production means and aggravates the consumption of the fossil fuel and environmental pollution. The electrolytic water is used for preparing hydrogen by consuming renewable electric energy and abundant water resources, has the advantages of convenient electric power transportation, low equipment requirement, no geographical condition limitation and the like, and is a hydrogen production method with great development potential. In the hydrogen production by water electrolysis, in order to reduce the loss of electric energy, a high-efficiency catalyst needs to be introduced to improve the hydrogen production efficiency and reduce the hydrogen production cost. Noble metal materials represented by platinum have excellent electrochemical hydrogen evolution catalytic performance, but are expensive and difficult to apply on a large scale. A range of non-noble metal materials were subsequently developed as hydrogen evolution catalysts. Among them, the transition metal sulfides, such as molybdenum sulfide, cobalt sulfide, nickel sulfide, etc., have the characteristics of low price, good stability, high catalytic activity, and are hydrogen evolution catalysts with the most application prospects.
Many methods for synthesizing transition metal sulfides exist, but the synthesized material cannot meet the requirements of hydrogen evolution catalysts, which is mainly reflected in the difficulty in macro preparation and low catalytic activity of the material, and is mainly limited by the material synthesis method. Transition metal sulfide can be synthesized by a hydrothermal method, for example, patent 1 'wu-zexing, songmine, etc., preparation and application of transition metal sulfide nanospheres [ P ], application No. 201910208038.0', transition metal salt and a sulfur source are mixed in water and ethanol, and a transition metal sulfide hydrogen evolution catalyst is prepared by a hydrothermal reaction. However, the method relates to a high-pressure process, has potential safety hazards and low yield, and cannot meet the requirement of large-scale application. The chemical vapor deposition method can also be used for preparing the transition metal sulfide hydrogen evolution catalyst. For example, patent 2 "zhanyanfeng, Huan yahuan, etc., discloses a method for preparing vertical transition metal sulfide nanosheet array and an electrocatalytic hydrogen evolution catalyst [ P ], application No. 201810117506.9" respectively heats elemental sulfur and transition metal chloride to different temperatures, and prepares the vertical transition metal sulfide hydrogen evolution catalyst on a substrate. However, the method has low yield and needs to be carried out at high temperature, so that the catalyst has few defect sites and low catalytic activity. The method can be used for preparing transition metal sulfide on a large scale based on high-temperature solid-phase reaction, and has the disadvantages of high energy consumption and low catalytic activity of the synthesized transition metal sulfide.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for synthesizing a transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt. The method utilizes the thiocyanate with low melting point as the molten salt, adds the transition metal source into the molten salt, and can prepare the transition metal sulfide hydrogen evolution catalyst without additionally adding a sulfur source. The invention aims to prepare the high-performance transition metal sulfide hydrogen evolution catalyst, improve the catalytic activity, simplify the preparation process, reduce the production cost and realize the quantitative production. The invention has important application value in the field of synthesizing transition metal sulfide hydrogen evolution catalysts.
Technical scheme
A method for synthesizing a transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt is characterized by comprising the following steps:
step 1, mixing powder: mixing thiocyanate with a transition metal source to obtain a precursor; the mass ratio of the transition metal source to the thiocyanate is 1-40: 200;
and 3, step 3: and washing and filtering the product after reaction by using deionized water, and drying to obtain the molten salt of the transition metal sulfide hydrogen evolution catalyst.
The thiocyanate is potassium cyanate, sodium thiocyanate or ammonium thiocyanate.
The transition metal source is one or more selected from sodium molybdate, ammonium molybdate, sodium tungstate, cobalt nitrate, cobalt acetate, cobalt sulfate, nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, ferric nitrate, molybdenum oxide, nickel oxide and nickel mesh.
Advantageous effects
The invention provides a method for synthesizing a transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt. And (2) uniformly mixing thiocyanate and a transition gold source to obtain a precursor, then loading the precursor into a container, heating the precursor in a muffle furnace for reaction, and washing the reactant with water after the reaction is finished to obtain the transition metal sulfide. The unreacted thiocyanate is recrystallized and recycled, so that the production cost is reduced. The raw materials related by the invention have low price, the synthesis temperature is low, harsh conditions such as high pressure, inert atmosphere and the like are not needed, and the equipment requirement is simple. The thiocyanate serves as a molten salt as a reaction medium and provides a sulfur source for the formation of sulfides, so that an external sulfur source is not needed in the material synthesis. The invention obviously simplifies the preparation process flow of the transition metal sulfide hydrogen evolution catalyst, improves the preparation efficiency of the transition metal sulfide material and is beneficial to industrial production and application.
The key point of the technical scheme of the invention is that thiocyanate and a transition metal source are used as raw materials, and the transition metal sulfide hydrogen evolution catalyst is synthesized at a low temperature. The thiocyanate not only serves as a stable reaction medium for molten salt, but also provides a sulfur source for the formation of sulfide. The obtained product is simply washed by water to obtain the required catalyst.
The invention has the following beneficial effects:
the technical scheme of the invention takes thiocyanate and a transition metal source as raw materials, and the hydrogen evolution catalyst of the transition metal sulfide can be obtained by stirring, mixing, low-temperature melting reaction treatment and water washing. Compared with the prior transition metal sulfide synthesis technology, the method has the following advantages: 1) the raw materials are wide: the invention takes thiocyanate and a transition metal source as precursors to prepare the transition metal sulfide hydrogen evolution catalyst, and has the characteristics of wide raw material source and low preparation cost; 2) the catalytic activity is high: the method provided by the invention can synthesize the transition metal sulfide hydrogen evolution catalyst under the low-temperature condition, is beneficial to the construction of the microstructure and the surface defects of the catalyst besides low energy consumption, and ensures the catalytic activity; 3) the equipment requirement is low: the thiocyanate can synthesize the transition metal sulfide under the conditions of normal pressure and air atmosphere, does not relate to harsh conditions such as high temperature, high pressure, inert atmosphere and the like, has low equipment requirement and is convenient for large-scale production; 4) the process flow is simple: the thiocyanate serves as a molten salt as a reaction medium and provides a sulfur source for the formation of sulfides, so that no additional sulfur source is needed in the material synthesis, the process flow of the preparation of the transition metal sulfide hydrogen evolution catalyst is simplified, and thioacetamide, thiourea, sodium sulfide, mercaptoethanol and other sulfur sources with strong pollution are not needed. The invention obviously simplifies the preparation process flow of the transition metal sulfide hydrogen evolution catalyst, improves the preparation efficiency of the existing transition metal sulfide and is beneficial to industrial production and application. The invention has important application value in the synthesis of transition metal sulfide and the preparation of high-performance transition metal sulfide hydrogen evolution catalyst.
Drawings
FIG. 1 is an SEM image of an iron sulfide material produced in accordance with example one;
FIG. 2 is a phase analysis XRD pattern of the iron sulfide material prepared in example one.
FIG. 3 is an SEM image of a nickel sulfide material produced by example two;
FIG. 4 is a phase analysis XRD pattern of the nickel sulfide material prepared in example II.
FIG. 5 is an SEM image of molybdenum sulfide material produced by example III;
FIG. 6 is an electrochemical test chart of the molybdenum sulfide material prepared in example III.
FIG. 7 is an electrochemical test chart of the molybdenum sulfide material prepared in example four.
FIG. 8 is an SEM image of a molybdenum sulfide and cobalt sulfide composite made according to example five;
FIG. 9 is an electrochemical test chart of the composite material of molybdenum sulfide and cobalt sulfide prepared in example V.
Detailed Description
The invention will now be further described with reference to the following examples, and the accompanying drawings:
example one
The embodiment is a molten salt synthesis method of a transition metal sulfide hydrogen evolution catalyst, which comprises the following specific processes:
step 1: mixing powder materials: weighing 20g of potassium thiocyanate, adding 1g of ferric nitrate, placing in a 100mL beaker, and stirring with a glass rod to uniformly mix the raw materials to obtain a precursor.
Step 2: the synthesis of the transition metal sulfide material comprises the following specific processes:
a. putting the beaker filled with the precursor obtained in the step 1 into a muffle furnace for heating reaction, heating the muffle furnace to 250 ℃ at a speed of 5 ℃/min in an atmospheric environment, and keeping the temperature for 2 hours;
b. washing the reacted product with deionized water, filtering and drying to obtain FeS 2 。
FeS obtained in this example 2 Is a mixture of flake and granule, and the product is FeS by XRD analysis as shown in figure 1 2 (FIG. 2). This embodiment is carried out under atmospheric conditions without the need for inert atmosphere protection and high pressure conditions, with low equipment requirements. This example demonstrates the successful synthesis of iron sulfide materials.
Example two
Step 1: mixing powder materials: weighing 20g of sodium thiocyanate, adding 4g of nickel acetate, placing in a 100mL beaker, and stirring with a glass rod to uniformly mix the raw materials to obtain a precursor.
Step 2: the synthesis of the transition metal sulfide material comprises the following specific processes:
a. putting the beaker filled with the precursor obtained in the step 1 into a muffle furnace for heating reaction; heating the heat treatment furnace to 300 ℃ at the speed of 20 ℃/min under the atmospheric environment, and preserving heat for 10 hours;
b. and washing the reacted product with deionized water, filtering and drying to obtain the product.
The product obtained in this example was predominantly hexagonal platelet-shaped with small particles present (see FIG. 3). XRD analysis shows that the product is mainly composed of NiS and Ni 3 S 4 (see fig. 4). In the embodiment, no additional sulfur source is added, so that the types of raw materials are reduced, the reaction residual components are simple and easy to treat, and the subsequent treatment cost and potential pollution to the environment are reduced.
EXAMPLE III
Step 1: mixing powder materials: weighing 20g of potassium thiocyanate, adding 2g of ammonium molybdate, placing in a beaker with the volume of 100mL, adding deionized water until the raw materials are just completely dissolved, and drying in an oven at 90 ℃ for 12 hours to obtain the precursor.
Step 2: the synthesis of the transition metal sulfide material comprises the following specific processes:
a. putting the beaker filled with the precursor obtained in the step 1 into a muffle furnace for heating reaction; heating the heat treatment furnace to 200 ℃ at the speed of 1 ℃/min under the atmospheric environment and preserving heat for 10 hours;
b. washing the reacted product with deionized water, filtering and drying to obtain MoS 2 And (3) obtaining the product.
The MoS prepared is shown in FIG. 5 2 The material is spherical, and the surface is petal-shaped. The catalyst has good hydrogen evolution catalytic activity, 10mA/cm 2 The overpotential of the current density is 200mV, which is superior to most of MoS reported at present 2 Catalytic activity of the catalyst (see fig. 6).
Example four
Step 1: mixing powder materials: weighing 20g of potassium thiocyanate, adding 2g of ammonium molybdate, placing the mixture in a 100mL beaker, adding deionized water until the raw materials are just completely dissolved, and drying the mixture in an oven at 90 ℃ for 12 hours to obtain a precursor.
Step 2: the synthesis of the transition metal sulfide material comprises the following specific processes:
a. putting the beaker filled with the precursor obtained in the step 1 into a muffle furnace for heating reaction, heating the heat treatment furnace to 350 ℃ at the speed of 1 ℃/min in the atmospheric environment, and preserving heat for 10 hours;
b. washing the reacted product with deionized water, filtering and drying to obtainTo MoS 2 And (3) obtaining the product.
Compared with example three, the synthesized MoS 2 The catalytic activity of the hydrogen evolution catalyst is obviously reduced, 10mA/cm 2 The overpotential at current density of (2) was 305mV (see FIG. 7), which is caused by the increase of the synthesis temperature. The fourth example shows that the synthesis of the transition metal sulfide under the low temperature condition is beneficial to improving the hydrogen evolution catalytic activity of the material.
EXAMPLE five
Step 1: mixing powder materials: weighing 80g of potassium thiocyanate, adding 4g of cobalt nitrate and 1g of ammonium molybdate, placing the mixture in a 100mL beaker, and stirring the mixture by using a glass rod to uniformly mix the raw materials to obtain a precursor.
And 2, step: the synthesis of the transition metal sulfide material comprises the following specific processes:
a. putting the beaker filled with the precursor obtained in the step 1 into a muffle furnace for heating reaction; heating the heat treatment furnace to 300 ℃ at the speed of 5 ℃/min in the atmospheric environment and preserving heat for 5 hours;
b. washing the reacted product with deionized water, filtering and drying to obtain MoS 2 And CoS 2 The complex of (1).
MoS obtained in this example 2 And CoS 2 Complex, product mainly spherical, phase-pure MoS as in example III 2 Compared with the prior art, the surface petal is not obvious enough, and the catalyst has better and higher electro-catalytic hydrogen evolution activity (as shown in figure 8). 10mA/cm 2 The overpotential at the current density of (1) was 144mV (see FIG. 9). Compared with the existing composite catalyst preparation, the material synthesis does not need multi-step reaction, and the high-efficiency composite catalyst can be synthesized by directly mixing various transition metal raw materials in molten thiocyanate salt for reaction, so that the preparation process is greatly simplified, and the catalytic activity of the catalyst is improved.
Claims (2)
1. A method for synthesizing a transition metal sulfide hydrogen evolution catalyst by low-temperature molten salt is characterized by comprising the following steps:
step 1, mixing powder: mixing thiocyanate with a transition metal source to obtain a precursor; the mass ratio of the transition metal source to the thiocyanate is 1-40: 200;
step 2, synthesis of transition metal sulfide material: placing the precursor into a container, and placing the container into a muffle furnace for a melting reaction; the reaction conditions are as follows: heating a muffle furnace to 175-300 ℃ at the speed of 1-20 ℃/min in an atmospheric environment, and reacting for 0.5-24 h;
and 3, step 3: washing and filtering the reacted product by using deionized water, and drying to obtain a transition metal sulfide hydrogen evolution catalyst;
the transition metal source is ammonium molybdate and cobalt nitrate.
2. The method for synthesizing a transition metal sulfide hydrogen evolution catalyst through low-temperature molten salt according to claim 1, wherein the method comprises the following steps: the thiocyanate is potassium cyanate, sodium thiocyanate or ammonium thiocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010098520.6A CN111111705B (en) | 2020-02-18 | 2020-02-18 | Method for synthesizing transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010098520.6A CN111111705B (en) | 2020-02-18 | 2020-02-18 | Method for synthesizing transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111111705A CN111111705A (en) | 2020-05-08 |
| CN111111705B true CN111111705B (en) | 2022-09-13 |
Family
ID=70491307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010098520.6A Active CN111111705B (en) | 2020-02-18 | 2020-02-18 | Method for synthesizing transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111111705B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491639A (en) * | 1982-09-30 | 1985-01-01 | Gas Research Institute | Methods of making high activity transition metal catalysts |
| CN106622301A (en) * | 2016-12-24 | 2017-05-10 | 青岛科技大学 | MoS2 nanosphere difunctional oxygen catalyst of hierarchy structure and preparation method and application thereof |
| CN108217728A (en) * | 2016-12-09 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of MoS2Nano-particle morphology controllable preparation method |
| CN109908922A (en) * | 2019-03-15 | 2019-06-21 | 皖西学院 | Transition metal chalcogenide homojunction and its preparation method and application |
| CN110028107A (en) * | 2019-03-19 | 2019-07-19 | 青岛科技大学 | The preparation and application of transient metal sulfide nanosphere |
| CN110697777A (en) * | 2019-10-09 | 2020-01-17 | 西北工业大学 | Preparation method of tin molybdenum disulfide with hollow structure |
| CN110790262A (en) * | 2019-10-31 | 2020-02-14 | 西北工业大学 | Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method |
-
2020
- 2020-02-18 CN CN202010098520.6A patent/CN111111705B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491639A (en) * | 1982-09-30 | 1985-01-01 | Gas Research Institute | Methods of making high activity transition metal catalysts |
| CN108217728A (en) * | 2016-12-09 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of MoS2Nano-particle morphology controllable preparation method |
| CN106622301A (en) * | 2016-12-24 | 2017-05-10 | 青岛科技大学 | MoS2 nanosphere difunctional oxygen catalyst of hierarchy structure and preparation method and application thereof |
| CN109908922A (en) * | 2019-03-15 | 2019-06-21 | 皖西学院 | Transition metal chalcogenide homojunction and its preparation method and application |
| CN110028107A (en) * | 2019-03-19 | 2019-07-19 | 青岛科技大学 | The preparation and application of transient metal sulfide nanosphere |
| CN110697777A (en) * | 2019-10-09 | 2020-01-17 | 西北工业大学 | Preparation method of tin molybdenum disulfide with hollow structure |
| CN110790262A (en) * | 2019-10-31 | 2020-02-14 | 西北工业大学 | Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method |
Non-Patent Citations (4)
| Title |
|---|
| Low-temperature molten salt synthesis and characterization of Cu2ZnSnS4 ultrafine powders;Mohamed Benchikhi et al.;《Optik》;20171231;568-572 * |
| MoS_2基复合材料的制备进展及其应用研究;高培玉等;《化工新型材料》;20150215(第02期);209-211 * |
| Synthesis ofCuInS2 nanometric powder by reaction in molten KSCN;Mohamed Benchikhi et al.;《MaterialsLetters》;20140826;433页左栏第1-2段 * |
| 水热法制备不同形貌纳米MoS_2研究进展;何江山等;《中国钼业》;20121231(第06期);42-45 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111111705A (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109569683B (en) | Preparation method and application of nitrogen-phosphorus-codoped porous carbon sheet/transition metal phosphide composite material | |
| CN110052277B (en) | Preparation method of transition metal group metal sulfide oxygen evolution catalyst | |
| CN108479808B (en) | 3D self-assembled flower ball-shaped vanadium modified Ni3S2Method of synthesis of | |
| CN110127655B (en) | Method for preparing biomass carbon-loaded cobalt phosphide electrode material by one-step calcination method | |
| CN110270353A (en) | The preparation and application of load transitions bimetallic chalcogen compound nano material in situ | |
| CN107519905B (en) | Vanadium carbide nano-sieve electrocatalytic material capable of being used in wide pH range and preparation method thereof | |
| CN112542592B (en) | Heteroatom-doped cobalt-molybdenum binary metal carbide nanocomposite and preparation method and application thereof | |
| CN109794246A (en) | A kind of monolithic devices honeycomb Ni@C/C catalyst and its preparation method and application | |
| CN113416975A (en) | Method for preparing biomass carbon-loaded molybdenum carbide electrode material by one-step calcination method | |
| CN110116025A (en) | Covalent triazine class framework compound and MoS2The preparation method of compound liberation of hydrogen catalyst and the application of liberation of hydrogen catalyst | |
| CN110586116A (en) | MoO of hydrogen evolution electrocatalyst2-Ni/CC composite material and preparation method thereof | |
| CN112108165A (en) | Preparation method and application of nitrogen and phosphorus double-doped carbon-coated molybdenum phosphide catalyst | |
| CN111036307B (en) | Preparation method of composite efficient oxygen evolution catalyst | |
| CN110013855B (en) | High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof | |
| CN109046394B (en) | Hollow tubular CoSe2Nano material and preparation method and application thereof | |
| CN108315759A (en) | A kind of Cu of vanadium modification2S self-supportings electrode material and its synthetic method | |
| CN110773202A (en) | Preparation method of yolk-shell structured nickel-molybdenum bimetallic sulfide applied to water cracking | |
| CN113463111A (en) | Method for preparing biomass carbon-loaded molybdenum sulfide electrode material by one-step method | |
| CN113600210A (en) | In-situ growth three-element composite photocatalyst and preparation method and application thereof | |
| CN111111705B (en) | Method for synthesizing transition metal sulfide hydrogen evolution catalyst by using low-temperature molten salt | |
| CN110015693B (en) | Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material | |
| CN115125547B (en) | Preparation and application of Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst | |
| CN115341236A (en) | Cobalt diselenide electrocatalyst and preparation method and application thereof | |
| CN112978815B (en) | Preparation method of nickel-tungsten phosphide-nickel-tungsten oxide with heterostructure | |
| CN113652698B (en) | Tungsten-doped nickel phosphide dual-functional catalytic material with crossed nano-sheet structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |