CN109468662B - Preparation method of copper-molybdenum composite material and application of copper-molybdenum composite material in catalyst for hydrogen evolution through water electrolysis - Google Patents
Preparation method of copper-molybdenum composite material and application of copper-molybdenum composite material in catalyst for hydrogen evolution through water electrolysis Download PDFInfo
- Publication number
- CN109468662B CN109468662B CN201811511437.6A CN201811511437A CN109468662B CN 109468662 B CN109468662 B CN 109468662B CN 201811511437 A CN201811511437 A CN 201811511437A CN 109468662 B CN109468662 B CN 109468662B
- Authority
- CN
- China
- Prior art keywords
- copper
- composite material
- solution
- precursor
- molybdenum composite
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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 provides a preparation method of a copper-molybdenum composite material and application of the copper-molybdenum composite material in an electrocatalyst for water electrolysis and hydrogen evolution: firstly, preparing a solution A: adding a precursor A into deionized water to obtain a solution A; preparing a solution B: adding the precursor B into deionized water, and adjusting the pH to 0-13 by using ammonia water and hydrochloric acid to obtain a solution B; and finally pouring the solution A into an empty beaker filled with magnetons, placing the beaker on a stirrer, controlling the rotating speed to be 1-1000RPM, adding the solution B into the beaker, stirring for 1-10h, pouring the solution into a centrifuge tube after the stirring is stopped, placing the centrifuge tube in a centrifuge for centrifugation at the rotating speed of 1-30000RPM for 1-30min, and after the centrifugation is finished, placing the lower-layer precipitate in a drying oven at the temperature of 1-100 ℃ for drying, thus obtaining the flower-shaped non-noble metal copper-molybdenum composite material. The composite material prepared by the invention has great advantages in the aspects of electrocatalytic hydrogen production, electrocatalytic oxygen evolution, electrocatalytic oxygen reduction and energy conversion, and can be applied to the fields of fuel cells and new energy conversion.
Description
Technical Field
The invention belongs to the field of nano composite material research, and the two solutions are slowly reacted at room temperature to form a copper-molybdenum composite material and the copper-molybdenum composite material is used for an electrocatalyst.
Background
In recent decades, with the development of science and technology, the demand of modern society for energy has increased dramatically, but with the burning of fossil fuels, the environmental problems have become more serious, the phenomena of air pollution, haze, global warming and the like have become more obvious, and the reserves of fossil fuels such as coal, petroleum and the like are limited, so that people need to search clean energy to replace the traditional fossil fuels, and in recent years, hydrogen energy has attracted extensive attention of people, and because the combustion product of hydrogen is water, the environment is friendly, and no pollution exists. However, to date, the source of hydrogen has relied primarily on fossil energy sources, such as petroleum cracking, steam methane reforming, water gas reforming, and the like. These production methods are not only inefficient and expensive, but also involve some specific reaction equipment, and also inevitably produce carbon dioxide and other contaminant gases during the production of hydrogen. Therefore, a method for preparing hydrogen in a green way is sought, and in recent years, hydrogen production by water electrolysis is regarded as an effective way for obtaining hydrogen, because the raw material of the hydrogen production reaction is water, the combustion product is also water, in the process, renewable energy sources such as wind power generation, hydroelectric power generation, solar power generation and the like can be used for providing electric energy required by water electrolysis to prepare hydrogen, and water is a substance with abundant reserves in nature, so that hydrogen production by water electrolysis attracts wide attention.
However, the ideal electrolytic water catalyst now being recognized is a platinum-based catalyst of noble metals, which limits its wide range of applications due to their high price. In recent years, research on replacing platinum-based materials with non-noble metals which are low in price and have no pollution to the environment becomes a hot point of research, and based on the above viewpoints, a simple method is researched to synthesize the molybdenum-copper composite material.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is to provide a preparation method of a copper-molybdenum composite material and application of the copper-molybdenum composite material in a catalyst for hydrogen evolution by water electrolysis. The preparation method is simple to operate, the prepared flower-shaped composite material has the advantages of multiple active sites, small electrochemical impedance, good hydrogen evolution performance and long catalytic life, and the composite material has the advantage of convenience for large-scale application in the aspect of electrocatalytic hydrogen evolution.
In order to achieve the above object, a first object of the present invention is to provide a method for preparing a copper-molybdenum composite material, which comprises the following steps:
(1) preparing a precursor A solution: adding a precursor A into deionized water to obtain a precursor A solution with the concentration of more than 0 and less than or equal to 10mol/L, wherein the precursor A is a copper ion compound which is easy to dissolve in water;
(2) preparing a precursor B solution: adding a precursor B into deionized water, and adjusting the pH to 0-13 by using ammonia water and hydrochloric acid to obtain a precursor B solution with the concentration of more than 0 and less than or equal to 10mol/L, wherein the precursor B is a molybdenum ion compound which is easily soluble in water;
(3) preparing a flower-shaped non-noble metal copper-molybdenum composite material: and (2) uniformly mixing the precursor solution A prepared in the step (1) with the precursor solution B under magnetic stirring to obtain a mixed solution, centrifuging, and after centrifuging is finished, placing the lower-layer precipitate in an oven for drying, so that the copper-molybdenum composite material can be obtained.
Further setting that in the step (3), the rotating speed in the stirrer is controlled to be 1-1000 RPM; stirring for 1-10 h; the rotating speed of the centrifugal machine is 1-30000 RPM; centrifuging for 1-30 min; the temperature of the oven is 1-100 ℃.
The copper-molybdenum composite material is further provided with a structure comprising a central tip part and at least four X-shaped crossed inclined edge walls with the upper ends extending and connected, and the whole structure is similar to a flower shape.
The precursor A is copper sulfate or/and copper chloride.
The precursor B is sodium molybdate or/and ammonium tetrathiomolybdate.
The volume ratio of the precursor A solution to the precursor B solution in the step (3) is further set to be (1: 1).
The invention also provides the copper-molybdenum composite material prepared by the preparation method.
The invention also provides a use method of the electrocatalyst based on the copper-molybdenum composite material for hydrogen evolution in electrolyzed water, which is characterized in that: adding the copper-molybdenum composite material into a mixed solution of ethanol and water, performing ultrasonic oscillation to form a suspension, dripping the suspension on the surface of a glassy carbon electrode, airing to form a uniform thin layer, obtaining the glassy carbon electrode modified by the copper-molybdenum composite material, and using the glassy carbon electrode modified by the copper-molybdenum composite material for electrolyzing water to separate hydrogen.
The method is further provided with the following steps that the glassy carbon electrode is pretreated before suspension is dripped, wherein the pretreatment comprises the following steps: polishing, water washing and 20KHz ultrasonic treatment are sequentially carried out for 60 s.
The volume ratio of the ethanol to the water in the mixed liquid of the ethanol and the water is further set to be 1: 3.
Further setting that the parameter of the ultrasonic oscillation is 50KHz ultrasonic for 2 h.
The copper-molybdenum-coated composite material (CuMoS) prepared by the inventionX) The glassy carbon electrode of (a) was subjected to electrochemical testing,
in a three-electrode system, the copper-molybdenum-coated composite material (CuMoS)X) Using a glassy carbon electrode as a working electrode, using a saturated calomel electrode as a reference electrode, and using a graphite electrode as a counter electrode), CuMoS is measuredXLinear sweep voltammogram. The electrolyte solution used for the test was a 0.5M sulfuric acid solution.
The flower-shaped copper-molybdenum composite material prepared by the method shows good electro-catalytic hydrogen evolution performance, and a novel and simple way is explored for the research of non-noble metal catalysts. Obviously, the above embodiments are only examples for clearly illustrating the technical solution of the present invention, and do not limit the embodiments. It will be apparent to those skilled in the art that other variations and modifications may be made in the foregoing description, and it is not necessary or necessary to exhaustively enumerate all embodiments herein. It is hereby intended that the application of the present material to electrocatalytic oxygen evolution, with obvious variations or modifications in electrocatalytic oxygen reduction, is within the scope of the present invention.
The method disclosed by the invention is simple to operate, mild in condition and unique and innovative, and the prepared composite material has great advantages in the aspects of electrocatalytic hydrogen production, electrocatalytic oxygen evolution, electrocatalytic oxygen reduction and energy conversion, and can be applied to the fields of fuel cells and new energy conversion.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a scanning electron microscope photograph of a flower-like copper-molybdenum composite material prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope picture and an EDS mapping picture of the flower-like copper-molybdenum composite material prepared in example 1 of the present invention;
FIG. 3 is a linear voltammogram of the flower-like copper molybdenum composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1: preparation of flower-like copper-molybdenum composite material (CuMoS)X)
(1) Preparing a solution A: adding copper sulfate into deionized water to obtain a copper sulfate solution; the concentration of the solution is 0-10 mol/L;
(2) preparing a solution B: adding ammonium tetrathiomolybdate into deionized water, and adjusting the pH to 0-13 by using ammonia water and hydrochloric acid to obtain an ammonium tetrathiomolybdate solution; the final concentration of the solution is 0-10 mol/L;
(3) preparing a flower-shaped non-noble metal copper-molybdenum composite material: taking an empty beaker filled with magnetons, pouring the solution A prepared in the step (1) into the empty beaker, then placing the empty beaker on a stirrer, controlling the rotating speed to be 1-1000RPM, then adding the solution B prepared in the step (2) into the beaker, stirring for 1-10h, after stirring is stopped, pouring the solution into a centrifuge tube, placing the centrifuge tube into a centrifuge for centrifugation at the rotating speed of 1-30000RPM for 1-30min, and after the centrifugation is finished, placing the lower-layer precipitate into a drying oven at the temperature of 1-100 ℃ for drying, thus obtaining the flower-shaped non-noble metal copper-molybdenum composite material.
(4) Pretreatment of the electrode: taking a glassy carbon electrode (PINE USA, a rotating disc electrode with the diameter of 5mm), and sequentially carrying out polishing, water washing and pretreatment of 20KHz ultrasonic for 60 s;
(5) preparing a glassy carbon electrode modified by a flower-shaped copper-molybdenum composite material: adding a certain amount of flower-shaped copper-molybdenum composite material into a mixed solution of ethanol and water in a volume ratio of 1:3, performing ultrasonic treatment for 2h at 50KHz to form a suspension, dripping the suspension on the surface of the glassy carbon electrode pretreated in the step (4), and naturally airing to form a uniform thin layer to obtain the glassy carbon electrode modified by the flower-shaped copper-molybdenum composite material;
(6) electrochemical testing: the flower-like copper-molybdenum-coated composite material (CuMoS) prepared in the three-electrode system (step (5))X) Using a glassy carbon electrode as a working electrode, using a saturated calomel electrode as a reference electrode, and using a graphite electrode as a counter electrode), CuMoS is measuredXLinear sweep voltammogram. The electrolyte solution used for the test was a 0.5M sulfuric acid solution. FIG. 3 shows that the composite material is at 10mA/cm2Now, the over-potential is lower, so that it can be seen that CuMoS prepared by the present exampleXHas good catalytic activity for hydrogen evolution.
Fig. 1 is a scanning microscope picture of the flower-shaped copper-molybdenum composite material, and it can be seen that the flower-shaped morphology changes with different stirring time. In the figure, a and b are the shapes with stirring time of 1 hour, c and d are the shapes with stirring time of 2 hours, e and f are the shapes with stirring time of 3 hours, and g and h are the shapes with stirring time of 4 hours.
FIG. 2 is a transmission electron microscope (FIG. 2a) and an EDS mapping image of the flower-shaped copper-molybdenum composite material.
Example 2: preparing a cluster-shaped copper-molybdenum composite material (CuMoS)X)
(1) Preparing a solution A: adding copper chloride into deionized water to obtain a copper chloride solution; the concentration of the solution is 0-10 mol/L;
(2) preparing a solution B: adding ammonium tetrathiomolybdate into deionized water, and adjusting the pH to 0-13 by using ammonia water and hydrochloric acid to obtain an ammonium tetrathiomolybdate solution; the final concentration of the solution is 0-10 mol/L;
(3) preparing a flower-shaped non-noble metal copper-molybdenum composite material: taking an empty beaker filled with magnetons, pouring the solution A prepared in the step (1) into the empty beaker, then placing the empty beaker on a stirrer, controlling the rotating speed to be 1-1000RPM, then adding the solution B prepared in the step (2) into the beaker, stirring for 1-10h, after stirring is stopped, pouring the solution into a centrifuge tube, placing the centrifuge tube into a centrifuge for centrifugation at the rotating speed of 1-30000RPM for 1-30min, and after the centrifugation is finished, placing the lower-layer precipitate into a drying oven at the temperature of 1-100 ℃ for drying, thus obtaining the flower-shaped non-noble metal copper-molybdenum composite material.
(4) Pretreatment of the electrode: taking a glassy carbon electrode (PINE USA, a rotating disc electrode with the diameter of 5mm), and sequentially carrying out polishing, water washing and pretreatment of 20KHz ultrasonic for 60 s;
(5) preparing a glassy carbon electrode modified by a flower-shaped copper-molybdenum composite material: adding a certain amount of flower-shaped copper-molybdenum composite material into a mixed solution of ethanol and water in a volume ratio of 1:3, performing ultrasonic treatment for 2h at 50KHz to form a suspension, dripping the suspension on the surface of the glassy carbon electrode pretreated in the step (4), and naturally airing to form a uniform thin layer to obtain the glassy carbon electrode modified by the flower-shaped copper-molybdenum composite material;
(6) electrochemical testing: the flower-like copper-molybdenum-coated composite material (CuMoS) prepared in the three-electrode system (step (5))X) Using a glassy carbon electrode as a working electrode, using a saturated calomel electrode as a reference electrode, and using a graphite electrode as a counter electrode), CuMoS is measuredXLinear sweep voltammogram. The electrolyte solution used for the test was a 0.5M sulfuric acid solution.
Example 3: preparation of porous flower-like copper molybdenum composite material (CuMoS)X)
(1) Preparing a solution A: adding copper sulfate into deionized water to obtain a copper sulfate solution; the concentration of the solution is 0-10 mol/L;
(2) preparing a solution B: adding sodium molybdate into deionized water, and adjusting the pH to 0-13 by using ammonia water and hydrochloric acid to obtain a sodium molybdate solution; the final concentration of the solution is 0-10 mol/L;
(3) preparing a flower-shaped non-noble metal copper-molybdenum composite material: taking an empty beaker filled with magnetons, pouring the solution A prepared in the step (1) into the empty beaker, then placing the empty beaker on a stirrer, controlling the rotating speed to be 1-1000RPM, then adding the solution B prepared in the step (2) into the beaker, stirring for 1-10h, after stirring is stopped, pouring the solution into a centrifuge tube, placing the centrifuge tube into a centrifuge for centrifugation at the rotating speed of 1-30000RPM for 1-30min, and after the centrifugation is finished, placing the lower-layer precipitate into a drying oven at the temperature of 1-100 ℃ for drying, thus obtaining the flower-shaped non-noble metal copper-molybdenum composite material.
(4) Pretreatment of the electrode: taking a glassy carbon electrode (PINE USA, a rotating disc electrode with the diameter of 5mm), and sequentially carrying out polishing, water washing and pretreatment of 20KHz ultrasonic for 60 s;
(5) preparing a glassy carbon electrode modified by a flower-shaped copper-molybdenum composite material: adding a certain amount of flower-shaped copper-molybdenum composite material into a mixed solution of ethanol and water in a volume ratio of 1:3, performing ultrasonic treatment for 2h at 50KHz to form a suspension, dripping the suspension on the surface of the glassy carbon electrode pretreated in the step (4), and naturally airing to form a uniform thin layer to obtain the glassy carbon electrode modified by the flower-shaped copper-molybdenum composite material;
(6) electrochemical testing: the flower-like copper-molybdenum-coated composite material (CuMoS) prepared in the three-electrode system (step (5))X) Using a glassy carbon electrode as a working electrode, using a saturated calomel electrode as a reference electrode, and using a graphite electrode as a counter electrode), CuMoS is measuredXLinear sweep voltammogram. The electrolyte solution used for the test was a 0.5M sulfuric acid solution.
The flower-shaped copper-molybdenum composite material prepared by the method shows good electro-catalytic hydrogen evolution performance, and a novel and simple way is explored for the research of non-noble metal catalysts. Obviously, the above embodiments are only examples for clearly illustrating the technical solution of the present invention, and do not limit the embodiments. It will be apparent to those skilled in the art that other variations and modifications may be made in the foregoing description, and it is not necessary or necessary to exhaustively enumerate all embodiments herein. It is hereby intended that the application of the present material to electrocatalytic oxygen evolution, with obvious variations or modifications in electrocatalytic oxygen reduction, is within the scope of the present invention.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (8)
1. Copper-molybdenum composite CuMoSXThe preparation method is characterized by comprising the following steps:
(1) preparing a precursor A solution: adding a precursor A into deionized water to obtain a precursor A solution with the concentration of more than 0 and less than or equal to 10mol/L, wherein the precursor A is a copper ion compound which is easy to dissolve in water;
(2) preparing a precursor B solution: adding a precursor B into deionized water, and adjusting the pH to 0-13 by using ammonia water and hydrochloric acid to obtain a precursor B solution with the concentration of more than 0 and less than or equal to 10mol/L, wherein the precursor B is a molybdenum ion compound which is easily soluble in water;
(3) preparing a non-noble metal copper-molybdenum composite material: uniformly mixing the precursor solution A prepared in the step (1) with the precursor solution B under magnetic stirring to obtain a mixed solution, centrifuging, and after centrifuging is finished, placing the lower-layer precipitate in an oven for drying, so that the copper-molybdenum composite material can be obtained;
the structure of the copper-molybdenum composite material comprises a central tip part and at least four X-shaped crossed oblique edge walls with the upper ends extending and connected;
the precursor B contains ammonium tetrathiomolybdate.
2. The copper molybdenum composite CuMoS according to claim 1XThe preparation method is characterized by comprising the following steps: the precursor A is copper sulfate or/and copper chloride.
3. The copper molybdenum composite CuMoS according to claim 1XThe preparation method is characterized by comprising the following steps:and (4) in the step (3), the volume ratio of the precursor solution A to the precursor solution B is 1: 1.
4. Copper molybdenum composite CuMoS prepared by the preparation method according to any one of claims 1 to 3X。
5. A method for using the copper-molybdenum composite material as the basis of claim 4 in an electrocatalyst for hydrogen evolution by electrolyzing water, which is characterized in that: adding the copper-molybdenum composite material into a mixed solution of ethanol and water, performing ultrasonic oscillation to form a suspension, dripping the suspension on the surface of a glassy carbon electrode, airing to form a uniform thin layer, obtaining the glassy carbon electrode modified by the copper-molybdenum composite material, and using the glassy carbon electrode modified by the copper-molybdenum composite material for electrolyzing water to separate hydrogen.
6. The method of claim 5, wherein: the glassy carbon electrode is pretreated before the suspension is dripped, and the pretreatment comprises the following steps: polishing, water washing and 20KHz ultrasonic treatment are sequentially carried out for 60 s.
7. The method of claim 5, wherein: the volume ratio of the ethanol to the water in the mixed liquid of the ethanol and the water is 1: 3.
8. The method of claim 5, wherein: the parameter of the ultrasonic oscillation is 50KHz ultrasonic for 2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811511437.6A CN109468662B (en) | 2018-12-11 | 2018-12-11 | Preparation method of copper-molybdenum composite material and application of copper-molybdenum composite material in catalyst for hydrogen evolution through water electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811511437.6A CN109468662B (en) | 2018-12-11 | 2018-12-11 | Preparation method of copper-molybdenum composite material and application of copper-molybdenum composite material in catalyst for hydrogen evolution through water electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109468662A CN109468662A (en) | 2019-03-15 |
| CN109468662B true CN109468662B (en) | 2021-04-20 |
Family
ID=65676165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811511437.6A Active CN109468662B (en) | 2018-12-11 | 2018-12-11 | Preparation method of copper-molybdenum composite material and application of copper-molybdenum composite material in catalyst for hydrogen evolution through water electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109468662B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180552B (en) * | 2019-06-28 | 2022-05-10 | 武汉工程大学 | Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273216C (en) * | 2004-04-29 | 2006-09-06 | 华东师范大学 | Modified cobalt-molybdenum based sulfide catalyst and its preparation method |
| CN101544404A (en) * | 2008-03-26 | 2009-09-30 | 南京理工大学 | Method for preparing monoclinic nanometer 3CuO.2MoO3.H2O by precipitation method |
| CN109201096B (en) * | 2017-07-03 | 2021-08-03 | 中国石油化工股份有限公司 | CO2Catalyst for preparing low-carbon mixed alcohol by hydrogenation and application thereof |
| CN107930671A (en) * | 2017-12-06 | 2018-04-20 | 福州大学 | A kind of ternary metal sulfide/graphite phase carbon nitride composite photocatalyst material and its preparation method and application |
| CN108126729B (en) * | 2018-01-10 | 2020-08-11 | 南京工程学院 | Graphene-like carbon nitride based composite photocatalyst and preparation method thereof |
| CN108354911A (en) * | 2018-04-19 | 2018-08-03 | 上海工程技术大学 | A kind of sulphur molybdenum copper nano-particle and its preparation method and application |
-
2018
- 2018-12-11 CN CN201811511437.6A patent/CN109468662B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109468662A (en) | 2019-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109569683B (en) | Preparation method and application of nitrogen-phosphorus-codoped porous carbon sheet/transition metal phosphide composite material | |
| CN105107536B (en) | A kind of preparation method of polyhedron shape phosphatization cobalt water electrolysis hydrogen production catalyst | |
| CN108411324A (en) | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application | |
| CN105749912B (en) | A kind of metal-doped W with multiform looks18O49Elctro-catalyst and its application in water electrolysis hydrogen production | |
| CN107335451B (en) | Platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst preparation method | |
| CN110075853B (en) | Electrocatalytic fully-decomposed water CoZn-LDHs-ZIF @ C composite structure material, and preparation method and application thereof | |
| CN104862758B (en) | A kind of aquatic products hydrogen that decomposes is with NiS/Ni (OH)2The preparation method of elctro-catalyst | |
| CN109989070B (en) | Three-dimensional grading FeP nanosheet hydrogen evolution electro-catalytic material and preparation method and application thereof | |
| CN108179433B (en) | Ordered mesopore carbon loads nanometer iridium base electrocatalytic hydrogen evolution electrode and its preparation and application | |
| CN109621981B (en) | Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN110052277A (en) | A kind of preparation method of transiting metal group metal sulfide oxygen-separating catalyst | |
| CN109174157B (en) | Preparation method of cobalt-nitrogen co-doped biomass carbon oxidation reduction catalyst | |
| CN108892175A (en) | A kind of preparation method and electro-catalysis application having defective vanadium doping molybdenum disulfide nano flower | |
| CN110339845B (en) | Preparation method and hydrogen evolution application of molybdenum disulfide flower-like nanospheres | |
| CN110624573A (en) | Nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst and preparation method thereof | |
| CN110048134A (en) | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst | |
| CN107937967A (en) | The transition metal phosphide carbon nano tube compound material of multi-pore channel and its preparation method based on small molecule regulation and application | |
| CN109023416A (en) | The preparation method of the efficient liberation of hydrogen composite material of NiCoP@graphene aerogel | |
| CN110965076A (en) | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure | |
| CN109860645B (en) | Preparation method and application of biogel nitrogen fixation doped porous carbon | |
| CN109136982A (en) | By sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst | |
| CN105778088B (en) | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application | |
| CN113443610B (en) | Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof | |
| CN110592616A (en) | Method for preparing platinum/titanium dioxide nanotube composite electrode by electroplating method | |
| CN109468662B (en) | Preparation method of copper-molybdenum composite material and application of copper-molybdenum composite material in catalyst for hydrogen evolution through water electrolysis |
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 |