CN114411196B - Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation - Google Patents

Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation Download PDF

Info

Publication number
CN114411196B
CN114411196B CN202210064644.1A CN202210064644A CN114411196B CN 114411196 B CN114411196 B CN 114411196B CN 202210064644 A CN202210064644 A CN 202210064644A CN 114411196 B CN114411196 B CN 114411196B
Authority
CN
China
Prior art keywords
edta
alkyne
copper
semi
hydrogenation
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
Application number
CN202210064644.1A
Other languages
Chinese (zh)
Other versions
CN114411196A (en
Inventor
姜毅
李冉
夏立新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liaoning University
Original Assignee
Liaoning University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Liaoning University filed Critical Liaoning University
Priority to CN202210064644.1A priority Critical patent/CN114411196B/en
Publication of CN114411196A publication Critical patent/CN114411196A/en
Application granted granted Critical
Publication of CN114411196B publication Critical patent/CN114411196B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to the technical field of catalysts, in particular to an application of an electrodeposited copper-based catalyst based on EDTA regulation in preparing alkene by electrocatalytic alkyne semi-hydrogenation. The method comprises the following steps: the method is characterized in that water is used as a hydrogen source, an electrodeposited copper-based catalyst regulated and controlled based on EDTA is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and alkyne is electrically catalyzed to prepare alkene by semi-hydrogenation under the voltage of minus 0.56V vs. RHE.

Description

Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation
Technical Field
The invention relates to the technical field of catalysts, in particular to an application of an electrodeposited copper-based catalyst based on EDTA regulation in electrocatalytic 4-ethynyl aniline.
Background
Electrolytic water hydrogen production is an efficient way to produce clean energy, however, hydrogen produced by electrolytic water is difficult to be effectively utilized because hydrogen is flammable and explosive and is not easy to store. Although many methods have been developed to utilize hydrogen generated by electrolysis of water, the utilization rate is hardly improved. Therefore, the hydrogen generated by electrolysis of water is used for reduction of organic matters, so that the utilization rate of the hydrogen is greatly improved. Particularly, the method is used for alkyne reduction, alkyne semi-hydrogenation can generate alkene with high added value, has important significance in chemical production, and realizes high hydrogen benefit by utilizing hydrogen generated by electrolysis of water. The experiment prepares a copper-based catalyst through EDTA regulated electrodeposition, takes hydrogen generated by water electrolysis as a hydrogen source, reduces 4-ethynyl aniline at a cathode, and generates 4-vinyl aniline with high added value.
Disclosure of Invention
The technical scheme of the invention is as follows: the application of an EDTA-regulated electrodeposited copper-based catalyst in preparing alkene by electrocatalytic alkyne semi-hydrogenation comprises the following steps: the method is characterized in that water is used as a hydrogen source, an electrodeposited copper-based catalyst regulated and controlled based on EDTA is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and alkyne is electrically catalyzed to prepare alkene by semi-hydrogenation under the voltage of minus 0.56V vs. RHE.
The application of the electrodeposited copper-based catalyst based on EDTA regulation in preparing alkene by electrocatalytic alkyne semi-hydrogenation is disclosed, wherein the alkyne is 4-ethynylaniline.
The application of the electrodeposited copper-based catalyst based on EDTA regulation in preparing olefin by electrocatalytic alkyne semi-hydrogenation is characterized in that a cosolvent is also added, and the cosolvent is 1, 4-dioxane.
The application of the electrodeposited copper-based catalyst based on EDTA regulation in preparing olefin by electrocatalytic alkyne semi-hydrogenation, and the preparation method of the electrodeposited copper-based catalyst based on EDTA regulation comprises the following steps:
1) Pretreatment of foam copper: cleaning foam copper and drying;
2) Pretreatment of carbon paper: soaking carbon paper in nitric acid, cleaning, drying and calcining;
3) Electrolyte solution: will H 2 SO 4 With CuSO 4 After uniformly mixing, EDTA is added to obtain electrolyte;
4) Based on EDTA regulation, copper-based catalysts were electrodeposited on carbon paper by constant current deposition: and (3) taking the pretreated foamy copper as a working electrode, taking the pretreated carbon paper as a counter electrode, adding electrolyte to perform electrodeposition experiments through constant current deposition, and drying after cleaning to obtain the EDTA-based regulated electrodeposition copper-based catalyst.
The application of the electrodeposited copper-based catalyst based on EDTA regulation in preparing olefin by electrocatalytic alkyne semi-hydrogenation is that in the step 2), the calcination temperature is 400 ℃, and the calcination time is 5 hours.
The application of the electrodeposited copper-based catalyst based on EDTA regulation in preparing olefin by electrocatalytic alkyne semi-hydrogenation is that the electrodepositing condition is-0.05A, 80s.
The invention has the beneficial effects that: according to the invention, EDTA is added into electrolyte to regulate electrochemical deposition to prepare a copper-based catalyst, water is used as a hydrogen source, 4-vinylaniline with high added value is prepared by electrocatalytic 4-ethynylaniline semi-hydrogenation in 1M KOH electrolyte, and the prepared olefin has high selectivity and selectivity performance reaching 95%.
Drawings
FIG. 1 is a scanning electron microscope image of an electrodeposited copper-based catalyst.
FIG. 2 is an X-ray diffraction pattern of an electrodeposited catalyst.
FIG. 3 is a linear sweep voltammogram of an electrodeposited copper-based catalyst regulated by the addition of EDTA to an electrolyte and carbon paper electrocatalytic alkyne semi-hydrogenation.
Detailed Description
Example 1 EDTA-based regulated electrodeposited copper-based catalyst
Electrodeposition preparation of copper-based catalyst:
1) Pretreatment of foam copper: sequentially washing with 3M hydrochloric acid, acetone, ethanol and water for 10min, and drying in oven at 60deg.C;
2) Pretreatment of carbon paper: cutting carbon paper into 1X 2cm, soaking in nitric acid for 60min, washing with deionized water, blow-drying, and burning in a muffle furnace at 400deg.C for 5 hr;
3) Electrolyte solution: 2M H 2 SO 4 30mL,0.2M CuSO 4 50mL, mix, add 1.86g EDTA.
4) Based on EDTA regulation, copper-based catalysts were electrodeposited on carbon paper by constant current deposition. Electrodeposition experiment working electrode: pretreated foamy copper. Counter electrode for electrodeposition experiments: pretreated carbon paper. Electrolyte for electrodeposition experiments: 10mL of the solution obtained in step 3) was taken as an electrolyte. Electrodeposition experiment: the catalyst was electrodeposited on carbon paper by constant current deposition under-0.05 a for 80s. And soaking the electrodeposited catalyst in deionized water for 30min, and then drying at room temperature to obtain the electrodeposited copper-based catalyst regulated and controlled based on EDTA.
As can be seen from a Scanning Electron Microscope (SEM) of fig. 1, the EDTA-regulated electrodeposited catalyst exhibited irregular spheres, exhibiting irregular stacking phenomena. As can be seen from the XRD pattern in FIG. 2, the peak at 36.43 corresponds to Cu 2 O; the peak at 43.47 corresponds to metallic Cu; indicating successful deposition of the copper-based catalyst, copper in the deposited copper-based catalyst is a valence of 0, +1.
The electrochemical workstation model in this experiment was CHI 760E.
Comparative example 1 plain carbon paper catalyst
Preparing a common carbon paper catalyst: the carbon paper is cut into 1X 2cm, soaked in nitric acid for 60min, washed clean with deionized water, dried and burned in a muffle furnace at 400 ℃ for 5h.
Example 2 electrochemical Performance test
Electrochemical performance test of electrodeposited copper-based catalyst: electrochemical performance of electrochemically deposited copper-based catalysts was tested using the CHI760 electrochemical workstation. Electrochemical performance tests were performed using an H-cell and a three electrode operating system. 15mL of electrolyte was added to each of the anode and cathode compartments using 1M KOH as the electrolyte, and 2.4mg of 4-ethynylaniline and 1.07mL of 1, 4-dioxane were added to the cathode compartment. The electrodeposited copper-based catalyst electrode is a working electrode, the carbon rod is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The cell was sealed and nitrogen was vented to the liquid surface for 30min to remove oxygen from the solution, followed by electrochemical performance testing to obtain the LSV curve for the electrodeposited catalyst, as shown in fig. 3. The voltages used herein are referenced to the standard hydrogen electrode potential.
In the experiment, the model of the electrochemical workstation is CHI 760E, the linear sweep voltammetry sweep parameter is the rotation rate of 1600rpm, and the sweep rate is 10mV s -1 。
Electrochemical performance test of plain carbon paper: the electrochemical performance of a common carbon paper (abbreviated as carbon paper) catalyst is tested by adopting a CHI760 electrochemical workstation. Electrochemical performance tests were performed using an H-cell and a three electrode operating system. 15mL of electrolyte was added to each of the anode and cathode compartments using 1M KOH as the electrolyte, and 2.4mg of 4-ethynylaniline and 1.07mL of 1, 4-dioxane were added to the cathode compartment. The carbon paper is a working electrode, the carbon rod is a counter electrode, and the Ag/AgCl electrode is a reference electrode. The cell was sealed and nitrogen was introduced into the liquid surface for 30min to remove oxygen from the solution, followed by electrochemical performance testing to obtain LSV curve of carbon paper as shown in fig. 3. By comparison, the current density of the electrodeposited catalyst is obviously higher than that of carbon paper, and the electrodeposited catalyst has better catalytic effect on the semi-hydrogenation of 4-ethynylaniline. The voltages used herein are referenced to the standard hydrogen electrode potential.
In the experiment, the model of the electrochemical workstation is CHI 760E, the linear sweep voltammetry sweep parameter is the rotation rate of 1600rpm, and the sweep rate is 10mV s -1 。
As can be seen from comparing the LSV curves of FIG. 3 by electrochemically testing the performance of the electrodeposited copper-based catalyst and plain carbon paper (abbreviated as carbon paper), the current density of the electrodeposited copper-based catalyst at-0.56V vs. RHE can reach 17.8mA/cm 2 When the carbon paper is at-0.56V vs. RHE, the current density is only 2.8mA/cm 2 At-0.56 v vs. rhe, the current density of EDTA-based regulated electrodeposited copper-based catalysts was about 6.3 times that of carbon paper. It can be seen from the LSV curve that the current density difference between the electrodeposited copper-based catalyst and the carbon paper is greatest at-0.56V vs. RHE. The voltages used herein are referenced to the standard hydrogen electrode potential.
By comparison, the current density of the electrodeposited copper-based catalyst regulated and controlled based on EDTA is obviously higher than that of carbon paper, and the electrodeposited copper-based catalyst has a good catalytic effect on alkyne semi-hydrogenation.
Example 3
Electrocatalytic alkyne semi-hydrogenation: the method is characterized in that water is used as a hydrogen source, an electrodeposited copper-based catalyst regulated and controlled based on EDTA is used as a working electrode, and the alkyne is electrically catalyzed to prepare alkene by a long-time timing current test (IT). Voltage for IT experiments: as can be seen from the LSV curve, the current density difference between the electrodeposited copper-based catalyst and the carbon paper is greatest at-0.56V vs. RHE, so IT experiments were performed at-0.56V vs. RHE; electrolytic cells and electrolytes for IT experiments: an H-type electrolytic cell is adopted, and in a cathode electrolytic cell, the electrolyte is as follows: 13.93ml of 1M KOH; the anolyte was 15ml of 1m KOH solution. The cathode and the anode electrolytic cell are connected through a proton exchange membrane. Performing electrocatalytic reaction in a cathode electrolytic cell, wherein the substrate for electrolysis is 2.4mg of 4-ethynylaniline, and adding 1.07ml of cosolvent 1, 4-dioxane; working electrode for IT experiments: electrodeposited copper-based catalysts based on EDTA regulation; counter electrode for IT experiments: a carbon rod; reference electrode for IT experiments: ag/AgCl electrode; and (3) carrying out a long-time timing current test (IT) under the voltage of-0.56V vs. RHE, and carrying out electrocatalytic 4-ethynylaniline to generate 4-vinylaniline, wherein the IT experiment time is 5h, and the rotating speed is 300r/min.
The electrochemical workstation model in this experiment was CHI 760E.
Detection of olefin products: extracting the electrolyte after 5h IT experiment with dichloromethane, taking the lower layer liquid, and adding an internal standard substance: n-octane, mixed with ultrasound for 10s, then 1 μl was taken and the gas phase was taken. The selectivity of the olefin product was calculated to be up to 95% by internal standard method. The gas chromatograph used in this experiment was GC-2014.

Claims (5)

1. The application of an EDTA-regulated electrodeposited copper-based catalyst in preparing alkene by electrocatalytic alkyne semi-hydrogenation is characterized by comprising the following steps of: using water as a hydrogen source, using an electrodeposited copper-based catalyst regulated and controlled based on EDTA as a working electrode, using an Ag/AgCl electrode as a reference electrode, and preparing alkene by electrocatalytic alkyne semi-hydrogenation under the voltage of minus 0.56V vs. RHE;
the preparation method of the electrodeposited copper-based catalyst based on EDTA regulation comprises the following steps:
1) Pretreatment of foam copper: cleaning foam copper and drying;
2) Pretreatment of carbon paper: soaking carbon paper in nitric acid, cleaning, drying and calcining;
3) Electrolyte solution: will H 2 SO 4 With CuSO 4 After uniformly mixing, EDTA is added to obtain electrolyte;
4) Based on EDTA regulation, copper-based catalysts were electrodeposited on carbon paper by constant current deposition: and (3) taking the pretreated foamy copper as a working electrode, taking the pretreated carbon paper as a counter electrode, adding electrolyte to perform electrodeposition experiments through constant current deposition, and drying after cleaning to obtain the EDTA-based regulated electrodeposition copper-based catalyst.
2. The use of an EDTA-regulated electrodeposited copper-based catalyst according to claim 1 for the preparation of olefins by electrocatalytic alkyne semi-hydrogenation, wherein the alkyne is 4-ethynylaniline.
3. The use of an EDTA-based regulated electrodeposited copper-based catalyst according to claim 2 for the preparation of olefins by electrocatalytic alkyne semi-hydrogenation, wherein a co-solvent is also added, said co-solvent being 1, 4-dioxane.
4. The use of an EDTA-based regulated electrodeposited copper-based catalyst according to claim 1 for the preparation of olefins by electrocatalytic alkyne semi-hydrogenation, wherein in step 2), the calcination temperature is 400 ℃ and the calcination time is 5h.
5. The use of an EDTA-based regulated electrodeposited copper-based catalyst according to claim 4 for the preparation of olefins by electrocatalytic alkyne semi-hydrogenation, characterized in that the conditions of electrodeposition are-0.05 a,80s.
CN202210064644.1A 2022-01-20 2022-01-20 Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation Active CN114411196B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210064644.1A CN114411196B (en) 2022-01-20 2022-01-20 Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210064644.1A CN114411196B (en) 2022-01-20 2022-01-20 Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation

Publications (2)

Publication Number Publication Date
CN114411196A CN114411196A (en) 2022-04-29
CN114411196B true CN114411196B (en) 2023-05-30

Family

ID=81275942

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210064644.1A Active CN114411196B (en) 2022-01-20 2022-01-20 Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation

Country Status (1)

Country Link
CN (1) CN114411196B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5457079A (en) * 1992-09-21 1995-10-10 Hitachi, Ltd. Copper-based oxidation catalyst and its applications
CN113430545A (en) * 2021-06-15 2021-09-24 华东理工大学 Copper-based catalyst and preparation method and application thereof
CN113502489A (en) * 2021-06-24 2021-10-15 杭州师范大学 Preparation method and application of electrocatalyst for reduction of alkyne into olefin
CN113789542A (en) * 2021-09-17 2021-12-14 中国石油大学(华东) Copper-based catalyst, preparation method thereof, catalytic electrode for electrocatalytic reduction of carbon dioxide and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5457079A (en) * 1992-09-21 1995-10-10 Hitachi, Ltd. Copper-based oxidation catalyst and its applications
CN113430545A (en) * 2021-06-15 2021-09-24 华东理工大学 Copper-based catalyst and preparation method and application thereof
CN113502489A (en) * 2021-06-24 2021-10-15 杭州师范大学 Preparation method and application of electrocatalyst for reduction of alkyne into olefin
CN113789542A (en) * 2021-09-17 2021-12-14 中国石油大学(华东) Copper-based catalyst, preparation method thereof, catalytic electrode for electrocatalytic reduction of carbon dioxide and application

Also Published As

Publication number Publication date
CN114411196A (en) 2022-04-29

Similar Documents

Publication Publication Date Title
CN106498434B (en) The preparation method of the Ni-based porous nickel phosphide hydrogen-precipitating electrode of integration
CN108796551B (en) Sea urchin-shaped cobalt sulfide catalyst loaded on foamed nickel, preparation method thereof and application of catalyst as electrolyzed water oxygen evolution catalyst
CN110526235B (en) Method for preparing in-situ oxygen-doped three-dimensional graphene through electrochemical stripping
CN111686743A (en) La/NF hydrogen evolution material and preparation method and application thereof
CN114657592B (en) Nickel-based catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof
CN113430559B (en) Application of copper-based catalyst in electrocatalytic hydrogenation
CN111939914B (en) Method for preparing high-activity ternary metal oxygen evolution catalyst by using waste copper foil
CN113373464A (en) Method for preparing cyclane by electrocatalytic conversion of lignin derivative
CN114411196B (en) Application of electrodeposited copper-based catalyst based on EDTA regulation in preparation of alkene by electrocatalytic alkyne semi-hydrogenation
CN116445972A (en) Cerium dioxide-transition metal phosphide composite self-supporting electrode material and preparation method and application thereof
CN110787820A (en) Heteroatom nitrogen surface modification MoS2Preparation and application of nano material
CN113430545B (en) Copper-based catalyst and preparation method and application thereof
CN114196984B (en) Constant-current electrodeposited copper-based catalyst on carbon paper, preparation method thereof and application thereof in electrocatalytic 4-ethynylaniline
CN113249743B (en) Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof
CN101425581B (en) Method for preparing double effect oxygen electrode catalyst
CN114737216B (en) Hydrogen evolution catalyst active material for electrolyzed water and preparation method thereof
CN115961296A (en) Preparation method of Cu/ZnO catalyst for electrocatalytic alkyne reduction
CN112981427B (en) Three-chamber two-membrane electrolytic tank for preparing sodium borohydride by direct-current electrolytic reduction
CN115011995B (en) Cerium-based hydrogen evolution electrocatalyst and preparation method and application thereof
CN115786931B (en) Preparation method and application of organic selenium molecule modified Co-doped transition metal sulfide
CN115198307A (en) Hydrogen and oxygen evolution dual-functional catalytic electrode based on foamed nickel self-supporting polymeric phenylboronate and preparation method and application thereof
CN117187841A (en) Large-size 5-hydroxymethylfurfural oxidation electrocatalyst and preparation method thereof
CN114318404A (en) Preparation method and application of Co-Ni-based electro-catalytic material
CN117822016A (en) Copper-silver solid solution alloy catalyst and preparation method and application thereof
CN117721487A (en) Preparation method of Cu-based catalyst based on rod-shaped ZnO load and application of Cu-based catalyst in electrocatalytic hydrogenation reaction

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