CN108767282B - Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles - Google Patents

Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles Download PDF

Info

Publication number
CN108767282B
CN108767282B CN201810679328.9A CN201810679328A CN108767282B CN 108767282 B CN108767282 B CN 108767282B CN 201810679328 A CN201810679328 A CN 201810679328A CN 108767282 B CN108767282 B CN 108767282B
Authority
CN
China
Prior art keywords
porous multi
branch
alloy
alloy nanoparticles
concentration
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
CN201810679328.9A
Other languages
Chinese (zh)
Other versions
CN108767282A (en
Inventor
吕一品
杨绍寒
高道伟
陈国柱
李春生
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.)
University of Jinan
Original Assignee
University of Jinan
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 University of Jinan filed Critical University of Jinan
Priority to CN201810679328.9A priority Critical patent/CN108767282B/en
Publication of CN108767282A publication Critical patent/CN108767282A/en
Application granted granted Critical
Publication of CN108767282B publication Critical patent/CN108767282B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles. According to the invention, chloroplatinic acid, copper chloride and nickel chloride are taken as raw materials, glycine and PVP are taken as double reducing agents, specific 1, 3-propylene glycol and NaF are added, and a microwave synthesis method is adopted to prepare porous multi-branched Pt-Ni-Cu alloy nanoparticles with high selectivity, so that the preparation method is green and efficient. The obtained porous multi-branch Pt-Ni-Cu alloy nano particle has more step atoms, high active site density, excellent methanol and formic acid electrochemical activity and wide application prospect.

Description

Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles
Technical Field
The invention belongs to the technical field of functional nano materials. Specifically, the invention adopts a microwave synthesis method to prepare porous multi-branch Pt-Ni-Cu alloy nanoparticles.
Background
The noble metal Pt nano-structured catalyst is widely applied to the fields of environmental protection catalysis, biochemistry and the like due to excellent stability and good catalytic performance. But due to higher use cost and easy poisoning in the use process, the excellent nano catalyst cannot be widely applied on a large scale. One of the effective ways to solve these problems is to combine Pt with three-dimensional transition metals such as Ni, Cu, Co to form a Pt-based binary/multi-element alloy catalyst, which has been demonstrated to have catalytic activity depending on the composition and surface morphology of alloy nanoparticles, showing higher catalytic activity and stability through synergistic effect of electrons and high density of step atoms on the particle surface.
There are many methods for preparing Pt-based binary/multi-element alloy nanoparticles, for example, wang et al prepared three-dimensional PtCu alloy nanoparticles with different morphologies by adjusting the amount of NaI (Nano research 2015,8 (3): 832-838). Furthermore, Zhang et al prepared morphology-tunable Pt-Ni-Cu ternary alloy nanoparticles (chem. Mater. 2015,27, 6402-6410) by using glycine, and confirmed that glycine plays an important role in nucleation and growth rate. The methods are all prepared by a hydrothermal method, and the obtained alloy nanoparticles have low shape selectivity which mainly depends on the slow heating rate of an oven, so that the design and development of the Pt-Ni-Cu alloy nanoparticles with high selectivity and catalytic activity have important significance. The invention uses microwave-assisted synthesis to prepare the porous multi-branch Pt-Ni-Cu alloy nano particles, greatly improves the step atom number of Pt, and increases the active site density of the Pt-Ni-Cu alloy.
The fuel cell is a device for converting chemical energy stored in fuel molecules into electric energy, has high starting speed, simple and convenient operation and environmental protection, and is a main energy generating device in the future. The proton exchange membrane fuel cell has small volume, quick start at room temperature and high energy density, and is an ideal power source in the future. In the development process of proton exchange membrane fuel cells, the catalyst has the disadvantages of high cost, low stability and the like, and the development of the proton exchange membrane fuel cells is seriously hindered. At present, a Pt-based catalyst is the catalyst with the best catalytic performance in a proton exchange membrane fuel cell, but the high cost of the Pt catalyst limits the industrialization process of the proton exchange membrane fuel cell to a certain extent, so that the research on a catalyst without platinum or with low platinum is used for reducing the use amount of Pt and improving the utilization rate of Pt, and the method has a very important significance for realizing the large-scale application of the proton exchange membrane fuel cell.
Disclosure of Invention
Aiming at the technical problems, the invention solves the technical problems of high price, low utilization rate, easy poisoning and the like of the existing Pt nano-structured catalyst, prepares the porous multi-branch Pt-Ni-Cu alloy nano-particle with high-density active sites and improves the performance of the Pt nano-structured catalyst.
In order to realize the purpose, the invention is realized by the following technical scheme:
the experimental steps of the preparation method of the porous multi-branch Pt-Ni-Cu alloy nano particle are as follows:
weighing 2.0mL of chloroplatinic acid aqueous solution with the concentration of 19.3mmol/L, 1.0mL of nickel chloride with the concentration of 20mmol/L, 1.0mL of copper chloride aqueous solution with the concentration of 20mmol/L and 0.7mL of 1, 3-propylene glycol into a 50mL beaker, adding glycine, polyvinylpyrrolidone K30 and NaF, stirring and dissolving by using a magnetic stirrer, transferring into a microwave reaction kettle, absolutely sealing, transferring into a microwave synthesizer, heating for reaction, and after the reaction is finished, carrying out water and ethanol centrifugal washing, freeze drying and other treatment steps to obtain the porous multi-branched Pt-Ni-Cu alloy nanoparticles.
Preferably, the amount of polyvinylpyrrolidone K30 is in the range of 170-230mg, more preferably 200 mg.
Preferably, the amount of NaF is in the range of 550-620mg, more preferably 580 mg.
Preferably, the amount of glycine is in the range of 280-330mg, more preferably 310 mg.
Preferably, the temperature range for the microwave heating reaction is 200 ℃.
Furthermore, the addition of 0.7mL of 1, 3-propanediol is also an essential factor for the synthesis of the porous multi-branched Pt-Ni-Cu alloy nanoparticles of the present invention, since 1, 3-propanediol has reducibility, at two OH groups-1Under the action of the alloy, the alloy and other experimental parameters form a mutually matched whole to promote the molding of the porous multi-branch morphology, and the porous multi-branch Pt-Ni-Cu alloy can be obtained only by the cooperation of the porous multi-branch morphology and the other experimental parameters.
The invention has the beneficial effects that: according to the invention, chloroplatinic acid, copper chloride and nickel chloride are taken as raw materials, glycine and PVP are taken as double reducing agents, specific 1, 3-propylene glycol and NaF are added, and a microwave synthesis method is adopted to prepare porous multi-branched Pt-Ni-Cu alloy nanoparticles with high selectivity, so that the preparation method is green and efficient. The obtained porous multi-branch Pt-Ni-Cu alloy nano particle has more step atoms, high active site density, excellent methanol and formic acid electrochemical activity and wide application prospect.
Drawings
FIG. 1 is an XRD pattern of porous multi-branched Pt-Ni-Cu alloy nanoparticles prepared in example 1.
FIG. 2 is a TEM spectrum of porous multi-branched Pt-Ni-Cu alloy nanoparticles prepared in example 1.
FIG. 3 is a comparison of cyclic voltammograms of the porous multi-branched Pt-Ni-Cu alloy nanoparticles prepared in example 1 and commercial Pt/C as a methanol electrooxidation catalyst.
FIG. 4 is a comparison of cyclic voltammograms of the porous multi-branched Pt-Ni-Cu alloy nanoparticles prepared in example 1 with commercial Pt/C as a formic acid electrooxidation catalyst.
FIG. 5 is a TEM spectrum of Pt-Ni-Cu alloy nanoparticles prepared in comparative example 1.
FIG. 6 is a TEM spectrum of Pt-Ni-Cu alloy nanoparticles prepared in comparative example 2.
Detailed Description
The following examples are intended to illustrate the practice and advantageous effects of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1
2.0mL of chloroplatinic acid aqueous solution with the concentration of 19.3mmol/L, 1.0mL of nickel chloride with the concentration of 20mmol/L, 1.0mL of copper chloride aqueous solution with the concentration of 20mmol/L and 0.7mL of 1, 3-propylene glycol are weighed into a 50mL beaker, then glycine, polyvinylpyrrolidone K30 and NaF are added, stirred and dissolved by a magnetic stirrer, then the obtained product is transferred into a microwave reaction kettle, and after absolute sealing, the obtained product is transferred into a microwave synthesizer to be heated for 30min at 200 ℃ for reaction, and after the reaction is finished, water and ethanol are centrifugally washed, freeze-dried and other treatment steps are carried out, wherein the polyvinylpyrrolidone K30 is used in a range of 200mg, the NaF is used in a range of 580mg, the glycine is used in a range, and the 1.3-propylene glycol is used in a range of 0.7mL, so that porous multi-branched Pt-Ni-Cu alloy nanoparticles are obtained (as shown in figure 2).
Methanol (formic acid) electrooxidation test: anodic electrooxidationChemical performance testing was performed on an electrochemical workstation model CHI650D using a conventional three-electrode system. The Saturated Calomel Electrode (SCE) is used as a reference electrode, the counter electrode is a platinum wire, and the working electrode is a glassy carbon electrode (GC) with the diameter of 3 mm. A certain amount of catalyst suspension (keeping the metal mass at 4. mu.g) was dropped on the surface of the GC electrode and dried under an infrared lamp, and then the end of the working electrode on which the sample was dropped was irradiated for 12 hours at intervals of 5 mm against an ultraviolet ozone lamp (emission wavelength of 185 nm and 254 nm, power of 10W) to remove organic molecules (e.g., PVP) on the surface of the sample. Then, 1.5. mu.L of a 0.5 wt% Nafion solution (diluted with ethanol) was dropped onto the surface of the working electrode. Catalyst electrochemical activation area test at 0.5M H2SO4The solution is used as electrolyte, and high-purity N is introduced for 30min before experiment2The electrolyte is deoxygenated, followed by Cyclic Voltammetry (CV) scanning at a rate of 50 mV/s, with a set sweep range of-0.24 to 1.0V. During the experiment, the upper part of the solution is kept to be N2An atmosphere. The methanol (formic acid) electrooxidation test is at 0.5M H2SO4 + 2 M CH3OH（0.5 M H2SO4+ 0.25M HCOOH) electrolyte, high purity N was passed before CV testing2And purging for 30min to remove dissolved oxygen in the electrolyte, wherein the set scanning range is-0.2-1.0V, and the scanning speed is determined to be 50 mV/s. Current density is measured as the electrochemical activation area per unit catalyst on the working electrode (cm)2) Is shown as the current above. Each working electrode was cycled at a rate of 50 mV/s for 50 cycles of a stable CV curve. For the porous multi-branched Pt-Ni-Cu nanoparticles prepared in example 1, the current density of which the positive scan peak is normalized to the electrochemical active area ECSA represents the intrinsic activity of the catalyst, and as can be seen from FIGS. 3 and 4, the highest current density of the porous multi-branched Pt-Ni-Cu nanoparticles in the electrooxidation of methanol is 4.88mA cm-2The highest current density in the formic acid electrooxidation experiment was 2.85mA cm-2The highest current density of methanol, much higher than that of commercial Pt/C, is 0.55mA cm-2The highest current density of formic acid is 0.29mA cm-2。
Comparative example 1
The amount was measured to be 2.0mLChloroplatinic acid aqueous solution with the concentration of 19.3mmol/L, 1.0mL nickel chloride with the concentration of 20mmol/L, 1.0mL copper chloride aqueous solution with the concentration of 20mmol/L and 0.7mL1, 3-propanediol are put in a 50mL beaker, then adding glycine, polyvinylpyrrolidone K30 and NaF, stirring and dissolving by a magnetic stirrer, then transferring into a microwave reaction kettle, absolutely sealing, transferring into a microwave synthesizer, heating at 200 deg.C for 30min for reaction, after the reaction is finished, performing water and ethanol centrifugal washing, freeze drying and other treatment steps, wherein the dosage range of polyvinylpyrrolidone K30 is 200mgNaF 550mg, the dosage range of glycine 310mg, Pt-Ni-Cu alloy nanoparticles (as shown in FIG. 5) are obtained, and the highest current density in the electrooxidation of methanol was 1.97mA cm using the same test conditions as in example 1.-2The highest current density in the formic acid electrooxidation experiment was 0.82mA cm-2。
Comparative example 2
2.0mL of an aqueous chloroplatinic acid solution having a concentration of 19.3mmol/L, 1.0mL of an aqueous nickel chloride solution having a concentration of 20mmol/L, 1.0mL of an aqueous copper chloride solution having a concentration of 20mmol/L and 0.7mL of 1, 3-propanediol were measured in a 50mL beaker, then adding glycine, polyvinylpyrrolidone K30 and NaF, stirring and dissolving by a magnetic stirrer, then transferring into a microwave reaction kettle, absolutely sealing, transferring into a microwave synthesizer, heating at 200 deg.C for 30min for reaction, after the reaction is finished, performing water and ethanol centrifugal washing, freeze drying and other treatment steps, wherein the dosage range of the polyvinylpyrrolidone K30 is 200mg, the dosage range of the NaF is 580mg, the dosage range of the glycine is 280mg, so as to obtain the Pt-Ni-Cu alloy nano particles (as shown in figure 6), and the highest current density in the electrooxidation of methanol was 1.75mA cm using the same test conditions as in example 1.-2The highest current density in the formic acid electrooxidation experiment was 0.54mA cm-2。
In addition, the invention also relates to a plurality of groups of comparative examples, and in view of space and no one-to-one list, one or more parameter variables are changed relative to the embodiment 1, and the result shows that the porous multi-branched Pt-Ni-Cu alloy nano particles of the invention can not be obtained under the condition of changing one or more than two variables, and the technical characteristics of the technical scheme of the invention have synergistic effect, and the catalytic activity is far lower than that of the embodiment 1 of the invention, thereby showing that the technical scheme of the invention achieves unexpected technical effect in terms of alloy morphology and catalytic activity.

Claims (1)

1. A preparation method of porous multi-branch Pt-Ni-Cu alloy nano catalyst particles comprises the specific steps of measuring 2.0mL of chloroplatinic acid aqueous solution with the concentration of 19.3mmol/L, 1.0mL of nickel chloride with the concentration of 20mmol/L, 1.0mL of copper chloride aqueous solution with the concentration of 20mmol/L and 0.7mL of 1, 3-propylene glycol in a 50mL beaker, adding 310mg of glycine, 200mg of polyvinylpyrrolidone K30 and 580mg of NaF, stirring and dissolving by using a magnetic stirrer, transferring into a microwave reaction kettle, absolutely sealing, transferring into a microwave synthesizer for heating and reacting, wherein the temperature of microwave heating reaction is 200 ℃, the reaction time is 30min, and after the reaction is finished, the porous multi-branch Pt-Ni-Cu alloy nano catalyst particles are obtained through the steps of water and ethanol centrifugal washing and freeze drying.
CN201810679328.9A 2018-06-27 2018-06-27 Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles Active CN108767282B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810679328.9A CN108767282B (en) 2018-06-27 2018-06-27 Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810679328.9A CN108767282B (en) 2018-06-27 2018-06-27 Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles

Publications (2)

Publication Number Publication Date
CN108767282A CN108767282A (en) 2018-11-06
CN108767282B true CN108767282B (en) 2021-01-26

Family

ID=63977878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810679328.9A Active CN108767282B (en) 2018-06-27 2018-06-27 Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles

Country Status (1)

Country Link
CN (1) CN108767282B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110380068A (en) * 2019-05-15 2019-10-25 济南大学 A kind of implementation method improving methanol fuel cell electrooxidation activity and stability using PtCuNi alloy
CN110212206A (en) * 2019-05-15 2019-09-06 济南大学 A kind of recessed shape of octahedron PtCuNi alloy nanoparticle and preparation method thereof
CN110165233A (en) * 2019-05-27 2019-08-23 苏州氢极能源科技有限公司 Catalyst of fuel batter with proton exchange film and preparation method thereof
CN110364744A (en) * 2019-07-23 2019-10-22 济南大学 A kind of preparation method of the extra small Pt-Ni-Cu alloy nanoparticle with high miller index surface
CN111230141B (en) * 2020-03-04 2022-10-25 王冲 Preparation method of PtRuCoS alloy nanocrystalline with floccule morphology
CN114725413A (en) * 2022-04-29 2022-07-08 内蒙古科技大学 PtCo high-index crystal face catalyst and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010105187A1 (en) * 2009-03-12 2010-09-16 Daimler Ag Platinum phosphide as a cathode catalyst for pemfcs and phosphorous treatment of catalysts for fuel cell
CN102500365A (en) * 2011-10-19 2012-06-20 华南理工大学 Preparation method of catalyst with core-shell structure for low-temperature fuel cell
CN102534687A (en) * 2011-12-30 2012-07-04 东南大学 PdNiCu ternary nanoporous metal and preparation and application thereof
CN105047952A (en) * 2015-06-02 2015-11-11 哈尔滨工业大学 Dendritic nanowire catalyst carrier with metal oxide/carbon core-sheath structure and preparation method of supported catalyst
CN107845815A (en) * 2017-10-23 2018-03-27 济南大学 A kind of implementation method for being used to improve methanol fuel cell electrooxidation activity

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010105187A1 (en) * 2009-03-12 2010-09-16 Daimler Ag Platinum phosphide as a cathode catalyst for pemfcs and phosphorous treatment of catalysts for fuel cell
CN102500365A (en) * 2011-10-19 2012-06-20 华南理工大学 Preparation method of catalyst with core-shell structure for low-temperature fuel cell
CN102534687A (en) * 2011-12-30 2012-07-04 东南大学 PdNiCu ternary nanoporous metal and preparation and application thereof
CN105047952A (en) * 2015-06-02 2015-11-11 哈尔滨工业大学 Dendritic nanowire catalyst carrier with metal oxide/carbon core-sheath structure and preparation method of supported catalyst
CN107845815A (en) * 2017-10-23 2018-03-27 济南大学 A kind of implementation method for being used to improve methanol fuel cell electrooxidation activity

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Microwave-assisted polyol synthesis of PtCu/carbon nanotube catalysts for electrocatalytic oxygen reduction";Heba El-Deeb等;《Journal of Power Sources》;20141113;第275卷;第893-900页 *
"One-Pot Synthesis of Ternary Pt−Ni−Cu Nanocrystals with High Catalytic Performance";Pengfang Zhang等;《Chem. Mater》;20150831;第27卷;第6402-6410页 *
"Pt-Ni-Cu三元合金纳米粒子形貌可控合成及电催化性能研究";张鹏方;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180415;第B020-288页 *

Also Published As

Publication number Publication date
CN108767282A (en) 2018-11-06

Similar Documents

Publication Publication Date Title
CN108767282B (en) Preparation method of porous multi-branch Pt-Ni-Cu alloy nanoparticles
CN108816258B (en) Hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, preparation method and application of hollow carbon material in hydrogen production by catalytic electrolysis of water
CN111437846B (en) Porous CoO/CoP nanotube and preparation method and application thereof
CN109718822B (en) Method for preparing metal-carbon composite catalytic material and application thereof
CN103413951A (en) Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof
CN107394215B (en) Preparation and application of heteroatom-doped functional carbon material
CN109888307A (en) A kind of cobalt sulphur compound/nitrogen sulfur doping carbon composite catalytic agent and preparation method thereof
CN107834079B (en) It is a kind of for improving the implementation method of aminic acid fuel battery electrooxidation activity
CN113881965B (en) Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof
CN107088432A (en) A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application
CN110117797B (en) Electrolytic cell and application thereof in hydrogen production by electrolyzing water
CN107845816A (en) A kind of coarse shape of octahedron PtCoFe alloy particles and preparation method thereof
CN113481004A (en) Carbon dots and preparation method and application thereof
CN104084193A (en) Method for preparing Pt catalyst
CN109731599B (en) 2D oxygen reduction catalyst Fe3O4Preparation method of @ FeNC nanosheet
CN113731431A (en) Preparation method and application of bismuth-copper bimetallic catalyst
CN112058297B (en) Nickel-based electro-catalytic material and preparation method and application thereof
CN114164449A (en) Method for preparing hydrogen peroxide by using covalent organic framework catalyst to catalyze oxygen reduction
CN113174053A (en) Mn-MOF based on urotropine and preparation method and application thereof
CN110354870B (en) Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst
CN114086202B (en) Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production
CN113430567B (en) Preparation method and application of carbon nanotube-loaded gold nanocluster catalyst
CN115261915A (en) Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof
CN112850860A (en) Preparation method and application of nitrogen-doped ordered mesoporous carbon electrode
CN111514912A (en) Three-dimensional Co-doped WP2Nanosheet array electrocatalyst and preparation method thereof

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