CN114686921B - Preparation of carbon-supported palladium-copper alloy catalyst and application of catalyst in synthesis of dimethyl carbonate - Google Patents
Preparation of carbon-supported palladium-copper alloy catalyst and application of catalyst in synthesis of dimethyl carbonate Download PDFInfo
- Publication number
- CN114686921B CN114686921B CN202210531944.6A CN202210531944A CN114686921B CN 114686921 B CN114686921 B CN 114686921B CN 202210531944 A CN202210531944 A CN 202210531944A CN 114686921 B CN114686921 B CN 114686921B
- Authority
- CN
- China
- Prior art keywords
- palladium
- carbon
- copper
- catalyst
- copper alloy
- 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
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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen 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
- C25B3/29—Coupling reactions
-
- 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
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a carbon-supported palladium-copper alloy electrocatalyst, which comprises the steps of dissolving palladium precursor salt and copper precursor salt in an ethanol-hydrochloric acid mixed solution, and uniformly mixing the solution with ultrasound at room temperature to obtain a brown yellow solution; the brown yellow solution is uniformly coated on the surface of hydrophobic carbon paper, and after drying, the brown yellow solution is subjected to rapid high-temperature pyrolysis, cooling and condensation by a Joule heat in-situ heating device, so that the palladium-copper alloy nanoparticle-loaded electrode catalyst is rapidly prepared (the millisecond level can be controlled), and the formed alloy nanoparticles are uniform in size and uniform in element distribution; and the strong interface combination of Pd and Cu alloy particles and the carbon substrate can effectively prevent the falling of active sites, so that the electrode is kept stable in the long-time catalysis process. The electrocatalytic performance test shows that the palladium-copper alloy structure catalyst has better performance than other single-metal supported or doped catalysts in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO.
Description
Technical Field
The invention relates to a Pd-based electrocatalyst, in particular to a preparation method of a carbon-supported palladium-copper alloy catalyst, which is mainly used in the reaction of synthesizing dimethyl carbonate by electrocatalytic coupling of methanol and CO, and belongs to the technical field of electrochemical oxo synthesis reaction.
Background
Dimethyl carbonate (DMC) is a versatile chemical with low biotoxicity and has potential to replace phosgene, dimethyl sulfate, methyl chloride and other carcinogens as methylation, carbonylation and transesterification reagents. Its use helps to reduce the dependence of the modern industry on toxic agents and is therefore considered a typical green chemical agent. At present, DMC is widely applied to the fields of energy material electrolyte, fuel oil additive, polar solvent and the like, is also a key intermediate for organic synthesis and chemical production, and is of great interest in multiple fields. Existing commercial DMC production processIncluding phosgene method, methanol oxidative carbonylation method, ester exchange method and CO 2 Direct methanol synthesis and urea methanol decomposition. Among them, the methanol oxidative carbonylation process is considered to be the most widely used route to DMC non-phosgene preparation at present. However, this route has a series of problems such as severe reaction conditions, easy explosion of raw material CO, and more byproducts, which hinders the expanded production of DMC. Therefore, developing a new and efficient green route for DMC production is one of the hot spots in this field.
Recently, new routes to form DMCs using electrochemical methods to catalyze coupling have received increasing attention. In contrast to conventional thermochemical methanol oxidative carbonylation processes, electrochemical processes utilize electron transfer to effect oxidation-reduction of a substrate rather than O 2 The reaction condition of the equal oxidant is safer and milder at normal temperature and normal pressure, the oxidation process can be realized simply by regulating and controlling the voltage, and H is avoided 2 And the formation of byproducts such as O. Noble metal catalysts, represented by Pd, have been found to achieve coupling of CO and methanol molecules at oxidation voltages to yield DMC. However, the current conversion efficiency of the process is limited, the required voltage is high, dimethyl oxalate (DMO) is a byproduct, and Pd is easily poisoned by CO to cause poor stability. Therefore, development of a new Pd-based electrocatalyst is needed to realize efficient and stable electrochemical process for synthesizing DMC by oxidative coupling of CO and methanol.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-supported palladium-copper catalyst, which aims to solve the technical defects of the catalyst in the aspects of selectivity, overpotential, stability and the like in the existing process of synthesizing DMC by oxidative coupling of CO and methanol.
It is still another object of the present invention to provide the application performance of the carbon-supported palladium-copper alloy catalyst in the electrochemical synthesis of dimethyl carbonate.
1. Preparation of carbon-supported palladium-copper alloy catalyst
The invention relates to a preparation method of a carbon-supported palladium-copper alloy catalyst, which comprises the steps of dissolving palladium precursor salt and copper precursor salt in an ethanol-hydrochloric acid mixed solution, and uniformly mixing the solution by ultrasonic waves at room temperature to obtain a brown yellow solution; and uniformly coating the brown yellow solution on the hydrophobic carbonPaper surface, after drying, at N 2 High-temperature pyrolysis is carried out for 1-2 s at 1450-1550 ℃ in an atmosphere; and cooling to room temperature to obtain the carbon-supported palladium-copper alloy catalyst.
The copper precursor salt is copper chloride, and the palladium precursor salt is palladium chloride; the molar ratio of the palladium chloride to the copper chloride is 2:1-5:1.
In the ethanol-hydrochloric acid mixed solution, the concentration of hydrochloric acid is 10-12 mol/l, and the volume ratio of ethanol to hydrochloric acid is 3:1-6:1. The concentration of the palladium precursor salt and the copper precursor salt in the ethanol-hydrochloric acid mixed solution is 8.76-8.80 mg/mL.
The pyrolysis may be operated using a joule heating device. The specific process comprises the following steps: fixing the hydrophobic carbon paper loaded with palladium-copper precursor in a heating tank of a Joule heating device, and introducing N 2 Replacing, wherein the set parameters are voltage 25-45V, current 45-55A, temperature 1700-1800K and operation time 1-2 s; and cooling to room temperature after the click operation is finished, and thus obtaining the carbon-supported palladium-copper alloy catalyst.
Preparation principle of carbon-supported catalyst: the hydrophobic carbon paper with the surface loaded with the uniformly mixed precursor salt is subjected to high-temperature (1700-1800K) impact, and the precursor salt is instantaneously decomposed into clusters of palladium and copper. And in the high-temperature maintained time of 1-2 s, the palladium atoms and the copper atoms are rapidly diffused and fused in an atomic scale to form a uniform solid solution. And then rapidly cooling and quenching to realize quick freezing of self-assembled alloy particles. In addition, at ultra-high temperatures, the surface of hydrophobic carbon paper exhibits highly defective graphitization transitions. The defects provide attachment points for alloy particles, so that the alloy particles and the alloy particles have stronger binding force, and the stability of the catalyst can be enhanced. High temperature pyrolysis allows precursor salts to be atomized, which is a prerequisite for achieving palladium-copper atomic scale mixing. The rapid cryocondensation process maintains the alloy particles in a small size and the elements are uniformly mixed. The temperature change detected by the heating table during the whole heating and cooling process is shown in fig. 1. It can be seen that when the heating is finished, the sample stage can complete the cooling in only two seconds. The rapid cooling process is helpful for preserving the alloy phase state formed at high temperature.
FIG. 2 is a schematic structural diagram (SEM image) of a carbon-supported Pd-Cu alloy catalyst prepared in accordance with the present invention. As can be seen from fig. 2, the active center of the catalyst is the upper Pd-Cu alloy particles supported on amorphous carbon, wherein the palladium and copper particles are disordered alloy nanoparticles with uniform size and uniform element distribution, the size of the disordered alloy nanoparticles is spherical particles ranging from 20 nm to 50 nm, and the palladium and copper elements are mixed in a distributed manner.
FIG. 3 is a schematic diagram (TEM image) of a carbon-supported Pd-Cu alloy catalyst prepared according to the present invention. As can be seen from fig. 3, the strong interfacial bonding between the Pd and Cu alloy particles and the carbon substrate can effectively prevent the active sites from falling off, so that the electrode is stable in the long-time catalysis process, and the defects of low intrinsic catalytic activity and short stability time of the conventional single-metal supported catalyst can be overcome.
FIG. 4 is a graph of current density versus time for a carbon supported Pd-Cu alloy catalyst in a CO atmosphere of 0.9V to 1.3V. As can be seen from fig. 4, the catalyst was stable for 1 hour at different potentials with less current density floating.
2. Electrocatalytic performance of carbon-supported palladium-copper alloy electrocatalysts
The hydrophobic carbon paper loaded with Pd-Cu alloy particles is used as an anode to be installed in a flow cell, the cathode is blank carbon paper, and the reference electrode is an Ag/AgCl electrode. One side of the anode is 0.1 mol/l NaClO 4 /CH 3 OH electrolyte, and the other side is CO gas. And (3) after the electrode is activated by fast cyclic voltammetry scanning in the voltage range of 0-1.6V vs. Ag/AgCl, carrying out current-time electrolysis test by the selected voltage. After 1 hour of electrolysis is completed, taking a liquid product for gas chromatography and nuclear magnetic resonance testing, determining the types and the amounts of the products, and calculating the Faraday efficiency of the products.
FIG. 5 shows the carbon-supported Pd-Cu alloy electrode (example 1) of the present invention in N 2 And cyclic voltammogram (left) and catalytic performance (right) in CO atmosphere. It can be seen that the carbon-supported Pd-Cu alloy catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency can reach 90% near 1V vs. Ag/AgCl. Our catalysts can achieve higher faraday efficiencies over a lower overpotential (voltage) range than the recently reported electrocatalytic DMC synthesis heterogeneous catalysts.
In summary, the precursor salts of palladium and copper are dissolved and then coated on carbon paper, and the rapid high-temperature pyrolysis, cooling and condensation are carried out by utilizing a Joule heat in-situ heating device, so that the rapid (controllable in millisecond level) preparation of the electrode catalyst loaded with palladium-copper alloy nanoparticles is realized, and the formed alloy nanoparticles are uniform in size and uniform in element distribution; and the strong interface combination of Pd and Cu alloy particles and the carbon substrate can effectively prevent the falling of active sites, so that the electrode is kept stable in the long-time catalysis process, and the defects of low intrinsic catalytic activity and short stabilization time of the traditional single-metal supported catalyst are overcome. The electrocatalytic performance test shows that the palladium-copper alloy structure catalyst has better performance than other single-metal supported or doped catalysts in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO.
Drawings
FIG. 1 is a schematic diagram of the preparation of a carbon supported Pd-Cu alloy catalyst of the present invention.
FIG. 2 is an SEM image of a carbon-supported Pd-Cu alloy catalyst of the present invention.
FIG. 3 is a TEM image of a carbon supported Pd-Cu alloy catalyst of the present invention.
FIG. 4 is a graph of current density versus time for a carbon supported Pd-Cu alloy catalyst of the present invention.
FIG. 5 shows the carbon-supported Pd-Cu alloy electrode of the present invention in N 2 And cyclic voltammogram (left) and catalytic performance (right) in CO atmosphere.
Detailed Description
The preparation of the carbon-supported Pd-Cu alloy catalyst of the present invention and its activity in the electrocatalytic carbonyl coupling reaction for preparing dimethyl carbonate are further described below by way of specific examples.
Example 1
Accurately weighing PdCl of 3.4 mg 2 And 1.1. 1.1 mg CuCl 2 ·2H 2 O, dissolving in 500 uL ethanol-hydrochloric acid mixed solution (the concentration of hydrochloric acid is 12 mol/l, and the volume ratio of ethanol to hydrochloric acid is 4:1.), and uniformly mixing at room temperature by ultrasonic to obtain a brown yellow solution; uniformly coating the solution on the surface of hydrophobic carbon paper for multiple times, and drying at 80 ℃;
fixing hydrophobic carbon paper coated with metal precursor salt to heating device of Joule heating deviceHeat tank, let in N 2 And replacing for 3 times, setting parameters to be voltage 30V, current 50A, temperature 1800K and clicking operation 1.5 s, cooling to room temperature, and taking out the prepared electrode plate;
the hydrophobic carbon paper loaded with Pd-Cu alloy particles is used as an anode to be installed in a flow cell, the cathode is blank carbon paper, and the reference electrode is an Ag/AgCl electrode. One side of the anode is 0.1 mol/l NaClO 4 /CH 3 OH electrolyte, and the other side is CO gas. And (3) after the electrode is activated by fast cyclic voltammetry scanning in the voltage range of 0-1.6V vs. Ag/AgCl, carrying out current-time electrolysis test by the selected voltage. After 1 hour of electrolysis is completed, taking a liquid product for gas chromatography and nuclear magnetic resonance testing, determining the types and the amounts of the products, and calculating the Faraday efficiency of the products. The catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency can reach 90% near 1V vs. Ag/AgCl.
Example 2
The precursor salt ratio in example 1 was changed to: 3.7 mg of PdCl 2 And 0.7. 0.7 mg CuCl 2 ·2H 2 O, ethanol-hydrochloric acid mixed solution ratio is changed to 3:1, and pyrolysis conditions are changed to: the parameters are voltage 28V, current 50A, temperature 1800K, click operation 1.2 s, and cooling to room temperature to obtain the catalyst. The catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency can reach 55% near 1V vs. Ag/AgCl.
Example 3
The precursor salt ratio in the embodiment 1 is changed to: 3.5 mg of PdCl 2 And 0.9. 0.9 mg CuCl 2 ·2H 2 O, ethanol-hydrochloric acid mixed solution is changed into: 4:1, the pyrolysis conditions are changed into: the parameters are voltage 30V, current 50A, temperature 1800K, click operation 1.4 s, and cooling to room temperature to obtain the catalyst. The catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency can reach 82% near 1V vs. Ag/AgCl.
Example 4
The precursor salt ratio in example 1 was changed to: pdCl of 3 mg 2 And 2.8. 2.8 mg CuCl 2 ·2H 2 O, ethanol-hydrochloric acid mixed solution is changed into: 5:1, the pyrolysis conditions are changed into: the parameters are voltage 35V, current 55A, temperature 1800K, click operation 1.6 s, and cooling to room temperature to obtain the catalyst. The catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency can reach 68% near 1V vs. Ag/AgCl.
Example 5
PdCl with precursor salt ratio changed to 4.4 mg in example 1 2 The ethanol-hydrochloric acid mixed solution is prepared by the following steps: 3:1, the pyrolysis conditions are changed into: the parameters are voltage 25V, current 50A, temperature 1700K, click operation 1 s and cooling to room temperature to obtain the catalyst. The catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency can reach 46% near 1V vs. Ag/AgCl.
Example 6
CuCl with precursor salt ratio changed to 4.3 mg in example 1 2 ·2H 2 O, ethanol-hydrochloric acid mixed solution is changed into: 6:1, the high-temperature pyrolysis conditions are changed into: the parameters are voltage 40V, current 60A, temperature 1700K, click operation 1.8 s, and cooling to room temperature to obtain the catalyst. The catalyst shows excellent activity in the reaction of preparing dimethyl carbonate by electrocatalytic coupling of methanol with CO, and the Faraday efficiency is almost 0% near 1V vs. Ag/AgCl.
Claims (5)
1. The preparation method of the carbon-supported palladium-copper alloy electrocatalyst comprises the steps of dissolving palladium precursor salt and copper precursor salt in an ethanol-hydrochloric acid mixed solution, and uniformly mixing the solution by ultrasonic waves at room temperature to obtain a brown yellow solution; uniformly coating the brown yellow solution on the surface of hydrophobic carbon paper, drying and then adding the solution into N 2 High-temperature pyrolysis is carried out for 1-2 s at 1450-1550 ℃ in an atmosphere; cooling to room temperature to obtain a carbon-supported palladium-copper alloy catalyst; the copper precursor salt is copper chloride, and the palladium precursor salt is palladium chloride; the molar ratio of the palladium chloride to the copper chloride is 2:1-5:1.
2. A method for preparing the carbon-supported palladium-copper alloy electrocatalyst according to claim 1, wherein: in the ethanol-hydrochloric acid mixed solution, the concentration of hydrochloric acid is 10-12 mol/l, and the volume ratio of ethanol to hydrochloric acid is 3:1-6:1.
3. A method for preparing the carbon-supported palladium-copper alloy electrocatalyst according to claim 1, wherein: the concentration of the palladium precursor salt and the copper precursor salt in the ethanol-hydrochloric acid mixed solution is 8.76-8.80 mg/mL.
4. A method for preparing the carbon-supported palladium-copper alloy electrocatalyst according to claim 1, wherein: the high-temperature pyrolysis is to fix the hydrophobic carbon paper loaded with palladium-copper precursor in a heating tank of a Joule heating device, and to introduce N 2 Replacing, setting parameters to be 25-40V, 45-55A, 1700-1800K and 1-2 s; and cooling to room temperature after the operation is finished, and thus obtaining the electrode catalyst.
5. Use of a carbon-supported palladium-copper alloy electrocatalyst prepared according to the method of claim 1 for synthesizing dimethyl carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210531944.6A CN114686921B (en) | 2022-05-17 | 2022-05-17 | Preparation of carbon-supported palladium-copper alloy catalyst and application of catalyst in synthesis of dimethyl carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210531944.6A CN114686921B (en) | 2022-05-17 | 2022-05-17 | Preparation of carbon-supported palladium-copper alloy catalyst and application of catalyst in synthesis of dimethyl carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114686921A CN114686921A (en) | 2022-07-01 |
| CN114686921B true CN114686921B (en) | 2023-09-08 |
Family
ID=82144143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210531944.6A Active CN114686921B (en) | 2022-05-17 | 2022-05-17 | Preparation of carbon-supported palladium-copper alloy catalyst and application of catalyst in synthesis of dimethyl carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114686921B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115360368A (en) * | 2022-09-02 | 2022-11-18 | 华中科技大学 | Method for preparing high-density and ultra-small nanoparticles at high temperature in ligand-assisted transient state |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111694A (en) * | 2020-01-20 | 2020-05-08 | 东华大学 | Preparation of copper-palladium bimetallic supported mesoporous carbon and carbon nanotube composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102093824B1 (en) * | 2018-05-02 | 2020-03-26 | 한국과학기술연구원 | Preparation method of carbon-supported platinum-transition metal alloy nanopaticle catalyst |
| US11183695B2 (en) * | 2018-12-26 | 2021-11-23 | Hyundai Motor Company | Heat treatment method for a carbon-supported metal catalyst for fuel cells and a carbon-supported metal catalyst prepared thereby |
-
2022
- 2022-05-17 CN CN202210531944.6A patent/CN114686921B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111694A (en) * | 2020-01-20 | 2020-05-08 | 东华大学 | Preparation of copper-palladium bimetallic supported mesoporous carbon and carbon nanotube composite material |
Non-Patent Citations (1)
| Title |
|---|
| New insights into enhanced electrocatalytic performance of carbon supported Pd–Cu catalyst for formic acid oxidation;Liang Lu et al.;Electrochimica Acta;第85卷;第187-194页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114686921A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Houache et al. | Selective Electrooxidation of Glycerol to Formic Acid over Carbon Supported Ni1–x M x (M= Bi, Pd, and Au) Nanocatalysts and Coelectrolysis of CO2 | |
| Zhu et al. | Bimetallic electrocatalysts for CO 2 reduction | |
| Xin et al. | Simultaneous generation of mesoxalic acid and electricity from glycerol on a gold anode catalyst in anion‐exchange membrane fuel cells | |
| Annen et al. | A biologically inspired organometallic fuel cell (OMFC) that converts renewable alcohols into energy and chemicals | |
| KR101541207B1 (en) | Process for producing a catalyst and use of the catalyst | |
| US6809060B2 (en) | Aerogel type platinum-tuthenium-carbon catalyst, method for manufacturing the same and direct methanol fuel cell comprising the same | |
| Soares et al. | Beneficial effects of rhodium and tin oxide on carbon supported platinum catalysts for ethanol electrooxidation | |
| CN101733095B (en) | Catalyst for water electrolysis and preparation and application thereof | |
| Chetty et al. | Direct ethanol fuel cells with catalysed metal mesh anodes | |
| US20110118110A1 (en) | Catalyst and process for producing it and its use | |
| Zanata et al. | Two-step synthesis of Ir-decorated Pd nanocubes and their impact on the glycerol electrooxidation | |
| US6855660B2 (en) | Rhodium electrocatalyst and method of preparation | |
| CN114686921B (en) | Preparation of carbon-supported palladium-copper alloy catalyst and application of catalyst in synthesis of dimethyl carbonate | |
| Daems et al. | Nickel-containing N-doped carbon as effective electrocatalysts for the reduction of CO 2 to CO in a continuous-flow electrolyzer | |
| Ouyang et al. | Promoting and controlling electron transfer of furfural oxidation efficiently harvest electricity, furoic acid, hydrogen gas and hydrogen peroxide | |
| Ávila-Bolívar et al. | On the activity and stability of Sb2O3/Sb nanoparticles for the electroreduction of CO2 toward formate | |
| Wang et al. | Unlocking Efficient Hydrogen Production: Nucleophilic Oxidation Reactions Coupled with Water Splitting | |
| Xia et al. | Methanol‐Facilitated Surface Reconstruction Catalysts for Near 200% Faradaic Efficiency in a Coupled System | |
| Yan et al. | Electrocatalytic conversion of methane: Recent progress and future prospects | |
| Al-Akraa et al. | Fabrication of CuOx‐Pd Nanocatalyst Supported on a Glassy Carbon Electrode for Enhanced Formic Acid Electro‐Oxidation | |
| US20160240860A1 (en) | Noble metal-free catalyst system for a fuel cell | |
| CN110560083A (en) | bimetal porous silver-copper network structure nitrogen reduction catalyst and preparation method thereof | |
| Lima et al. | CO2 reduction on Cu/C used as a cathode in a polymeric electrolyte reactor-Fuel cell type | |
| Mulero et al. | An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone | |
| WO2008116930A1 (en) | Electrocatalysts consisting of noble metals deposited on nickel based materials, their preparation and use and fuel cells that contain them |
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 |