CN111659437B - Preparation method of nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide - Google Patents
Preparation method of nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide Download PDFInfo
- Publication number
- CN111659437B CN111659437B CN202010470059.2A CN202010470059A CN111659437B CN 111659437 B CN111659437 B CN 111659437B CN 202010470059 A CN202010470059 A CN 202010470059A CN 111659437 B CN111659437 B CN 111659437B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- solution
- mixed solution
- doped graphene
- benzimidazole
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000011258 core-shell material Substances 0.000 title claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 24
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 78
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 69
- 229910021389 graphene Inorganic materials 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 37
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000013084 copper-based metal-organic framework Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000012621 metal-organic framework Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 110
- 238000002474 experimental method Methods 0.000 description 21
- 229920006395 saturated elastomer Polymers 0.000 description 14
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 12
- 235000015497 potassium bicarbonate Nutrition 0.000 description 12
- 239000011736 potassium bicarbonate Substances 0.000 description 12
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide, and relates to a preparation method of a nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst. The invention aims to solve the problems of poor product selectivity and low stability of the existing porous carbon supported metal catalyst. The method comprises the following steps: 1. preparing a precursor solution; 2. carrying out hydrothermal reaction; 3. cleaning and drying; 4. and carbonizing the product. The preparation method is used for preparing the nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by carbon dioxide electrocatalysis.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst.
Background
The acceleration of human industrialization and urbanization processes has increased the demand for various fuels, and the fuel burns CO discharged 2 The global "greenhouse effect" is continuously aggravated, and thus the double problems of energy crisis and environmental pollution are increasingly serious. CO as a carbon-containing resource with abundant reserves 2 Not only can relieve CO in the atmosphere 2 Concentration, thereby reducing the greenhouse effect and alleviating the shortage crisis of increasingly short resources. Due to CO 2 The molecules are stable and require the application of higher energy to activate them, resulting in CO in the atmosphere 2 Deficiency of effective utilization5.5%. Therefore, searching for efficient transformation approaches, and constructing reasonable transformation methods has attracted global attention. Electrochemical catalytic reduction of CO compared to biological and photocatalytic methods 2 Can be realized at normal temperature and normal pressure. The method is simple and convenient to operate and easy to control, and the selection of the product can be effectively controlled by changing the electrolysis conditions. Thus, the designed synthesis of highly efficient, stable and highly selective catalysts is the electroreduction of CO 2 The key of the reaction is also the research focus and difficulty in the current field. The copper-based metal organic framework material (Cu-MOF) is a good precursor template due to the advantages of large specific surface area, high porosity, adjustable pore size, adjustable structure and the like, and the porous carbon-supported metal catalyst prepared by the method is used for CO 2 Catalytic studies of (2). However, this type of catalyst has poor selectivity to formic acid, often accompanied by the production of small molecule alcohols in the product, and has the significant disadvantage of low stability (typically less than 10 h).
Disclosure of Invention
The invention aims to solve the problems of poor product selectivity and low stability of the existing porous carbon supported metal catalyst, and provides a preparation method of a nitrogen-doped graphene supported core-shell copper-carbon composite catalyst for producing formic acid by carbon dioxide electrocatalysis.
The preparation method of the nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide comprises the following steps:
1. preparing a precursor solution:
adding nitrogen doped reduced graphene oxide into a mixed solution of N, N-dimethylformamide and ethanol for full dispersion, and then adding Cu (NO 3 ) 2 ·3H 2 Continuously stirring O until the O is completely dissolved to obtain a mixed solution; dissolving benzimidazole in a mixed solution of N, N-dimethylformamide and ethanol, and stirring until the benzimidazole is dissolved to obtain a benzimidazole solution; dissolving trimesic acid in a mixed solution of N, N-dimethylformamide and ethanol, and stirring until the trimesic acid is dissolved to obtain a trimesic acid solution;
cu (NO) in the mixed solution 3 ) 2 ·3H 2 O (O)The concentration is 2.5 mg/mL-3.0 mg/mL; cu (NO) in the mixed solution 3 ) 2 ·3H 2 The mass ratio of O to the nitrogen doped reduced graphene oxide is 1 (0.1-0.3); the concentration of benzimidazole in the benzimidazole solution is 10 mg/mL-15 mg/mL; the concentration of the trimesic acid in the trimesic acid solution is 1.0 mg/mL-1.5 mg/mL;
2. hydrothermal reaction:
mixing and stirring the mixed solution and the benzimidazole solution until the mixed solution is bright blue, adding the trimesic acid solution into the mixed solution, continuously mixing and stirring the mixed solution to obtain a precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction for 5-8 h under the constant temperature condition of 80-100 ℃ to obtain a Cu-MOF precursor loaded by the nitrogen-doped graphene;
cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to benzimidazole is 1 (3-5); cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to trimesic acid is 1 (0.7-1.0);
3. cleaning and drying:
centrifuging a Cu_MOF precursor loaded by nitrogen-doped graphene, washing the precursor for a plurality of times by using absolute ethyl alcohol, and then placing the precursor in a vacuum drying oven for drying to obtain a dried product;
4. carbonizing the product:
placing the dried product into a tubular furnace, introducing high-purity Ar gas, heating to 700-1000 ℃ at a heating rate of 1-5 ℃/min, and calcining for 3-8 h at 700-1000 ℃ to obtain the nitrogen-doped graphene-loaded core-shell structure Cu 2 O/Cu@C composite catalyst.
The beneficial effects of the invention are as follows:
1. the invention adopts a simple hydrothermal synthesis method to prepare the Cu-MOF precursor loaded by the nitrogen-doped graphene, and prepares the Cu with the core-shell structure loaded by the nitrogen-doped graphene by a high-temperature carbonization method 2 The O/Cu@C composite catalyst effectively improves the electrochemical activity of the catalyst.
2. The invention introduces nitrogen doped graphene and Cu 2 Compared with the O/Cu@C catalyst, the nitrogen doped graphene can disperse effective metal sites, so that the electrochemical active surface area of the catalyst is increased by 4.3 times and reaches 47.2mF/cm 2 The internal resistance of charge transfer is reduced to 3.91 omega, which is reduced by 48.8%; in addition, the catalyst pair CO 2 The adsorption capacity of the catalyst is increased by 2.3 times and reaches 0.95mmol/g, thereby obviously improving the electrocatalytic reduction of CO by the Cu catalyst 2 Activity. Nitrogen-doped graphene-loaded core-shell structure Cu 2 The Faraday efficiency of the O/Cu@C composite catalyst on reducing carbon dioxide to formic acid is up to 82.9%, and the synthesis rate of formic acid is up to 430.2mg/L/h/m 2 。
3. The nitrogen-doped graphene-loaded core-shell structure Cu prepared by the invention 2 The O/Cu@C composite catalyst has good stability, and after continuous electrolysis for 30 hours, the Faraday current efficiency of formic acid is still maintained to be more than 73%.
The invention relates to a preparation method of a nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by carbon dioxide electrocatalysis.
Drawings
FIG. 1 is a nitrogen-doped graphene-supported core-shell structure Cu prepared in example one 2 Scanning electron microscope image of O/Cu@C composite catalyst, wherein A is octahedral Cu 2 O/Cu@C, wherein B is Cu particles, and C is nitrogen-doped graphene;
FIG. 2 is a nitrogen-doped graphene-supported core-shell structure Cu prepared in example one 2 Testing an obtained LSV graph of the O/Cu@C composite catalyst under the condition of nitrogen and carbon dioxide, wherein A is an LSV curve obtained under the condition of nitrogen, and B is an LSV curve under the condition of carbon dioxide;
FIG. 3 is a core-shell Cu structure prepared by a comparative experiment 2 Testing an obtained LSV graph of the O/Cu@C catalyst under the condition of nitrogen and carbon dioxide, wherein A is an LSV curve obtained under the condition of nitrogen, and B is an LSV curve under the condition of carbon dioxide;
FIG. 4 is a catalyst in CO 2 Faraday efficiency map of formic acid production by electrolysis of 1 hour in saturated 0.1mol/L potassium bicarbonate solution, a being trueNitrogen-doped graphene-supported core-shell structure Cu prepared in embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst;
FIG. 5 is a catalyst in CO 2 Formic acid production rate chart of 1 hour of electrolysis in saturated 0.1mol/L potassium bicarbonate solution, wherein a is nitrogen-doped graphene-loaded core-shell structure Cu prepared in example one 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst;
FIG. 6 is a catalyst in CO 2 A linear fit plot of current in saturated 0.1mol/L potassium bicarbonate solution versus sweep rate; a is Cu of a nitrogen-doped graphene-supported core-shell structure prepared in the first embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst;
FIG. 7 is a catalyst in CO 2 Nyquist pattern in saturated 0.1mol/L potassium bicarbonate solution; a is Cu of a nitrogen-doped graphene-supported core-shell structure prepared in the first embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst;
FIG. 8 catalyst vs. CO 2 Adsorption curve of (2); a is Cu of a nitrogen-doped graphene-supported core-shell structure prepared in the first embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst;
FIG. 9 is a nitrogen-doped graphene-supported core-shell structure Cu prepared in example one 2 Stability test curve of O/Cu@C composite catalyst, 1 is current density, and 2 is Faraday efficiency.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment is a preparation method of a nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide, which comprises the following steps:
1. preparing a precursor solution:
adding nitrogen doped reduced graphene oxide into a mixed solution of N, N-dimethylformamide and ethanol for full dispersion, and then adding Cu (NO 3 ) 2 ·3H 2 Continuously stirring O until the O is completely dissolved to obtain a mixed solution; dissolving benzimidazole in a mixed solution of N, N-dimethylformamide and ethanol, and stirring until the benzimidazole is dissolved to obtain a benzimidazole solution; dissolving trimesic acid in a mixed solution of N, N-dimethylformamide and ethanol, and stirring until the trimesic acid is dissolved to obtain a trimesic acid solution;
cu (NO) in the mixed solution 3 ) 2 ·3H 2 The concentration of O is 2.5 mg/mL-3.0 mg/mL; cu (NO) in the mixed solution 3 ) 2 ·3H 2 The mass ratio of O to the nitrogen doped reduced graphene oxide is 1 (0.1-0.3); the concentration of benzimidazole in the benzimidazole solution is 10 mg/mL-15 mg/mL; the concentration of the trimesic acid in the trimesic acid solution is 1.0 mg/mL-1.5 mg/mL;
2. hydrothermal reaction:
mixing and stirring the mixed solution and the benzimidazole solution until the mixed solution is bright blue, adding the trimesic acid solution into the mixed solution, continuously mixing and stirring the mixed solution to obtain a precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction for 5-8 h under the constant temperature condition of 80-100 ℃ to obtain a Cu-MOF precursor loaded by the nitrogen-doped graphene;
cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to benzimidazole is 1 (3-5); cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to trimesic acid is 1 (0.7-1.0);
3. cleaning and drying:
centrifuging a Cu_MOF precursor loaded by nitrogen-doped graphene, washing the precursor for a plurality of times by using absolute ethyl alcohol, and then placing the precursor in a vacuum drying oven for drying to obtain a dried product;
4. carbonizing the product:
placing the dried product in a tube furnace, introducing high-purity Ar gas,heating to 700-1000 ℃ at a heating rate of 1-5 ℃/min, and calcining for 3-8 h at 700-1000 ℃ to obtain the nitrogen-doped graphene-loaded core-shell structure Cu 2 O/Cu@C composite catalyst.
In the embodiment, the graphene is used as a carrier to load Cu 2 The O/Cu@C constructed composite catalyst can obviously improve the electrocatalytic performance of the catalyst. The graphene can disperse metal catalytic sites, and doping of hetero atoms can improve the conductivity of the whole composite catalyst and CO 2 Adsorption of molecules, cu 2 O/Cu@C serving as catalytic site improves CO under the action of nitrogen doped graphene 2 The activation of the molecules and the synergistic effect of the molecules improve the catalysis of the composite catalyst.
The beneficial effects of this embodiment are: 1. in the embodiment, a simple hydrothermal synthesis method is adopted to prepare a Cu-MOF precursor loaded by the nitrogen-doped graphene, and a high-temperature carbonization method is adopted to prepare Cu with a core-shell structure loaded by the nitrogen-doped graphene 2 The O/Cu@C composite catalyst effectively improves the electrochemical activity of the catalyst.
2. In the embodiment, nitrogen doped graphene and Cu are introduced 2 Compared with the O/Cu@C catalyst, the nitrogen doped graphene can disperse effective metal sites, so that the electrochemical active surface area of the catalyst is increased by 4.3 times and reaches 47.2mF/cm 2 The internal resistance of charge transfer is reduced to 3.91 omega, which is reduced by 48.8%; in addition, the catalyst pair CO 2 The adsorption capacity of the catalyst is increased by 2.3 times and reaches 0.95mmol/g, thereby obviously improving the electrocatalytic reduction of CO by the Cu catalyst 2 Activity. Nitrogen-doped graphene-loaded core-shell structure Cu 2 The Faraday efficiency of the O/Cu@C composite catalyst on reducing carbon dioxide to formic acid is up to 82.9%, and the synthesis rate of formic acid is up to 430.2mg/L/h/m 2 。。
3. Nitrogen-doped graphene-loaded core-shell structure Cu prepared in this embodiment 2 The O/Cu@C composite catalyst has good stability, and after continuous electrolysis for 30 hours, the Faraday current efficiency of formic acid is still maintained to be more than 73%.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the nitrogen-doped reduced graphene oxide in the first step is specifically prepared by the following steps: adding graphene oxide powder into deionized water, adding urea, transferring to a reaction kettle, and reacting for 3-8 hours at the temperature of 150-200 ℃ to obtain nitrogen-doped reduced graphene oxide; the volume ratio of the graphene oxide powder to the deionized water is 1mg (1-5) mL; the mass ratio of the graphene oxide powder to the urea is 1 (20-40). The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the purity of the high-purity Ar gas in the fourth step is 99.99%. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the volume ratio of the N, N-dimethylformamide to the ethanol in the mixed solution of the N, N-dimethylformamide and the ethanol in the step one is 1 (0.5-2.0). The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and in the third step, drying in a vacuum drying oven, specifically in a vacuum drying oven with the temperature of 60 ℃. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: cu (NO) in the mixed solution described in step one 3 ) 2 ·3H 2 The concentration of O is 2.7 mg/mL-3.0 mg/mL; cu (NO) in the mixed solution described in step one 3 ) 2 ·3H 2 The mass ratio of O to the nitrogen doped reduced graphene oxide is 1 (0.2-0.3); the concentration of benzimidazole in the benzimidazole solution in the first step is 11.2 mg/mL-15 mg/mL; the concentration of the trimesic acid in the trimesic acid solution in the step one is 1.2 mg/mL-1.5 mg/mL. The others are the same as in one of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: and step two, mixing and stirring the mixed solution and the benzimidazole solution until the mixed solution is bright blue, adding the trimesic acid solution into the mixed solution, continuously mixing and stirring the mixed solution to obtain a precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal reaction for 6-8 hours under the constant temperature condition of 90-100 ℃ to obtain the Cu-MOF precursor loaded by the nitrogen-doped graphene. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: cu (NO) in the precursor solution described in step two 3 ) 2 ·3H 2 The mass ratio of O to benzimidazole is 1 (4.2-5); cu (NO) in the precursor solution described in step two 3 ) 2 ·3H 2 The mass ratio of O to trimesic acid is 1 (0.88-1.0). The other is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: and step four, heating to 800-1000 ℃ under the condition that the heating rate is 2-5 ℃/min. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: and step four, calcining for 5 to 8 hours at the temperature of 800 to 1000 ℃. The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide comprises the following steps:
1. preparing a precursor solution:
adding nitrogen doped reduced graphene oxide into a mixed solution of N, N-dimethylformamide and ethanol for full dispersion, and then adding Cu (NO 3 ) 2 ·3H 2 Continuously stirring O until O is completely dissolved to obtain a mixed solution, and mixing benzoImidazole is dissolved in a mixed solution of N, N-dimethylformamide and ethanol, and is stirred until the imidazole is dissolved, so that a benzimidazole solution is obtained, and trimesic acid is dissolved in a mixed solution of N, N-dimethylformamide and ethanol, and is stirred until the trimesic acid is dissolved, so that a trimesic acid solution is obtained;
cu (NO) in the mixed solution 3 ) 2 ·3H 2 The concentration of O is 2.7mg/L; cu (NO) in the mixed solution 3 ) 2 ·3H 2 The mass ratio of O to the nitrogen doped reduced graphene oxide is 1:0.2; the concentration of benzimidazole in the benzimidazole solution is 11.2mg/L; the concentration of trimesic acid in the trimesic acid solution is 1.2mg/L;
2. hydrothermal reaction:
mixing the mixed solution and the benzimidazole solution, stirring until the mixed solution is bright blue, adding the trimesic acid solution into the mixed solution, continuously mixing and stirring to obtain a precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100mL, and performing hydrothermal reaction for 6 hours under the constant temperature condition of 90 ℃ to obtain a Cu-MOF precursor loaded by the nitrogen-doped graphene;
cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to benzimidazole is 1:4.2; cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to trimesic acid is 1:0.88;
3. cleaning and drying:
centrifuging a Cu_MOF precursor loaded by nitrogen-doped graphene, washing for several times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain a dried product;
4. carbonizing the product:
placing the dried product in a tube furnace, introducing high-purity Ar gas, heating to 800 ℃ at a heating rate of 2 ℃/min, and calcining for 5 hours at the temperature of 800 ℃ to obtain the nitrogen-doped graphene-loaded core-shell structure Cu 2 O/Cu@C composite catalyst.
The nitrogen-doped reduced graphene oxide in the first step is specifically prepared by the following steps: 50mg of graphene oxide powder is added into 100mL of deionized water, then 1.5g of urea is added, and the mixture is transferred into a reaction kettle and reacted for 5 hours at the temperature of 180 ℃ to obtain the nitrogen-doped reduced graphene oxide.
The purity of the high-purity Ar gas in the fourth step is 99.99%.
The volume ratio of the N, N-dimethylformamide to the ethanol in the mixed solution of the N, N-dimethylformamide and the ethanol in the step one is 1:1.
Nitrogen-doped graphene-loaded core-shell structure Cu prepared in embodiment one by utilizing Prlington electrochemical workstation 2 The O/Cu@C composite catalyst is subjected to electrochemical property test, a nitrogen saturated 0.1mol/L potassium bicarbonate solution or a carbon dioxide saturated 0.1mol/L potassium bicarbonate solution is used as an electrolyte solution, the test result is shown in figure 2, and figure 2 shows the nitrogen doped graphene loaded core-shell structure Cu prepared in the first embodiment 2 The O/Cu@C composite catalyst is tested to obtain an LSV graph under the condition of nitrogen and carbon dioxide, wherein A is an LSV curve obtained under the condition of nitrogen, and B is an LSV curve under the condition of carbon dioxide. As can be seen from comparison of the two conditions, the current density obtained in the carbon dioxide saturated electrolyte is higher than the corresponding current density under nitrogen. Illustrating the nitrogen-doped graphene-supported core-shell structure Cu obtained in embodiment one 2 The O/Cu@C composite catalyst has a certain reduction effect on carbon dioxide reduction.
FIG. 1 is a nitrogen-doped graphene-supported core-shell structure Cu prepared in example one 2 Scanning electron microscope image of O/Cu@C composite catalyst, wherein A is octahedral Cu 2 O/Cu@C, wherein B is Cu particles, and C is nitrogen-doped graphene; from the figure, the octahedral Cu_MOF grows on the surface of the graphene and in the interlayer, and the carbonized Cu_MOF still maintains the original octahedral structure. These MOF particles exhibit a typical core-shell structure, each carbon core containing several Cu nanoparticles with a particle size in the range of 40-200 nm. From this, it is known that the use of nitrogen-doped graphene can effectively disperse metal sites.
Comparison experiment: the method comprises the following steps:
1. preparing a precursor solution:
cu (NO) 3 ) 2 ·3H 2 Adding O into the mixed solution of N, N-dimethylformamide and ethanol, and dispersing thoroughly to obtain Cu (NO) 3 ) 2 ·3H 2 O solution, namely dissolving benzimidazole in a mixed solution of N, N-dimethylformamide and ethanol, stirring until the benzimidazole is dissolved to obtain a benzimidazole solution, dissolving trimesic acid in a mixed solution of N, N-dimethylformamide and ethanol, and stirring until the trimesic acid is dissolved to obtain a trimesic acid solution;
said Cu (NO) 3 ) 2 ·3H 2 Cu (NO) in O solution 3 ) 2 ·3H 2 The concentration of O is 2.7mg/L; the concentration of benzimidazole in the benzimidazole solution is 11.2mg/L; the concentration of trimesic acid in the trimesic acid solution is 1.2mg/L;
2. hydrothermal reaction:
cu (NO) 3 ) 2 ·3H 2 Mixing the O solution and the benzimidazole solution, stirring until the mixed solution shows bright blue, adding the trimesic acid solution into the mixed solution, continuously mixing and stirring to obtain a precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100mL for hydrothermal reaction, and reacting for 6h at the temperature of 90 ℃ to obtain a precursor;
cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to benzimidazole is 1:4.2; cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to trimesic acid is 1:0.88;
3. cleaning and drying:
centrifuging the precursor, washing the precursor for a plurality of times by using absolute ethyl alcohol, and then placing the precursor in a vacuum drying oven at 60 ℃ for drying to obtain a dried product;
4. carbonizing the product:
placing the dried product in a tubular furnace, introducing high-purity Ar gas, heating to 800 ℃ at a heating rate of 2 ℃/min, and calcining for 5 hours at 800 ℃ to obtain the core-shell structure Cu 2 O/Cu@C catalyst.
The purity of the high-purity Ar gas in the fourth step is 99.99%.
The volume ratio of the N, N-dimethylformamide to the ethanol in the mixed solution of the N, N-dimethylformamide and the ethanol in the step one is 1:1.
Core-shell structure Cu prepared by utilizing Prins ston electrochemical workstation contrast experiment 2 The O/Cu@C catalyst is subjected to electrochemical property test, a nitrogen saturated 0.1mol/L potassium bicarbonate solution or a carbon dioxide saturated 0.1mol/L potassium bicarbonate solution is used as an electrolyte solution, the test result is shown in figure 3, and figure 3 is core-shell structure Cu prepared by a comparison experiment 2 The O/Cu@C catalyst is tested under nitrogen and carbon dioxide to obtain an LSV graph, wherein A is an LSV curve obtained under the nitrogen condition, and B is an LSV curve under the carbon dioxide condition. As can be seen from comparison of the two conditions, the current density obtained in the carbon dioxide saturated electrolyte is higher than the corresponding current density under nitrogen. Illustrating core-shell structure Cu prepared by comparison experiment 2 The O/Cu@C catalyst has a certain reduction effect on carbon dioxide reduction.
As can be seen from comparison between fig. 2 and fig. 3, the current density of the catalyst obtained in the first embodiment is high under the condition of the same applied potential, i.e. the use of the nitrogen doped graphene effectively improves the Cu of the core-shell structure 2 Electrochemical activity of the O/Cu@C catalyst.
The catalyst obtained in example one and comparative experiments was used as a working electrode, a platinum sheet was used as a counter electrode, silver chloride was used as a reference electrode, and electrolysis was performed at-1.4V potential for 1 hour, and the faraday efficiency of formic acid production by reduction of carbon dioxide was analyzed and calculated, as shown in fig. 4. FIG. 4 is a catalyst in CO 2 Faraday efficiency graph of formic acid production by electrolysis for 1 hour in saturated 0.1mol/L potassium bicarbonate solution, wherein a is nitrogen-doped graphene-loaded core-shell structure Cu prepared in example one 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst. From the figure, the nitrogen-doped graphene-supported core-shell structure Cu obtained in the first embodiment 2 O/Cu@C composite catalyst for reducing carbon dioxide to produce formic acidThe Faraday efficiency is up to 82.9%, and the contrast experiment is improved by 61.1%.
FIG. 5 is a catalyst in CO 2 Formic acid production rate chart of 1 hour of electrolysis in saturated 0.1mol/L potassium bicarbonate solution, wherein a is nitrogen-doped graphene-loaded core-shell structure Cu prepared in example one 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst. As can be seen from the graph, compared with the comparative experiment, the synthesis rate of formic acid reaches 430.2mg/L/h/m 2 The improvement is 2.9 times.
FIG. 6 is a catalyst in CO 2 A linear fit plot of current in saturated 0.1mol/L potassium bicarbonate solution versus sweep rate; a is Cu of a nitrogen-doped graphene-supported core-shell structure prepared in the first embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst. As can be seen from the figure, the electrochemically active surface area of example one was 47.2mF/cm 2 Compared with the comparative experiment, the method has the advantage of improving the yield by 4.3 times.
FIG. 7 is a catalyst in CO 2 Nyquist pattern in saturated 0.1mol/L potassium bicarbonate solution; a is Cu of a nitrogen-doped graphene-supported core-shell structure prepared in the first embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst. As can be seen from the graph, the internal resistance of charge transfer in the first example was 3.91 Ω, which was reduced by 48.8% compared to the comparative experiment.
FIG. 8 catalyst vs. CO 2 Adsorption curve of (2); a is Cu of a nitrogen-doped graphene-supported core-shell structure prepared in the first embodiment 2 O/Cu@C composite catalyst, b is core-shell structure Cu prepared by comparison experiment 2 O/Cu@C catalyst. As can be seen, example one shows CO at a relative pressure of 1 2 The adsorption quantity of the catalyst is 0.95mmol/g, and is improved by 2.3 times compared with a comparison experiment.
FIG. 9 is a nitrogen-doped graphene-supported core-shell structure Cu prepared in example one 2 Stability test curve of O/Cu@C composite catalyst, 1 is current density, and 2 is Faraday efficiency. As can be seen from the graph, the composite catalyst has good stability, and after continuous electrolysis for 30 hours, the Faraday current efficiency of formic acid is still maintained at 73 percentAnd (3) upper part.
Claims (1)
1. The preparation method of the nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide is characterized by comprising the following steps of:
1. preparing a precursor solution:
adding nitrogen doped reduced graphene oxide into a mixed solution of N, N-dimethylformamide and ethanol for full dispersion, and then adding Cu (NO 3 ) 2 ·3H 2 Continuously stirring O until the O is completely dissolved to obtain a mixed solution, stirring benzimidazole into a mixed solution of N, N-dimethylformamide and ethanol to obtain a benzimidazole solution, and stirring trimesic acid into a mixed solution of N, N-dimethylformamide and ethanol to obtain a trimesic acid solution;
cu (NO) in the mixed solution 3 ) 2 ·3H 2 The concentration of O is 2.7mg/L; cu (NO) in the mixed solution 3 ) 2 ·3H 2 The mass ratio of O to the nitrogen doped reduced graphene oxide is 1:0.2; the concentration of benzimidazole in the benzimidazole solution is 11.2mg/L; the concentration of trimesic acid in the trimesic acid solution is 1.2mg/L;
2. hydrothermal reaction:
mixing the mixed solution and the benzimidazole solution, stirring until the mixed solution is bright blue, adding the trimesic acid solution into the mixed solution, continuously mixing and stirring to obtain a precursor solution, transferring the precursor solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100mL, and performing hydrothermal reaction for 6 hours under the constant temperature condition of 90 ℃ to obtain a Cu-MOF precursor loaded by the nitrogen-doped graphene;
cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to benzimidazole is 1:4.2; cu (NO) in the precursor solution 3 ) 2 ·3H 2 The mass ratio of O to trimesic acid is 1:0.88;
3. cleaning and drying:
centrifuging a Cu_MOF precursor loaded by nitrogen-doped graphene, washing for several times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain a dried product;
4. carbonizing the product:
placing the dried product in a tube furnace, introducing high-purity Ar gas, heating to 800 ℃ at a heating rate of 2 ℃/min, and calcining for 5 hours at the temperature of 800 ℃ to obtain the nitrogen-doped graphene-loaded core-shell structure Cu 2 O/Cu@C composite catalyst;
the nitrogen-doped reduced graphene oxide in the first step is specifically prepared by the following steps: adding 50mg of graphene oxide powder into 100mL of deionized water, then adding 1.5g of urea, transferring into a reaction kettle, and reacting for 5 hours at 180 ℃ to obtain nitrogen-doped reduced graphene oxide;
the purity of the high-purity Ar gas in the fourth step is 99.99 percent;
the volume ratio of the N, N-dimethylformamide to the ethanol in the mixed solution of the N, N-dimethylformamide and the ethanol in the step one is 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010470059.2A CN111659437B (en) | 2020-05-28 | 2020-05-28 | Preparation method of nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010470059.2A CN111659437B (en) | 2020-05-28 | 2020-05-28 | Preparation method of nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111659437A CN111659437A (en) | 2020-09-15 |
| CN111659437B true CN111659437B (en) | 2023-05-12 |
Family
ID=72385096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010470059.2A Active CN111659437B (en) | 2020-05-28 | 2020-05-28 | Preparation method of nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111659437B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430830B (en) * | 2020-12-01 | 2022-03-29 | 大连理工大学 | Preparation method and application of electrocatalytic reduction carbon dioxide electrode |
| CN113737218B (en) * | 2021-09-29 | 2023-02-07 | 中国石油化工股份有限公司 | Copper-based graphene aerogel composite catalyst, gas diffusion electrode and application |
| CN114452995A (en) * | 2022-01-06 | 2022-05-10 | 天津大学 | Nitrogen-doped porous carbon and multivalent copper composite material as well as preparation method and application thereof |
| CN114836781B (en) * | 2022-02-28 | 2023-10-03 | 郑州大学 | Preparation method and application of lamellar Cu-based N-doped graphene catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616775A (en) * | 2012-04-16 | 2012-08-01 | 南京大学 | Preparation method for water phase of nitrogen-doped graphene |
| CN103990484A (en) * | 2014-05-26 | 2014-08-20 | 西北工业大学 | Preparation method of nitrogen doped and graphene loaded Cu-Cu2O nanocomposites |
| KR20180031233A (en) * | 2016-09-19 | 2018-03-28 | 한국과학기술연구원 | Catalyst for dehydrogenation reaction of formic acid and method for preparing the same |
| CN108273504A (en) * | 2018-01-17 | 2018-07-13 | 浙江大学 | A kind of nitrogen-doped graphene load ferrum-based catalyst and its preparation method and application |
-
2020
- 2020-05-28 CN CN202010470059.2A patent/CN111659437B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616775A (en) * | 2012-04-16 | 2012-08-01 | 南京大学 | Preparation method for water phase of nitrogen-doped graphene |
| CN103990484A (en) * | 2014-05-26 | 2014-08-20 | 西北工业大学 | Preparation method of nitrogen doped and graphene loaded Cu-Cu2O nanocomposites |
| KR20180031233A (en) * | 2016-09-19 | 2018-03-28 | 한국과학기술연구원 | Catalyst for dehydrogenation reaction of formic acid and method for preparing the same |
| CN108273504A (en) * | 2018-01-17 | 2018-07-13 | 浙江大学 | A kind of nitrogen-doped graphene load ferrum-based catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 《MOF-Derived Cu2O/Cu Nanospheres Anchored in Nitrogen-Doped Hollow Porous Carbon Framework for Increasing the Selectivity and Activity of Electrochemical CO2-to-Formate Conversion》;Da Li,et al.;《AACS Appl. Mater. Interfaces》;20200122;第12卷;第7031页左栏第4段-右栏第1段 * |
| 《N-doped reduced graphene oxide supported Cu2O nanocubes as high active catalyst for CO2 electroreduction to C2H4》;Hui Ning.et al.;《Journal of Alloys and Compounds》;20190114;第785卷;第8页左栏第2段-右栏第3段，第9页左栏第3段-第11页右栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111659437A (en) | 2020-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111659437B (en) | Preparation method of nitrogen-doped graphene-supported core-shell copper-carbon composite catalyst for producing formic acid by electrocatalytic carbon dioxide | |
| CN107649160B (en) | Graphene-loaded transition group metal monodisperse atomic catalyst and preparation method and application thereof | |
| CN112495408B (en) | Preparation method of electrocatalytic hydrogen evolution nano material | |
| CN110767914B (en) | Co-N doped porous carbon-coated carbon nanotube core-shell structure catalyst and preparation method and application thereof | |
| CN108315758B (en) | Catalyst for producing hydrogen by electrolyzing water and preparation method thereof | |
| CN111545208A (en) | Cobalt-nickel bimetallic catalyst and preparation method thereof | |
| CN110961162B (en) | Catalyst carrier, precious metal catalyst, and preparation method and application thereof | |
| CN110694693A (en) | Carbon cloth loaded MoSx/UiO-66 composite material, preparation method and application | |
| CN111282588A (en) | Catalyst for hydrogen evolution by electrolyzing water and preparation method and application thereof | |
| CN113862693A (en) | Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst | |
| CN112522726A (en) | Preparation method and application of nitrogen-doped porous carbon/molybdenum disulfide composite material derived from natural agar | |
| CN114522706A (en) | Carbide-supported noble metal monatomic catalyst, and preparation and application thereof | |
| CN111653792A (en) | Method for synchronously preparing hierarchical pore cobalt and nitrogen co-doped nanorod supported platinum-cobalt alloy nano oxygen reduction electrocatalyst | |
| CN111659394A (en) | Copper-based catalyst and preparation method and application thereof | |
| CN115404513A (en) | Carbon-coated heterostructure electrocatalyst and preparation and application thereof | |
| CN111408372B (en) | Copper-based CO with hollow nanosphere morphology 2 Preparation process of electro-reduction catalyst | |
| CN111715256B (en) | Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles | |
| CN114574890B (en) | Self-forming phosphorus-doped redox graphene aerogel catalyst and preparation method and application thereof | |
| CN116364960B (en) | ZIF-8/lignin-based iron-nitrogen-sulfur co-doped porous carbon material and preparation method and application thereof | |
| CN115125578B (en) | Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst | |
| CN116334689B (en) | PVP modified NiMoS electrocatalyst and preparation method thereof | |
| CN114225953B (en) | Core-shell spherical B, N, P co-doped carbon nanosphere electrocatalyst and preparation method and application thereof | |
| CN114574898B (en) | Mn doped Co 2 P core-shell nanosphere and preparation method and application thereof | |
| CN117779097A (en) | Preparation method of micro Ni and N doped irregular blocky activated carbon catalyst | |
| CN117385375A (en) | Copper-cobalt bimetallic nitride nano-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 |