CN111036261A - Supported monatomic metal catalyst and preparation method and application thereof - Google Patents
Supported monatomic metal catalyst and preparation method and application thereof Download PDFInfo
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- CN111036261A CN111036261A CN201911224654.1A CN201911224654A CN111036261A CN 111036261 A CN111036261 A CN 111036261A CN 201911224654 A CN201911224654 A CN 201911224654A CN 111036261 A CN111036261 A CN 111036261A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000197 pyrolysis Methods 0.000 claims description 17
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B01J35/391—
-
- 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
-
- B01J35/33—
-
- B01J35/394—
-
- B01J35/56—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
Abstract
The invention specifically relates to a preparation method of a supported monatomic metal catalyst, which comprises the following steps: heating and evaporating a mixed solution containing a carbon source, metal salt and an organic solvent to dryness, then carrying out heat treatment in an ammonia atmosphere, and cooling to obtain the supported monatomic catalyst. The method can enable the supported monatomic catalyst to be generated in one step and compounded in situ, has cheap and easily obtained raw materials and simple process flow, and meets the application requirements of industrial production. According to the catalyst prepared by the method, the active component metal is loaded on the nitrogen-doped ordered porous carbon in a monodisperse manner, and the catalyst has the characteristics of high activity and high stability when being used for electrocatalytic carbon dioxide reduction reaction.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a supported monatomic metal catalyst, a preparation method thereof and application thereof in electrocatalytic reduction reaction of carbon dioxide.
Background
The excessive carbon dioxide in the atmosphere brings serious environmental problems such as global warming and the like, has attracted wide attention of the international society, and the scientific community actively seeks an effective solution. The carbon dioxide electrochemical reduction method has the advantages of less device investment, mild reaction conditions and low cost, and is a green chemical method. The carbon dioxide is converted into useful chemicals such as carbon monoxide, methane, formic acid, alcohols, hydrocarbons, carbonates and the like, and has important significance for relieving environmental and energy crisis. Therefore, it is necessary to design and develop a highly active electrocatalytic material.
The single atom catalysis is a new concept in the field of heterogeneous catalysis, and the uniform active sites with dispersed atoms can maximize the utilization rate of metal atoms and effectively reduce the cost of the catalyst; the catalyst not only has the characteristics of consistent and isolated active sites of homogeneous catalysis, but also has the characteristics of easy separation and repeated cyclic utilization of heterogeneous catalysts. The existing preparation methods of the monatomic catalyst comprise an impregnation method, a high-speed ball milling method, ALD (atomic layer deposition), a photoreduction method and the like, but most of the preparation methods are complicated and are not easy to realize industrialization, and due to the high energy of the monatomic, the monatomic catalyst is easy to agglomerate in the preparation process, and the monatomic catalyst is difficult to achieve monolayer distribution of atoms.
Disclosure of Invention
The invention aims to provide a preparation method of a supported monatomic metal catalyst, which can be used for generating the supported monatomic metal catalyst in one step and compounding the catalyst in situ, has cheap and easily obtained raw materials and simple process flow, and meets the application requirements of industrial production. According to the catalyst prepared by the method, the active component metal is loaded on the nitrogen-doped ordered porous carbon in a monodisperse manner, and the catalyst has the characteristics of high activity and high stability when being used for electrocatalytic carbon dioxide reduction reaction.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a supported monatomic catalyst comprises the following steps: heating and evaporating a mixed solution containing a carbon source, metal salt and an organic solvent to dryness, then carrying out heat treatment in an ammonia atmosphere, and cooling to obtain the supported monatomic catalyst.
Preferably, the carbon source is any one or a mixture of more than one of glucose, sucrose and starch.
Preferably, the metal salt is soluble salt of Ni, Fe, Co.
Preferably, the organic solvent is water and ethanol, and the ethanol accounts for 0-100% of the solvent by volume and does not comprise 0% and 100%.
Preferably, the mass ratio of the carbon source to the metal salt is (12-25): 1.
preferably, the flow velocity of the ammonia gas is 60-100 cm3/min。
Preferably, the pyrolysis temperature is 700-900 ℃, and the pyrolysis time is 1-2 h.
The supported monatomic metal catalyst prepared by the method is applied to electrocatalytic reduction of carbon dioxide.
The invention has the beneficial effects that:
1. the load type monatomic metal catalyst provided by the invention is produced in one step by using cheap glucose, sucrose and starch as carbon sources and cheap nickel salt, cobalt salt and iron salt as metal precursors through in-situ pyrolysis reaction, and monatomic metal is uniformly and stably loaded on uniformly-distributed honeycomb-shaped nitrogen-doped ordered porous carbon. The preparation method provided by the invention has the advantages of cheap and easily available raw materials and simple process flow, greatly reduces the production cost and is beneficial to large-scale industrial application.
2. The supported monatomic metal catalyst is composed of monatomic metal and nitrogen-doped ordered porous carbon, the ordered porous carbon has the characteristics of rich pore passages and large specific surface area, the dispersion of the monatomic metal is facilitated, and meanwhile, N atoms doped on the ordered porous carbon are beneficial to anchoring monatomic metal particles, so that the size of the monatomic metal particles is reduced, the dispersion degree of active components is improved, and the acting force between the metal and a carrier is improved; each component has certain catalytic activity of electrocatalysis of carbon dioxide reduction, and the synergistic effect of various active substances is obvious, so that the catalyst has high catalytic activity and stability.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The invention discloses a preparation method of a supported monatomic catalyst, which comprises the following steps: heating and evaporating a mixed solution containing a carbon source, metal salt and an organic solvent to dryness, then carrying out heat treatment in an ammonia atmosphere, and cooling to obtain the supported monatomic catalyst.
Preferably, the carbon source is any one or a mixture of more than one of glucose, sucrose and starch.
Preferably, the metal salt is soluble salt of Ni, Fe, Co, for example, it can be any one or mixture of more than one of chloride, nitrate, acetate of Ni, Fe, Co.
Preferably, the organic solvent is water and ethanol, and the ethanol accounts for 0-100% of the solvent by volume and does not include 0 and 100%, and for example, the volume ratio of the ethanol to the solvent may be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%.
Preferably, the heating and drying temperature is 50-100 ℃.
Preferably, the mass ratio of the carbon source to the metal salt is (12-25): 1 may be, for example, 12:1, 15:1, 20:1, 25: 1.
Preferably, the flow velocity of the ammonia gas is 60-100 cm3Permin, for example, may be 60cm3/min、70cm3/min、80cm3/min、90cm3/min、100cm3/min。
Preferably, the pyrolysis temperature is 700-900 ℃, for example 700 ℃, 800 ℃, 900 ℃, and the pyrolysis time is 1-2 h, for example 1h, 2 h.
The supported monatomic rhodium-based catalyst prepared by the method is applied to electrocatalytic reduction of carbon dioxide.
The performance evaluation of the catalyst is carried out in a sealed H-shaped glass colorimetric tank, and the method specifically comprises the following steps:
(1) 5mg of the supported monatomic metal catalyst prepared by the invention is mixed with a mixed solution of 1mL of ethanol and 100 mu L of 5 wt% Nafion solution, the mixture is uniformly dispersed by ultrasonic, 80 mu L of the mixture is dripped on the surface of a glassy carbon electrode for 5 times, and the glassy carbon electrode modified with the catalyst is obtained by placing and airing at room temperatureA pole; wherein the size of the glassy carbon electrode is 1cm multiplied by 2cm, and the loading amount of the catalyst is 0.2mg/cm2GC310 type glassy carbon electrode produced by tianjin ada heng cheng science and technology limited;
(2) in a sealed H-type glass colorimetric tank, an electrochemical workstation (French Bio-Logic VMP3) is taken as a testing instrument, a three-electrode system is adopted for testing, a platinum sheet is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode, a glassy carbon electrode modified with the catalyst is taken as a working electrode, 0.5mol/L KHCO3 electrolyte solution is respectively filled in a cathode tank and an anode tank, CO2 is introduced to the cathode tank and the anode tank until the cathode tank and the anode tank are saturated, and then carbon dioxide is reduced at a constant potential of-0.8V vs. RHE for 4 hours under the condition that the flow rate is 5mL/min CO 2.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the examples are conventional methods unless otherwise specified; the materials used, unless otherwise specified, were purchased from conventional biochemical manufacturers.
Example 1
Adding 1.2g of glucose and 0.1g of nickel nitrate into a mixed solvent of 2mL of water and 18mL of ethanol, stirring and mixing uniformly, heating at 50 ℃ until the liquid is evaporated to dryness, pyrolyzing the evaporated product in a 700 ℃ tubular furnace for 1h, and introducing the liquid with the flow rate of 60cm all the time in the pyrolysis process3And (4) taking out the ammonia gas per minute, and cooling the product after pyrolysis to room temperature to obtain the supported monatomic metal catalyst.
In the reaction of electrocatalytic reduction of carbon dioxide by the catalyst, the carbon dioxide can be efficiently electrocatalytic reduced under the potential of-0.8 Vvs. RHE, and the catalytic current density reaches 25mA/cm2The highest faradaic efficiency of the product is close to 100%. Meanwhile, after the catalyst catalyzes the reaction of electrocatalytic reduction of carbon dioxide for 5 times, the catalytic current density reaches 22mA/cm2The highest faradaic efficiency of the product is close to 95%.
Example 2
Adding 2.5g of glucose and 0.1g of nickel nitrate into a mixed solvent of 18mL of water and 2mL of ethanol, stirring and mixing uniformly, heating at 100 ℃ until the liquid is evaporated to dryness, and putting the evaporated product in a 900 ℃ tubular furnacePyrolyzing for 2h, wherein the flow rate is 100cm in the pyrolysis process3And (4) taking out the ammonia gas per minute, and cooling the product after pyrolysis to room temperature to obtain the supported monatomic metal catalyst.
In the reaction of electrocatalytic reduction of carbon dioxide by the catalyst, the carbon dioxide can be efficiently electrocatalytic reduced under the potential of-0.8V vs. RHE, and the catalytic current density reaches 30mA/cm2The highest faradaic efficiency of the product is close to 100%. Meanwhile, after the catalyst catalyzes the reaction of electrocatalytic reduction of carbon dioxide for 5 times, the catalytic current density reaches 27mA/cm2The highest faradaic efficiency of the product is close to 98%.
Example 3
Adding 2g of glucose and 0.1g of nickel nitrate into a mixed solvent of 10mL of water and 10mL of ethanol, stirring and mixing uniformly, heating at 80 ℃ until the liquid is evaporated to dryness, pyrolyzing the evaporated product in a 800 ℃ tubular furnace for 1h, and introducing 80cm of flow velocity in the pyrolysis process3And (4) taking out the ammonia gas per minute, and cooling the product after pyrolysis to room temperature to obtain the supported monatomic metal catalyst.
In the reaction of electrocatalytic reduction of carbon dioxide by the catalyst, the carbon dioxide can be efficiently electrocatalytic reduced under the potential of-0.8V vs. RHE, and the catalytic current density reaches 28mA/cm2The highest faradaic efficiency of the product is close to 100%. Meanwhile, after the catalyst catalyzes the reaction of electrocatalytic reduction of carbon dioxide for 5 times, the catalytic current density reaches 25mA/cm2The highest faradaic efficiency of the product is nearly 97%.
Example 4
Adding 2g of glucose and 0.1g of cobalt nitrate into a mixed solvent of 10mL of water and 10mL of ethanol, stirring and mixing uniformly, heating at 80 ℃ until the liquid is evaporated to dryness, pyrolyzing the evaporated product in a 800 ℃ tubular furnace for 1h, and introducing 80cm of flow velocity in the pyrolysis process3And (4) taking out the ammonia gas per minute, and cooling the product after pyrolysis to room temperature to obtain the supported monatomic metal catalyst.
In the reaction of electrocatalytic reduction of carbon dioxide by the catalyst, the carbon dioxide can be efficiently electrocatalytic reduced under the potential of-0.8V vs. RHE, and the catalytic current density reaches 22mA/cm2The highest faradaic efficiency of the product is close to 100%. All in oneWhen the catalyst is used for catalyzing the reaction of electrocatalytic reduction of carbon dioxide for 5 times, the catalytic current density reaches 20mA/cm2The highest faradaic efficiency of the product is close to 96%.
Example 5
Adding 2g of glucose and 0.1g of ferric nitrate into a mixed solvent of 10mL of water and 10mL of ethanol, stirring and mixing uniformly, heating at 80 ℃ until the liquid is evaporated to dryness, pyrolyzing the evaporated product in a 800 ℃ tubular furnace for 1h, and introducing 80cm of flow rate all the time in the pyrolysis process3And (4) taking out the ammonia gas per minute, and cooling the product after pyrolysis to room temperature to obtain the supported monatomic metal catalyst.
In the reaction of electrocatalytic reduction of carbon dioxide by the catalyst, the carbon dioxide can be efficiently electrocatalytic reduced under the potential of-0.8V vs. RHE, and the catalytic current density reaches 23mA/cm2The highest faradaic efficiency of the product is close to 100%. Meanwhile, after the catalyst catalyzes the reaction of electrocatalytic reduction of carbon dioxide for 5 times, the catalytic current density reaches 21mA/cm2The highest faradaic efficiency of the product is close to 95%.
The embodiment shows that the supported monatomic metal catalyst of the invention is used in the electrocatalytic reduction reaction of carbon dioxide, shows the characteristic of high activity, keeps high catalytic activity after multiple catalytic reactions, has stable catalytic property and is convenient for recycling the catalyst, and the catalytic activity of the catalyst is not greatly reduced.
The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a supported monatomic metal catalyst is characterized by comprising the following steps: heating and evaporating a mixed solution containing a carbon source, metal salt and an organic solvent to dryness, then carrying out heat treatment in an ammonia atmosphere, and cooling to obtain the supported monatomic catalyst.
2. The method according to claim 1, wherein the carbon source is any one or a mixture of more than one of glucose, sucrose and starch.
3. The method according to claim 1, wherein the metal salt is a soluble salt of Ni, Fe, Co.
4. The preparation method according to claim 1, wherein the organic solvent is water and ethanol, and the ethanol accounts for 0-100% of the solvent by volume and does not include 0% and 100%.
5. The preparation method according to claim 1, wherein the heating and evaporating temperature is 50-100 ℃.
6. The preparation method according to claim 1, wherein the mass ratio of the carbon source to the metal salt is (12-25): 1.
7. the method according to claim 1, wherein the flow rate of the ammonia gas is 60 to 100cm3/min。
8. The preparation method according to claim 1, wherein the pyrolysis temperature is 700-900 ℃ and the pyrolysis time is 1-2 h.
9. The supported monatomic metal catalyst produced by the production method according to any one of claims 1 to 8.
10. Use of the supported monatomic metal catalyst of claim 9 wherein said supported monatomic metal catalyst is used in the electrocatalytic reduction of carbon dioxide.
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| CN201911224654.1A CN111036261A (en) | 2019-12-04 | 2019-12-04 | Supported monatomic metal catalyst and preparation method and application thereof |
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| CN201911224654.1A CN111036261A (en) | 2019-12-04 | 2019-12-04 | Supported monatomic metal catalyst and preparation method and application thereof |
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| CN112206802A (en) * | 2020-09-28 | 2021-01-12 | 苏州阿德旺斯新材料有限公司 | Preparation method of monatomic catalyst, prepared product and application |
| CN113118451A (en) * | 2021-03-26 | 2021-07-16 | 中南大学 | Preparation method of magnesium monoatomic catalyst applied to efficient carbon dioxide reduction reaction for generating carbon monoxide |
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| CN113117679A (en) * | 2021-04-15 | 2021-07-16 | 赵石永 | Catalyst-loaded carbon fiber cloth and preparation method and application thereof |
| CN113737217A (en) * | 2021-09-29 | 2021-12-03 | 天津理工大学 | High-load metal Co monatomic catalyst and preparation method and application thereof |
| CN114703505A (en) * | 2022-04-04 | 2022-07-05 | 昆明理工大学 | Preparation method of metal atom electrocatalyst with stable carbon atom coordination |
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| CN115041214A (en) * | 2022-06-21 | 2022-09-13 | 浙江工业大学 | High-proportion Fe-N loaded in hydrophilic pore channel 4 Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN115401210A (en) * | 2022-07-15 | 2022-11-29 | 周口师范学院 | Preparation method for synthesizing metal monatomic material by biomass |
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