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Preparing method of carbon-loaded monoatomic metal nitrogen-containing compound oxygen reduction catalyst and obtained catalyst

A technology of composites and catalysts, applied in the direction of physical/chemical process catalysts, chemical instruments and methods, chemical/physical processes, etc., can solve the problem that catalysts are not resistant to acid and alkali electron transport, cannot be prepared on a large scale, and have low pH universality, etc. problems, to achieve the effect of favorable electron transport, excellent catalytic performance, and low raw material cost

Inactive Publication Date: 2019-09-06
PEKING UNIV SHENZHEN GRADUATE SCHOOL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this type of catalyst still has the following problems: First, there are defects in the catalyst structure. On the one hand, although the prepared catalyst metal exists in the form of single atoms and has a high loading capacity, due to the relatively closed structure, the actual atom utilization rate is low. On the other hand, due to the neglect of the graphitization structure of the carbon support, the catalyst is not resistant to acid and alkali and the electron transport is weak, so the overall catalytic performance is not good; second, the pH universality is low, and the performance in alkaline electrolyte It has excellent catalytic performance, stability and methanol resistance, but it cannot have matching performance under the more practical neutral and acidic electrolytes; third, it is difficult to mass-produce, and the current preparation of carbon-supported transition metal The methods of single-atom catalysts include but are not limited to template method, wet chemical method, atomic layering method, chemical vapor layering method and other methods. Even if high-efficiency catalysts can be prepared, they cannot be prepared on a large scale due to the complexity of the preparation process; the fourth , the cost is high, and the carbon carrier chooses expensive graphene, carbon nanotubes, etc., and the preparation process requires high equipment, etc.
In particular, recent studies reported that by maximizing the construction of M-N x It is an important method to improve the performance of M-N / C catalysts (ACS Catal. 2018, 8, 2824-2832; Adv. Mater. 2018, 1802304; Angew, 2016, 55, 10800) However, how to prepare M-N / C catalysts with 100% atomic utilization is still the most important challenge

Method used

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  • Preparing method of carbon-loaded monoatomic metal nitrogen-containing compound oxygen reduction catalyst and obtained catalyst
  • Preparing method of carbon-loaded monoatomic metal nitrogen-containing compound oxygen reduction catalyst and obtained catalyst
  • Preparing method of carbon-loaded monoatomic metal nitrogen-containing compound oxygen reduction catalyst and obtained catalyst

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Embodiment 1

[0038] Embodiment 1: the preparation of Fe-SAC catalyst

[0039] Put 3 g of chitin in a muffle furnace, raise the temperature to 250° C. and keep it for 2 hours to obtain pre-oxidized chitin-based cracked carbon. After cooling to room temperature, the pre-oxidized chitin-based pyrolysis carbon was taken out, and 3 g of ferric chloride solid (as a transition metal source) and 9 g of zinc chloride solid (as a pore-forming agent) were added and mixed uniformly to obtain a reaction mixture. The reaction mixture was put into a porcelain boat (length 80mm*width 60mm*height 30mm), and then placed in a laboratory tube furnace. Nitrogen gas was introduced into the furnace to replace the air, and then the furnace was heated to 800° C. at a temperature increase rate of 5° C. / min, and the reaction mixture was roasted for 2 hours to obtain a roasted product. After cooling to room temperature, pickle with a sufficient amount of hydrochloric acid solution with a concentration of 2 mol / L for...

Embodiment 2

[0040] Embodiment 2: the preparation of Co-SAC catalyst

[0041] Put 3 g of chitin in a muffle furnace, raise the temperature to 200° C. and keep it for 5 hours to obtain pre-oxidized chitin-based cracked carbon. After cooling to room temperature, the pre-oxidized chitin-based pyrolysis carbon was taken out, 12g of cobalt sulfate solid (as a transition metal source) and 6g of zinc chloride (as a pore-forming agent) were added, and mixed uniformly to obtain a reaction mixture. The reaction mixture was placed in a porcelain boat and placed in a laboratory tube furnace. Nitrogen gas was introduced into the furnace to replace the air, and then the furnace was heated to 1100° C. at a rate of 10° C. / min, and the reaction mixture was calcined for 1 hour to obtain a calcined product. After cooling to room temperature, pickle with a sufficient amount of sulfuric acid solution with a concentration of 1mol / L for 40 hours, and then wash with a sufficient amount of deionized water for sev...

Embodiment 3

[0042] Embodiment 3: the preparation of Mn-SAC catalyst

[0043] Put 3 g of chitin in a muffle furnace, raise the temperature to 300° C. and keep for 1 hour to obtain pre-oxidized chitin-based cracked carbon. After cooling to room temperature, the pre-oxidized chitin-based pyrolysis carbon was taken out, and 6 g of manganese nitrate solid (as a transition metal source) and 12 g of zinc chloride solid (as a pore-forming agent) were added and mixed uniformly to obtain a reaction mixture. The reaction mixture was placed in a porcelain boat and placed in a laboratory tube furnace. Nitrogen gas was introduced into the furnace to replace the air, and then the furnace was heated to 1100° C. at a rate of 10° C. / min, and the reaction mixture was calcined for 1 hour to obtain a calcined product. After cooling to room temperature, pickle with a sufficient amount of nitric acid solution with a concentration of 1mol / L for 25 hours, and then wash with a sufficient amount of deionized water...

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Abstract

The invention provides a preparing method of a carbon-loaded monoatomic metal nitrogen-containing compound oxygen reduction catalyst. The method comprises the steps of pre-oxidizing nitrogen-containing biomass at a first high temperature, after a pre-oxidized product is uniformly mixed with a transition metal source and a pore-forming agent, conducting first calcination at a second high temperature in an inert gas atmosphere, after a calcined product is subjected to acid pickling, washing and drying, conducting second calcination again at the second high temperature, and finally, obtaining thecarbon-loaded monoatomic metal nitrogen-containing compound oxygen reduction catalyst. The preparing method has the advantages of being low in raw material cost, simple in preparing technology and the like; the prepared catalyst has the advantages of being high in pH universality, atom utilization rate, catalytic performance and stability, excellent in methyl alcohol resistance and the like, is expected to replace expensive carbon-loaded platinum catalysts, and is about to have a wide application prospect in efficient and cheap large-scale commercialized fuel cells.

Description

technical field [0001] The invention relates to the technical field of electrocatalytic materials and new energy, in particular to a preparation method of a carbon-supported single-atom metal nitrogen-containing composite oxygen reduction catalyst and the carbon-supported single-atom metal nitrogen-containing composite oxygen reduction catalyst prepared by the preparation method catalyst. Background technique [0002] Energy shortage and environmental pollution are major problems that human society is facing urgently. The development of sustainable clean energy and advanced energy conversion technology can provide a good solution to these problems. Among them, the polymer electrolyte membrane fuel cell (PEMFC), which uses hydrogen as fuel, has the advantages of non-toxic, non-polluting, high specific energy, high specific power, etc., and has great application potential in the battery field. Fuel cell vehicles driven by fuel cells are also considered to be an important choi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J35/10H01M4/90
CPCB01J27/24H01M4/9083B01J35/33B01J35/617Y02E60/50
Inventor 龙霞杨世和钟文华
Owner PEKING UNIV SHENZHEN GRADUATE SCHOOL
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