{"title":"利用自愈胶囊对稀释二氧化碳源进行酶活化和连续电化学生产甲烷。","authors":"Jinfeng Wang, Xu Jing, Yang Yang, Baijie Xu, Ruiming Jia, Chunying Duan","doi":"10.1021/jacs.4c03367","DOIUrl":null,"url":null,"abstract":"<p><p>Converting dilute CO<sub>2</sub> source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption and greenhouse gas emission, but integrating electrocatalysis with CO<sub>2</sub> capture still faced marked challenges. Herein, we show that a self-healing metal-organic macrocycle functionalized as an electrochemical catalyst to selectively produce methane from flue gas and air with the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through an enzymatic activation fashion. The capsule emulates the enzyme' pocket to abstract one <i>in situ</i>-formed CO<sub>2</sub>-adduct molecule with the commercial amino alcohols, forming an easy-to-reduce substrate-involving clathrate to combine the CO<sub>2</sub> capture with electroreduction for a thorough CO<sub>2</sub> reduction. We find that the self-healing system exhibited enzymatic kinetics for the first time with the Michaelis-Menten mechanism in the electrochemical reduction of CO<sub>2</sub> and maintained a methane Faraday efficiency (FE) of 74.24% with a selectivity of over 99% for continuous operation over 200 h. A consecutive working lab at 50 mA·cm<sup>-2</sup>, in an eleven-for-one (10 h working and 1 h healing) electrolysis manner, gives a methane turnover number (TON) of more than 10,000 within 100 h. The integrated electrolysis with CO<sub>2</sub> capture facilitates the thorough reduction of flue gas (ca. 13.0% of CO<sub>2</sub>) and first time of air (ca. 400 ppm of CO<sub>2</sub> to 42.7 mL CH<sub>4</sub> from 1.0 m<sup>3</sup> air). The new self-healing strategy of molecular electrocatalyst with an enzymatic activation manner and anodic shifting of the applied potentials provided a departure from the existing electrochemical catalytic techniques.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enzymatic Activation and Continuous Electrochemical Production of Methane from Dilute CO<sub>2</sub> Sources with a Self-Healing Capsule.\",\"authors\":\"Jinfeng Wang, Xu Jing, Yang Yang, Baijie Xu, Ruiming Jia, Chunying Duan\",\"doi\":\"10.1021/jacs.4c03367\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Converting dilute CO<sub>2</sub> source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption and greenhouse gas emission, but integrating electrocatalysis with CO<sub>2</sub> capture still faced marked challenges. Herein, we show that a self-healing metal-organic macrocycle functionalized as an electrochemical catalyst to selectively produce methane from flue gas and air with the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through an enzymatic activation fashion. The capsule emulates the enzyme' pocket to abstract one <i>in situ</i>-formed CO<sub>2</sub>-adduct molecule with the commercial amino alcohols, forming an easy-to-reduce substrate-involving clathrate to combine the CO<sub>2</sub> capture with electroreduction for a thorough CO<sub>2</sub> reduction. We find that the self-healing system exhibited enzymatic kinetics for the first time with the Michaelis-Menten mechanism in the electrochemical reduction of CO<sub>2</sub> and maintained a methane Faraday efficiency (FE) of 74.24% with a selectivity of over 99% for continuous operation over 200 h. A consecutive working lab at 50 mA·cm<sup>-2</sup>, in an eleven-for-one (10 h working and 1 h healing) electrolysis manner, gives a methane turnover number (TON) of more than 10,000 within 100 h. The integrated electrolysis with CO<sub>2</sub> capture facilitates the thorough reduction of flue gas (ca. 13.0% of CO<sub>2</sub>) and first time of air (ca. 400 ppm of CO<sub>2</sub> to 42.7 mL CH<sub>4</sub> from 1.0 m<sup>3</sup> air). The new self-healing strategy of molecular electrocatalyst with an enzymatic activation manner and anodic shifting of the applied potentials provided a departure from the existing electrochemical catalytic techniques.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2024-07-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.4c03367\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/7/4 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c03367","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/7/4 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Enzymatic Activation and Continuous Electrochemical Production of Methane from Dilute CO2 Sources with a Self-Healing Capsule.
Converting dilute CO2 source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption and greenhouse gas emission, but integrating electrocatalysis with CO2 capture still faced marked challenges. Herein, we show that a self-healing metal-organic macrocycle functionalized as an electrochemical catalyst to selectively produce methane from flue gas and air with the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through an enzymatic activation fashion. The capsule emulates the enzyme' pocket to abstract one in situ-formed CO2-adduct molecule with the commercial amino alcohols, forming an easy-to-reduce substrate-involving clathrate to combine the CO2 capture with electroreduction for a thorough CO2 reduction. We find that the self-healing system exhibited enzymatic kinetics for the first time with the Michaelis-Menten mechanism in the electrochemical reduction of CO2 and maintained a methane Faraday efficiency (FE) of 74.24% with a selectivity of over 99% for continuous operation over 200 h. A consecutive working lab at 50 mA·cm-2, in an eleven-for-one (10 h working and 1 h healing) electrolysis manner, gives a methane turnover number (TON) of more than 10,000 within 100 h. The integrated electrolysis with CO2 capture facilitates the thorough reduction of flue gas (ca. 13.0% of CO2) and first time of air (ca. 400 ppm of CO2 to 42.7 mL CH4 from 1.0 m3 air). The new self-healing strategy of molecular electrocatalyst with an enzymatic activation manner and anodic shifting of the applied potentials provided a departure from the existing electrochemical catalytic techniques.
期刊介绍:
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