Zhiyong Zhu , Shuai Lv , Xinyi Sun , Cong Liu , Xinke Qi , Xiao Liu , Li Wang , Jinglai Zhang
{"title":"通过氮磷共掺剂提高镍基单原子催化剂对二氧化碳还原的电催化活性","authors":"Zhiyong Zhu , Shuai Lv , Xinyi Sun , Cong Liu , Xinke Qi , Xiao Liu , Li Wang , Jinglai Zhang","doi":"10.1016/j.apcata.2024.119824","DOIUrl":null,"url":null,"abstract":"<div><p>Electrochemical carbon dioxide reduction (CO<sub>2</sub>RR) is a promising approach to accomplish the CO<sub>2</sub> net emission. Ni-based single-atom catalysts (Ni-SACs) with the Ni-N-C structure have been the hotspot in this field. However, its catalytic activity is still unsatisfied. Regulation of the coordination environment of the active site via heteroatom doping is an efficient strategy to improve its catalytic characteristics and activity. Herein, the heteroatom phosphorus is introduced into the N-doped carbon supporter to form Ni-SA/CN-P catalyst achieving the CO Faraday efficiency of 91.8 % at a potential of -1.1 V along with the CO current density 91.2 mA cm<sup>-2</sup> in the flow cell, which is superior to the sample Ni-SA/CN without P dopant. It is attributed that the more defects are built in the Ni-SA/CN-P catalyst due to the different atomic radiuses of P and N atoms. Moreover, the gap between d-band center and Femi energy level is narrowed due to the doped P atoms, which reduces the rate-limiting barrier height leading to the promoted catalytic performance. The cooperation of various items finally results in the overall performance. This work provides a simple method for establishing single-atom catalysts with P doping to improve catalytic performance for CO<sub>2</sub>RR.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7000,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Promoting the electrocatalytic activity for Ni-based single atom catalysts by nitrogen and phosphorus codopant towards CO2 reduction\",\"authors\":\"Zhiyong Zhu , Shuai Lv , Xinyi Sun , Cong Liu , Xinke Qi , Xiao Liu , Li Wang , Jinglai Zhang\",\"doi\":\"10.1016/j.apcata.2024.119824\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Electrochemical carbon dioxide reduction (CO<sub>2</sub>RR) is a promising approach to accomplish the CO<sub>2</sub> net emission. Ni-based single-atom catalysts (Ni-SACs) with the Ni-N-C structure have been the hotspot in this field. However, its catalytic activity is still unsatisfied. Regulation of the coordination environment of the active site via heteroatom doping is an efficient strategy to improve its catalytic characteristics and activity. Herein, the heteroatom phosphorus is introduced into the N-doped carbon supporter to form Ni-SA/CN-P catalyst achieving the CO Faraday efficiency of 91.8 % at a potential of -1.1 V along with the CO current density 91.2 mA cm<sup>-2</sup> in the flow cell, which is superior to the sample Ni-SA/CN without P dopant. It is attributed that the more defects are built in the Ni-SA/CN-P catalyst due to the different atomic radiuses of P and N atoms. Moreover, the gap between d-band center and Femi energy level is narrowed due to the doped P atoms, which reduces the rate-limiting barrier height leading to the promoted catalytic performance. The cooperation of various items finally results in the overall performance. This work provides a simple method for establishing single-atom catalysts with P doping to improve catalytic performance for CO<sub>2</sub>RR.</p></div>\",\"PeriodicalId\":243,\"journal\":{\"name\":\"Applied Catalysis A: General\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2024-05-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis A: General\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926860X24002692\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X24002692","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
电化学二氧化碳还原(CO2RR)是实现二氧化碳净排放的一种前景广阔的方法。具有 Ni-N-C 结构的镍基单原子催化剂(Ni-SAC)一直是该领域的热点。然而,其催化活性仍未得到满足。通过掺杂杂原子调节活性位点的配位环境是提高其催化特性和活性的有效策略。本文将杂原子磷引入到掺杂 N 的碳支持物中,形成了 Ni-SA/CN-P 催化剂,在电位为 -1.1 V 时,CO 法拉第效率达到 91.8%,流动池中的 CO 电流密度为 91.2 mA cm-2,优于不掺杂 P 的样品 Ni-SA/CN。这是因为 P 原子和 N 原子的原子半径不同,导致 Ni-SA/CN-P 催化剂中产生了更多的缺陷。此外,由于掺杂了 P 原子,d 波段中心和 Femi 能级之间的间隙变窄,从而降低了限速势垒高度,提高了催化性能。各个环节相互配合,最终实现了整体性能。这项工作提供了一种建立掺杂 P 原子的单原子催化剂的简单方法,从而提高 CO2RR 的催化性能。
Promoting the electrocatalytic activity for Ni-based single atom catalysts by nitrogen and phosphorus codopant towards CO2 reduction
Electrochemical carbon dioxide reduction (CO2RR) is a promising approach to accomplish the CO2 net emission. Ni-based single-atom catalysts (Ni-SACs) with the Ni-N-C structure have been the hotspot in this field. However, its catalytic activity is still unsatisfied. Regulation of the coordination environment of the active site via heteroatom doping is an efficient strategy to improve its catalytic characteristics and activity. Herein, the heteroatom phosphorus is introduced into the N-doped carbon supporter to form Ni-SA/CN-P catalyst achieving the CO Faraday efficiency of 91.8 % at a potential of -1.1 V along with the CO current density 91.2 mA cm-2 in the flow cell, which is superior to the sample Ni-SA/CN without P dopant. It is attributed that the more defects are built in the Ni-SA/CN-P catalyst due to the different atomic radiuses of P and N atoms. Moreover, the gap between d-band center and Femi energy level is narrowed due to the doped P atoms, which reduces the rate-limiting barrier height leading to the promoted catalytic performance. The cooperation of various items finally results in the overall performance. This work provides a simple method for establishing single-atom catalysts with P doping to improve catalytic performance for CO2RR.
期刊介绍:
Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications.
Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.