{"title":"在硒化镍铁中加入硫,用于高效碱性海水电解","authors":"Xuanwa Chen, Yanhui Yu, Xingqi Han, Huan Wang, Yingjie Hua, Daoxiong Wu, Peilin Deng, Juanxiu Xiao, Xinlong Tian, Jing Li","doi":"10.1007/s11426-023-1965-y","DOIUrl":null,"url":null,"abstract":"<p>Seawater electrolysis is an effective way to obtain hydrogen (H<sub>2</sub>) in a sustainable manner. However, the lack of electrocatalysts with high activity, stability, and selectivity for oxygen evolution reaction (OER) severely hinders the development of seawater electrolysis technology. Herein, sulfur-doped nickel-iron selenide nanosheets (S-NiFeSe<sub>2</sub>) were prepared by an ion-exchange strategy and served as highly active OER electrocatalyst for alkaline seawater electrolysis. The overpotential is 367 mV, and it can run stably for over 50 h at 100 mA cm<sup>−2</sup>. Excitingly, the S-NiFeSe<sub>2</sub>∥Pt/C pair exhibits cell voltage of 1.54 V at 10 mA cm<sup>−2</sup> under alkaline seawater conditions, which can run smoothly for 100 h without decay, and the efficiency of electricity-to-hydrogen (ETH) energy conversion reaches more than 80%. Such electrode, with abundant accessible reactive sites and good corrosion resistance, is a good candidate for seawater electrolysis. Moreover, density functional theory calculations reveal that the surface sulfur atoms can activate the adjacent Ni sites and decrease the free energy changes of the associated intermediates at the adjacent Ni sites for OER, and the step of *OH → *O is the potential rate-limiting step. In this work, the true reactive site in nickel-iron selenides is the Ni sites, but not the Fe sites as commonly believed.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":null,"pages":null},"PeriodicalIF":10.4000,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Introducing sulfur to nickel-iron selenide for high-efficiency alkaline seawater electrolysis\",\"authors\":\"Xuanwa Chen, Yanhui Yu, Xingqi Han, Huan Wang, Yingjie Hua, Daoxiong Wu, Peilin Deng, Juanxiu Xiao, Xinlong Tian, Jing Li\",\"doi\":\"10.1007/s11426-023-1965-y\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Seawater electrolysis is an effective way to obtain hydrogen (H<sub>2</sub>) in a sustainable manner. However, the lack of electrocatalysts with high activity, stability, and selectivity for oxygen evolution reaction (OER) severely hinders the development of seawater electrolysis technology. Herein, sulfur-doped nickel-iron selenide nanosheets (S-NiFeSe<sub>2</sub>) were prepared by an ion-exchange strategy and served as highly active OER electrocatalyst for alkaline seawater electrolysis. The overpotential is 367 mV, and it can run stably for over 50 h at 100 mA cm<sup>−2</sup>. Excitingly, the S-NiFeSe<sub>2</sub>∥Pt/C pair exhibits cell voltage of 1.54 V at 10 mA cm<sup>−2</sup> under alkaline seawater conditions, which can run smoothly for 100 h without decay, and the efficiency of electricity-to-hydrogen (ETH) energy conversion reaches more than 80%. Such electrode, with abundant accessible reactive sites and good corrosion resistance, is a good candidate for seawater electrolysis. Moreover, density functional theory calculations reveal that the surface sulfur atoms can activate the adjacent Ni sites and decrease the free energy changes of the associated intermediates at the adjacent Ni sites for OER, and the step of *OH → *O is the potential rate-limiting step. In this work, the true reactive site in nickel-iron selenides is the Ni sites, but not the Fe sites as commonly believed.</p>\",\"PeriodicalId\":772,\"journal\":{\"name\":\"Science China Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.4000,\"publicationDate\":\"2024-06-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science China Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1007/s11426-023-1965-y\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science China Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1007/s11426-023-1965-y","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
海水电解是一种可持续获取氢气(H2)的有效方法。然而,氧气进化反应(OER)缺乏高活性、高稳定性和高选择性的电催化剂,这严重阻碍了海水电解技术的发展。本文采用离子交换策略制备了掺硫硒化镍铁纳米片(S-NiFeSe2),并将其作为高活性 OER 电催化剂用于碱性海水电解。其过电位为 367 mV,在 100 mA cm-2 的条件下可稳定运行 50 小时以上。令人兴奋的是,在碱性海水条件下,S-NiFeSe2∥Pt/C对在10 mA cm-2条件下显示出1.54 V的电池电压,可平稳运行100 h而无衰减,电-氢(ETH)能量转换效率达到80%以上。这种电极具有丰富的可触及反应位点和良好的耐腐蚀性,是海水电解的良好候选材料。此外,密度泛函理论计算表明,表面硫原子可激活邻近的镍位点,并降低邻近镍位点上相关中间产物的自由能变化,以实现 OER,而 *OH → *O 步骤是潜在的限速步骤。在这项工作中,镍铁硒化物中真正的反应位点是镍位点,而不是通常认为的铁位点。
Introducing sulfur to nickel-iron selenide for high-efficiency alkaline seawater electrolysis
Seawater electrolysis is an effective way to obtain hydrogen (H2) in a sustainable manner. However, the lack of electrocatalysts with high activity, stability, and selectivity for oxygen evolution reaction (OER) severely hinders the development of seawater electrolysis technology. Herein, sulfur-doped nickel-iron selenide nanosheets (S-NiFeSe2) were prepared by an ion-exchange strategy and served as highly active OER electrocatalyst for alkaline seawater electrolysis. The overpotential is 367 mV, and it can run stably for over 50 h at 100 mA cm−2. Excitingly, the S-NiFeSe2∥Pt/C pair exhibits cell voltage of 1.54 V at 10 mA cm−2 under alkaline seawater conditions, which can run smoothly for 100 h without decay, and the efficiency of electricity-to-hydrogen (ETH) energy conversion reaches more than 80%. Such electrode, with abundant accessible reactive sites and good corrosion resistance, is a good candidate for seawater electrolysis. Moreover, density functional theory calculations reveal that the surface sulfur atoms can activate the adjacent Ni sites and decrease the free energy changes of the associated intermediates at the adjacent Ni sites for OER, and the step of *OH → *O is the potential rate-limiting step. In this work, the true reactive site in nickel-iron selenides is the Ni sites, but not the Fe sites as commonly believed.
期刊介绍:
Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field.
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