表面氯掺杂钙钛矿型钴酸镧催化水氧化

doi:10.1016/S1872-2067(21)64004-4

催化学报 ›› 2022, Vol. 43 ›› Issue (6): 1485-1492.DOI: 10.1016/S1872-2067(21)64004-4

表面氯掺杂钙钛矿型钴酸镧催化水氧化

沈巍^a^,^†, 靳晶^a^,^†, 胡阳^a, 侯亦超^a, 殷杰^a, 马振辉^b, 赵永青^a, 席聘贤^a^,^*()

^a兰州大学化学化工学院, 甘肃省有色金属化学与资源利用重点实验室, 稀有同位素前沿科学中心, 应用有机化学国家重点实验室, 甘肃兰州730000
^b北京工商大学物理系, 北京100048

收稿日期:2021-11-13 接受日期:2021-11-13 出版日期:2022-06-18 发布日期:2022-04-14
通讯作者: 席聘贤
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21931001);国家自然科学基金(21922105);国家自然科学基金(51771085);国家自然科学基金(51801088);甘肃省引导科技创新发展专项基金(2019ZX-04);111项目(B20027);中央高校基本科研业务费专项资金(lzujbky-2021-pd04);中央高校基本科研业务费专项资金(lzujbky-2021-it12);中央高校基本科研业务费专项资金(lzujbky-2021-37);中国博士后科学基金(2021M691375);博士后创新人才支持计划(BX20200157)

Surface chlorine doped perovskite-type cobaltate lanthanum for water oxidation

Wei Shen^a^,^†, Jing Jin^a^,^†, Yang Hu^a, Yichao Hou^a, Jie Yin^a, Zhenhui Ma^b, Yong-Qing Zhao^a, Pinxian Xi^a^,^*()

^aState Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
^bDepartment of Physics, Beijing Technology and Business University, Beijing 100048, China

Received:2021-11-13 Accepted:2021-11-13 Online:2022-06-18 Published:2022-04-14
Contact: Pinxian Xi
About author:First author contact:
作者简介:^† Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21931001);National Natural Science Foundation of China(21922105);National Natural Science Foundation of China(51771085);National Natural Science Foundation of China(51801088);Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019ZX-04);111 Project(B20027);Fundamental Research Funds for the Central Universities(lzujbky-2021-pd04);Fundamental Research Funds for the Central Universities(lzujbky-2021-it12);Fundamental Research Funds for the Central Universities(lzujbky-2021-37);China Postdoctoral Science Foundation(2021M691375);China National Postdoctoral Program for Innovative Talents(BX20200157)

摘要/Abstract

摘要：

随着化石燃料的快速消耗和由此产生的环境问题, 研究人员正在努力寻找可持续的替代能源和能源储存转换方法. 电解水所制备的氢气是一种最佳的能量载体. 然而, 阳极析氧反应(OER)的缓慢动力学是限制电催化水分解转化效率和阻碍其广泛应用的瓶颈之一.
贵金属氧化物IrO₂/RuO₂和贵金属铂基材料被认为是较好的OER和氢析出反应(HER)电催化剂, 但资源稀缺和高成本限制了其广泛应用. 与其他催化材料相比, 钙钛矿型氧化物具有成本低廉、易于大规模制备等特点. 钙钛矿结构通过将缺陷引入A、B或氧位点而表现出可调节和可变的特性. 但人们对氯掺杂钙钛矿作为有效的OER催化剂关注较少. 在氧位点掺杂一些非氧阴离子有时会产生特殊性质, 从而提高催化剂催化性能. 卤素相对于氧的电负性较低, 掺杂后可使金属-氧共价性质增强, 这有利于电催化过程中的电荷转移. 氯取代可以降低电化学活性电位从而触发原位形成氯掺杂金属(氧化物)氢氧化物相. 与此相反, 无氯催化材料需要更高的电化学活性电位来引发或者更多的循环才能完成表面重构, 从而导致OER催化性能较差. 因此, 对于实现高效电催化水分解, 合理控制原位形成催化剂的催化活性表面仍然是一个挑战.
本文提出了一种阳离子氧化方法, 可以调节原位催化剂的浸出并产生自驱动表面重构的La-OH用于OER反应. 通过甘氨酸螯合的合成策略, 利用甘氨酸经过水热反应螯合金属离子形成前驱体, 之后高温合成空心立方体型的氯掺杂的LaCoO₃ (Cl-LaCoO₃)纳米晶体, 并采用X射线粉末衍射和Cs校正扫描透射电子显微镜来表征. Cl-LaCoO₃纳米晶体在10 mA cm^-2的电流密度下表现出342 mV的超低过电位和76.2 mV dec^-1的Tafel斜率. OER过程中形成的La-OH结构有利于提高材料的结构稳定性和电催化活性, 氯的掺杂也有助于提高材料的电催化活性. 此外, 原位拉曼光谱、X射线光电子能谱等进一步表明了由于稀土镧和氧之间的强相互作用, 氯溶解并产生自驱动的La-OH结构可以显著提高材料的催化稳定性. 综上, 本文为设计掺杂型钙钛矿纳米晶体的高效电催化剂提供了新策略, 并为可再生能源系统的应用提出了更多可能性.

关键词: 表面重构, 钴酸镧, 氯掺杂, 空心立方体, 析氧反应

Abstract:

Rationally manipulating the in-situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis. Here, we report a cationic oxidation method which can adjust the leaching of the in-situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction (OER). The chlorine doping can reduce the possibility of triggering in-situ cobalt oxidation and chlorine leaching, leading to a transformation of the surface chlorine doped LaCoO₃ (Cl-LaCoO₃) into an intricate amorphous (oxygen) hydroxide phase. And thus, Cl-LaCoO₃ nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm ^-2 and Tafel slope of 76.2 mV dec^-1. Surface reconstructed Cl-LaCoO₃ is better than many of the most advanced OER catalysts and has proven significant stability. This work provides a new prospect for designing a high-efficiency electrocatalyst with optimized perovskite-structure in renewable energy system.

Key words: Surface reconstruction, LaCoO₃, Chlorine doped, Hollow cube, Oxygen evolution reaction

沈巍, 靳晶, 胡阳, 侯亦超, 殷杰, 马振辉, 赵永青, 席聘贤. 表面氯掺杂钙钛矿型钴酸镧催化水氧化[J]. 催化学报, 2022, 43(6): 1485-1492.

Wei Shen, Jing Jin, Yang Hu, Yichao Hou, Jie Yin, Zhenhui Ma, Yong-Qing Zhao, Pinxian Xi. Surface chlorine doped perovskite-type cobaltate lanthanum for water oxidation[J]. Chinese Journal of Catalysis, 2022, 43(6): 1485-1492.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64004-4

https://www.cjcatal.com/CN/Y2022/V43/I6/1485

图/表 4

Fig. 1. XRD patterns (a), SEM (b), HRTEM (c,d), EDS mapping (e,f) images of La, Co, O, Cl. SAED pattern (g) and atomic resolution HAADF-STEM image (h) and corresponding EDS elemental mapping images (i) of hollow cube structure LaCoO3 and Cl-LaCoO3.

Fig. 2. Raman spectra (a), crystal structure (b), XPS spectra (c) of Cl-LaCoO3. XPS spectra of La 3d5/2 (d), Co 2p3/2 (e) and O 1s (f) for those obtained catalysts.

Fig. 3. (a) Scheme of experimental setup for in-situ Raman spectrometry. (b,c) In-situ Raman signals during OER. (d) IR-corrected LSV curves for OER in 1.0 mol/L KOH. (e) Schematic diagram of self-driven surface reconstruction. (f) Comparison of merit with respect to both kinetics (Tafel slope) and activity. (g) Total ECSA of LSV curves for OER in 1.0 mol/L KOH. (h) Chronoamperometric response for OER. (i) EIS curves of LaCoO3 and Cl-LaCoO3.

Fig. 4. SEM and TEM (a), HRTEM (b), SAED pattern (c) of Cl-LaCoO3 after OER. (d) EELS before and after OER in 1.0 mol/L KOH. (e,f) EDS mapping images of La, Co, O, Cl of those obtained catalysts after OER.

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表面氯掺杂钙钛矿型钴酸镧催化水氧化

Surface chlorine doped perovskite-type cobaltate lanthanum for water oxidation

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