| Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction | |
| Liu, Jing1; Bao, Hongliang2; Zhang, Bingsen3; Hua, Qingfeng1; Shang, Mingfeng2; Wang, Jianqiang2; Jiang, Luhua1 | |
| Corresponding Author | Wang, Jianqiang(wangjianqiang@sinap.ac.cn) ; Jiang, Luhua(luhuajiang@qust.edu.cn) |
| 2019-04-03 | |
| Source Publication | ACS APPLIED MATERIALS & INTERFACES
 |
| ISSN | 1944-8244 |
| Volume | 11Issue:13Pages:12525-12534 |
| Abstract | Cobalt oxides, including spinel Co3O4 and rock-salt CoO, have been widely reported as promising catalysts for oxygen reduction reaction (ORR). However, three types of cobalt ions, i.e., Co2+ in the tetrahedral site (Co-Td(2+)), Co3+ in the octahedral site (Co-Oh(3+)), and Co2+ in the octahedral site (Co-Oh(2+)), are included in these oxides, and the roles of cobalt geometric occupancy and valance states have remained elusive. Here, for the first time, we investigated the effects of cobalt geometric occupancy on the ORR activity by substituting Co-Td(2+) and Co-Oh(3+) of Co3O4 with inactive Zn2+ and Al3+, respectively. The ORR activity decreases in the order of Co3O4 (Co-Oh(3+), Co-Td(2+)) < ZnCo2O4 (Co-Oh(3+)) << CoAl2O4 (Co-Td(2+)) in accordance with the ORR overpotentials at the current density of 0.1 mA cm(Ox)(-2). Furthermore, by comparatively investigating the activity and stability of Co3O4 (Co-Oh(3+)) and CoO (Co-Oh(2+)) nanoparticles, by virtue of the electrochemical technique, the high-resolution transmission electron microscopy, and the in operando fuel cell-X-ray absorption spectroscopy techniques, it was revealed that Co-Oh(2+), in CoO is the main active site, which under electrochemical conditions tends to transform into Co-Oh(3+), and form Co3O4 with a hollow structure due to the Kirkendall effect; nevertheless, it retains decent ORR activity due to the formation of the unique hollow structure. |
| Keyword | cobalt oxide oxygen reduction reaction geometric occupancy valance state octahedral coordination |
| Funding Organization | Key Research and Development Project of Shandong Province ; National Science Foundation of China ; Taishan Scholars special project funding of Shandong Province |
| DOI | 10.1021/acsami.9b00481 |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | Key Research and Development Project of Shandong Province[2017GGX20107] ; National Science Foundation of China[21776146] ; National Science Foundation of China[21576258] ; Taishan Scholars special project funding of Shandong Province[ts201712046] |
| WOS Research Area | Science & Technology - Other Topics ; Materials Science |
| WOS Subject | Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary |
| WOS ID | WOS:000463843900039 |
| Publisher | AMER CHEMICAL SOC |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.imr.ac.cn/handle/321006/132786 |
| Collection | 中国科学院金属研究所 |
| Corresponding Author | Wang, Jianqiang; Jiang, Luhua |
| Affiliation | 1.Qingdao Univ Sci & Technol, Coll Mat Sci & Engn, Nanomat & Electrocatalysis Lab, 53 Zhengzhou Rd, Qingdao 266042, Shandong, Peoples R China 2.Chinese Acad Sci, Shanghai Inst Appl Phys, 239 Zhangheng Rd, Shanghai 201204, Peoples R China 3.Chinese Acad Sci, Inst Met Res, 72 Wenhua Rd, Shenyang 110016, Liaoning, Peoples R China |
| Recommended Citation GB/T 7714 | Liu, Jing,Bao, Hongliang,Zhang, Bingsen,et al. Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction[J]. ACS APPLIED MATERIALS & INTERFACES,2019,11(13):12525-12534. |
| APA | Liu, Jing.,Bao, Hongliang.,Zhang, Bingsen.,Hua, Qingfeng.,Shang, Mingfeng.,...&Jiang, Luhua.(2019).Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction.ACS APPLIED MATERIALS & INTERFACES,11(13),12525-12534. |
| MLA | Liu, Jing,et al."Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction".ACS APPLIED MATERIALS & INTERFACES 11.13(2019):12525-12534. |
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