Manipulating Spin Polarization of Defected Co3O4 for Highly Efficient Electrocatalysis

Yue Li; Tianzuo Wang; Muhammad Asim; Lun Pan; Rongrong Zhang; Zhen-Feng Huang; Zhichao Chen; Chengxiang Shi; Xiangwen Zhang; Ji-Jun Zou

doi:10.1007/s12209-022-00320-3

Transactions of Tianjin University ›› 2022, Vol. 28 ›› Issue (3) : 163 -173. DOI: 10.1007/s12209-022-00320-3

Research Article

Manipulating Spin Polarization of Defected Co₃O₄ for Highly Efficient Electrocatalysis

Yue Li ¹
, Tianzuo Wang ¹
, Muhammad Asim ¹
, Lun Pan ¹^,²^,³^,⁴^,^d
, Rongrong Zhang ¹
, Zhen-Feng Huang ¹^,²^,³^,⁴
, Zhichao Chen ¹
, Chengxiang Shi ¹
, Xiangwen Zhang ¹^,²^,³^,⁴
, Ji-Jun Zou ¹^,²^,³^,⁴^,^k

Author information +

¹ Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, 300072, Tianjin, China

² Haihe Laboratory of Sustainable Chemical Transformations, 300192, Tianjin, China

³ Zhejiang Institute of Tianjin University, 315201, Ningbo, Zhejiang, China

⁴ Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), 300072, Tianjin, China

^d panlun76@tju.edu.cn

^k jj_zou@tju.edu.cn

Assoc. Prof. Lun Pan received his B.S. and Ph.D. degrees from the School of Chemical Engineering & Technology, Tianjin University, China, in 2009 and 2014, respectively. He was a visiting scholar in Georgia Institute of Technology from 2016 to 2017 and now he is an associate professor in Tianjin University. His research interests mainly focus on the design and synthesis of functional photocatalysts, their related modulation of morphology, facets, and surface defects, and their applications in photocatalysis, such as photocatalytic isomerization, hydrogen generation, and environmental remediation.

Prof. Ji-Jun Zou received his B.S., M.S., and Ph.D. degrees in chemical engineering from Tianjin University in 2000, 2002, and 2005, respectively. Then he became an assistant professor at School of Chemical Engineering and Technology, Tianjin University and was promoted as full professor from 2013. His research interests mainly surround nanostructured catalysts for photo/electrocatalysis, fuel processing, and biomass conversion. He has received several awards including Changjiang Scholar by MOE and Technological Leading Scholar of 10000 Talent project by MOST. He is also an associate editor of RSC Advances.

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Abstract

Electrocatalytic water splitting is limited by kinetics-sluggish oxygen evolution, in which the activity of catalysts depends on their electronic structure. However, the influence of electron spin polarization on catalytic activity is ambiguous. Herein, we successfully regulate the spin polarization of Co₃O₄ catalysts by tuning the concentration of cobalt defects from 0.8 to 14.5%. X-ray absorption spectroscopy spectra and density functional theory calculations confirm that the spin polarization of Co₃O₄ is positively correlated with the concentration of cobalt defects. Importantly, the enhanced spin polarization can increase hydroxyl group absorption to significantly decrease the Gibbs free energy change value of the OER rate-determining step and regulate the spin polarization of oxygen species through a spin electron-exchange process to easily produce triplet-state O₂, which can obviously increase electrocatalytic OER activity. In specific, Co₃O₄-50 with 14.5% cobalt defects exhibits the highest spin polarization and shows the best normalized OER activity. This work provides an important strategy to increase the water splitting activity of electrocatalysts via the rational regulation of electron spin polarization.

Keywords

Co₃O₄ / Cobalt defect / Oxygen evolution reaction / Spin polarization / Transition metals / Water splitting

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Yue Li, Tianzuo Wang, Muhammad Asim, Lun Pan, Rongrong Zhang, Zhen-Feng Huang, Zhichao Chen, Chengxiang Shi, Xiangwen Zhang, Ji-Jun Zou. Manipulating Spin Polarization of Defected Co₃O₄ for Highly Efficient Electrocatalysis. Transactions of Tianjin University, 2022, 28(3): 163-173 DOI:10.1007/s12209-022-00320-3

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