Extraordinary p-d Hybridization Interaction in Heterostructural Pd-PdSe Nanosheets Boosts C-C Bond Cleavage of Ethylene Glycol Electrooxidation

Yuchen Qin; Wenlong Zhang; Fengqi Wang; JunJun Li; Jinyu Ye; Xia Sheng; Chenxi Li; Xiaoyu Liang; Pei Liu; Xiaopeng Wang; Xin Zheng; Yunlai Ren; Cuilian Xu; Zhicheng Zhang

doi:10.1002/anie.202200899

Extraordinary p-d Hybridization Interaction in Heterostructural Pd-PdSe Nanosheets Boosts C-C Bond Cleavage of Ethylene Glycol Electrooxidation

Angew Chem Int Ed Engl. 2022 Apr 11;61(16):e202200899. doi: 10.1002/anie.202200899. Epub 2022 Feb 7.

Authors

Yuchen Qin¹, Wenlong Zhang¹, Fengqi Wang¹, JunJun Li², Jinyu Ye³, Xia Sheng¹, Chenxi Li⁴, Xiaoyu Liang¹, Pei Liu¹, Xiaopeng Wang¹, Xin Zheng¹, Yunlai Ren¹, Cuilian Xu¹, Zhicheng Zhang²

Affiliations

¹ College of sciences, Henan Agricultural University, Zhengzhou, 450000, P. R. China.
² Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University & Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, P. R. China.
³ State Key Laboratory of Physical Chemistry of Solid Surfaces, college of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. China.
⁴ College of Life Science, Chongqing Normal University, Chongqing, 401331, P. R. China.

PMID: 35083836
DOI: 10.1002/anie.202200899

Abstract

Advanced electrocatalysts for complete oxidation of ethylene glycol (EG) in direct EG fuel cells are strongly desired owing to the higher energy efficiency. Herein, Pd-PdSe heterostructural nanosheets (Pd-PdSe HNSs) have been successfully fabricated via a one-step approach. These Pd-PdSe HNSs feature unique electronic and geometrical structures, in which unconventional p-d hybridization interactions and tensile strain effect co-exist. Compared with commercial Pd/C and Pd NSs catalysts, Pd-PdSe HNSs display 5.5 (6.6) and 2.5 (2.6) fold enhancement of specific (mass) activity for the EG oxidation reaction (EGOR). Especially, the optimum C1 pathway selectivity of Pd-PdSe HNSs reaches 44.3 %, illustrating the superior C-C bond cleavage ability. Electrochemical in situ FTIR spectroscopy and theoretical calculations demonstrate that the extraordinary p-d hybridization interaction and tensile strain effect could effectively reduce the activation energy of C-C bond breaking and accelerate CO* oxidation, boosting the complete oxidation of EG and improving the catalytic performance.

Keywords: C−C Bond Cleavage; Ethylene Glycol Oxidation Reaction; Pd-PdSe Heterostructural Nanosheets; Tensile Strain; p-d Hybridization.

Abstract

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