河南农业大学秦毓辰团队报道了异结构Pd-PdSe纳米片中特殊的p-d杂交相互作用促进乙二醇电氧化的C-C键断裂。相关研究成果于2022年1月26日发表于国际一流学术期刊《德国应用化学》。

乙二醇(EG)在直接EG燃料电池中完全氧化的新型电催化剂因其更高的能源效率而备受青睐。

该文中，研究人员通过一步法成功制备了Pd-PdSe异质结构纳米片（Pd-PdSe-HNSs）。这些Pd-PdSe-HNSs具有独特的电子和几何结构，其中非常规的p-d杂化作用和拉伸应变效应共存。与市售Pd/C和Pd-NSs催化剂相比，Pd-PdSe-HNSs催化剂的EG氧化反应（EGOR）比（质量）活性分别提高了5.5倍（6.6）和2.5倍（2.6）。尤其是Pd-PdSe-HNSs的最佳C1路径选择性达到44.3%，说明其具有优越的C–C键断裂能力。

电化学原位FTIR光谱和理论计算表明，特殊的p-d杂交作用和拉伸应变效应可以有效降低C–C键断裂的活化能，加速CO*氧化，促进EG的完全氧化，提高催化性能。

附：英文原文

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

Author: 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

Issue&Volume: 2022-01-26

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 one-step approach. These Pd-PdSe HNSs feature unique electronic and geometrical structure, in which unconventional  p-d  hybridization interaction 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) folds enhancement of specific (mass) activity for 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 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.

DOI: 10.1002/anie.202200899

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202200899