Enhancing C─C Bond Cleavage of Glycerol Electrooxidation Through Spin‐Selective Electron Donation in Pd–PdS <sub>2</sub> –Co <sub>x</sub> Heterostructural Nanosheets
Pei Liu, Hao Ma, Yuchen Qin, Junjun Li, Fengwang Li, Jinyu Ye, Qiudi Guo, Ning Su, Chao Gao, Lixia Xie, Xia Sheng, Shiju Zhao, Guangce Jiang, Yunlai Ren, Yuanmiao Sun, Zhicheng Zhang
Abstract
Abstract As a 4 d transition metal, the spin state of Pd is extremely difficult to directly regulate for the optimized d orbital states owing to the strong spin‐orbit coupling effect and further extended d orbital. Herein, we devise a “spin‐selective electron donation” strategy to tune specific d orbital electrons of Pd inspired by the Dewar−Chatt−Duncanson model theory. Co−S−Pd bridges with different spin‐states of Co III have been constructed in a series of Pd–PdS 2 –Co x HNSs with tunable Co content. Experiments and theoretical calculations indicate that low‐spin Co III (t 2g 6 e g 0 ) with fully occupied t 2g orbitals and empty orbitals can accurately alter the electron of Pd by σ‐donation via the Co−S−Pd bridge. In contrast, the unfilled d xy orbital of high‐spin Co III (t 2g 5 e g 1 ) is essential for controlling the d xy electron of Pd via π‐donation. Benefiting from state optimization by σ‐donation, Pd–PdS 2 –Co 4.0 delivers superior performance toward various bio‐alcohols (ethanol, ethylene glycol, and glycerol) with enhanced C─C bond cleavage. Furthermore, coupling the glycerol oxidation reaction with the CO 2 reduction reaction (GOR||CO 2 RR), the electricity consumption of GOR||CO 2 RR drops 46.4% compared to the state‐of‐art system (OER||CO 2 RR). Moreover, anodic Faraday efficiency (FE) of formic acid can be attainable at more than 90% at low voltage regions.