Enhancing C─C Bond Cleavage of Glycerol Electrooxidation Through Spin‐Selective Electron Donation in Pd–PdS2–Cox Heterostructural Nanosheets

As a 4d 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 elec...

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Vydáno v:Angewandte Chemie International Edition Ročník 64; číslo 27; s. e202506032 - n/a
Hlavní autoři: Liu, Pei, Ma, Hao, Qin, Yuchen, Li, Junjun, Li, Fengwang, Ye, Jinyu, Guo, Qiudi, Su, Ning, Gao, Chao, Xie, Lixia, Sheng, Xia, Zhao, Shiju, Jiang, Guangce, Ren, Yunlai, Sun, Yuanmiao, Zhang, Zhicheng
Médium: Journal Article
Jazyk:angličtina
Vydáno: Weinheim Wiley Subscription Services, Inc 01.07.2025
Vydání:International ed. in English
Témata:
Alcohols
Carbon dioxide
Chemical bonds
Chemical reduction
Cleavage
Cobalt
Coupling
C─C bond cleavage
Electricity consumption
Electron spin
Electrons
Ethanol
Ethylene glycol
Formic acid
Glycerol
Glycerol oxidation reaction
Low voltage
Orbitals
Oxidation
Palladium
Pd–PdS2–Co heterostructural nanosheets
Spin state regulation
Spin‐selective electron donation
Transition metals
ISSN:1433-7851, 1521-3773, 1521-3773
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Shrnutí:As a 4d 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 CoIII have been constructed in a series of Pd–PdS2–Cox HNSs with tunable Co content. Experiments and theoretical calculations indicate that low‐spin CoIII (t2g6eg0) with fully occupied t2g orbitals and empty dz2$d_{{z^2}}$ orbitals can accurately alter the dz2$d_{{z^2}}$ electron of Pd by σ‐donation via the Co−S−Pd bridge. In contrast, the unfilled dxy orbital of high‐spin CoIII (t2g5eg1) is essential for controlling the dxy electron of Pd via π‐donation. Benefiting from dz2$d_{{z^2}}$ state optimization by σ‐donation, Pd–PdS2–Co4.0 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 CO2 reduction reaction (GOR||CO2RR), the electricity consumption of GOR||CO2RR drops 46.4% compared to the state‐of‐art system (OER||CO2RR). Moreover, anodic Faraday efficiency (FE) of formic acid can be attainable at more than 90% at low voltage regions. The “spin‐selective electron donation” strategy effectively modulates the electronic states of Pd's d orbitals (dz2${d_{{z^2}}}$ and dxy) through distinct pathway: σ‐donation from low‐spin CoIII (t2g6eg0) and π‐donation from high‐spin CoIII (t2g5eg1).
Bibliografie:Both authors contributed equally to this work.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202506032