Sulfur filling activates vacancy-induced C-C bond cleavage in polyol electrooxidation  

作　　者：Jianqiao Shi Wei Chen Yandong Wu Yanwei Zhu Chao Xie Yimin Jiang Yu-Cheng Huang Chung-Li Dong Yuqin Zou 

机构地区：[1]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Advanced Catalytic Engineering Research Center of the Ministry of Education,Hunan University,Changsha 410082,China [2]Research Center for X-ray Science&Department of Physics,Tamkang University,New Taipei City 25137,China

出　　处：《National Science Review》2024年第10期277-290,共14页国家科学评论（英文版）

基　　金：supported by the National Key R&D Program of China(2023YFA1507400);the National Natural Science Foundation of China(22122901,22402056,21902047,21825201,U19A2017 and 22102054);Changsha Natural Science Foundation(kq2402052);the Provincial Natural Science Foundation of Hunan(2021JC0008 and 2021RC3054).

摘　　要：Using the electrochemical polyol oxidation reaction(POR)to produce formic acid over nickel-based oxides/hydroxides(NiO_(x)H_(y))is an attractive strategy for the electrochemical upgrading of biomass-derived polyols.The key step in the POR,i.e.the cleavage of the C-C bond,depends on an oxygen-vacancy-induced mechanism.However,a high-energy oxygen vacancy is usually ineffective for Schottky-type oxygen-vacancy-richβ-Ni(OH)_(2)(VSO-β-Ni(OH)_(2)).As a result,bothβ-Ni(OH)_(2)and VSO-β-Ni(OH)_(2)cannot continuously catalyze oxygen-vacancy-induced C-C bond cleavage during PORs.Here,we report a strategy of oxygen-vacancy-filling with sulfur to synthesize aβ-Ni(OH)_(2)(S-VO-β-Ni(OH)_(2))catalyst,w hose ox ygen vacancies are protected by filling with sulfur atoms.During PORs over S-VO-β-Ni(OH)_(2),the pre-electrooxidation-induced loss of sulfur and structural self-reconstruction cause the in-situ generation of stable Frenkel-type oxygen vacancies for activating vacancy-induced C-C bond cleavage,thus leading to excellent POR performances.This work provides an intelligent approach for guaranteeing the sustaining action of the oxygen-vacancy-induced catalytic mechanism in electrooxidation reactions.

关 键 词：oxygen vacancy vacancy filling alcohol electrooxidation polyol electrooxidation C-C bond cleavage 

分 类 号：O64[理学—物理化学]