CO_(2) adsorption and activation on p-block catalyst Ga_(2)O_(3)  

CO_(2)在p族催化剂Ga_(2)O_(3)上的吸附与活化

作　　者：Zhizhuang Liu Xiaoxu Kuang Baowen Li Chenghua Sun Rong Tu Song Zhang 刘之壮;匡晓旭;李宝文;孙成华;涂溶;章嵩(Chaozhou Branch of Chemistry and Chemical Engineering Guangdong Laboratory,Chaozhou 521000,China;School of Materials Science and Engineering,Wuhan University of Technology,Wuhan 430070,China;Department of Chemistry and Biotechnology,Swinburne University of Technology,Hawthorn,Victoria 3122,Australia;State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,Wuhan 430070,China)

机构地区：[1]Chaozhou Branch of Chemistry and Chemical Engineering Guangdong Laboratory,Chaozhou 521000,China [2]School of Materials Science and Engineering,Wuhan University of Technology,Wuhan 430070,China [3]Department of Chemistry and Biotechnology,Swinburne University of Technology,Hawthorn,Victoria 3122,Australia [4]State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,Wuhan 430070,China

出　　处：《Science China Materials》2025年第2期590-596,共7页中国科学(材料科学)(英文版)

基　　金：supported by the Key Research and Development Program of Hubei Province(2023BAB032);the Chaozhou Ceramic Industry Talent Revitalization Plan-Talent Support Project for Basic Research Platform of Ceramic Material Application;the Self-Innovation Research Funding Project of Hanjiang Laboratory(HJL2023001);the Hubei Provincial Natural Science Foundation of China(2023AFB1000)。

摘　　要：The fixation and conversion of CO_(2)frommedium-and high-temperature industrial exhaust gases arescientifically important and challenging tasks owing to theharsh conditions required.Ga_(2)O_(3),a stable p-block compound,is surprisingly active in the thermal conversion of hot CO_(2)waste gas,but its underlying mechanism remains unclear.Inthis study,we investigated CO_(2)adsorption and activationacross 11 different Ga_(2)O_(3)-terminated faces using densityfunctional theory.Charge transfer and chemical bond analysesrevealed the occurrence of two distinct activation mechanismsinvolving synchronous electron gain and loss,driven by astrong synergetic effect between Ga cations and O anions onthe substrate surface.This Ga-O synergy enhances the CO_(2)activation efficiency compared with single active sites,with CO_(2)^(δ+) cation more readily capturing H atom than CO_(2)^(δ–).Tothe best of our knowledge,such a dual activation mechanismhas not been reported before,particularly for p-block catalysts.Our findings provide new insights into the direct catalyticconversion of CO_(2)emissions and offer strategies for the rational design of industrial-grade catalysts for medium-andhigh-temperature CO_(2)tail gas conversion.处于极端环境下的中高温工业废气中CO_(2)的固定和转化是一项兼具重要科学意义和挑战性的任务.Ga_(2)O_(3)是一种稳定的p-族化合物,在热催化高温CO_(2)废气中表现出惊人的活性,但我们其仍不清楚其反应机理.在本工作中,我们用密度泛函理论研究了11种不同Ga_(2)O_(3)表面的CO_(2)的吸附和活化过程.电荷转移和化学键分析表明,在基底表面Ga阳离子和O阴离子之间强大的协同效应驱动下,同时出现了电子增加和电子减少两种不同的CO_(2)活化机制.与单一活性位点相比,这种Ga-O协同作用提高了CO_(2)的活化效率,其中CO_(2)^(δ+)阳离子比CO_(2)^(δ-)阴离子更容易捕获H原子.据我们所知,这种双重活化机制以前从未被报道过,尤其是对于p族催化剂.我们的发现为中高温CO_(2)废气排放的直接催化转化提供了新的见解,并为处理CO_(2)尾气的工业级催化剂的设计提供了合理的策略.

关 键 词：p-block catalyst gallium oxide carbon dioxide density functional theory synergetic mechanism 

分 类 号：O64[理学—物理化学]