Activity origin of boron doped carbon cluster for thermal catalytic oxidation: Coupling effects of dopants and edges.
Activity origin of boron doped carbon cluster for thermal catalytic oxidation: Coupling effects of dopants and edges.
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DOI：
10.1016/j.jcis.2022.01.017
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发表时间：
2022-01
影响因子：
9.9
通讯作者：
Zhibin Qu;Fei Sun;Jihui Gao;Guang-bo Zhao
中科院分区：
文献类型：
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作者：
Zhibin Qu;Fei Sun;Jihui Gao;Guang-bo Zhao
催化氧化在能源转化和环境保护方面具有重要作用。硼掺杂的晶态碳催化剂已被证明是有效的，然而，硼掺杂的非晶态碳催化剂的应用潜力仍有待开发。对于无定形碳材料，有限尺寸的碳团簇是其基本结构单元，由于边缘效应和尺寸效应，它们表现出独特的活性。本文以二氧化硫（SO2）和一氧化碳（CO）氧化为探针热催化反应，发现硼掺杂碳团簇中活性中心的分布和活性同时受掺杂物和边缘的影响。通过比较对称和非对称碳团簇不同位置氧的化学吸附能，发现最具活性的位置是具有高供电子能力的边缘碳原子，该位置可以通过亲电福井函数准确识别.更重要的是，硼掺杂团簇的反应性同时受到掺杂构型和边缘类型的影响，基于此，嵌入K区边缘的-O-B-O-构型（不属于Clar六重态的孤立碳-碳双键）被预测在各种硼掺杂构型中表现出最高的反应性。本工作阐明了杂原子掺杂无定形碳材料独特的活性起源，为设计高性能碳催化剂提供了新的见解。
Catalytic oxidation plays important roles in energy conversion and environment protection. Boron-doped crystalline carbocatalyst has been demonstrated effective; however, the application potential of boron-doped amorphous carbocatalyst remains to be explored. For amorphous carbon material, finite-sized carbon clusters are the basic structural units, which exhibit unique activity due to edge and size effect. Herein, using sulfur dioxide (SO2) and carbon monoxide (CO) oxidation as probe thermal-catalysis reactions, we found the distribution and reactivity of active sites in boron-doped carbon clusters are simultaneously determined by dopants and edges. According to comparisons of oxygen (O2) chemisorption energy at different sites of symmetric and non-symmetric carbon cluster, the most active site is found to be the edge carbon atom with high electron donation ability, which can be accurately identified by electrophilic Fukui function. More importantly, the reactivity of boron-doped cluster is simultaneously influenced by doping configuration and the type of edge, based on which -O-B-O- configuration embedded into K-region edge (isolated carbon–carbon double bonds that do not belong to Clar sextet) is predicted to exhibit the highest reactivity among various boron doping configurations. This work clarifies unique activity origin of heteroatom-doped amorphous carbon materials, providing new insights into designing high-performance carbocatalysts.