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.
Keywords: Amorphous carbon material; Boron doping; Carbon cluster; Density functional theory; Edge; O(2) activation; electrophilic Fukui function.
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