Neighboring sp-Hybridized Carbon Participated Molecular OxygenActivation on the Interface of Sub-nanocluster CuO/Graphdiyne

作者：Pan, Chuanqi; Wang, Chenyang; Zhao, Xinya; Xu, Peiyan; Mao, Feihong; Yang, Ji; Zhu, Yuhua; Yu, Ruohan; Xiao, Shiyi; Fang, Yarong; Deng, Hongtao; Luo, Zhu; Wu, Jinsong; Li, Junbo; Liu, Shoujie; Xiao, Shengqiang; Zhang, Lizhi; Guo, Yanbing^*

来源：Journal of the American Chemical Society, 2022, 144(11): 4942-4951.

DOI：10.1021/jacs.1c12772

• PREFERENTIAL CO OXIDATION
• OXYGEN REDUCTION REACTION
• EFFICIENT CATALYST
• O-2 ACTIVATION
• GRAPHDIYNE
• PERFORMANCE
• SURFACE
• NANOTUBES
• GRAPHENE
• SIZE

Activation of O2is a crucial step in oxidation processes. Here, the conceptof sp-hybridized C & xe0c9;C triple bonds as an electron donor is adopted to develop highlyactive and stable catalysts for molecular oxygen activation. We demonstrate that theneighboring sp-hybridized C and Cu sites on the interface of the sub-nanocluster CuO/graphdiyne are the key structures to effectively modulate the O2activation process in thebridging adsorption mode. The as-prepared sub-nanocluster CuO/graphdiyne catalystexhibited the highest CO oxidation activity and readily converted 50% CO at around 133 degrees C, which is 34 and 94 degrees C lower than that for CuO/graphene and CuO/active carboncatalysts, respectively. In situ diffused reflectance infrared Fourier transform spectroscopyand density functional theory calculation results proved that the neighboring sp-hybridizedC is more favorable to promote the rapid dissociation of carbonate than sp2-hybridized C without overcoming any energy barrier.The gaseous CO directly reacts with the active molecular oxygen and tends to proceed through the E-R mechanism with a relativelylow energy barrier (0.20 eV). This work revealed that sp-hybridized C of graphdiyne-based materials could effectively improve theO2activation efficiency, which could facilitate the low-temperature oxidation processes.

• 单位
  武汉理工大学; 武汉工程大学