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

Issue&Volume: March 9, 2022

Abstract: Activation of O2 is a crucial step in oxidation processes. Here, the concept of sp-hybridized C≡C triple bonds as an electron donor is adopted to develop highly active and stable catalysts for molecular oxygen activation. We demonstrate that the neighboring sp-hybridized C and Cu sites on the interface of the sub-nanocluster CuO/graphdiyne are the key structures to effectively modulate the O2 activation process in the bridging adsorption mode. The as-prepared sub-nanocluster CuO/graphdiyne catalyst exhibited the highest CO oxidation activity and readily converted 50% CO at around 133 °C, which is 34 and 94 °C lower than that for CuO/graphene and CuO/active carbon catalysts, respectively. In situ diffused reflectance infrared Fourier transform spectroscopy and density functional theory calculation results proved that the neighboring sp-hybridized C 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 relatively low energy barrier (0.20 eV). This work revealed that sp-hybridized C of graphdiyne-based materials could effectively improve the O2 activation efficiency, which could facilitate the low-temperature oxidation processes.

DOI: 10.1021/jacs.1c12772

Source: https://pubs.acs.org/doi/10.1021/jacs.1c12772

 

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