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Single-atom catalysts (SACs) have provoked significant curiosity in heterogeneous catalysis due to the benefits of maximum metal atoms usage, robust metal-support interaction, single-metal-atom active sites, and high catalytic efficiency. In this study, the electronic structures and catalytic mechanism of ethyne hydrogenation of SACs with the group-9 metal atoms M1 (M1= Co, Rh, Ir) anchored on PTA (phosphotungstic acid) cluster have been explored by using first-principles quantum calculations. It is found that the catalytic activity of ethyne (C2H2) hydrogenation is determined by two critical parameters: the adsorption energies of the adsorbate (H2, C2H2) and the activation energy barrier of ethyne hydrogenation. We have shown that the reaction pathway of ethyne hydrogenation reaction on the experimentally characterized Rh1/PTA at room temperature consists of three steps: C2H2 and H2 coadsorption on Rh1/PTA, H2 attacking C2H2 to form C2H4, then C2H4 desorbing or further reacting with H2 to produce C2H6 and completing the catalytic cycle. The Rh1/PTA possesses fair catalytic activity with a C2H4 desorption energy of 1.46 eV and a 2.59 eV barrier for ethylene hydrogenation. Moreover, micro-kinetics analysis is also carried out to understand the mechanism and catalytic performance further. The work reveals that the PTA-supported SACs can be a promising catalyst for alkyne hydrogenation.
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