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Elucidating the Mechanism of Simultaneous Activation of CH4 and CO2 Mediated by Single Group 10 Metal Anions in Gas Phase

Von Wiley-VCH zur Verfügung gestellt

Group 10 metal anions Ni/Pd/Pt behave differently in mediating the co-conversion of CO2/CH4 to C−C coupling and hydrogenation products.


Quantum chemistry calculations predict that besides the reported single metal anion Pt, Ni can also mediate the co-conversion of CO2 and CH4 to form [CH3−M(CO2)−H] complex, followed by transformation to C−C coupling product [H3CCOO−M−H] (A), hydrogenation products [H3C−M−OCOH] (B) and [H3C−M−COOH]. For Pd, a fourth product channel leading to PdCO2 …CH4 becomes more competitive. For Ni, the feed order must be CO2 first, as the weaker donor-acceptor interaction between Ni and CH4 increases the C−H activation barrier, which is reduced by [Ni−CO2]. For Ni/Pt, the highly exothermic products A and B are similarly stable with submerged barrier that favors B. The smaller barrier difference between A and B for Ni suggests the C−C coupling product is more competitive in the presence of Ni than Pt. The charge redistribution from M is the driving force for product B channel. This study adds our understanding of single atomic anions to activate CH4 and CO2 simultaneously.

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