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Direct CO2 hydrogenation offers an important strategy for promoting the global carbon balance, but high thermodynamic and kinetic stability of CO2 has restricted its applicability to only a handful of industrial sectors. Here, we introduce a proof-of-concept application of the electron-rich Pt surface to promote hydrogen donation for electron-rich MoC particles acting as hydrogen acceptors, thereby constructing hydrogen-rich surface of MoC active centers. Moreover, the formed hydrogen-rich and electron-rich surface could greatly decrease reaction activation energy to boost the efficient CO2 hydrogenation into formic acid over the MoC centers. The optimized MoC@NC/Pt-0.1 (NC: nitrogen-doped carbon) catalyst exhibits a high turnover frequency (TOF) value of 1.2 h−1 at a lower temperature of 60 °C and a TOF of 24.2 h−1 under standard reaction conditions widely used in the literature, exceeding 7 times of MoC@NC catalyst and surpassing the benchmark classical non-noble metal active center-based heterogeneous catalyst.

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