Developing and fabricating a heterogeneous catalyst for efficient formic acid (FA) dehydrogenation coupled with CO2 hydrogenation back to FA is a promising approach to constructing a complete CO2-mediated hydrogen release-storage system, which remains challenging. Herein, a facile two-step strategy involving high-temperature pyrolysis and wet chemical reduction processes can synthesize efficient pyridinic-nitrogen-modified carbon-loaded gold-palladium alloy nanodots (AuPd alloy NDs). These NDs exhibit a prominent electron synergistic effect between Au and Pd components and tunable alloy-support interactions. The pyridinic-N dosage in carbon substrate improves the surface electron density of the alloy catalyst, thus regulating the chemical adsorption of FA molecules. Specifically, the engineered Au3Pd7/CN0.25 demonstrates an outstanding room-temperature FA dehydrogenation efficiency, achieving ≈100% conversion and an initial turnover frequency (TOF) of up to 9049 h-1. The versatile AuPd alloy NDs also show the ability to convert CO2, one of the products of FA dehydrogenation, into FA (formate) with a 90.8% yield under mild conditions. Moreover, in-depth insights into the unique alloyed microstructure, structure-activity relationship, key intermediates, and the alloy-driven five-step reaction mechanism involving the rate-determining step of C─H bond cleavage from critical *HCOO species via D-labeled isotope, in situ infrared spectroscopy, and theoretical calculations are investigated.
Keywords: *HCOO species; AuPd alloy nanodots; Au–Pd synergy effect; CO2 hydrogenation; formic acid dehydrogenation.
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