CO ₂ ‐Mediated Hydrogen Energy Release‐Storage Enabled by High‐Dispersion Gold‐Palladium Alloy Nanodots

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/CN_0.25 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.