Electronic structure modulating of PtFe dual-atom catalyst for efficient hydrogen splitting and almost 100 % selective hydrogenation of α,β-unsaturated aldehydes

The selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols is a cornerstone of fine chemical synthesis, yet it remains a formidable challenge due to competing hydrogenation of thermodynamically favored C C bonds over kinetically sluggish C O bonds. Here, we present a PtFe dual-atom catalyst anchored on defective polymeric carbon nitride (DPCN), which achieves nearly complete conversion and exceptional selectivity toward cinnamyl alcohol (COL) under mild conditions. Particularly, the PtFe/DPCN exhibits a superior turnover frequency and achieves 99.02 % conversion of cinnamaldehyde (CAL) with 99.34 % selectivity for COL at 70 °C and 2 MPa H 2 . Kinetic studies and in-situ DRIFTS analyses reveal that this dual-atom architecture facilitates preferential C O adsorption and hydrogenation while suppressing C C activation. In addition, DFT calculations further show that the Pt-Fe dual atomic pair lowers the activation barrier by modulating the d -band center and Gibbs free energy profiles, enhancing H 2 splitting and intermediate stabilization. This work demonstrates a promising strategy for fine-tuning electronic and geometric structures via dual-atom design, offering an effective route for developing highly selective hydrogenation catalysts under industrially viable conditions.