Designing Efficient Single-Atom Alloy Catalysts for Selective C═O Hydrogenation: A First-Principles, Active Learning and Microkinetic Study

Selective hydrogenation of α,β-unsaturated aldehydes into unsaturated alcohols is a process in high demand in organic synthesis, pharmaceuticals, and food production. This process requires the precise hydrogenation of C═O bonds, a challenge that requires a tailored catalyst. Single-atom alloys (SAAs), where individual atoms of one metal are distributed in a host metal matrix, offer a potential solution to this challenge. Nevertheless, identifying the appropriate SAA capable of targeted adsorption and the efficient activation of C═O bonds remains a substantial hurdle. In this work, we synergistically combine density functional theory (DFT) calculations, active learning, and microkinetic simulations to design SAAs for the efficient and selective hydrogenation of α,β-unsaturated aldehydes. We first comprehensively assessed the potential of 66 SAAs across 264 surfaces (including (100), (110), (111), and (320) crystal planes), to gauge their potential in activating C═C and C═O bonds. Our assessment unveiled the excellent selectivity of the Ti₁Au SAA in activating C═O bonds. Moreover, our detailed DFT calculations further demonstrated the high catalytic activity of Ti₁Au(320) and Ti₁Au(111) surfaces with a low activation energy barrier of only 0.60 eV. Subsequently, we conducted microkinetic simulations on the selective hydrogenation process of crotonaldehyde, by selecting Ti₁Au (320) and (111) surfaces as the catalysts and demonstrated that they exhibited a remarkable selectivity and nearly 100% conversion toward crotyl alcohol in the temperature range from 373 to 553 K. The present study not only reveals novel SAAs for targeted hydrogenation of α,β-unsaturated aldehydes but also establishes a promising path toward efficient design of selective hydrogenation catalysts more broadly.