Single-Atom Alloys as a Reductionist Approach to the Rational Design of Heterogeneous Catalysts (2018)

Heterogeneous catalysts are workhorses in the industrial production of most commodity and specialty chemicals, and have widespread energy and environmental applications, with the annual market value of the catalysts themselves reaching almost $20 billion in 2018. These catalysts are complex, comprising multicomponent materials and multiple structures, making their rational design challenging, if not impossible. Furthermore, typical active metals like Pt, Pd, and Rh are expensive and can be susceptible to poisoning by CO, coking, and they are not always 100% selective. Efforts to use these elements sparingly and improve their selectivity has led to recent identification of single-atom heterogeneous catalysts in which individual transition metal atoms anchored on oxide or carbon-based supports are excellent catalysts for reactions like the CO oxidation, water-gas shift, alcohol dehydrogenation, and steam reforming. In this Account, we describe a new class of single-atom heterogeneous catalysts, namely, Single-Atom Alloys (SAAs) that comprise catalytically active elements like Pt, Pd, and Ni alloyed in more inert host metals at the single-atom limit. These materials evolved by complementary surface science and scanning probe studies using single crystals, and catalytic evaluation of the corresponding alloy nanoparticles with compositions informed by the surface science findings. The well-defined nature of the active sites in SAAs makes accurate modeling with theory relatively easy, enabling the rational design of SAA catalysts via a complementary three-prong approach, encompassing surface science model catalysts, theory, and real catalyst synthesis and testing under industrially relevant conditions. SAAs constitute one of just a few examples of when heterogeneous catalyst design has been guided by an understanding of fundamental surface processes. The Account starts by describing scanning tunneling microscopy studies of highly dilute alloys formed by doping small amounts of a catalytically active element into a more inert host metal. We first discuss hydrogenation reactions in which dissociation of H<sub>2</sub> is often rate limiting. Results indicate how the SAA geometry allows the transition state and the binding site of the reaction intermediates to be decoupled, which enables both facile dissociation of reactants and weak binding of intermediates, two key factors for efficient and selective catalysis. These results were exploited to design the first PtCu SAA hydrogenation catalysts which showed high selectivity, stability and resistance to poisoning in industrially relevant hydrogenation reactions, such as the selective conversion of butadiene to butenes. Model studies also revealed spillover of hydrogen atoms from the Pt site where dissociation of H<sub>2</sub> occurs to Cu sites where selective hydrogenation is facilitated in a bifunctional manner. We then discuss selective dehydrogenations on SAAs demonstrating that they enable efficient C-H activation, while being resistant to coking that plagues typical Pt catalysts. SAA PtCu nanoparticle catalysts showed excellent stability in butane dehydrogenation for days-on-stream at 400 °C. Another advantage of SAA catalysts is that on many alloy combinations CO, a common catalyst poison, binds more weakly to the alloy than the pure metal. We conclude by discussing recent theory results that predict the energetics of many key reaction steps on a wide range of SAAs and the exciting possibilities this reductionist approach to heterogeneous catalysis offers for the rational design of new catalysts.