Direct Comparison of the Activity and Selectivity of Rh1Cu and Ni1Cu Single-Atom Alloy Sites for Ethanol Decomposition

Abstract

Ethanol is an important source of clean hydrogen, acetaldehyde, acetic acid, acetate esters, and light hydrocarbons. Controlling the divergent reaction pathways to these products requires understanding how different active sites influence the elementary steps involved. Herein, we present a combined surface science, theory, and nanoparticle catalysis study demonstrating how two single-atom dopants (Rh and Ni) in a Cu host can distinctively alter the selectivity of alcohol conversion. Specifically, our model studies reveal that ethanol reacts on Ni₁Cu single-atom alloys to selectively produce acetaldehyde, whereas methane and CO are also formed on Rh₁Cu single-atom alloys. Interestingly, these different reactivities are in contrast to the behavior of the pure metals as Ni(111) and Rh(111) surfaces favor methane/CO and surface carbon/CO, respectively. DFT calculations of reaction pathways and simulated product desorption based on microkinetic analyses explain these reactivity differences, demonstrating that C–C cleavage leading to methane formation has a lower barrier on Rh single-atom sites. To test the catalytic relevance of these fundamental results we synthesized and characterized supported Ni₁Cu and Rh₁Cu single-atom alloy nanoparticles with dopant:Cu ratios of 1:200. Flow reactor results revealed that both Ni and Rh increased ethanol conversion over Cu and that Ni₁Cu catalysts were >99.9% selective to acetaldehyde, while Rh₁Cu also produced 0.6%–2.6% of equimolar methane and CO between 433 and 493 K, demonstrating that C–C bond cleavage is enabled by isolated Rh sites. These catalytic results bridge the pressure and materials gaps, and together, this study provides insights into how different isolated dopant sites promote different catalytic pathways.