Graphical abstract

Decomposition of tartaric acid (TA, HO₂CCH(OH)CH(OH)CO₂H) and aspartic acid (Asp, HO2CCH(NH₂)CH₂CO₂H) on Cu surfaces occurs via a vacancy-mediated surface explosion mechanism with nonlinear kinetics: r_e = k_eθ(1 – θ)², where θ is the adsorbate coverage, and (1 – θ) is the vacancy coverage. During temperature-programmed reaction experiments on naturally chiral Cu(hkl)^R&S surfaces, these kinetics, coupled with the chirality of the adsorbates, lead to highly enantiospecific decomposition rates. Herein, it is demonstrated that, in the presence of a thermal molecular beam with a constant Asp flux, F_Asp, the decomposition of Asp on Cu(111) occurs catalytically and in steady-state to turnover numbers >40 without contamination or deactivation of the surface. Moreover, the decomposition rates at a given (T, F_Asp) manifest the two different steady-states predicted by the nonlinearity of the decomposition kinetics. The unusual ability to catalytically decompose Asp on Cu, coupled with the ability to distinguish between _d- and ¹³C-l-Asp using mass spectrometry, opens an avenue for the future study of enantioselective catalysis on Cu(hkl)^R&S surfaces.