Shape-Controlled CO 2 Electrochemical Reduction on Nanosized Pd Hydride Cubes and Octahedra
Electrochemical CO 2 reduction reaction (CO 2 RR) provides a potential pathway to mitigate challenges related to CO 2 emissions. Pd nanoparticles have shown interesting properties as CO 2 RR electrocatalysts, while how different facets of Pd affect its performance in CO 2 reduction to synthesis gas with controlled H 2 to CO ratios has not been studied. Herein, we synthesized nano-sized Pd cubes and octahedra particles dominated by Pd(100) and Pd(111) facets, respectively. Here, the Pd octahedra particles show higher CO selectivity (up to 95%) and better activity than Pd cubes and commercial particles. For both Pd octahedra and cubes, the ratio of H 2 /CO products was tunable between 1 and 2, a desirable ratio for methanol production and the Fischer-Tropsch processes. Further studies of Pd octahedra in a 25-cm 2 flow cell showed a total CO current of 5.47 A was achieved at a potential of 3.4 V, corresponding to a CO partial current density of 220 mA/cm -2 . In situ X-ray absorption spectroscopy studies showed that regardless of facet Pd transformed into Pd hydride (PdH) under reaction conditions. DFT calculations show that the reduced binding energies of CO and HOCO intermediates on PdH(111) are key parameters to the high current density and Faradaic efficiency in CO 2 to CO conversion.