posted on 2021-09-07, 15:07authored bySayan Banerjee, Arvin Kakekhani, Robert B. Wexler, Andrew M. Rappe
Recently, nickel phosphides (NixPy) have been reported to enable selective
electrochemical formation of multicarbon products (C3 and
C4) via the CO2 reduction reaction
(CO2RR); nevertheless, their activities remain low. In
order to understand the roots of their high selectivity and low activity
and to direct the design of more active NixPy-based CO2RR catalysts,
we investigate the CO2RR mechanism on Ni2P using
density functional theory (DFT) calculations. We reveal that the reaction
proceeds through the formate pathway, followed by formaldehyde (H2CO*) formation and self-condensation. Moreover, we demonstrate
that surface hydride transfer steps, along with surface-mediated C–C
coupling, are essential in order to avoid C1 product formation
and boost selectivity toward multicarbon products. In addition, we
find that the thermal surface hydride transfer from the surface to
the physisorbed CO2 is one of the key rate-limiting steps,
and since it is not electroactive, it cannot be accelerated by applying
an overpotential. Finally, our results also show that the hydrogen
affinity of the surface and the dynamic surface reconstruction via H adsorption facilitate selective CO2 reduction
and C–C coupling on Ni2P. These findings provide
an impetus for exploring materials design space to identify the physical
principles that govern the thermodynamics of rate-limiting thermal
steps in electrocatalytic processes.