Phase-Dependent Electrocatalytic CO 2 Reduction on Pd 3 Bi Nanocrystals.

Alloying is a general strategy for modulating the electronic structures of catalyst materials. Compared to more common solid-solution alloys, intermetallic alloys feature well-defined atomic arrangements and provide the unique platform for studying the structure-performance correlations. It is, unfortunately, synthetically challenging to prepare the nanostructures of intermetallic alloys for catalysis research. In this contribution, we prepare intermetallic Pd ₃ Bi nanocrystals of a uniform size via a facile solvothermal method. These nanocrystals can phase-transform into solid solution alloy via thermal annealing while retaining a similar composition and size. In 0.1 M KHCO ₃ aqueous solution, the intermetallic Pd ₃ Bi can selectively reduce CO ₂ to formate with high selectivity (≈100 %) and stability even at <-0.35 V versus reversible hydrogen electrode, whereas the solid solution alloy has limited formate selectivity of <60 %. Such unique phase-dependence is understood via theoretical simulations showing that the crystallographic ordering of Pd and Bi atoms within intermetallic alloys can suppress CO poisoning and enhance the *OCHO adsorption during electrochemical CO ₂ reduction to formate.
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