Transition Metal Nitrides as Promising Catalyst Supports for Tuning CO/H2Syngas Production from Electrochemical CO2Reduction

Abstract

AbstractThe electrochemical carbon dioxide reduction reaction (CO2RR) to produce synthesis gas (syngas) with tunable CO/H2ratios has been studied by supporting Pd catalysts on transition metal nitride (TMN) substrates. Combining experimental measurements and density functional theory (DFT) calculations, Pd‐modified niobium nitride (Pd/NbN) is found to generate much higher CO and H2partial current densities and greater CO Faradaic efficiency than Pd‐modified vanadium nitride (Pd/VN) and commercial Pd/C catalysts. In‐situ X‐ray diffraction identifies the formation of PdH in Pd/NbN and Pd/C under CO2RR conditions, whereas the Pd in Pd/VN is not fully transformed into the active PdH phase. DFT calculations show that the stabilized *HOCO and weakened *CO intermediates on PdH/NbN are critical to achieving higher CO2RR activity. This work suggests that NbN is a promising substrate to modify Pd, resulting in an enhanced electrochemical conversion of CO2to syngas with a potential reduction in precious metal loading.