Self-driven electron enrichment of ultrafine PdAu nanoparticles for electrochemical CO2 reduction: High applicability of work function as an activity descriptor

Highly coupled metal/dopant-incorporated carbon dyads provide a possibility to modulate the electron density of metallic materials by forming a rectifying interface, thus showing an enhanced activity in electrochemical CO2 reduction reaction (ECRR). However, understanding the promotion effects of dopants for ECRR is limited to the prediction by theoretical interpretation and case-by-case studies. Herein, we report the direct experimental evidence that the work function, regulated by single structural factor-dopant contents, is significantly correlated to the ECRR reaction activity and kinetics. We prepared a series of PdAu/NxC electrocatalysts composed of ultrafine (~5.7 nm) PdAu bimetallic nanoparticles and tailorable N-doped carbon supports. The wide range of the amount of N dopants allowed the modification of the band gap of the carbon easily. Using ultraviolet photoelectron spectroscopy (UPS) measurements, we demonstrate that the reactivity and kinetics trends of the PdAu/NxC in the ECRR can be intrinsically correlated with the work function of the catalysts. PdAu/N7.50C electrocatalyst with the highest N contents displays a 100% CO2-to-CO conversion and high conversion efficiency over a wide potential window, superior over other reported PdAu catalysts. This work provides a novel way to boost ECRR performance by deliberately lowering the work function of the metal/carbon electrocatalysts through the enhancement by dopants.