(Invited) Critical Effect of Particle Size in Ru-Catalyzed Electrosynthesis of Ammonia

Abstract

Electrochemical reduction of N2 to NH3 has recently received considerable attention, because it may enable sustainable, distributed production of NH3 when powered by solar- or wind-generated electricity. However, typical catalysts show a low activity and selectivity for N2 reduction reaction (NRR) due to the barrier for N2 activation and the competing hydrogen evolution reaction (HER). A rational design of NRR catalysts relies on our understandings of structure-activity relationships and active sites for the NRR, and such study requires model catalysts with well-defined structures. Here we present a study of size-dependent activity for the NRR on Ru nanoparticle catalysts. We first tried colloidal synthesis method with polyvinylpyrrolidine (PVP) as a surfactant to control the size of Ru nanoparticles, while the derived Ru catalysts showed negligible activity for NRR, which was attributed to residual surfactant molecules that blocked catalyst surfaces. Therefore, we used atomic layer deposition (ALD) method to prepare Ru nanoparticles with controlled sizes and clean surfaces. We also quantified the electrochemical active surface areas of Ru samples and measured surface-area-normalized activity for the NRR. Consequently, the effect of Ru nanoparticle size on the NRR activity and Faradaic efficiency was revealed, which can provide insights into the active sites for the NRR and guidance on the design of NRR catalysts via surface site engineering.