Ru single atoms and nanoparticles on carbon nanotubes as multifunctional catalysts

Abstract

In the last decade we have witnessed increasing interest in the production of renewable energy and value-added chemicals through sustainable and low-cost technologies where catalysts play a crucial role. Herein, we report the application of a Ru/CNT material containing a mixture of Ru single atoms and Ru nanoparticles as a multifunctional catalyst for both the catalytic reduction of nitroarenes and the electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The catalytic activity of the Ru-CNT material was evaluated in the reduction of 4-nitrophenol (4-NP), 4-nitroaniline (4-NA) and 2-nitrophenol (2-NP) in the presence of sodium borohydride as a reducing agent at room temperature, showing high catalytic activity with normalized rate constants (k_nor) of 19.0 × 10³, 57.7 × 10³ and 16.6 × 10³ min^-1 mmol^-1 respectively. Furthermore, the catalyst could be reused in at least 10 cycles without catalytic activity loss, confirming the high stability and robustness of the material. The Ru/CNT material also showed good ORR electrocatalytic activity in alkaline medium with E_onset of 0.76 V vs. RHE, a diffusion-limited current density of 3.89 mA cm^-2 and ñ_O₂ of 3.3. In addition, Ru/CNT was remarkably insensitive to methanol with a current retention of 93% (51% for Pt/C) and competitive electrochemical stability of 80% after 20 000 s. Moreover, Ru/CNT was active for the OER with j_max = 29.5 mA cm^-2 at E = 1.86 V vs. RHE, η₁₀ = 0.50 V and good stability (η₁₀ changed to 0.01 V and j_max only decreased by ≈12% after 500 cycles).