Concurrent Oxidation-Reduction Reactions in a Single System Using a Low-Plasma Phenomenon: Excellent Catalytic Performance and Stability in the Hydrogenation Reaction.

Abstract

The catalytic activity and stability of metal nanocatalysts toward agglomeration and detachment during their preparation on a support surface are major challenges in practical applications. Herein, we report a novel, one-step, synchronized electro-oxidation-reduction "bottom-up" approach for the preparation of small and highly stable Cu nanoparticles (NPs) supported on a porous inorganic (TiO2@SiO2) coating with significant catalytic activity and stability. This unique embedded structure restrains the sintering of CuNPs on a porous TiO2@SiO2 surface at a high temperature and exhibits a high reduction ratio (100% in 60 s) and no decay in activity even after 30 cycles (>98% conversion in 3 min). This occurs in a model reaction of 4-nitrophenol (4-NP) hydrogenation, far exceeding the performance of most common catalysts observed to date. More importantly, nitroarene, ketone/aldehydes, and organic dyes were reduced to the corresponding compounds with 100% conversion. Density functional theory (DFT) calculations of experimental model systems with six Cu, two Fe, and four Ag clusters anchored on the TiO2 surface were conducted to verify the experimental observations. The experimental results and DFT calculations revealed that CuNPs not only favor the adsorption on the TiO2 surface over those of Fe and AgNPs but also boost the adsorption energy and activity of 4-NP. This strategy has also been extended to the preparation of other single-atom catalysts (e.g., FeNPs-TiO2@SiO2 and AgNPs-TiO2@SiO2), which exhibit excellent catalytic performance.