Nano-Sized NiO Immobilized on Au/CNT for Benzyl Alcohol Oxidation: Influences of Hybrid Structure and Interface.

Tiny gold nanoparticles were successfully anchored on carbon nanotubes (CNT) with NiO decoration by a two-step synthesis. Characterizations suggested that Ni species in an oxidative state preferred to be highly dispersed on CNT. During the synthesis, in situ reduction by NaBH4 and thermal treatment in oxidation atmosphere were consequently carried out, causing the formation of Au-Ni-Ox interfaces and bimetal hybrid structure depending on the Ni/Au atomic ratios. With an appropriate Ni/Au atomic ratio of 8:1, Ni atoms migrated into the sub-layers of Au particles and induced the lattice contraction of Au particles, whilst a higher Ni/Au atomic ratio led to the accumulation of NiO fractions surrounding Au particles. Both contributed to the well-defined Au-Ni-Ox interface and accelerated reaction rates. Nickel species acted as structure promoters with essential Au-Ni-Ox hybrid structure as well as the active oxygen supplier, accounting for the enhanced activity for benzyl alcohol oxidation. However, the over-layer of unsaturated gold sites easily occured under a high Ni/Au ratio, resulting in a lower reaction rate. With an Au/Ni atomic ratio of 8:1, the specific rate of AuNi8/CNT reached 185 µmol/g/s at only 50 °C in O2 at ordinary pressure.

Boosting the catalytic behavior and stability of a gold catalyst with structure regulated by ceria.

In this work, a series of colloidal gold nanoparticles with controllable sizes were anchored on carbon nanotubes (CNT) for the aerobic oxidation of benzyl alcohol. The intrinsic influence of Au particles on the catalytic behavior was unraveled based on different nanoscale-gold systems. The Au/CNT-A sample with smaller Au sizes deserved a faster reaction rate, mainly resulting from the higher dispersion degree (23.5%) of Au with the available exposed sites contributed by small gold particles. However, monometallic Au/CNT samples lacked long-term stability. CeO2 was herein decorated to regulate the chemical and surface structure of the Au/CNT. An appropriate CeO2 content tuned the sizes and chemical states of Au by electron delivery with better metal dispersion. Small CeO2 crystals that were preferentially neighboring the Au particles facilitated the generation of Au-CeO2 interfaces, and benefited the continuous supplementation of oxygen species. The collaborative functions between the size effect and surface chemistry accounted for the higher benzaldehyde yield and sustainably stepped-up reaction rates by Au-Ce5/CNT with 5 wt% CeO2.