It was shown for the first time that cyclohexanone oxime (CHO) can be selectively produced by heterogeneous copper-catalyzed hydrogenative transformation of nitrocyclohexane (NC). The combination of Cu0 and Cu+ and their cooperative interaction with weakly acidic SiO2 supports elicited a significantly unique and selective catalysis in the hydrogenation of NC to CHO.

Reductive amination (RA) constitutes an attractive and practical strategy for discovering protocols capable of converting biomass into valuable N-containing compounds. Described herein is a versatile and sustainable RA of 5-hydroxymethyl-furfural (HMF), an important biomass-derived aldehyde, using abundant and cheaply available CO and water as reductants. A single phase rutile titania supported gold (Au/TiO2-R) catalyst is shown to efficiently catalyze this CO/H2O-mediated RA under mild and convenient conditions. With this system, a broad spectrum of primary and secondary amines can be used as suitable substrates and the desired reaction can proceed favourably in a highly chemoselective, efficient and atom-economical fashion. In particular, this protocol can also allow convenient access to bis(hydroxylmethylfurfuryl)-amines, a new group of furan-based monomers with great potential to form functional biopolymers with tunable properties. Moreover, this CO-assisted RA is more efficient (higher TON and TOF) and more eco-friendly (increased resource efficiency) than the previous state-of-the-art technique.

Liquid-phase selective monohydrogenation of various substituted dinitroaromatics to the corresponding valuable nitroanilines was investigated on gold-based catalysts. Special attention was paid to the effect of Au particle size on this monoreduction reaction. Interestingly, TiO2 supported gold catalysts containing a relatively larger mean Au particle size (>5 nm) showed far superior chemoselectivity for specific mono-hydrogenation of dinitroaromatics, with the highest performance attainable for the catalyst bearing Au particles of ca. 7.5 nm. Results in the intermolecular competitive hydrogenation showed that the intrinsic higher accumulation rates of the desired nitroanilines associated with the catalyst possessing larger Au particles were responsible for the high chemoselectivity observed.

A new efficient method for chemo- and regio-selective semireduction of alkynes using CO/H2O as the hydrogen source catalyzed by gold supported on high surface area TiO2 was developed. A facile and practical synthesis of 1,2-dideuterioalkenes was also realized by using CO/D2O as the reducing agent.

Ordered vanadosilicate mesoporous material with large (∼15 nm), uniform, novel cage-like mesopores was synthesized under acidic aqueous conditions from tetraethyl orthosilicate in the presence of ammonia vanadiate, using P123 with CTAB as cotemplate and TMB as a swelling agent. The catalysts were extensively characterized by a combination of different techniques (N2 adsorption, small-angle X-ray scattering (SAXS), transmission electron microscope (TEM), UV Raman, and UV−vis spectra) in relation to their performance for oxidation dehydrogenation of propane. SAXS and TEM analysis showed that the as-synthesized vanadosilicate samples have a uniform, well-defined cage-like mesostructure. UV Raman and UV−vis spectra revealed that the vanadium species was isolated and presented as a highly dispersed state in the framework of the vanadosilicate samples. Significantly enhanced catalytic activity was observed for the vanadosilicate catalysts, as compared with the 1.0 V-SBA-15 prepared by conventional impregnation. The enhanced catalytic activity of the vanadosilicate catalyst was attributed to the beneficial presence of a larger amount of isolated and highly dispersed V-species, as well as the cage-like mesoporous structure.

It was shown for the first time that cyclohexanone oxime (CHO) can be selectively produced by heterogeneous copper-catalyzed hydrogenative transformation of nitrocyclohexane (NC). The combination of Cu0 and Cu+ and their cooperative interaction with weakly acidic SiO2 supports elicited a significantly unique and selective catalysis in the hydrogenation of NC to CHO.

A new efficient method for chemo- and regio-selective semireduction of alkynes using CO/H2O as the hydrogen source catalyzed by gold supported on high surface area TiO2 was developed. A facile and practical synthesis of 1,2-dideuterioalkenes was also realized by using CO/D2O as the reducing agent.