Nanoengineered Design of inside‐Heating Hot Nanoreactor Surrounded by Cool Environment for Selective Hydrogenations

Catalysts with designable intelligent nanostructure may potentially drive the changes in chemical reaction techniques. Herein, a multi-function integrating nanocatalyst, Pt-containing magnetic yolk-shell carbonaceous structure, having catalysis function, microenvironment heating, thermal insulation, and elevated pressure into a whole is designed, which induces selective hydrogenation within heating-constrained nanoreactors surrounded by ambient environment. As a demonstration, carbonyl of α, β-unsaturated aldehydes/ketones are selectively hydrogenated to unsaturated alcohols with a >98% selectivity at a nearly complete conversion under mild conditions of 40 °C and 3 bar instead of harsh requirements of 120 °C and 30 bar. It is creatively demonstrated that the locally increased temperature and endogenous pressure (estimated as ≈120 °C, 9.7 bar) in the nano-sized space greatly facilitate the reaction kinetics under an alternating magnetic field. The outward-diffused products to the "cool environment" remain thermodynamically stable, avoiding the over-hydrogenation that often occurs under constantly heated conditions of 120 °C. Regulation of the electronic state of Pt by sulfur doping of carbon allows selective chemical adsorption of the CO group and consequently leads to selective hydrogenation. It is expected that such a multi-function integrated catalyst provides an ideal platform for precisely operating a variety of organic liquid-phase transformations under mild reaction conditions.