Ti3+ Tuning the Ratio of Cu+ /Cu0 in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction

Abstract

Hydrogenation of diesters to diols is a vital process for chemical industry. The inexpensive Cu⁺ /Cu⁰ -based catalysts are highly active for the hydrogenation of esters, however, how to efficiently tune the ratio of Cu⁺ /Cu⁰ and stabilize the Cu⁺ is a great challenge. In this work, it is demonstrated that doped Ti ions can tune the ratio of Cu⁺ /Cu⁰ and stabilize the Cu⁺ by the TiOCu bonds in Ti-doped SiO₂ supported Cu nanoparticle (Cu/Ti-SiO₂ ) catalysts for the high conversion of dimethyl adipate to 1,6-hexanediol. In the synthesis of the catalysts, the Ti⁴⁺ OCu²⁺ bonds promote the reduction of Cu²⁺ to Cu⁺ by forming Ti³⁺ O_V Cu⁺ (O_V : oxygen vacancy) bonds and the amount of Ti doping can tune the ratio of Cu⁺ /Cu⁰ . In the catalytic reaction, the O vacancy activates CO in the ester by forming new Ti^{3+ δ} O_R Cu^{1+ δ} bonds (O_R : reactant oxygen), and Cu⁰ activates hydrogen. After the products are desorbed, the Ti^{3+ δ} O_R Cu^{1+ δ} bonds return to the initial state of Ti³⁺ O_V Cu⁺ bonds. The reversible TiOCu bonds greatly improve the activity and stability of the Cu/Ti-SiO₂ catalysts. When the content of Ti is controlled at 0.4 wt%, the conversion and selectivity can reach 100% and 98.8%, respectively, and remain stable for 260 h without performance degradation.

Keywords: Cu +/Cu 0 tuning; Ti O Cu bonds; hydrogenation; reversible conversion; ultrafine Cu nanoparticles.