Surface-sealing encapsulation of phosphotungstic acid in microporous UiO-66 as a bifunctional catalyst for transfer hydrogenation of levulinic acid to γ-valerolactone.

The efficient production of γ-valerolactone (GVL) from renewable lignocellulose that is synthesized in plants by photosynthesis to replace the declining fossil resources conforms to the principles of circular economy. Compared to direct hydrogenation by H2 molecules, catalytic transfer hydrogenation (CTH) of levulinic acid (LA) and/or its esters to GVL with organic alcohols as a hydrogen source is a much milder route. The synergistic catalysis between Lewis and Brønsted acids is indispensable in the CTH process. Considering that unsaturated coordinated Zr species could act as Lewis acid sites and phosphotungstic acid (PTA) could dissociate protons as Brønsted acid sites, UiO-66 (Zr) was thus "acidified" by encapsulating PTA in its channels to tune the ratio of Brønsted to Lewis acid sites as a bifunctional catalyst so as to better understand the catalytic structure-performance relationship in the CTH process. To address the dilemma of encapsulated PTA that is prone to leach, a rapid surface sealing strategy was adopted to establish a polyimide (PI) coating over the surface of UiO-66 introducing a space confinement effect via an anhydride-amine coupling reaction. The as-synthesized PTA/UiO-66@PI catalyst exhibited 100% of LA conversion, a 93.2% of GVL yield and high recyclability for at least five consecutive cycles. Moreover, a reaction pathway followed by esterification, hydrogenation and dealcoholization as well as a catalytic hydrogenation mechanism based on intermolecular hydride ß-H transfer were proposed. Current work not only provides a high-performance and high-stability catalytic system to selectively produce GVL from LA or its esters, but also sheds light on the catalytic mechanism of the CTH process at the molecular level.

Enhanced metal-support interaction between Pd and hierarchical Nb2O5via oxygen defect induction to promote CO oxidative coupling to dimethyl oxalate.

Production of ethylene glycol from coal is a particularly interesting route as it is an economic alternative to the petrochemical-based route. In this process, effectively generating dimethyl oxalate (DMO) is a crucial step by CO oxidative coupling reaction under Pd-based catalysts. However, the aggregation of Pd species over the support is still an issue that relates to the deterioration of catalytic activity and stability. To this end, enhancing the metal-support interaction is urgently required. In this work, hierarchical Nb2O5 (H-Nb2O5) microspheres with abundant oxygen defects were synthesized to anchor the Pd species thus promoting the electron transfer between Pd species and Nb species associated with the generation of interfacial Pd-NbOx sites. Besides, the thinned electron density of Pd species resulting from the electron-withdrawing effect of Nb species is beneficial for activating the adsorbed CO molecules, leading to superior catalytic activity. The Pd/H-Nb2O5 catalyst exhibited 63.1% of CO conversion (theoretical maximum conversion: 64.3%) and 92.9% of DMO selectivity, with a DMO weight time yield of 1297.9 g kgcat.-1 h-1, and remained robust even after 50 h of time on stream evaluation. Current work provides a deep insight into the CO activation mechanism and helps improve the catalytic stability by boosting interfacial electron interaction via oxygen defects induction, and also sheds light on the design and synthesis of high-performance catalysts in other heterogeneous catalysis fields.