Microenvironment Engineering of Ruthenium Nanoparticles Incorporated into Silica Nanoreactors for Enhanced Hydrogenations

Abstract

It is ac hallenging task to promote the activity and selectivity of ac atalyst via precisely engineering the microenvironment, an important factor related with the catalytic performance of natural catalysts.Motivated by the water effect in promoting the catalytic activity explored in this work, an anoreactor modified with phosphine ligand enabled the efficient hydrogenation of benzoica cid (BA) over Ru nanoparticles (NPs) in organic solvent under mild conditions,which cannot be achieved in unmodified nanoreactors.B oth density functional theory (DFT) calculations and catalytic performance tests showed that the phosphine ligands can manipulate the adsorption strength of BA on Ru NPs by tuning the surface properties as well as preferentially interacting with the carboxyl of BA.T he insights obtained in the present study provide an ovel concept of nanoreactor design by anchoring ligands near catalytically active centers.

Nature‐Inspired Construction of MOF@COF Nanozyme with Active Sites in Tailored Microenvironment and Pseudopodia‐Like Surface for Enhanced Bacterial Inhibition

“…For example, some amino acids within the binding pocket are around the catalytic active sites of enzymes, which could assist enriching, organizing, and activating substrates via non‐covalent interactions [23–25] . Recently, several types of functional groups, such as amines, guanidines and carboxylic groups, etc., have been exploited to mimic the functions of amino acid residues owing to their Lewis acid‐base nature that can effect proton and electron transfer [26–29] . Inspired by these unique features, we envision that tailoring microenvironment around the active sites of MOF‐based nanozymes via installing specific functional groups and constructing favorable spatial structure may be a promising strategy to make them more closely mimic the natural enzymes.…”

Engineering of Yolk/Core–Shell Structured Nanoreactors for Thermal Hydrogenations

“…[133] Furthermore, when Ru NPs were modified with PPh 3 and incorporated into a silica nanoreactor, the Ru/ PPh 3 @FDU catalyst showcased efficient catalytic performance in the hydrogenation of benzoic acid to cyclohexanecarboxylic acid. [134] With the development of covalent organic frameworks (COFs), a representative yolk-shell structured MNPs@COF, namely Pd@H-TpPa was also reported to exhibit superior catalytic performance than Pd@ZIF-8 for the transfer hydrogenation of 4-nitrophenol by NaBH 4 . [135]…”

Pt/TiO2 Catalyzed Hydrogenation of Benzoic Acid with Unprecedented High Activity

“…The typical solvation effect is possibly related with the preferential adsorption of aromatic ring on metal surface induced by the interaction of carboxyl group with H 2 O molecules [13,14] and the participation of H* from the dissociated H 2 O molecules in the reaction [2,15]. Though water could modify the adsorption mode of substrates, it may also block the surface active sites [16,17].…”

“…The selective hydrogenation of benzoic acid (BA) or its derivatives has been widely used for the production of ne chemicals, intermediates and industrial raw materials [1][2][3]. For example, BA hydrogenation to cyclohexanecarboxylic acid (CCA) is an important step in the production of nylon-6 in industry [4][5].…”

“…This may be the reason that most metal NPs showed relatively low activity in BA hydrogenation. Recently, our group reported that the activity of Ru NPs was greatly enhanced in BA hydrogenation by tuning the adsorption mode of BA on metal surface with phosphine ligands [2]. Therefore, to realize the e cient BA hydrogenation, the supported metal NPs with appropriate adsorption strength towards carboxyl group and aromatic ring may be the good choice.…”