Oxidative Esterification of Methacrolein to Methyl Methacrylate over Gold Nanoparticles on Hydroxyapatite

• Published in: ChemCatChem Vol. 9; no. 7; pp. 1230 - 1241
• Main Authors: Gao, Jun, Fan, Guoli, Yang, Lan, Cao, Xinzhong, Zhang, Peng, Li, Feng
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 07.04.2017
• Subjects: gold; nanoparticles; oxidation; polymorphism; supported catalysts
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.201601560

The catalytic production of methyl methacrylate through the direct oxidative esterification of methacrolein is important in terms of green chemistry and sustainable development. In the present work, Au nanoparticles supported on three needle‐like, lamella‐like, and rodlike hydroxyapatites were synthesized. We demonstrated that needle‐like hydroxyapatite could facilitate the higher dispersion of Au species because of its high specific surface area, and the strong interaction between the Au nanoparticles and the support resulted in the formation of more surface defects because of the existence of partially encapsulated Au particles by the needle‐like hydroxyapatite. The surface defects were related closely to the generation of strong basic sites. Compared with the other two materials, the Au supported on the needle‐like hydroxyapatite catalyst, which had a large amount of surface acid–base sites, exhibited a much higher catalytic activity and selectivity to methyl methacrylate in the direct oxidative esterification of methacrolein with methanol under mild reaction conditions (i.e., ambient pressure, low reaction temperature of 70 °C, and low methanol/aldehyde ratio of 8:1). The superior catalytic performance of the Au supported on needle‐like hydroxyapatite catalyst was attributable to a cooperative effect between abundant acid–base sites for the preferential chemisorption of methacrolein and highly dispersed active Au species for the favorable formation of β‐hydride and oxygen activation. The present findings open a new and promising route for the practical production of methyl methacrylate using high‐performance hydroxyapatite‐supported metal catalyst systems. Hip HAP: Three nanocatalysts of Au supported on needle‐like, lamella‐like, and rodlike hydroxyapatite (N‐HAP, L‐HAP, and R‐HAP) are employed in the direct oxidative esterification of methacrolein to produce methyl methacrylate. N‐HAP‐supported Au has the best catalytic performance because of surface cooperative effects between the abundant acid–base sites for the preferential chemisorption of methacrolein and highly dispersed active Au species for the favorable formation of β‐hydride and oxygen activation.