Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Hammond-Pereira, Ellis; Bryant, Kristin; Graham, Trenton R.; Yang, Chen; Mergelsberg, Sebastian T.; Wu, Di; Saunders, Steven R.

doi:10.1039/D0RE00198H

Title: Mesoporous silica-encapsulated gold core–shell nanoparticles for active solvent-free benzyl alcohol oxidation

Journal Article · Thu Oct 01 00:00:00 EDT 2020 · Reaction Chemistry & Engineering

DOI:https://doi.org/10.1039/D0RE00198H· OSTI ID:1699507

Hammond-Pereira, Ellis ^[1]; Bryant, Kristin ^[1];

^[2]; Yang, Chen ^[1]; Mergelsberg, Sebastian T. ^[2]; Wu, Di ^[1]; Saunders, Steven R. ^[1]

Washington State University
BATTELLE (PACIFIC NW LAB)

Silica-encapsulated gold core@shell nanoparticles (Au@SiO2 CSNPs) were synthesized via a bottom-up procedure and used to catalyze the selective oxidation of benzyl alcohol. The pore size, morphology, crystallinity and composition of Au@SiO2 was evaluated using non-local density functional theory, transmission electron microscopy, high-energy x-ray diffraction and inductively coupled plasma-mass spectroscopy, respectively. The nanoparticles exhibit a mesoporous shell with an average thickness of 25.5 Å which can enhance selectivity via preferential transport of the desired product (i.e., benzaldehyde) relative to larger, undesired products (i.e, benzoic acid/benzyl benzoate). GC-FID analysis revealed the addition of potassium carbonate to the solvent-free oxidation of benzyl alcohol increased conversion from 17.3 to 60.4% while decreasing selectivity from 98.7 to 75.0%. Under equivalent conditions, a bare gold nanoparticle control catalyst deposited on a silica support with a similar gold surface area took 6 times as long to reach the same conversion, achieving only 49.4% selectivity. These results suggest that the pore size distribution within the inert silica shell of Au@SiO2 CSNPs inhibits the formation of undesired products to facilitate the selective oxidation of benzaldehyde despite a basic environment, which reduces selectivity under typical conditions. The CSNPs demonstrated a much lower activation energy than the Au-SiO2 control catalyst, 37 ± 1.9 kJ/mol and 72 ± 7.1 kJ/mol, respectively. Thiele modulus analysis indicates the CSNP pore structure does not create a mass transport limitation due to the nano-scale path of diffusion through the pore structure to the active surface. The lower activation energy and mesopore distribution together suggest the Au@SiO2 catalyst demonstrates higher activity through beneficial in-pore orientation, both reducing competitive adsorption and promoting a single, lower activation energy mechanistic pathway.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1699507

Report Number(s):: PNNL-SA-151451

Journal Information:: Reaction Chemistry & Engineering, Vol. 5, Issue 10

Country of Publication:: United States

Language:: English

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