Kinetics of the functionalization of mesoporous silica nanoparticles: Implications on surface group distributions, adsorption and catalysis

Manzano, J. Sebastián; Wang, Hsin; Kobayashi, Takeshi; Naik, Pranjali; Lai, King C.; Evans, James W.; Slowing, Igor I.

doi:10.1016/j.micromeso.2020.110276

Title: Kinetics of the functionalization of mesoporous silica nanoparticles: Implications on surface group distributions, adsorption and catalysis

Journal Article · Thu Apr 30 00:00:00 EDT 2020 · Microporous and Mesoporous Materials

DOI:https://doi.org/10.1016/j.micromeso.2020.110276· OSTI ID:1632000

Manzano, J. Sebastián ^[1]; Wang, Hsin ^[1]; Kobayashi, Takeshi ^[2];

^[1];

^[1]

Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Ames Lab., Ames, IA (United States)

The post-synthesis functionalization (grafting) kinetics of mesoporous silica nanoparticles (MSN) with organotrimethoxysilanes (R-TMS) is studied via solution ¹H NMR spectroscopy. The process involves a rapid adsorption/ desorption pre-equilibrium followed by reaction of R-TMS with surface silanols. Grafting rates are affected by the functional group in R-TMS. For example, the grafting rate of aminopropyl-trimethoxysilane (AP-TMS) is one order of magnitude higher than other R-TMS. High concentrations of AP-TMS result in substrate-inhibition kinetics, likely due to steric and mobility constraints for reactant alignment at high coverage. The higher rates of AP-TMS grafting indicate a catalytic effect of amine groups. This effect depends on the amine’s basicity and can be used to control the grafting rates and degree of condensation of other R-TMS. Adjusting the rate of mercaptopropyl-trimethoxysilane (MP-TMS) grafting using amines gives MP-MSN materials of varying adsorptive and catalytic activities, illustrated by Pd scavenging experiments and use of Pd@MP-MSN as catalysts for a Suzuki-Miyaura cross-coupling reaction.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1632000

Alternate ID(s):: OSTI ID: 1631340

Report Number(s):: IS-J-10,232

Journal Information:: Microporous and Mesoporous Materials, Vol. 305, Issue C; ISSN 1387-1811

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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