In Situ 29Si solid-state NMR study of grafting of organoalkoxysilanes to mesoporous silica nanoparticles

Cui, Jinlei; Chatterjee, Puranjan; Slowing, Igor I.; Kobayashi, Takeshi

doi:10.1016/j.micromeso.2022.112019

In Situ ²⁹Si solid-state NMR study of grafting of organoalkoxysilanes to mesoporous silica nanoparticles

Journal Article · Wed May 25 00:00:00 UTC 2022 · Microporous and Mesoporous Materials

DOI:https://doi.org/10.1016/j.micromeso.2022.112019· OSTI ID:1872222

Cui, Jinlei ^[1]; Chatterjee, Puranjan ^[2]; ^[2]; ^[1]

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

We report that since the catalytic activity and the stability of silica-bound organometallic complexes are affected by their interactions with hydroxyl groups on the surface, isolated hydroxyls are often created prior to the introduction of catalytic species. Here, we investigate a method to remove the indigenous hydroxyls and create new isolated hydroxyls by grafting organo-trimethoxysilane (R-TMS) to generate a silicon T² site, (≡SiO-)₂SiR(-OH). We used in situ ²⁹Si solid-state NMR experiments to monitor the evolution of Tⁿ sites, (≡SiO^-)_nSiR(-OH)_3-n (n = 1, 2, 3). The study indicates that i) the grafting proceeds in a consecutive manner as T¹ → T² → T³, and ii) the kinetics depend on the type of functional groups in the silane. However, the rates of T¹ formation and T² → T³ conversion are also controlled to a significant extent by the entropy loss associated to the initial silane binding and the spatial arrangement of surface hydroxyls, respectively. The grafting of R-TMS with a basic functional group leads to a lower concentration of T¹ sites. The nucleophilicity of the functional group facilitates the grafting process by lowering the enthalpy barrier, while the T¹ formation rate is more influenced by the entropy barrier than the T¹ → T² conversion rate. Thus, the basic functional group promotes the T¹ → T² conversion more than the T¹ formation, resulting in a lower concentration of T¹ sites.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1872222

Alternate ID(s):: OSTI ID: 1871037

Report Number(s):: IS-J-10,822

Journal Information:: Microporous and Mesoporous Materials, Journal Name: Microporous and Mesoporous Materials Vol. 339; ISSN 1387-1811

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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