Modeling of linear nanopores in a-SiO2 tuning pore surface structure

New strategies are presented for the generation of models for linear nanopores in amorphous silica (a-SiO2) with surface structure tuned to match experimental observations. Specifically, the models successfully target not only the overall density of surface silanol groups, but also the proportion of geminal versus mono silanols for which additional experimental NMR data is reported. The latter quantity has not been appropriately described in previous modeling, and in fact has typically not been considered. Strategies include “pore drilling” of bulk a-SiO2, and “cylindrical resist” methodology forming a-SiO2 around a cylindrical exclusion region, followed by dehydroxylation and hydroxylation processes, respectively. However, these latter processes must be judiciously tailored in order to tune the proportion of geminals, in addition to the overall silanol density, to achieve experimental values. Such tailoring has not been incorporated into previous modeling. Another approach considered tunes surface structure of pores obtained by “pore drilling” through mild annealing.This is a manuscript of an article published as Fought, Ellie L., Yong Han, Theresa L. Windus, Igor I. Slowing, Takeshi Kobayashi, and James W. Evans. "Modeling of linear nanopores in a-SiO2 tuning pore surface structure." Microporous and Mesoporous Materials 341 (2022): 112077. DOI: 10.1016/j.micromeso.2022.112077. Copyright 2022 Elsevier Inc. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0). Posted with permission. DOE Contract Number(s): AC02-07CH11358

Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D ¹H–²⁹Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D ¹H–²⁹Si HETCOR and dipolar 2D ¹H–¹H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Instead the 2D NMR spectra illustrate that there is large distribution of ¹H and ²⁹Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected ¹H–²⁹Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the ²⁹Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH₃), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed ¹H and ²⁹Si chemical shifts. The approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials