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Title: Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles (2): a study by 1H triple-quantum fast-MAS solid-state NMR

Abstract

The distribution of organic functional groups attached to the surface of mesoporous silica nanoparticles (MSNs) via co-condensation was scrutinized using 1D and 2D 1H solid-state NMR, including the triple-quantum/single-quantum (TQ/SQ) homonuclear correlation technique. The excellent sensitivity of 1H NMR and high resolution provided by fast magic angle spinning (MAS) allowed us to study surfaces with very low concentrations of aminopropyl functional groups. The sequential process, in which the injection of tetraethyl orthosilicate (TEOS) into the aqueous mother liquor was followed by dropwise addition of the organosilane precursor, resulted in deployment of organic groups on the surface, which were highly clustered even in a sample with a very low loading of ~0.1 mmol g -1. The underlying mechanism responsible for clustering could involve fast aggregation of the aminopropyltrimethoxysilane (APTMS) precursor within the liquid phase, and/or co-condensation of the silica-bound molecules. Understanding the deposition process and the resulting topology of surface functionalities with atomic-scale resolution, can help to develop novel approaches to the synthesis of complex inorganic–organic hybrid materials.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1467595
Alternate Identifier(s):
OSTI ID: 1464972
Report Number(s):
IS-J-9736
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 34; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Kobayashi, Takeshi, Singappuli-Arachchige, Dilini, Slowing, Igor I., and Pruski, Marek. Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles (2): a study by 1H triple-quantum fast-MAS solid-state NMR. United States: N. p., 2018. Web. doi:10.1039/C8CP04425B.
Kobayashi, Takeshi, Singappuli-Arachchige, Dilini, Slowing, Igor I., & Pruski, Marek. Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles (2): a study by 1H triple-quantum fast-MAS solid-state NMR. United States. doi:10.1039/C8CP04425B.
Kobayashi, Takeshi, Singappuli-Arachchige, Dilini, Slowing, Igor I., and Pruski, Marek. Fri . "Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles (2): a study by 1H triple-quantum fast-MAS solid-state NMR". United States. doi:10.1039/C8CP04425B. https://www.osti.gov/servlets/purl/1467595.
@article{osti_1467595,
title = {Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles (2): a study by 1H triple-quantum fast-MAS solid-state NMR},
author = {Kobayashi, Takeshi and Singappuli-Arachchige, Dilini and Slowing, Igor I. and Pruski, Marek},
abstractNote = {The distribution of organic functional groups attached to the surface of mesoporous silica nanoparticles (MSNs) via co-condensation was scrutinized using 1D and 2D 1H solid-state NMR, including the triple-quantum/single-quantum (TQ/SQ) homonuclear correlation technique. The excellent sensitivity of 1H NMR and high resolution provided by fast magic angle spinning (MAS) allowed us to study surfaces with very low concentrations of aminopropyl functional groups. The sequential process, in which the injection of tetraethyl orthosilicate (TEOS) into the aqueous mother liquor was followed by dropwise addition of the organosilane precursor, resulted in deployment of organic groups on the surface, which were highly clustered even in a sample with a very low loading of ~0.1 mmol g-1. The underlying mechanism responsible for clustering could involve fast aggregation of the aminopropyltrimethoxysilane (APTMS) precursor within the liquid phase, and/or co-condensation of the silica-bound molecules. Understanding the deposition process and the resulting topology of surface functionalities with atomic-scale resolution, can help to develop novel approaches to the synthesis of complex inorganic–organic hybrid materials.},
doi = {10.1039/C8CP04425B},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 34,
volume = 20,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

Spatial distribution of organic functional groups supported on mesoporous silica nanoparticles: a study by conventional and DNP-enhanced 29 Si solid-state NMR
journal, January 2017

  • Kobayashi, Takeshi; Singappuli-Arachchige, Dilini; Wang, Zhuoran
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 3
  • DOI: 10.1039/C6CP07642D

Study of Intermolecular Interactions in the Corrole Matrix by Solid-State NMR under 100 kHz MAS and Theoretical Calculations
journal, November 2013

  • Kobayashi, Takeshi; Mao, Kanmi; Paluch, Piotr
  • Angewandte Chemie International Edition, Vol. 52, Issue 52
  • DOI: 10.1002/anie.201305475

Templating of Mesoporous Molecular Sieves by Nonionic Polyethylene Oxide Surfactants
journal, September 1995


Molecular ordering of mixed surfactants in mesoporous silicas: A solid-state NMR study
journal, May 2011

  • Kobayashi, Takeshi; Mao, Kanmi; Wang, Shy-Guey
  • Solid State Nuclear Magnetic Resonance, Vol. 39, Issue 3-4
  • DOI: 10.1016/j.ssnmr.2011.02.001

BaBa-xy16: Robust and broadband homonuclear DQ recoupling for applications in rigid and soft solids up to the highest MAS frequencies
journal, September 2011

  • Saalwächter, Kay; Lange, Frank; Matyjaszewski, Krzysztof
  • Journal of Magnetic Resonance, Vol. 212, Issue 1
  • DOI: 10.1016/j.jmr.2011.07.001

Wet-Chemical Analysis of Surface Concentration of Accessible Groups on Different Amino-Functionalized Mesoporous SBA-15 Silicas
journal, October 2007

  • Rosenholm, Jessica M.; Lindén, Mika
  • Chemistry of Materials, Vol. 19, Issue 20
  • DOI: 10.1021/cm071289n

The effect of molecular interaction on magnetic shielding constants
journal, July 1958


Synthesis of bifunctionalized-pore mesoporous organosilica. Study of the accessibility and the distribution of functions in the pore channels
journal, January 2006

  • Mouawia, Rola; Mehdi, Ahmad; Rey?, Catherine
  • New Journal of Chemistry, Vol. 30, Issue 7
  • DOI: 10.1039/b603530b

Solid-State NMR Study of MCM-41-type Mesoporous Silica Nanoparticles
journal, March 2005

  • Trébosc, Julien; Wiench, Jerzy W.; Huh, Seong
  • Journal of the American Chemical Society, Vol. 127, Issue 9
  • DOI: 10.1021/ja043567e

SIMPSON: A General Simulation Program for Solid-State NMR Spectroscopy
journal, December 2000

  • Bak, Mads; Rasmussen, Jimmy T.; Nielsen, Niels Chr
  • Journal of Magnetic Resonance, Vol. 147, Issue 2
  • DOI: 10.1006/jmre.2000.2179

Triple-quantum NMR spectroscopy in dipolar solids
journal, March 1998


Resolution Enhancement in Multiple-Quantum MAS NMR Spectroscopy
journal, July 1998

  • Schnell, Ingo; Lupulescu, Adonis; Hafner, Siegfried
  • Journal of Magnetic Resonance, Vol. 133, Issue 1
  • DOI: 10.1006/jmre.1998.1432

Tailoring nanohybrids and nanocomposites for catalytic applications
journal, January 2013

  • de Clippel, Filip; Dusselier, Michiel; Van de Vyver, Stijn
  • Green Chemistry, Vol. 15, Issue 6
  • DOI: 10.1039/c3gc37141g

Multiple-Quantum 1 H MAS NMR Studies of Defect Sites in As-Made All-Silica ZSM-12 Zeolite
journal, July 2000

  • Shantz, Daniel F.; Schmedt auf der Günne, Jörn; Koller, Hubert
  • Journal of the American Chemical Society, Vol. 122, Issue 28
  • DOI: 10.1021/ja000374s

Solvent Effects in Nuclear Magnetic Resonance Spectra
journal, April 1960

  • Buckingham, A. D.; Schaefer, T.; Schneider, W. G.
  • The Journal of Chemical Physics, Vol. 32, Issue 4
  • DOI: 10.1063/1.1730879

Mesoporous materials by templating of liquid crystalline phases
journal, May 1997


A Simple NMR-Based Method for Studying the Spatial Distribution of Linkers within Mixed-Linker Metal-Organic Frameworks
journal, July 2015

  • Krajnc, Andraž; Kos, Tomaž; Zabukovec Logar, Nataša
  • Angewandte Chemie International Edition, Vol. 54, Issue 36
  • DOI: 10.1002/anie.201504426

Measuring Long-Range 13 C– 13 C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance
journal, October 2017

  • Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek
  • The Journal of Physical Chemistry C, Vol. 121, Issue 44
  • DOI: 10.1021/acs.jpcc.7b08841

Directly and indirectly detected through-bond heteronuclear correlation solid-state NMR spectroscopy under fast MAS
journal, December 2009


A new family of mesoporous molecular sieves prepared with liquid crystal templates
journal, December 1992

  • Beck, J. S.; Vartuli, J. C.; Roth, W. J.
  • Journal of the American Chemical Society, Vol. 114, Issue 27, p. 10834-10843
  • DOI: 10.1021/ja00053a020

An Investigation of Weak CH···O Hydrogen Bonds in Maltose Anomers by a Combination of Calculation and Experimental Solid-State NMR Spectroscopy
journal, July 2005

  • Yates, Jonathan R.; Pham, Tran N.; Pickard, Chris J.
  • Journal of the American Chemical Society, Vol. 127, Issue 29
  • DOI: 10.1021/ja051019a

Polarity Control at Interfaces: Quantifying Pseudo-solvent Effects in Nano-confined Systems
journal, August 2016

  • Singappuli-Arachchige, Dilini; Manzano, J. Sebastian; Sherman, Lindy M.
  • ChemPhysChem, Vol. 17, Issue 19
  • DOI: 10.1002/cphc.201600740

Selective functionalization of the mesopores of SBA-15
journal, February 2015


Multifunctional hybrids by combining ordered mesoporous materials and macromolecular building blocks
journal, January 2011

  • Soler-Illia, Galo J. A. A.; Azzaroni, Omar
  • Chemical Society Reviews, Vol. 40, Issue 2, p. 1107-1150
  • DOI: 10.1039/c0cs00208a

Selective and Efficient Silylation of Mesoporous Silica: A Quantitative Assessment of Synthetic Strategies by Solid-State NMR
journal, March 2012

  • Hara, Kenji; Akahane, Saiko; Wiench, Jerzy W.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 12
  • DOI: 10.1021/jp300580f

Selective Functionalization of the Outer and Inner Surfaces in Mesoporous Silica Nanoparticles
journal, December 2008

  • Kecht, Johann; Schlossbauer, Axel; Bein, Thomas
  • Chemistry of Materials, Vol. 20, Issue 23
  • DOI: 10.1021/cm801484r

Analysis of networks of coupled spins by multiple quantum N.M.R.
journal, February 1983

  • Braunschweiler, Lukas; Bodenhausen, Geoffrey; Ernst, R. R.
  • Molecular Physics, Vol. 48, Issue 3
  • DOI: 10.1080/00268978300100381

Organic Functionalization and Morphology Control of Mesoporous Silicas via a Co-Condensation Synthesis Method
journal, November 2003

  • Huh, Seong; Wiench, Jerzy W.; Yoo, Ji-Chul
  • Chemistry of Materials, Vol. 15, Issue 22, p. 4247-4256
  • DOI: 10.1021/cm0210041

Hydrogen Bonding of Water Confined in Mesoporous Silica MCM-41 and SBA-15 Studied by 1 H Solid-State NMR
journal, October 2004

  • Grünberg, Bob; Emmler, Thomas; Gedat, Egbert
  • Chemistry - A European Journal, Vol. 10, Issue 22
  • DOI: 10.1002/chem.200400351

Spacing and Site Isolation of Amine Groups in 3-Aminopropyl-Grafted Silica Materials:  The Role of Protecting Groups
journal, October 2006

  • Hicks, Jason C.; Dabestani, Reza; Buchanan, A. C.
  • Chemistry of Materials, Vol. 18, Issue 21
  • DOI: 10.1021/cm061382w

Hybrid Inorganic-Organic Mesoporous Silicates—Nanoscopic Reactors Coming of Age
journal, October 2000


Dipolar truncation in magic-angle spinning NMR recoupling experiments
journal, March 2009

  • Bayro, Marvin J.; Huber, Matthias; Ramachandran, Ramesh
  • The Journal of Chemical Physics, Vol. 130, Issue 11
  • DOI: 10.1063/1.3089370

Luminescence of Tris(2,2‘-bipyridine)ruthenium(II) Cations ([Ru(bpy) 3 ] 2+ ) Adsorbed in Mesoporous Silicas Modified with Sulfonated Phenethyl Group
journal, August 2007

  • Sohmiya, Minoru; Sugahara, Yoshiyuki; Ogawa, Makoto
  • The Journal of Physical Chemistry B, Vol. 111, Issue 30
  • DOI: 10.1021/jp064654r

Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores
journal, January 1998


Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism
journal, October 1992

  • Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.
  • Nature, Vol. 359, Issue 6397, p. 710-712
  • DOI: 10.1038/359710a0

Selective Functionalization of Mesoporous Silica
journal, March 2000


Conformations of Silica-Bound (Pentafluorophenyl)propyl Groups Determined by Solid-State NMR Spectroscopy and Theoretical Calculations
journal, September 2010

  • Mao, Kanmi; Kobayashi, Takeshi; Wiench, Jerzy W.
  • Journal of the American Chemical Society, Vol. 132, Issue 35
  • DOI: 10.1021/ja105007b

    Works referencing / citing this record:

    A 29Si, 1H, and 13C Solid-State NMR Study on the Surface Species of Various Depolymerized Organosiloxanes at Silica Surface
    journal, May 2019

    • Protsak, Iryna S.; Morozov, Yevhenii M.; Dong, Wen
    • Nanoscale Research Letters, Vol. 14, Issue 1
    • DOI: 10.1186/s11671-019-2982-2