High-Resolution Solid-State NMR in St Andrews: Development and Applications
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
The proposal aims to provide modern equipment in St Andrews which will enable the development of new Nuclear Magnetic Resonance (NMR) experiments to provide insight into structure of solids. NMR spectroscopy utilises the inherent magnetism of atomic nuclei to probe the local structural and dynamic environment of a material. However, for solids the orientational dependence of many of the interactions which affect NMR spectra (and which are averaged in liquids by rapid molecular tumbling) results in large broadenings and uninformative spectra. Much work has focussed on the removal of this broadening through techniques such as magic-angle spinning (MAS) and multiple-quantum MAS (MQMAS). Recent improvements in magnet technology, hardware and methodological development have advanced solid-state NMR to the stage where it can now be employed to provide detailed information on chemically-complex systems of industrial, biological and geological relevance.We aim to use the new equipment to develop new experiments and improve existing techniques to acquire both high-resolution spectra, and provide structural information through experiments which correlate different nuclei (demonstrating, for example, the spatial proximity of two species or providing information on the nature of their chemical bonding). This type of information is a crucial step in linking the atomic scale structure of a material to its macroscopic properties. Furthermore, we will widen the applicability of these approaches to the more challenging and unusual nuclei present in many materials of industrial and commercial interest. These include nuclei with low sensitivity (89Y, 39K), low natural abundances (17O, 25Mg), long relaxation times (89Y), and larger quadrupolar couplings (45Sc, 71Ga, 93Nb) in materials where structural disorder, significant dynamic behaviour, or the presence of paramagnetic ions, for example, are a problem. The use of modern probe hardware and increased magnetic field strength will be crucial in achieving these goals.We will utilise these state-of-the-art experiments in a range of areas including 17O and 25Mg NMR of the high-pressure silicate minerals in the inner layers of the Earth, where NMR sensitivity is limited by the small amount of sample produced (typically 3-15 mg) in the high-pressure synthesis. Also we will study the local structure and ordering by 89Y, 17O and 119Sn NMR in pyrochlore ceramic materials, which have been proposed as host phases for the encapsulation and long-term storage of nuclear waste. A further area of interest is the characterisation of the local structure and geometry of microporous framework materials (through 27Al, 31P, 45Sc and 71Ga NMR), which have applications as catalysts and gas storage media.
Organisations
Publications
Griffin J
(2008)
Solid-State 17 O NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics
in The Journal of Physical Chemistry C
Han Z
(2009)
Novel Large-Pore Aluminophosphate Molecular Sieve STA-15 Prepared Using the Tetrapropylammonium Cation As a Structure Directing Agent
in Chemistry of Materials
Ashbrook S
(2009)
Transformation of AlPO-53 to JDF-2: Reversible Dehydration of a Templated Aluminophosphate Studied by MAS NMR and Diffraction
in The Journal of Physical Chemistry C
Reader S
(2009)
Cation Disorder in Pyrochlore Ceramics: 89 Y MAS NMR and First-Principles Calculations
in The Journal of Physical Chemistry C
Greer H
(2009)
Early stage reversed crystal growth of zeolite A and its phase transformation to sodalite.
in Journal of the American Chemical Society
Ashbrook SE
(2009)
Recent advances in solid-state NMR spectroscopy of quadrupolar nuclei.
in Physical chemistry chemical physics : PCCP
Byrne P
(2009)
Structure and NMR assignment in AlPO4-15: A combined study by diffraction, MAS NMR and first-principles calculations
in Solid State Sciences
Castro M
(2010)
Molecular Modeling, Multinuclear NMR, and Diffraction Studies in the Templated Synthesis and Characterization of the Aluminophosphate Molecular Sieve STA-2
in The Journal of Physical Chemistry C
Griffin JM
(2010)
Dynamics on the microsecond timescale in hydrous silicates studied by solid-state (2)H NMR spectroscopy.
in Physical chemistry chemical physics : PCCP
Johnston KE
(2010)
The polar phase of NaNbO(3): a combined study by powder diffraction, solid-state NMR, and first-principles calculations.
in Journal of the American Chemical Society
Griffin JM
(2010)
High-resolution (19)F MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate.
in Journal of the American Chemical Society
Modeshia D
(2010)
Disordered lithium niobate rock-salt materials prepared by hydrothermal synthesis
in Dalton Transactions
Wheatley P
(2010)
Task specific ionic liquids for the ionothermal synthesis of siliceous zeolites
in Chemical Science
Carnevale D
(2010)
Detecting solid-state reactivity in 10-hydroxy-10,9-boroxophenanthrene using NMR spectroscopy
in Tetrahedron
Griffin JM
(2011)
Observation of "hidden" magnesium: first-principles calculations and 25Mg solid-state NMR of enstatite.
in Solid state nuclear magnetic resonance
Mowat J
(2011)
Synthesis, characterisation and adsorption properties of microporous scandium carboxylates with rigid and flexible frameworks
in Microporous and Mesoporous Materials
Mitchell MR
(2011)
(119)Sn MAS NMR and first-principles calculations for the investigation of disorder in stannate pyrochlores.
in Physical chemistry chemical physics : PCCP
Johnston KE
(2011)
93Nb NMR and DFT investigation of the polymorphs of NaNbO3.
in Physical chemistry chemical physics : PCCP
Lorena Picone A
(2011)
A co-templating route to the synthesis of Cu SAPO STA-7, giving an active catalyst for the selective catalytic reduction of NO
in Microporous and Mesoporous Materials
Griffin J
(2011)
77 Se Solid-State NMR of Inorganic and Organoselenium Systems: A Combined Experimental and Computational Study
in The Journal of Physical Chemistry C
Amri M
(2012)
A Multinuclear Solid-State NMR Study of Templated and Calcined Chabazite-Type GaPO-34
in The Journal of Physical Chemistry C
Mowat JP
(2012)
A novel structural form of MIL-53 observed for the scandium analogue and its response to temperature variation and CO2 adsorption.
in Dalton transactions (Cambridge, England : 2003)
Wharmby M
(2012)
Synthesis and crystal chemistry of the STA-12 family of metal N,N'-piperazinebis(methylenephosphonate)s and applications of STA-12(Ni) in the separation of gases
in Microporous and Mesoporous Materials
Description | This grant funded new NMR equipment for the University of St Andrews, which has been used continuously for the last 8 years, producing many publications primarily concerned with the characterisation of local structure and disorder in materials. |
Exploitation Route | The work provides a fundamental insight into the structure of solids. Others may build on this to develop materials with new or better properties, and to exploit commercial opportunities. |
Sectors | Chemicals Energy |
URL | http://chemistry.st-andrews.ac.uk/staff/sa/group/Site/Home.html |