Recent progress in solid‐state nuclear magnetic resonance of half‐integer spin low‐<i>γ</i> quadrupolar nuclei applied to inorganic materials

Smith, Mark E.

doi:10.1002/mrc.5116

Cited by 20 publications

(22 citation statements)

References 236 publications

(453 reference statements)

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“…One technique that is particularly well-suited to study the connection between atomic structure and ionic mobility of specific atomic species is solid-state nuclear magnetic resonance (ssNMR) spectroscopy . The development of probes that are able to operate over the temperature range of interest for CO 2 capture has meant that gleaning specific mechanistic information at realistic temperatures is possible. , There have been a number of studies using 7 Li ssNMR to elucidate mechanisms of Li ion mobility in different materials.…”

Section: Mechanistic Insights Into Parameters Influencing Co2 Absorpt...mentioning

confidence: 99%

CO₂ Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

et al. 2021

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Carbon dioxide capture and mitigation form a key part of the technological response to combat climate change and reduce CO2 emissions. Solid materials capable of reversibly absorbing CO2 have been the focus of intense research for the past two decades, with promising stability and low energy costs to implement and operate compared to the more widely used liquid amines. In this review, we explore the fundamental aspects underpinning solid CO2 sorbents based on alkali and alkaline earth metal oxides operating at medium to high temperature: how their structure, chemical composition, and morphology impact their performance and long-term use. Various optimization strategies are outlined to improve upon the most promising materials, and we combine recent advances across disparate scientific disciplines, including materials discovery, synthesis, and in situ characterization, to present a coherent understanding of the mechanisms of CO2 absorption both at surfaces and within solid materials.

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Section: Mechanistic Insights Into Parameters Influencing Co2 Absorpt...mentioning

confidence: 99%

CO₂ Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

et al. 2021

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“…It is a distinct advantage to perform such experiments under very-fast MAS (here 79 kHz). Indeed, the spectral resolution is drastically increased leading to an Nevertheless four main experimental approaches have been successfully developed during the last few years: (i) using large volume rotors (7 mm, ~ 400 mg of sample) at high magnetic field (20 T), under moderate MAS (~ 5 kHz) and implementing DFS (Double Frequency Sweep) excitation scheme (section 7), (ii) using much smaller rotors (3.2 mm, ~ 20 mg of sample at to strongly enhance the 43 Ca polarization, usually in the indirect mode (from 1 H to 43 Ca), (iv) labeling in 43 Ca (starting from an enriched calcite precursor) (Laurencin et al, 2021;Smith, 2020;Laurencin and Smith, 2013). Here, we follow the approach (i) which is by far the easiest to implement in most NMR facilities worldwide (as long as a low-γ probe is available).…”

Section: T2*( 1 H) Editing and 1 H− 1 H Dq Experimentsmentioning

confidence: 99%

A novel multinuclear solid state NMR approach for the characterization of kidney stones

Leroy¹,

Bonhomme-Coury²,

Gervais³

et al. 2021

Preprint

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Abstract. The spectroscopic study of pathological calcifications (including kidney stones) is extremely rich and helps to improve the understanding of the physical and chemical processes associated with their formation. While FTIR imaging and optical/electron microscopies are routine techniques in hospitals, there has been a dearth of solid state NMR studies introduced into this area of medical research, probably due to the scarcity of this analytical technique in hospital facilities. This work introduces effective multinuclear and multi-dimensional solid state NMR methodologies to study the complex chemical and structural properties characterising kidney stone composition. As a basis for comparison three hydrates (n = 1, 2 and 3) of calcium oxalate are examined along with nine representative kidney stones. The multinuclear MAS NMR approach adopted investigates the 1H, 13C, 31P and 43Ca nuclei, with the 1H and 13C MAS NMR data able to be readily deconvoluted into the constituent elements associated with the different oxalates and organics present. For the first time, the full interpretation of highly resolved 1H NMR spectra is presented for the three hydrates, based on structure and local dynamics. The corresponding 31P MAS NMR data indicates the presence of low-level inorganic phosphate species, however the complexity of these data make the precise identification of the phases difficult to assign. This work provides physicians, urologists and nephrologists with additional avenues of spectroscopic investigation to interrogate this complex medical dilemma that requires real multi technique approaches to generate effective outcomes.

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“…From an NMR perspective, all atoms present in these phases have at least one NMR-active isotope which can be studied by NMR, making them potentially attractive targets of analysis: 1 H (I = 1/2, 100% natural abundance), 13 C (I = 1/2, 1.07% natural abundance), 17 O (I = 5/2, 0.04% natural abundance) and 67 Zn (I = 5/2, 4.11% natural abundance). Even though 67 Zn NMR has recently shown promising results for providing a detailed description of zinc local environments, it is still considered as very challenging, [83] because of the quadrupolar nature of zinc-67 (which can lead to very broad lines), [84] and its poor receptivity (low natural abundance and very low resonance frequency (νL( 67 Zn) < 10% νL( 1 H)). [83], [85] In the present work, we thus set our focus on the other 3 nuclei ( 13 C, 17 O and 1 H) to reach a more detailed description of the binding mode of the dicarboxylate ligands and for positioning the H-atoms of the hydroxyls within the structures.…”

Section: Kinetic Study Of the Transformationsmentioning

confidence: 99%

“…Even though 67 Zn NMR has recently shown promising results for providing a detailed description of zinc local environments, it is still considered as very challenging, [83] because of the quadrupolar nature of zinc-67 (which can lead to very broad lines), [84] and its poor receptivity (low natural abundance and very low resonance frequency (νL( 67 Zn) < 10% νL( 1 H)). [83], [85] In the present work, we thus set our focus on the other 3 nuclei ( 13 C, 17 O and 1 H) to reach a more detailed description of the binding mode of the dicarboxylate ligands and for positioning the H-atoms of the hydroxyls within the structures.…”

Section: Kinetic Study Of the Transformationsmentioning

confidence: 99%

From operando Raman mechanochemistry to "NMR crystallography": understanding the structures and interconversion of Zn-terephthalate networks using selective 17O-labelling.

Leroy

Métro

Hung

et al. 2021

Preprint

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The description of the formation, structure and reactivity of coordination networks and MOFs remains a real challenge in a number of cases. This is notably true for compounds composed of Zn2+ ions and terephthalate ligands (benzene 1,4-dicarboxylate, BDC), because of the difficulties in isolating them as pure phases and/or because of the presence of structural defects. Here, using mechanochemistry in combination with operando Raman spectroscopy, the observation of the formation of various zinc-terephthalate compounds was rendered possible, allowing the distinction and isolation of three intermediates during the ball-milling synthesis of Zn3(OH)4(BDC). An “NMR crystallography” approach was then used, combining solid-state NMR (1H, 13C and 17O) and DFT calculations, in order to refine the poorly described crystallographic structures of these phases. Particularly noteworthy are the high-resolution 17O NMR analyses, which were made possible in a highly efficient and cost-effective way, thanks to the selective 17O-enrichment of either hydroxyl or terephthalate groups by ball-milling. This allowed the presence of defect sites to be identified for the first time in one of the phases, and the nature of the H-bonding network of the hydroxyls to be established in another. Lastly, the possibility of using deuterated precursors (e.g. D2O and d4-BDC) during ball-milling is also introduced, as a means for observing specific transformations during operando Raman spectroscopy studies, that would not have been possible with hydrogenated equivalents. Overall, the synthetic and spectroscopic approaches developed herein are expected to push forward the understanding of the structure and reactivity of other complex coordination networks and MOFs.

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Recent progress in solid‐state nuclear magnetic resonance of half‐integer spin low‐γ quadrupolar nuclei applied to inorganic materials

Cited by 20 publications

References 236 publications

CO₂ Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

CO₂ Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

A novel multinuclear solid state NMR approach for the characterization of kidney stones

From operando Raman mechanochemistry to "NMR crystallography": understanding the structures and interconversion of Zn-terephthalate networks using selective 17O-labelling.

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Recent progress in solid‐state nuclear magnetic resonance of half‐integer spin low‐γ quadrupolar nuclei applied to inorganic materials

Cited by 20 publications

References 236 publications

CO2 Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

CO2 Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

A novel multinuclear solid state NMR approach for the characterization of kidney stones

From operando Raman mechanochemistry to "NMR crystallography": understanding the structures and interconversion of Zn-terephthalate networks using selective 17O-labelling.

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Product

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CO₂ Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances

CO₂ Capture at Medium to High Temperature Using Solid Oxide-Based Sorbents: Fundamental Aspects, Mechanistic Insights, and Recent Advances