Monitoring the Activation Process of the Giant Pore MIL-100(Al) by Solid State NMR

Haouas, Mohamed; Volkringer, Christophe; Loiseau, Thierry; Férey, Gérard; Taulèlle, Francis

doi:10.1021/jp206513v

Cited by 76 publications

(166 citation statements)

References 55 publications

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“…The significant enhancement of e scan on/off E 13 for direct 13 C polarization (with MAS but without resorting to CP) corroborates the presence of TOTAPOL in the pores of MIL-100(Al) (Fig. S4a, ESI †).…”

Section: Larmor Frequenciessupporting

confidence: 61%

“…13 Fig. 1e and g show DNP enhancements per scan, e scan on/off E 8.5, which are identical for all 13 affect the linewidths of 27 Al and 13 C CP-MAS signals. 14 As for other biradicals, the build-up time of the DNP-induced 1 H polarization is equal to T 1 ( 1 H) = 0.7 s, as determined without mw irradiation in the same sample.…”

Section: Larmor Frequenciesmentioning

confidence: 65%

“…Besides, DNP-enhanced 27 Al- 13 C correlation experiments prove that the MIL-100(Al) framework is not altered by impregnation with a TOTAPOL solution. So far, DNP of MOFs has only been demonstrated for 1D spectra under Magic-Angle Spinning (MAS) using 1 H -13 C and 1 H -15 N cross-polarisation (CP) and 2D 1 H- 13 C correlation spectroscopy of In-based MIL-68. 10 So far, 27 Al DNP has only been reported for g-and mesoporous alumina.…”

Section: Larmor Frequenciesmentioning

confidence: 86%

“…We report here the first observation of 27 Al- 13 C proximities in MOFs using advanced NMR methods combined with a frequency splitter. 7,8 We show that Dynamic Nuclear Polarization (DNP) can significantly reduce acquisition times for MIL-100(Al) at 100 K. EPR spectroscopy and DNP enhancements prove that the biradical TOTAPOL 9 enters the MIL-100(Al) cavities within tens of minutes, although its apertures are smaller than 0.88 nm.…”

Section: Larmor Frequenciesmentioning

confidence: 99%

“…The acquisition of these spectra was made possible by combining a frequency splitter with DNP for sensitivity enhancement. 7 Without DNP, no signal could be seen after three days in a D-HMQC spectrum of dry MIL-100(Al) using 1 H -13 C CP excitation (CP-D-HMQC) and 13 C detection (denoted 13 C-{ 27 Al} hereafter), whereas the signal-to-noise ratio (S/N) of the CP-D-HMQC spectrum with 27 Al detection (denoted 27 Al-{ 13 C}) was S/N o 2 after 17 h (Fig. S7, ESI †).…”

Section: Larmor Frequenciesmentioning

confidence: 99%

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Probing²⁷Al–¹³C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

et al. 2014

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We show how 27 Al-13 C proximities in the microporous metal-organic framework MIL-100(Al) can be probed using advanced 27 Al-13 C NMR methods boosted by Dynamic Nuclear Polarization.Metal-organic frameworks (MOFs) have attracted increasing attention owing to their high surface area and their wide range of three-dimensional (3D) architectures that exhibit different pore apertures and chemical tunabilities. These hybrid materials represent promising systems for gas storage, catalysis, capture of radioactive compounds, and drug delivery. 1 Amongst them, aluminium-based MOFs, such as MIL-100(Al), 2 present many advantages, including low cost, density and toxicity, remarkable thermal stability and high Lewis acidity that should allow many industrial applications. 3 Rational design of MOFs requires a clear understanding of structure-property relationships and hence calls for characterization methods endowed with atomic resolution. In particular, solid-state NMR is well suited to assess structural models of MOF frameworks, to probe the organization of extra-framework entities, 4 and to analyze atomic-level dynamics. 5,6 However, the poor sensitivity of NMR limits the observation of adsorbed species, defects, etc., particularly when the observed nuclei have low gyromagnetic ratios, low natural abundances or long longitudinal relaxation times (T 1 ). Besides, the observation of 27 Al-13 C proximities by NMR in Al-based MOFs has hitherto been hindered by limitations of common NMR probes, which cannot be tuned simultaneously to nearby 27 Al and 13 C Larmor frequencies. We report here the first observation of 27 Al-13 C proximities in MOFs using advanced NMR methods combined with a frequency splitter. 7,8 We show that Dynamic Nuclear Polarization (DNP) can significantly reduce acquisition times for MIL-100(Al) at 100 K. EPR spectroscopy and DNP enhancements prove that the biradical TOTAPOL 9 enters the MIL-100(Al) cavities within tens of minutes, although its apertures are smaller than 0.88 nm. Besides, DNP-enhanced 27 Al-13 C correlation experiments prove that the MIL-100(Al) framework is not altered by impregnation with a TOTAPOL solution. So far, DNP of MOFs has only been demonstrated for 1D spectra under Magic-Angle Spinning (MAS) using 1

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Section: Larmor Frequenciessupporting

confidence: 61%

Section: Larmor Frequenciesmentioning

confidence: 65%

Section: Larmor Frequenciesmentioning

confidence: 86%

Section: Larmor Frequenciesmentioning

confidence: 99%

Section: Larmor Frequenciesmentioning

confidence: 99%

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Probing²⁷Al–¹³C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

et al. 2014

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The Use of²⁷Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years

Martineau

Taulèlle

Haouas

2016

Patai's Chemistry of Functional Groups

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Use of 27 Al nuclear magnetic resonance (NMR) spectroscopy for the study of the chemistry of aluminum in a variety of compounds during the last 25 years is reported. A compilation of NMR data, including chemical shifts and heteronuclear scalar couplings, is provided for a wide range of families of aluminum compounds in both solution and solid state. Recent methodological and technological advances in the field of quadrupolar NMR are detailed and their applications to 27 Al nucleus are illustrated. The potential of this technique is exemplified with some representative studies of relevance to mineral, biological, and organic aluminum‐based systems.

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Nuclear Magnetic Resonance of Metal-Organic Frameworks (MOFs)

Brückner

Pallmann

Brunner

2016

The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization, and Applications

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Monitoring the Activation Process of the Giant Pore MIL-100(Al) by Solid State NMR

Cited by 76 publications

References 55 publications

Probing²⁷Al–¹³C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

Probing²⁷Al–¹³C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

The Use of²⁷Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years

Nuclear Magnetic Resonance of Metal-Organic Frameworks (MOFs)

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Monitoring the Activation Process of the Giant Pore MIL-100(Al) by Solid State NMR

Cited by 76 publications

References 55 publications

Probing27Al–13C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

Probing27Al–13C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

The Use of27Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years

Nuclear Magnetic Resonance of Metal-Organic Frameworks (MOFs)

Contact Info

Product

Resources

About

Probing²⁷Al–¹³C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

Probing²⁷Al–¹³C proximities in metal–organic frameworks using dynamic nuclear polarization enhanced NMR spectroscopy

The Use of²⁷Al NMRto Study Aluminum Compounds: A Survey of the Last 25 Years