Efficient acquisition of ultra-wideline solid-state NMR powder patterns is a continuing challenge. In particular, when the breadth of the powder pattern is much larger than the cross-polarization (CP) excitation bandwidth, transfer efficiencies suffer and experimental times are greatly increased. Presented herein is a CP pulse sequence with an excitation bandwidth that is up to ten times greater than that available from a conventional spin-locked CP pulse sequence. The pulse sequence, broadband adiabatic inversion CP (BRAIN-CP), makes use of the broad, uniformly large frequency profiles of chirped inversion pulses, to provide these same characteristics to the polarization transfer process. A detailed theoretical analysis is given, providing insight into the polarization transfer process involved in BRAIN-CP. Experiments on spin-1/2 nuclei including (119)Sn, (199)Hg and (195)Pt nuclei are presented, and the large bandwidth improvements possible with BRAIN-CP are demonstrated. Furthermore, it is shown that BRAIN-CP can be combined with broadband frequency-swept versions of the Carr-Purcell-Meiboom-Gill experiment (for instance with WURST-CPMG, or WCPMG for brevity); the combined BRAIN-CP/WCPMG experiment then provides multiplicative signal enhancements of both CP and multiple-echo acquisition over a broad frequency region.
Microporous metal-organic frameworks (MOFs) have high surface areas and porosities, and are well-suited for CO2 capture. MIL-53 features corner-sharing MO4(OH)2 (M = Al, Ga, Cr, etc.) octahedra interconnected by benzenedicarboxylate linkers that form one-dimensional rhombic tunnels, and exhibits an excellent adsorption ability for guest molecules such as CO2. Studying the behavior of adsorbed CO2 in MIL-53 via solid-state NMR (SSNMR) provides rich information on the dynamic motion of guest molecules as well as their binding strengths to the MOF host, and sheds light on the specific guest adsorption mechanisms. Variable-temperature (13)C SSNMR spectra of (13)CO2 adsorbed within various forms of MIL-53 are acquired and analyzed. CO2 undergoes a combination of two motions within MIL-53; we report the types of motion present, their rates, and rotational angles. (1)H-(13)C CP SSNMR experiments are used to examine the proximity of (1)H atoms in the MOF to (13)C atoms in CO2 guests. By replacing (1)H with (2)H in MIL-53, the location of the CO2 adsorption site in MIL-53 is experimentally confirmed by (1)H-(13)C CP SSNMR. The binding strength of CO2 within these MIL-53 MOFs follows the order MIL-53-NH2 (Al) > MIL-53-NH2 (Ga) > MIL-53 (Al) > MIL-53 (Ga).
Loading metal guests within metal-organic frameworks (MOFs) via secondary functional groups is a promising route for introducing or enhancing MOF performance in various applications. In this work, 14 metal ions (Li, Na, K, Mg, Ca, Ba, Zn, Co, Mn, Ag, Cd, La, In, and Pb) have been successfully introduced within the MIL-121 MOF using a cost-efficient route involving free carboxylic groups on the linker. The local and long-range structure of the metal-loaded MOFs is characterized using multinuclear solid-state NMR and X-ray diffraction methods. Li/Mg/Ca-loaded MIL-121 and Ag nanoparticle-loaded MIL-121 exhibit enhanced H and CO adsorption; Ag nanoparticle-loaded MIL-121 also demonstrates remarkable catalytic activity in the reduction of 4-nitrophenol.
Metal−organic frameworks (MOFs) have shown great promise for the adsorption and separation of gases, including the greenhouse gas CO 2 . In order to improve performance and realize practical applications for MOFs as CO 2 adsorbents, a deeper understanding of the number and type of CO 2 adsorption mechanisms must be unlocked, along with fine details of CO 2 motion within MOFs. Using several complementary characterization methods is a promising protocol for comprehensively investigating the various host− guest interactions between MOFs and CO 2 . In this work, a combination of solid state NMR (SSNMR) and single crystal X-ray diffraction (SCXRD) has been utilized to reveal both the location and dynamics of adsorbed CO 2 within the related PbSDB and CdSDB MOFs, as well as to probe the role of metal centers in CO 2 adsorption. 13 C SSNMR experiments targeting CO 2 reveal the number of unique adsorption sites and the types of CO 2 dynamics present, as well as their associated motional rates and angles. 111 Cd and 207 Pb SSNMR methods are used to probe the influence of CO 2 adsorption on the MOF metal centers, and also to investigate the possibility of any metal−guest interactions. SCXRD experiments yield the exact locations and occupancies of adsorbed CO 2 in both MOFs; by pairing this information with SSNMR data, a comprehensive model of CO 2 adsorption and dynamics in PbSDB and CdSDB has been established. Both MOFs share a common adsorption site in the V-shaped "π-pocket" formed by the phenyl rings of an individual V-shaped organic linker, while CdSDB also features an additional π-pocket adsorption site arising from the phenyl rings of two linkers joined by Cd. SCXRD and SSNMR data indicate that CO 2 adsorbed at the SDB-based π pocket in both MOFs exhibits a local rotation or "wobbling" at an individual adsorption site, as well as a nonlocalized jumping or "hopping" between symmetry-equivalent adsorption sites. The combined analysis of SCXRD and SSNMR data has the potential to yield rich information regarding guest dynamics, adsorption locations, and host−guest interactions in many MOFs.
An exciting advance in materials science is the discovery of hybrid organic-inorganic solids known as metal-organic frameworks (MOFs). Although they have numerous important applications, the local structures, specific molecular-level features, and guest behaviors underpinning desirable properties and applications are often unknown. Solid-state nuclear magnetic resonance (SSNMR) is a powerful tool for MOF characterization as it provides information complementary to that from X-ray diffraction (XRD). We describe our novel pursuits in the three primary applications of SSNMR for MOF characterization: interrogating the metal center, targeting linker molecules, and probing guests. MOFs have relatively low densities, and the incorporated metals are often quadrupolar nuclei, making SSNMR detection difficult. Recently, we examined the local structures of metal centers (i.e., Mg,Ti, Cu,Zn, Ga,Zr, In,Ba, La,Al) in representative MOFs by SSNMR at a high magnetic field of 21.1 T, addressing several important issues: (1) resolving chemically and crystallographically nonequivalent metal sites; (2) exploring the origin of disorder around metals; (3) refining local metal geometry; (4) probing the effects of activation and adsorption on the metal local environment; and (5) monitoring in situ phase changes in MOFs. Organic linkers can be characterized by H,C, and O SSNMR. Although the framework structure can be determined by X-ray diffraction, hydrogen atoms cannot be accurately located, and thus the local structure about hydrogen is poorly characterized. Our work demonstrates that magic-angle spinning (MAS) experiments at very high magnetic field along with ultrafast spinning rates and isotope dilution enables one to obtain ultrahigh resolutionH MAS spectra of MOFs, yielding structural information truly complementary to that obtained from single-crystal XRD. Oxygen is a key constituent of many important MOFs but O SSNMR work on MOFs is scarce due to the low natural abundance ofO. O enriched MOFs can now be prepared in an efficient and economically feasible manner using solvothermal approaches involving labeled HO water; the resulting O SSNMR spectra provide distinct spectral signatures of various key oxygen species in representative MOFs. MOFs are suitable for the capture of the greenhouse gas CO and the storage of energy carrier gases such as H and CH. A better understanding of gas adsorption obtained using C,H, and O SSNMR will enable researchers to improve performance and realize practical applications for MOFs as gas adsorbents and carriers. The combination of SSNMR with XRD allows us to determine the number of adsorption sites in the framework, identify the location of binding sites, gain physical insight into the nature and strength of host-guest interactions, and understand guest dynamics.
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