Deconvolution of metal apportionment in bulk metal-organic frameworks

Xu, Jingyi; Liu, Xing-Wu; Liu, Xingchen; Yan, Tao; Wan, Hongliu; Cao, Zhi; Reimer, Jeffrey A.

doi:10.1126/sciadv.add5503

Cited by 8 publications

(7 citation statements)

References 58 publications

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“…Although the assignment of 1 H peaks to μ 3 -OH and μ 1 -H 2 O hydrogens is straightforward, further assignment of individual peaks to a corresponding crystallographically distinct hydrogen site is much more challenging, especially for μ 3 -OH hydrogens because their local environments are very similar. In recent years, it has been described that DFT calculations are reliable in predicting the relative peak positions for sequential NMR peaks in various systems. − ,, Accordingly, the calculated 1 H δ iso values were used to tentatively assign the resolved 1 H peaks to hydrogen sites within crystal structure of LYH-Br (Table ). For example, the order of calculated δ iso values for μ 3 -OH is H7 < H8 < H5 < H6 < H9 < H10 < H3 < H1 < H4 < H2.…”

Section: Resultsmentioning

confidence: 99%

“…In recent years, it has been described that DFT calculations are reliable in predicting the relative peak positions for sequential NMR peaks in various systems. [29][30][31][32]66,67 Accordingly, the calculated 1 H δ iso values were used to tentatively assign the resolved 1 H peaks to hydrogen sites within crystal structure of LYH-Br (Table 1). For example, the order of calculated δ iso values for μ 3 -OH is H7 < H8 < H5 < H6 < H9 < H10 < H3 < H1 < H4 < H2.…”

Section: Identification Of Hydrous Speciesmentioning

confidence: 99%

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Mapping Hydrogens in Hydrous Materials

et al. 2023

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Hydrous materials such as clays, cements, hydroxyapatite, and metal hydroxides have been known and extensively used since antiquity. However, experimental elucidation of hydrogen in hydrous materials remains challenging due to the intrinsic insensitivity, limited accessibility, sample damage, or poor spectral resolution of many characterization methods. 1 H solid-state NMR spectroscopy has evolved into an ideal site-specific characterization tool of hydrogen-containing materials, but its current application in hydrous materials is hampered by the low resolution of 1 H NMR spectra in the solid state due to the presence of intense dipolar coupling networks and a narrow 1 H chemical shift range. Herein, a significant advance in the characterization of hydrogens in hydrous materials is reported. A combination of magic-angle spinning (MAS) NMR, moderate 2 H substitution, and high magnetic fields has unlocked the capacity of identifying many chemically similar while crystallographically distinct hydrogen sites in a prototypical hydrous material Y 4 (OH) 10 Br 2 •3H 2 O (LYH-Br) by 1D 1 H solid-state NMR experiments. 1 H NMR peaks were first tentatively assigned in accordance with the density functional theory (DFT) calculation results, and the assignment was further refined by 2D 1 H− 89 Y heteronuclear correlation (HETCOR) and 1 H− 1 H doublequantum (DQ) MAS NMR data. The order of 1 H chemical shift (δ iso ) values provides valuable information on the relative strength of hydrogen bond for ten hydroxide hydrogen sites. The power of very high spectral resolution is further described by observing all triple-quantum (TQ) coherences in the 2D 1 H− 1 H TQ MAS NMR spectrum, in which all spatial proximities among three hydrogen sites are resolved. This demonstration of the very high spectral resolution obtained in 1D and 2D 1 H solid-state NMR experiments illustrates how scientists in various communities can now study the multiple hydrous species of hydrous materials and obtain previously inaccessible fine structural information.

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Section: Resultsmentioning

confidence: 99%

Section: Identification Of Hydrous Speciesmentioning

confidence: 99%

Mapping Hydrogens in Hydrous Materials

et al. 2023

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“…[21][22][23][24][25][26][27] However, the performance of a material depends on its internal structure, such as the atomic structure, atomic bonding, atomic arrangement, and so on. 28 Therefore, through studying the structure and properties of titanium alloys at the atomic scale, a better understanding of their deformation behavior can be achieved. Meanwhile, it is also crucial for designing more optimized titanium alloys.…”

Section: Introductionmentioning

confidence: 99%

Deformation mechanisms based on the multiscale molecular dynamics of a gradient TA1 titanium alloy

Jiang,

Feng,

Tao

2024

Nanoscale

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“…However, the application of SSNMR spectroscopy in resolving the spatial apportionment of metal ions has been rarely explored ( 23 ). Recently, we developed a general route to deconvolute the metal apportionment in bulk mixed-metal MOFs using SSNMR spectroscopy, exemplified by the study of Mg 1− x Ni x -MOF-74 ( 24 ). The efficacy of the SSNMR strategy stems from the effects of paramagnetic Ni 2+ ions ( S = 1) on the carboxylate 13 C signals of organic ligands, enabling the experimental identification and quantification of multiple (eight) atomic-scale metal apportionments in MOFs with infinite number of metal permutations.…”

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confidence: 99%

Unraveling the molecular mechanism for enhanced gas adsorption in mixed-metal MOFs via solid-state NMR spectroscopy

Yan,

Hou,

et al. 2024

Proc. Natl. Acad. Sci. U.S.A.

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The incorporation of multiple metal ions in metal–organic frameworks (MOFs) through one-pot synthesis can induce unique properties originating from specific atomic-scale spatial apportionment, but the extraction of this crucial information poses challenges. Herein, nondestructive solid-state NMR spectroscopy was used to discern the atomic-scale metal apportionment in a series of bulk Mg 1− x Co x -MOF-74 samples via identification and quantification of eight distinct arrangements of Mg/Co ions labeled with a 13 C-carboxylate, relative to Co content. Due to the structural characteristics of metal-oxygen chains, the number of metal permutations is infinite for Mg 1− x Co x -MOF-74, making the resolution of atomic-scale metal apportionment particularly challenging. The results were then employed in density functional theory calculations to unravel the molecular mechanism underlying the macroscopic adsorption properties of several industrially significant gases. It is found that the incorporation of weak adsorption sites (Mg 2+ for CO and Co 2+ for CO 2 adsorption) into the MOF structure counterintuitively boosts the gas adsorption energy on strong sites (Co 2+ for CO and Mg 2+ for CO 2 adsorption). Such effect is significant even for Co 2+ remote from Mg 2+ in the metal-oxygen chain, resulting in a greater enhancement of CO adsorption across a broad composition range, while the enhancement of CO 2 adsorption is restricted to Mg 2+ with adjacent Co 2+ . Dynamic breakthrough measurements unambiguously verified the trend in gas adsorption as a function of metal composition. This research thus illuminates the interplay between atomic-scale structures and macroscopic gas adsorption properties in mixed-metal MOFs and derived materials, paving the way for developing superior functional materials.

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Deconvolution of metal apportionment in bulk metal-organic frameworks

Cited by 8 publications

References 58 publications

Mapping Hydrogens in Hydrous Materials

Mapping Hydrogens in Hydrous Materials

Deformation mechanisms based on the multiscale molecular dynamics of a gradient TA1 titanium alloy

Unraveling the molecular mechanism for enhanced gas adsorption in mixed-metal MOFs via solid-state NMR spectroscopy

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