Understanding Cu(i) local environments in MOFs via63/65Cu NMR spectroscopy.

The field of metal-organic frameworks (MOFs) includes a vast number of hybrid organic and inorganic porous materials with wide-ranging applications. In particular, the Cu(i) ion exhibits rich coordination chemistry in MOFs and can exist in two-, three-, and four-coordinate environments, which gives rise to many structural motifs and potential applications. Direct characterization of the structurally and chemically important Cu(i) local environments is essential for understanding the sources of specific MOF properties. For the first time, 63/65Cu solid-state NMR has been used to investigate a variety of Cu(i) sites and local coordination geometries in Cu MOFs. This approach is a sensitive probe of the local Cu environment, particularly when combined with density functional theory calculations. A wide range of structurally-dependent 63/65Cu NMR parameters have been observed, including 65Cu quadrupolar coupling constants ranging from 18.8 to 74.8 MHz. Using the data from this and prior studies, a correlation between Cu quadrupolar coupling constants, Cu coordination number, and local Cu coordination geometry has been established. Links between DFT-calculated and experimental Cu NMR parameters are also presented. Several case studies illustrate the feasibility of 63/65Cu NMR for investigating and resolving inequivalent Cu sites, monitoring MOF phase changes, interrogating the Cu oxidation number, and characterizing the product of a MOF chemical reaction involving Cu(ii) reduction to Cu(i). A convenient avenue to acquire accurate 65Cu NMR spectra and NMR parameters from Cu(i) MOFs at a widely accessible magnetic field of 9.4 T is described, with a demonstrated practical application for tracking Cu(i) coordination evolution during MOF anion exchange. This work showcases the power of 63/65Cu solid-state NMR spectroscopy and DFT calculations for molecular-level characterization of Cu(i) centers in MOFs, along with the potential of this protocol for investigating a wide variety of MOF structural changes and processes important for practical applications. This approach has broad applications for examining Cu(i) centers in other weight-dilute systems.

Enhancing CO2 adsorption capacity of ZIF-8 by synergetic effect of high pressure and temperature.

Metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) are promising porous materials for adsorption and storage of greenhouse gases, especially CO2. In this study, guided by the CO2 phase diagram, we explore the adsorption behavior of solid CO2 loaded with ZIF-8 framework by heating the sample under high pressures, resulting in a drastic improvement in the CO2 uptake. The behavior of CO2 under simultaneous high temperature (T) and pressure (P) conditions is directly monitored by in situ FTIR spectroscopy. The remarkable enhancement in CO2 adsorption capability observed can be attributed to the synergetic effect of high T and P: high temperature greatly enhances the transport property of solid CO2 by facilitating its diffusion into the framework; high pressure effectively modifies the pore size and shape via changing the linker orientation and creating new adsorption sites within ZIF-8. Our study thus provides important new insights into the tunability and enhancement of CO2 adsorptive capability in MOFs/ZIFs using pressure and temperature combined as a synergetic approach.

Developing Insoluble Polyoxometalate Clusters to Bridge Homogeneous and Heterogeneous Water Oxidation Photocatalysis.

Cluster catalysts are attractive for their atomically precise structures, defined compositions, tunable coordination environments, uniform active sites, and their ability to transfer multiple electrons, but they suffer from poor stability and recyclability. Here, we report a general approach to the direct insolubilization of a water soluble polyoxometalate (POM) [{(B-α-PW9 O34 )Co3 (OH)(H2 O)2 (O3 PC(O)-(C3 H6 NH3 )PO3 )}2 Co]14- (Co7 ) and formation of a series of POM-based solid catalysts with the counter-cations Ag+ , Cs+ , Sr2+ , Ba2+ , Pb2+ , Y3+ , and Ce3+ . They exhibit improved catalytic activities for visible-light-driven water oxidation following the trend CsCo7 >SrCo7 >AgCo7 >CeIII Co7 >BaCo7 >YCo7 >PbCo7 . While CsCo7 exhibits mainly homogeneous catalysis, the others are predominantly heterogeneous catalysts. An optimal oxygen yield of 41.3 % and a high apparent quantum yield (AQY) of 30.6 % for SrCo7 is obtained, which is comparable to that of the parent homogeneous POM. Band gap structures, UV/Vis spectra, and real-time laser flash photolysis experiments collectively suggest that easier electron transfer from the solid POM catalyst to the photosensitizer promotes photocatalytic water oxidation performance. These solid POM catalysts exhibit good stability, which is directly confirmed by a combination of Fourier-transform infrared spectroscopy, electron microscopy, X-ray diffraction patterns, Raman spectroscopy, X-ray photoelectron spectroscopy, five cycles of tests, and poisoning experiments.

Multinuclear solid-state NMR: Unveiling the local structure of defective MOF MIL-120.

Metal-organic frameworks (MOFs) are emerging materials with many current and potential applications due to their unique properties. One critical feature is that the physical and chemical properties of MOFs are tunable. One of the methods for tuning MOF properties is to introduce defects by design for desired applications. Characterization of MOF defects is important, but very challenging due to the local nature and short-range ordering. In this work, we have introduced the ordered vacancies (the defects) in the form of the coordinatively unsaturated sites (CUSs) into the framework of MOF MIL-120(Al). The creation of ordered vacancies is achieved by replacing one quarter of the BTEC (1,2,4,5-benzenetetracarboxylate) with BDC (benzene-1,4-dicarboxylate) linkers. Both parent and defective MOFs were characterized by multinuclear solid-state NMR spectroscopy. 1H MAS NMR is used to characterize the hydrogen bonding in these MOFs, whereas 13C CP MAS NMR confirms unambiguously that the BDC is incorporated into the framework. One-dimensional 27Al MAS NMR provides direct evidence of the coordinatively unsaturated Al sites (the defects). Furthermore, 27Al 3QMAS experiments at 21.1 â€‹T allow direct identification of one penta-coordinated and three chemically inequivalent octahedral Al sites in the defective MIL-120(Al). Two of the above-mentioned octahedral Al sites are in the domain which appears defect-free. The third octahedral Al site is near the defective site. This work clearly demonstrates the power of solid-state NMR spectroscopy for characterization of defective MOFs.

Estimation of sarcopenia prevalence in individuals at different ages from Zheijang province in China.

In this study, we analyzed sarcopenia prevalence and the cut-off points for skeletal muscle mass index (SMI), gait speed, and handgrip strength in young (18-39 years), middle-aged (40-59 years), and elderly (>60 years) individuals (n=1685) from Zhejiang Province in China. The prevalence of sarcopenia among individuals above 65 years was 2.21%, 4.87%, 5.31%, 14.16%, and 16.37% according to five diagnostic criteria (AWGS2019, AWGS2014, EWGSOP1, EWGSOP2, and local standard). The mean SMI (Kg/m2) was 7.961±0.7966, 7.801±0.7276, and 7.544±0.7493, respectively, in young, middle-aged, and elderly males. The mean SMI in young, middle-aged, and elderly females was 6.1570±0.5658, 6.604±0.5658, and 6.248±0.7483, respectively. SMI correlated negatively with age (r=-0.2344, P<0.001), but was not associated with age in females (r=0.0573, P=0.1463). The cut-off point of SMI for sarcopenia was ≤6.3678 kg/m2 in males and ≤5.0254 kg/m2 in females. These findings shows that the prevalence of sarcopenia increased gradually with age and varied significantly based on the diagnostic criteria used for this analysis. The mean SMI of young women was lower than in middle-aged women, making them an unsuitable reference population for determining cut-off values for sarcopenia diagnosis.

Ultramicropore Engineering by Dehydration to Enable Molecular Sieving of H2 by Calcium Trimesate.

The high energy footprint of commodity gas purification and increasing demand for gases require new approaches to gas separation. Kinetic separation of gas mixtures through molecular sieving can enable separation by molecular size or shape exclusion. Physisorbents must exhibit the right pore diameter to enable separation, but the 0.3-0.4 nm range relevant to small gas molecules is hard to control. Herein, dehydration of the ultramicroporous metal-organic framework Ca-trimesate, Ca(HBTC)⋅H2 O (H3 BTC=trimesic acid), bnn-1-Ca-H2 O, affords a narrow pore variant, Ca(HBTC), bnn-1-Ca. Whereas bnn-1-Ca-H2 O (pore diameter 0.34 nm) exhibits ultra-high CO2 /N2 , CO2 /CH4 , and C2 H2 /C2 H4 binary selectivity, bnn-1-Ca (pore diameter 0.31 nm) offers ideal selectivity for H2 /CO2 and H2 /N2 under cryogenic conditions. Ca-trimesate, the first physisorbent to exhibit H2 sieving under cryogenic conditions, could be a prototype for a general approach to exert precise control over pore diameter in physisorbents.

Anhydride Post-Synthetic Modification in a Hierarchical Metal-Organic Framework.

Metal-organic frameworks (MOFs) are important porous materials. Post-synthetic modification (PSM) of MOFs via the pendant groups or secondary functional groups of organic linkers has been widely used to introduce new or enhance existing properties of MOFs for various practical applications. In this work, we have constructed, for the first time, a novel platform for PSM of MOFs by introducing an anhydride functional group into a hierarchically porous MOF (MIL-121) as an effective anchor. We have demonstrated that the combination of the high reactivity of anhydride and hierarchical porosity makes this protocol particularly novel and important, as it led to excellent opportunities of incorporating not only a wide variety of organic molecules with different sizes and chemical nature but also the noble metal complexes in MOFs. Specifically, we show that the anhydride group decorated in the MOF exhibits a high reactivity toward covalently binding 10 different guest molecules including alcohols, amines, thiols, and noble metal (Pt(II)/Pt(IV)) complexes, whereas the hierarchical pores created in the MOF allow the incorporation of guest species varying in size from methanol to larger molecules such as polyaromatic amines. This novel approach provides the community with a new avenue to prepare MOF-based materials for targeted applications. To illustrate this point, we furnish an example of using this new platform to prepare a Pt-based electrocatalyst which shows excellent catalytic activity toward the oxygen reduction reaction (ORR), a pivotal half-reaction in hydrogen-oxygen fuel cells and other energy storage and conversion devices.

Cleaving Carboxyls: Understanding Thermally Triggered Hierarchical Pores in the Metal-Organic Framework MIL-121.

Carboxylic acid linker ligands are known to form strong metal-carboxylate bonds to afford many different variations of permanently microporous metal-organic frameworks (MOFs). A controlled approach to decarboxylation of the ligands in carboxylate-based MOFs could result in structural modifications, offering scope to improve existing properties or to unlock entirely new properties. In this work, we demonstrate that the microporous MOF MIL-121 is transformed to a hierarchically porous MOF via thermally triggered decarboxylation of its linker. Decarboxylation and the introduction of hierarchical porosity increases the surface area of this material from 13 to 908 m2/g and enhances gas adsorption uptake for industrially relevant gases (i.e., CO2, C2H2, C2H4, and CH4). For example, CO2 uptake in hierarchically porous MIL-121 is improved 8.5 times over MIL-121, reaching 215.7 cm3/g at 195 K and 1 bar; CH4 uptake is 132.3 cm3/g at 298 K and 80 bar in hierarchically porous MIL-121 versus zero in unmodified MIL-121. The approach taken was validated using a related aluminum-based MOF, ISOMIL-53. However, many specifics of the decarboxylation procedure in MOFs have yet to be unraveled and demand prompt examination. Decarboxylation, the formation of heterogeneous hierarchical pores, gas uptakes, and host-guest interactions are comprehensively investigated using variable-temperature multinuclear solid-state NMR spectroscopy, X-ray diffraction, electron microscopy, and gas adsorption; we propose a mechanism for how decarboxylation proceeds and which local structural features are involved. Understanding the complex relationship among the molecular-level MOF structure, thermal stability, and the decarboxylation process is essential to fine-tune MOF porosity, thus offering a systematic approach to the design of hierarchically porous, custom-built MOFs suited for targeted applications.

CO Guest Interactions in SDB-Based Metal-Organic Frameworks: A Solid-State Nuclear Magnetic Resonance Investigation.

Metal-organic frameworks (MOFs) are promising materials for greener carbon monoxide (CO) capture and separation processes. SDB-based (SDB = 4,4'-sulfonyldibenzoate) MOFs are particularly attractive due to their remarkable gas adsorption capacity under humid conditions. However, to the best of our knowledge, their CO adsorption abilities have yet to be investigated. In this report, CO-loaded PbSDB and CdSDB were characterized using variable-temperature (VT) 13C solid-state nuclear magnetic resonance (SSNMR) spectroscopy. These MOFs readily captured CO, with the adsorbed CO exhibiting dynamics as indicated by the temperature-dependent changes in the SSNMR spectra. Spectral simulations revealed that the CO simultaneously undergoes a localized wobbling about the adsorption site and a nonlocalized hopping between adjacent adsorption sites. The wobbling and hopping angles were also found to be temperature-dependent. From the appearance of the VT spectra and the extracted motional data, the CO adsorption mechanism was concluded to be analogous to that of CO2. To gain a better understanding on the gas adsorption properties of these MOFs and their CO capture abilities, we subsequently compared the motional data to those reported for CO2 in SDB-based MOFs and CO in MOF-74, respectively. A significant contrast in adsorption strength was observed in both cases because of the different physical properties of the guests (i.e., CO vs CO2) and the MOF frameworks (i.e., SDB-based MOFs vs MOFs with open metal sites). Our results demonstrate that SSNMR spectroscopy can be employed to probe variations in binding behavior.

Elucidation of the Structural Origins and Contrasting Guest-Host Interactions in CO2 -Loaded CdSDB and PbSDB Metal-Organic Frameworks at High Pressures.

PbSDB and CdSDB (SDB=4,4'-sulfonyldibenzoate) are two structurally related SDB-based metal-organic frameworks (MOFs) that demonstrate promising potential for selective CO2 adsorption capabilities. The structural stabilities and guest-host interactions between CO2 and PbSDB or CdSDB frameworks at high pressures up to 13 GPa in situ were comparatively investigated by Raman spectroscopy, FTIR spectroscopy, and synchrotron X-ray diffraction. Although both empty frameworks exhibited high chemical stabilities upon compression, they show different pressure-induced modifications in crystallinity. This difference can be attributed to their different coordination topologies that result in near isotropic contraction of unit cells for the CdSDB framework but anisotropic for the PbSDB framework. Furthermore, the CO2 -loaded PbSDB and CdSDB frameworks at high pressures show strongly contrasting guest-host interactions in terms of the pressure-regulated CO2 adsorption sites. In both frameworks, pressure can highly efficiently promote the formation of new CO2 adsorption sites and the enhancement of guest-host interactions. In the CO2 -loaded PbSDB framework, in particular, the peculiar pressure-tuned CO2 population was observed preferentially on one of the two adsorption sites in response to external compression. These unique guest-host interaction behaviors can also be unambiguously correlated to their different topological origins. These findings for the PbSDB and CdSDB frameworks provide in-depth understanding of the structure-property relationship, which is of fundamental importance for CO2 storage application in SDB-based MOFs.

Loading across the Periodic Table: Introducing 14 Different Metal Ions To Enhance Metal-Organic Framework Performance.

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+, Mg2+, Ca2+, Ba2+, Zn2+, Co2+, Mn2+, Ag+, Cd2+, La3+, In3+, and Pb2+) 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 H2 and CO2 adsorption; Ag nanoparticle-loaded MIL-121 also demonstrates remarkable catalytic activity in the reduction of 4-nitrophenol.

Probing Calcium-Based Metal-Organic Frameworks via Natural Abundance 43 Ca Solid-State NMR Spectroscopy.

Calcium-based metal-organic frameworks (MOFs) are of high importance due to their low cost and bio-compatible metal centers. Understanding the local environment of calcium in these materials is critical for unraveling the origins of specific MOF properties. 43 Ca solid-state NMR spectroscopy is one of the very few techniques that can directly characterize calcium metal centers, however, the 43 Ca nucleus is a very challenging target for solid-state NMR spectroscopy due to its extremely low natural abundance and resonant frequency. In this work, natural abundance 43 Ca solid-state NMR spectroscopy, at a high magnetic field of 21.1 T, has been employed to characterize several calcium-based MOFs. We demonstrate that 43 Ca NMR spectra and quantum chemical calculations can probe the local structure of calcium metal centers within MOFs, investigate the presence of guests, and monitor phase changes.

Characterization of Metal-Organic Frameworks: Unlocking the Potential of Solid-State NMR.

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., 25Mg, 47/49Ti, 63/65Cu, 67Zn, 69/71Ga, 91Zr, 115In, 135/137Ba, 139La, 27Al) 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 1H, 13C, and 17O 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 resolution 1H 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 17O SSNMR work on MOFs is scarce due to the low natural abundance of 17O. 17O enriched MOFs can now be prepared in an efficient and economically feasible manner using solvothermal approaches involving labeled H217O water; the resulting 17O SSNMR spectra provide distinct spectral signatures of various key oxygen species in representative MOFs. MOFs are suitable for the capture of the greenhouse gas CO2 and the storage of energy carrier gases such as H2 and CH4. A better understanding of gas adsorption obtained using 13C, 2H, and 17O 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.

Graphene homojunction: closed-edge bilayer graphene by pseudospin interaction.

Depending on the sublattices they are propagated in, low-energy electrons or holes are labeled with pseudospin. By engineering pseudospin interactions, we propose that two critical features of a junction, i.e., band gap opening and spatial charge separation, can be realized in graphene layers with proper stacking. We also demonstrate theoretically that such a graphene diode may play a role in future pseudospin electronics such as for harvesting solar energy.

Stacking-Dependent Interlayer Coupling in Trilayer MoS2 with Broken Inversion Symmetry.

The stacking configuration in few-layer two-dimensional (2D) materials results in different structural symmetries and layer-to-layer interactions, and hence it provides a very useful parameter for tuning their electronic properties. For example, ABA-stacking trilayer graphene remains semimetallic similar to that of monolayer, while ABC-stacking is predicted to be a tunable band gap semiconductor under an external electric field. Such stacking dependence resulting from many-body interactions has recently been the focus of intense research activities. Here we demonstrate that few-layer MoS2 samples grown by chemical vapor deposition with different stacking configurations (AA, AB for bilayer; AAB, ABB, ABA, AAA for trilayer) exhibit distinct coupling phenomena in both photoluminescence and Raman spectra. By means of ultralow-frequency (ULF) Raman spectroscopy, we demonstrate that the evolution of interlayer interaction with various stacking configurations correlates strongly with layer-breathing mode (LBM) vibrations. Our ab initio calculations reveal that the layer-dependent properties arise from both the spin-orbit coupling (SOC) and interlayer coupling in different structural symmetries. Such detailed understanding provides useful guidance for future spintronics fabrication using various stacked few-layer MoS2 blocks.

Feedforward Categorization on AER Motion Events Using Cortex-Like Features in a Spiking Neural Network.

This paper introduces an event-driven feedforward categorization system, which takes data from a temporal contrast address event representation (AER) sensor. The proposed system extracts bio-inspired cortex-like features and discriminates different patterns using an AER based tempotron classifier (a network of leaky integrate-and-fire spiking neurons). One of the system's most appealing characteristics is its event-driven processing, with both input and features taking the form of address events (spikes). The system was evaluated on an AER posture dataset and compared with two recently developed bio-inspired models. Experimental results have shown that it consumes much less simulation time while still maintaining comparable performance. In addition, experiments on the Mixed National Institute of Standards and Technology (MNIST) image dataset have demonstrated that the proposed system can work not only on raw AER data but also on images (with a preprocessing step to convert images into AER events) and that it can maintain competitive accuracy even when noise is added. The system was further evaluated on the MNIST dynamic vision sensor dataset (in which data is recorded using an AER dynamic vision sensor), with testing accuracy of 88.14%.

Efficient feedforward categorization of objects and human postures with address-event image sensors.

This paper proposes an algorithm for feedforward categorization of objects and, in particular, human postures in real-time video sequences from address-event temporal-difference image sensors. The system employs an innovative combination of event based hardware and bio-inspired software architecture. An event-based temporal difference image sensor is used to provide input video sequences, while a software module extracts size and position invariant line features inspired by models of the primate visual cortex. The detected line features are organized into vectorial segments. After feature extraction, a modified line segment Hausdorff distance classifier combined with on-the-fly cluster-based size and position invariant categorization. The system can achieve about 90 percent average success rate in the categorization of human postures, while using only a small number of training samples. Compared to state-of-the-art bio-inspired categorization methods, the proposed algorithm requires less hardware resource, reduces the computation complexity by at least five times, and is an ideal candidate for hardware implementation with event-based circuits.