High-pressure Nuclear Magnetic Resonance Research Articles

Disentangling the Li-Ion transport and Boundary Phase Transition Processes in Li10 GeP2 S12 Electrolyte by In-Operando High-Pressure and High-Resolution NMR Spectroscopy.

Li-ion transport and phase transition of solid electrolytes are critical and fundamental issues governing the rate and cycling performances of solid-state batteries. In this work, in-operando high-pressure nuclear magnetic resonance (NMR) spectroscopy for the solid-state battery is developed and applied, in combination with 6 Li-tracer NMR and high-resolution NMR spectroscopy, to investigate the Li10 GeP2 S12 electrolyte under true-to-life operation conditions. The results reveal that the Li10 GeP2 S12 phase may become more disordered and a large amount of conductive metastable β-Li3 PS4 as the glassy matrix in the electrolyte transforms into less conductive phases, mainly γ-Li3 PS4 , when high current densities (e.g., ≥0.5mA cm-2 ) are applied to the electrolyte. The overall Li-transport also varies and shows a tendency of boundary phases and Li10 GeP2 S12 synergistic dominant conduction at high currents. Accordingly, a mechanism of structural change induced by stress variation due to the drastic morphological change during Li-In alloying at high currents, and the local Li+ diffusion coefficient discrepancy is proposed. These new findings of Li-ion transport and boundary phase transition in Li10 GeP2 S12 solid electrolyte under high-pressure and high current density are first reported and will help provide previously lacking insights into the relationship of structure and performance of Li10 GeP2 S12 .

Kinetics of Guest-Induced Structural Transitions in Metal–Organic-Framework MIL-53(Al)-NH2 Probed by High-Pressure Nuclear Magnetic Resonance

A nuclear magnetic resonance (NMR) study of a pore opening in amino-functionalized metal-organic framework (MOF) MIL-53(Al) in response to methane pressure variation is presented. Variations of both NMR signal intensities and transversal relaxation rates for methane are found to reveal hysteretic structural transitions in the MOF material, which are smeared out over broad pressure ranges. Experiments with pressure reversals upon an incomplete adsorption/desorption gave deeper insight into the microscopic transition mechanisms. These experiments have unequivocally proven that the non-stepwise pore opening/closing transitions observed in the experiments are governed by a distribution of the opening/closing pressures over different MOF crystallites, for example, due to a distribution of the crystal sizes or shapes. The slow kinetics of the structural transitions measured in the hysteresis regime revealed a complex free energy landscape for the phase transition process.

Superconductivity Experiments Confirm an Important Mechanism for Increasing the Maximum Critical Temperature in Cuprates

Some cuprate superconductors exhibit high critical temperatures at atmospheric pressure. To understand the underlying processes, researchers recently carried out high-pressure nuclear magnetic resonance experiments on the cuprate YBa2Cu3O6+y to determine the charge densities at the Cu and O sites of its CuO2 plane with high precision. Their results revealed that the more generous the in-plane Cu atoms are in transferring their hole content to the O atoms, the higher the critical temperatures that can be achieved.

Reppe‐Carbonylation of Alkenes with Carboxylic Acids: A Catalytic and Mechanistic Study

AbstractIn this work, a green‐catalytic procedure is used to demonstrate the synthesis of long‐chain anhydrides. This is accomplished by the carbonylation of alkenes with carboxylic acids. Anhydrides are important intermediates, finding specific applications as acetylation agents. The process is catalyzed by a Pd phosphine catalyst system in the presence of an acid promotor. Through optimization experiments, the importance of the phosphine ligand and acid promotor is demonstrated, without which the catalyst shows no activity. Although the yield was limited because of catalyst deactivation (42 %), to the best of our knowledge, the synthesis of long‐chain anhydrides through this route have not been reported previously. It therefore represents a significant result. Isolation of the anhydrides were also successfully demonstrated, however, as a result of the sensitivity of the anhydrides to water, the isolated yields were much lower than the HPLC yield. Furthermore, a mechanistic study by means of HP‐NMR (High Pressure Nuclear Magnetic Resonance) spectroscopy provided significant insights into the mechanism of the reaction.

Approaching Protein Aggregation and Structural Dynamics by Equilibrium and Nonequilibrium Paramagnetic Perturbation.

PENELOP (Paramagnetic Equilibrium vs Nonequilibrium magnetization Enhancement or LOss Perturbation) is the presented nuclear magnetic resonance (NMR) approach to identify at once the location of proteins' exposed surface, hindered accessibility, and exchange processes occurring on a μs-ms time scale. In addition to mapping the protein surface accessibility, the application of this method under specific conditions makes it possible to distinguish conformational mobility and chemical exchange processes, thereby providing an alternative to characterization by more demanding techniques (transverse relaxation dispersion, saturation transfer, and high-pressure NMR). Moreover, its high sensitivity enables studying samples at low, physiologically more relevant concentrations. Association, dynamics, and oligomerization are addressed by PENELOP for a component of SARS-CoV-2 replication transcription complex and an amyloidogenic protein.

A Smart Colorimetric Platform for Detection of Methanol, Ethanol and Formic Acid.

Carbon dioxide (CO2) is a greenhouse gas in the atmosphere and scientists are working on converting it to useful products, thereby reducing its quantity in the atmosphere. For converting CO2, different approaches are used, and among them, electrochemistry is found to be the most common and more efficient technique. Current methods for detecting the products of electrochemical CO2 conversion are time-consuming and complex. To combat this, a simple, cost-effective colorimetric method has been developed to detect methanol, ethanol, and formic acid, which are formed electrochemically from CO2. In the present work, the highly efficient sensitive dyes were successfully established to detect these three compounds under optimized conditions. These dyes demonstrated excellent selectivity and showed no cross-reaction with other products generated in the CO2 conversion system. In the analysis using these three compounds, this strategy shows good specificity and limit of detection (LOD, ~0.03–0.06 ppm). A cost-effective and sensitive Internet of Things (IoT) colorimetric sensor prototype was developed to implement these dyes systems for practical and real-time application. Employing the dyes as sensing elements, the prototype exhibits unique red, green, and blue (RGB) values upon exposure to test solutions with a short response time of 2 s. Detection of these compounds via this new approach has been proven effective by comparing them with nuclear magnetic resonance (NMR). This novel approach can replace heavy-duty instruments such as high-pressure liquid chromatography (HPLC), gas chromatography (G.C.), and NMR due to its extraordinary selectivity and rapidity.

In situ high-pressure nuclear magnetic resonance crystallography in one and two dimensions

Recent developments in in situ nuclear magnetic resonance (NMR) spectroscopy under extreme conditions have led to the observation of a wide variety of physical phenomena that are not accessible with standard high-pressure experimental probes. However, inherent di- or quadrupolar line broadening in diamond anvil cell (DAC)-based NMR experiments often limits detailed investigation of local atomic structures, especially if different phases or local environments coexist. Here, we describe our progress in the development of high-resolution NMR experiments in DACs using one- and two-dimensional homonuclear decoupling experiments at pressures up to the megabar regime. Using this technique, spectral resolutions of the order of 1 ppm and below have been achieved, enabling high-pressure structural analysis. Several examples are presented that demonstrate the wide applicability of this method for extreme conditions research.

Absence of proton tunneling during the hydrogen-bond symmetrization in δ−AlOOH

$\delta$-AlOOH is of significant crystallochemical interest due to a subtle structural transition near 10 GPa from a $P2_1nm$ to a $Pnnm$ structure, the nature and origin of hydrogen disorder, the symmetrization of the O-H$\cdots$O hydrogen bond and their interplay. We perform a series of density functional theory based simulations in combination with high-pressure nuclear magnetic resonance experiments on $\delta$-AlOOH up to 40 GPa with the goal to better characterize the hydrogen potential and therefore the nature of hydrogen disorder. Simulations predict a phase transition in agreement with our nuclear magnetic resonance experiments at $10-11$ GPa and hydrogen bond symmetrization at $14.7$ GPa. Calculated hydrogen potentials do not show any double-well character and there is no evidence for proton tunneling in our nuclear magnetic resonance data.

Nonmagnetic-magnetic transition and magnetically ordered structure in SmS

SmS, a prototypical intermediate valence compound, has been studied by performing high-pressure nuclear magnetic resonance measurements on a $^{33}$S-enriched sample. The observation of an additional signal below 15-20 K above a nonmagnetic-magnetic transition pressure $P_{\rm c2} \approx 2$ GPa gives evidence of a magnetic transition. The absence of a Curie-term in the Knight shift near $P_{\rm c2}$ indicates that the localized character of $4f$ electrons is entirely screened and the mechanism of the magnetic ordering is not described within a simple localized model. Simultaneously, the line shape in the magnetically ordered state is incompatible with a spin density wave order. These suggest that the magnetic order in SmS may require an understanding beyond the conventional framework for heavy fermions. The fact that hyperfine fields from the ordered moments cancel out at the S site leads us to a conclusion that the ordered phase has a type II antiferromagnetic structure.

Nuclear spin coupling crossover in dense molecular hydrogen

One of the most striking properties of molecular hydrogen is the coupling between molecular rotational properties and nuclear spin orientations, giving rise to the spin isomers ortho- and para-hydrogen. At high pressure, as intermolecular interactions increase significantly, the free rotation of H2 molecules is increasingly hindered, and consequently a modification of the coupling between molecular rotational properties and the nuclear spin system can be anticipated. To date, high-pressure experimental methods have not been able to observe nuclear spin states at pressures approaching 100 GPa (Meier, Annu. Rep. NMR Spectrosc. 94:1–74, 2017; Meier, Prog. Nucl. Magn. Reson. Spectrosc. 106–107:26–36, 2018) and consequently the effect of high pressure on the nuclear spin statistics could not be directly measured. Here, we present in-situ high-pressure nuclear magnetic resonance data on molecular hydrogen in its hexagonal phase I up to 123 GPa at room temperature. While our measurements confirm the presence of ortho-hydrogen at low pressures, above 70 GPa, we observe a crossover in the nuclear spin statistics from a spin-1 quadrupolar to a spin-1/2 dipolar system, evidencing the loss of spin isomer distinction. These observations represent a unique case of a nuclear spin crossover phenomenon in quantum solids.

High-Temperature and High-Pressure In situ Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy.

Nuclear magnetic resonance (NMR) spectroscopy represents an important technique to understand the structure and bonding environments of molecules. There exists a drive to characterize materials under conditions relevant to the chemical process of interest. To address this, in situ high-temperature, high-pressure MAS NMR methods have been developed to enable the observation of chemical interactions over a range of pressures (vacuum to several hundred bar) and temperatures (well below 0 °C to 250 °C). Further, the chemical identity of the samples can be comprised of solids, liquids, and gases or mixtures of the three. The method incorporates all-zirconia NMR rotors (sample holder for MAS NMR) which can be sealed using a threaded cap to compress an O-ring. This rotor exhibits great chemical resistance, temperature compatibility, low NMR background, and can withstand high pressures. These combined factors enable it to be utilized in a wide range of system combinations, which in turn permit its use in diverse fields as carbon sequestration, catalysis, material science, geochemistry, and biology. The flexibility of this technique makes it an attractive option for scientists from numerous disciplines.

Proton mobility in metallic copper hydride from high-pressure nuclear magnetic resonance

Atomic and electronic structures of Cu2H and CuH have been investigated by high pressure NMR spectroscopy, X-ray diffraction and ab-initio calculations. Metallic Cu2H was synthesized at a pressure of 40 GPa, and semi-metallic CuH at 90 GPa, found stable up to 160 GPa. Experiments and computations suggest the formation of a metallic 1H-sublattice as well as a high 1H mobility of ~10-7 cm2/s in Cu2H. Comparison of Cu2H and FeH data suggests that deviations from Fermi gas behavior, formation of conductive hydrogen networks, and high 1H mobility could be common features of metal hydrides.

Application of the combination of high-pressure mercury injection and nuclear magnetic resonance to the classification and evaluation of tight sandstone reservoirs: A case study of the Linxing Block in the Ordos Basin

Tight sandstone gas reservoirs have poorer porosity–permeability relationships, so conventional reservoir classification schemes can hardly satisfy the classification and evaluation demand of this type of reservoirs. To solve this problem, this paper took the Permian tight sandstone gas reservoir in the Linxing Block along the eastern margin of the Ordos Basin as an example to describe the micro-structures of the tight sandstone reservoirs by means of high-pressure mercury injection, nuclear magnetic resonance (NMR), scanning electron microscope (SEM) and so on. Then, the control effect of micro-structure parameters on the macrophysical properties was studied. Finally, classification and evaluation of tight sandstone reservoirs were carried out on this basis. And the following research results were obtained. First, NMR can identify the distribution of pores of different sizes, and high-pressure mercury injection can reflect the pore–throat configuration and percolation capacity of a reservoir. Second, both methods are better coincident in the description results. With an increase of the right peak of T2 spectra, the mercury intrusion curve presents a concave shape and the pore throat radius increases while the pore type gradually changes from intragranular dissolution pores and intercrystalline pores to intergranular pores and intergranular dissolution pores and the reservoir quality gets better. Third, micro-pore structure controls reservoir physical properties and fluid mobility. And the porosity of large pores is best correlated with the effective porosity, so it can be used to evaluate the reservoir capacity of tight sandstone. Fourth, the throat radius R15 obtained by high pressure mercury injection is in the best correlation with porosity and permeability, so it can be used to evaluate the percolation capacity of tight sandstone. Fifth, by combining the porosity of large pores with the R15, the tight sandstone reservoirs in the Linxing Block are classified into 4 categories, and the classification results are in a good agreement with the on-site well test data. It is concluded that the combination of high-pressure mercury injection and NMR can effectively identify the key parameters which reflect the reservoir capacity and percolation capacity of tight sandstone, and improve the reliability and integrity of reservoir classification. And by selecting the key parameters that reflect reservoir capacity and percolation capacity, it can provide guidance for the classification and evaluation of tight sandstone reservoirs.

Boron needle stitches carbon thread

Organic Chemistry The Fischer-Tropsch process relies on transition metal catalysis at high temperature to stitch together carbon monoxide and hydrogen into hydrocarbon chains. Phanopoulos et al. now report that a pair of boron reagents can do something similar at room temperature, albeit less efficiently. Specifically, the combination of a terminal alkyl borane and triethylborohydride can catenate as many as eight carbon monoxide equivalents, producing a mixture of linear aldehydes after oxidative workup. Theoretical simulations and high-pressure nuclear magnetic resonance spectroscopy elucidated the catalytic role of the terminal boron center. J. Am. Chem. Soc. 142 , 14064 (2020).

High-temperature and high-pressure NMR investigations of low viscous fluids confined in mesoporous systems

Abstract In this contribution, the relaxation and diffusional behaviors of low viscous fluids, water and methanol confined into mesoporous silica and controlled size pore glass were investigated. The engineered porous systems are relevant to geologically important subsurface energy materials. The engineered porous proxies were characterized by Brunauer–Emmett–Teller (BET) surface analyzer, nuclear magnetic resonance (NMR) spectroscopy, and electron microscopy (EM) to determine surface area, pore-wall protonation and morphology of these materials, respectively. The confined behavior of the low viscous fluids was studied by varying pore diameter, fluid-to-solid ratio, temperature, and pressure, and then compared to bulk liquid state. Both relaxation and diffusion behaviors for the confined fluids showed increasing deviation from pure bulk fluids as the fluid-to-solid ratio was decreased, and surface-to-volume ratio (S/V) was varied. Variable pressure deuteron NMR relaxation of confined D2O and confined methanol, deuterated at the hydroxyl or methyl positions, were performed to exploit the sensitivity of the deuteron quadrupole moment to molecular rotation. The methanol results demonstrated greater pressure dependence than those for water only in bulk. The deviations from bulk liquid behavior arise from different reasons such as confinement and the interactions between confined fluid and the nano-pore wall. The results of the present report give insight into the behavior of low viscosity fluid in nano-confined geometries under different state conditions.

Experimental evaluation of the salt dissolution in inter-salt shale oil reservoirs

By using salt dissolution experiment, imbibition experiment and high temperature and high pressure nuclear magnetic resonance (NMR) on-line test, the evaluation methods for salt dissolution of inter salt shale oil-bearing cores were established, and the effects of salt dissolution on spontaneous imbibition and permeability were analyzed. The intensity of salt dissolution is quantitatively evaluated by comparing the signal quantity and distribution characteristics of T2 spectrum (transverse relaxation time) measured at different times. In salt dissolution experiment, salt in the core is gradually dissolved as the injected water is continuously immersed in the core. The spontaneous imbibition experiment of inter-salt shale oil-bearing core can be divided into three stages: strong imbibition and weak salt dissolution, strong salt dissolution promoting imbibition, and weak salt dissolution and weak imbibition. The salt dissolution in spontaneous imbibition is very obvious, and the salt dissolution contributes more than 60% of recovery. The micro-pore structure in different cross sections or different parts of inter-salt shale oil-bearing core isn't uniform, and the pore volume, porosity and permeability increase after salt dissolution.

Experimental study on EOR by CO2 huff-n-puff and CO2 flooding in tight conglomerate reservoirs with pore scale

CO2-assisted EOR technologies appear to be low-cost and eco-friendly means to boost crude oil production of dense reservoirs. The potential of CO2 huff-n-puff process and CO2 flooding processes have been extensively investigated in tight sandstone reservoirs, while few work has been done in tight conglomerate reservoirs, which exhibit strong micro-heterogeneity. In the present work, we quantitatively investigated the potential of CO2 injection processes in tight conglomerate reservoirs under reservoir conditions (formation pressure 23 MPa, temperature 69 °C). High temperature and high pressure nuclear magnetic resonance (NMR) online monitoring system was used to pore-scale monitoring the change of oil saturation in-situ through NMR T2 spectrum, one-dimensional (1D) NMR spatial distribution of signal and two-dimensional (2D) NMR images. It was demonstrated that CO2 injection processes were applicable in target tight conglomerate reservoir with recovery factors of about 35%. The results of this study pore-scale revealed the feasibility of CO2-assisted EOR technologies in tight conglomerate reservoirs.

Two-Phase Fluid Flow Experiments Monitored by NMR

We present a newly developed high-pressure nuclear magnetic resonance (NMR) flow cell, which allows for the simultaneous determination of water saturation, effective gas permeability and NMR relaxation time distribution in two-phase fluid flow experiments. We introduce both the experimental setup and the experimental procedure on a tight Rotliegend sandstone sample. The initially fully water saturated sample is systematically drained by a stepwise increase of gas (Nitrogen) inlet pressure and the drainage process is continuously monitored by low field NMR relaxation measurements. After correction of the data for temperature fluctuations, the monitored changes in water saturation proved very accurate. The experimental procedure provides quantitative information about the total water saturation as well as about its distribution within the pore space at defined differential pressure conditions. Furthermore, the relationship between water saturation and relative (or effective) apparent permeability is directly determined.

Table-top nuclear magnetic resonance system for high-pressure studies with in situ laser heating.

High pressure Nuclear Magnetic Resonance (NMR) is known to reveal the behavior of matter under extreme conditions. However, until now, significant maintenance demands, space requirements, and high costs of superconducting magnets render its application unfeasible for regular modern high pressure laboratories. Here, we present a table-top NMR system based on permanent Halbach magnet arrays with a diameter of 25 cm and height of 4 cm. At the highest field of 1013 mT, 1H-NMR spectra of ice VII have been recorded at 25 GPa and ambient temperature. The table-top NMR system can be used together with double sided laser heating setups. Feasibility of high-pressure high-temperature NMR was demonstrated by collecting 1H-NMR spectra of H2O at 25 GPa and 1063(50) K. The change in the signal intensity in a laser-heated NMR diamond anvil cell has been found to yield a convenient way for temperature measurements.

Local unfolding of the HSP27 monomer regulates chaperone activity

The small heat-shock protein HSP27 is a redox-sensitive molecular chaperone that is expressed throughout the human body. Here, we describe redox-induced changes to the structure, dynamics, and function of HSP27 and its conserved α-crystallin domain (ACD). While HSP27 assembles into oligomers, we show that the monomers formed upon reduction are highly active chaperones in vitro, but are susceptible to self-aggregation. By using relaxation dispersion and high-pressure nuclear magnetic resonance (NMR) spectroscopy, we observe that the pair of β-strands that mediate dimerisation partially unfold in the monomer. We note that numerous HSP27 mutations associated with inherited neuropathies cluster to this dynamic region. High levels of sequence conservation in ACDs from mammalian sHSPs suggest that the exposed, disordered interface present in free monomers or oligomeric subunits may be a general, functional feature of sHSPs.