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An extensive correlated molecular orbital theory study of the reactions of CO2 with a range of substituted amines and H2O in the gas phase and aqueous solution was performed at the G3(MP2) level with a self-consistent reaction field approach. The G3(MP2) calculations were benchmarked at the CCSD(T)/CBS level for NH3 reactions. A catalytic NH3 reduces the energy barrier more than a catalytic H2O for the formation of H2NCOOH and H2CO3. In aqueous solution, the barriers to form both H2NCOOH and H2CO3 are reduced, with HCO3- formation possible with one amine present and H2NCOO- formation possible only with two amines. Further reactions of H2NCOOH to form HNCO and urea via the Bazarov reaction have high barriers and are unlikely in both the gas phase and aqueous solution. Reaction coordinates for CH3NH2, CH3CH2NH2, (CH3)2NH, CH3CH2CH2NH2, (CH3)3N, and DMAP were also calculated. The barrier for proton transfer correlates with amine basicity for alkylammonium carbamate (ΔG‡aq < 15 kcal/mol) and alkylammonium bicarbonate (ΔG‡aq < 30 kcal/mol) formation. In aqueous solution, carbamic acids, carbamates, and bicarbonates can all form in small amounts with ammonium carbamates dominating for primary and secondary alkylamines. These results have implications for CO2 capture by amines in both the gas phase and aqueous solution as well as in the solid state, if enough water is present.

Nesquehonite is a magnesium carbonate mineral relevant to carbon sequestration envisioned for carbon capture and storage of CO

The preferential adsorption of SOx versus water in Mg-MOF-74 from a humid SOx gas stream has been investigated via materials studies and nuclear magnetic resonance (NMR). Mg-MOF-74 has been synthesized and subsequently loaded simultaneously with water vapor and SOx (62-96 ppm) in an adsorption chamber at room temperature over a time period of 4 days with a sample taken every 24 h. Each sample was analyzed by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA)-mass spectrometry, and scanning electron microscopy-energy-dispersive spectroscopy. The metal-organic framework (MOF) showed retained crystallinity and peak intensity in PXRD, and after 2 days, it showed no obvious degradation to the structure. Use of multiple techniques, including TGA, identified 10% by weight of SOx species, specifically H2S and SO2, within the MOF. 1H solid-state NMR shows a substantial reduction of H2O when SOx is present, which is consistent with SOx preferentially binding to the oxophilic metal site of the framework. After 14 weeks aging, the sulfur remains present in the three-dimensional MOF, with only half being desorbed after 23 weeks in air.

Nonthermal plasma (NTP) offers a unique synthesis environment capable of producing nanocrystals of high melting point materials at relatively low gas temperatures. Despite the rapidly growing material library accessible through NTP synthesis, designing processes for new materials is predominantly empirically driven. Here, we report on the synthesis of both amorphous alumina and γ-Al2O3 nanocrystals and present a simple particle heating model that is suitable for predicting the plasma power necessary for crystallization. The heating model only requires the composition, temperature, and pressure of the background gas along with the reactor geometry to calculate the temperature of particles suspended in the plasma as a function of applied power. Complete crystallization of the nanoparticle population was observed when applied power was greater than the threshold where the calculated particle temperature is equal to the crystallization temperature of amorphous alumina.

The alkali metal salts of m-bromocinnamic acid and their photodimerization products are analyzed by solid-state NMR. Cesium, rubidium, and potassium salts show well-resolved signals in the 13C CPMA...

The structure of aluminum carbide (from two different manufacturers) has been interrogated by 27Al solid-state NMR in an effort to accurately characterize the material. Quadrupolar lineshapes for 2...

An in-depth study on post-synthetic modification of residual metal in carbide-derived carbons (CDCs) from an Al4C3 starting material has been performed. Ambient temperature high humidity studies reveal the conversion of residual parent nanoparticles to poly(aluminum chloride) (PAC). Alkaline modification was employed resulting in the formation of amorphous Al(OH)3 nanoparticles within 24 h of reaction. After aging for up to 11 days, amorphous nanoparticles convert to well-crystallized α-Al(OH)3 (bayerite). Al4C3-CDCs with amorphous Al(OH)3 display significantly-enhanced interactions with SO2 and CO2 while X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance infrared (ATR-IR) spectroscopy indicated no significant change in the surface chemistry of the carbon. SO2 breakthrough results at 1000 ppm SO2 exhibit uptakes near 2 mmol g−1, displaying viability for these adsorbents in flue gas remediation applications. The results of this work provide detailed modification strategies for tuning the extent and type of residual metal embedded in the final CDC structure, along with further insights into the ramifications of oxygen functionalities and pore size distribution of CDCs for SO2 adsorption.

An extensive correlated molecular orbital theory study of the reactions of CO

Nonthermal plasma (NTP) offers a unique synthesis environment capable of producing nanocrystals of high melting point materials at relatively low gas temperatures. Despite the rapidly growing material library accessible through NTP synthesis, designing processes for new materials is predominantly empirically driven. Here, we report on the synthesis of both amorphous alumina and γ-Al2O3 nanocrystals and present a simple particle heating model that is suitable for predicting the plasma power necessary for crystallization. The heating model only requires the composition, temperature, and pressure of the background gas along with the reactor geometry to calculate the temperature of particles suspended in the plasma as a function of applied power. Complete crystallization of the nanoparticle population was observed when applied power was greater than the threshold where the calculated particle temperature is equal to the crystallization temperature of amorphous alumina.

The physical phenomena governing hyperpolarization through optical pumping of conduction electrons continue to be explored in multiple semiconductor systems. One early finding has been the asymmetry between the optically pumped nuclear magnetic resonance (OPNMR) signals when generated by different circular polarizations (i.e., light helicities). Because these resonances are asymmetric, the midpoint between the signals prepared with each of the two circular polarizations is either a positive or negative value, termed an “offset” that is representative of an optical Overhauser enhancement. Both negative offsets (in GaAs) and positive offsets (in CdTe) have been observed. The origins of these offsets in semiconductors are believed to arise from thermalized electrons; however, to the best of our knowledge, no study has systematically tested this hypothesis. To that end, we have adopted two configurations for OPNMR experiments—one in which the Poynting vector of the laser light and magnetic field are parallel, and one in which they are antiparallel, while other experimental conditions are kept the same. We find that the OPNMR signal response to a fixed helicity of light depends on the experimental configuration, and this configuration needs to be accounted for in order to properly describe the OPNMR results. Further, studying the offsets as a function of field strength shows that the optical Overhauser enhancement (the offset) increases in magnitude with field strength. Finally, by describing all angular momentum and phasing conventions unambiguously, we are able to determine that the absorptively-phased appearance of 113 Cd (and 125 Te) OPNMR in CdTe is a consequence of the sign of the nuclear gyromagnetic ratios for these isotopes.

Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for obtaining precise information about the local bonding of materials, but difficult to interpret without a well-vetted dataset of reference spectra. The ability to predict NMR parameters and connect them to three-dimensional local environments is critical for understanding more complex, long-range interactions. New computational methods have revealed structural information available from 29Si solid-state NMR by generating computed reference spectra for solids. Such predictions are useful for the identification of new silicon-containing compounds, and serve as a starting point for determination of the local environments present in amorphous structures. In this study, we have used 42 silicon sites as a benchmarking set to compare experimentally reported 29Si solid-state NMR spectra with those computed by CASTEP-NMR and Vienna Ab Initio Simulation Program (VASP). Data-driven approaches enable us to identify the source of discrepancies across a range of experimental and computational results. The information from NMR (in the form of an NMR tensor) has been validated, and in some cases corrected, in an effort to catalog these for the local spectroscopy database infrastructure (LSDI), where over 10,000 29Si NMR tensors for crystalline materials have been computed. Knowledge of specific tensor values can serve as the basis for executing NMR experiments with precision, optimizing conditions to capture the elements accurately. The ability to predict and compare experimental observables from a wide range of structures can aid researchers in their chemical assignments and structure determination, since the computed values enables the extension beyond tables of typical chemical shift (or shielding) ranges.

Here, we employ a combination of 27Al solid-state nuclear magnetic resonance (SSNMR) and conventional spectroscopic and microscopic techniques to investigate the structural evolution of aqueous aluminum precursors to a uniform and smooth aluminum oxide film. The route involves no organic ligands and relies on dehydration, dehydroxylation, and nitrate loss for condensation and formation of the three-dimensional aluminum oxide structure. Local chemical environments are tracked as films evolve over the temperature range 200–1100 °C. 27Al SSNMR reveals that Al centers are predominantly four- and five-coordinate in amorphous films annealed between 200 and 800 °C and four- and six-coordinate in crystalline phases that form above 800 °C. The Al coordination of the aqueous-deposited aluminum oxide films are compared to data from SSNMR studies on vapor-phase-deposited aluminum oxide thin films. Additionally, dielectric constants of aluminum oxide-based capacitors are measured and correlated with the SSNMR results....

Most studies exploring the capture of CO2 on solid-supported amines have focused on unhindered amines or alkylimine polymers. It has been observed in extensive solution studies that another class of amines, namely sterically hindered amines, can exhibit enhanced CO2 capacity when compared to their unhindered counterparts. In contrast to solution studies, there has been limited research conducted on sterically hindered amines on solid supports. In this work, one hindered primary amine and two hindered secondary amines are grafted onto mesoporous silica at similar amine coverages, and their adsorption performances are investigated through fixed bed breakthrough experiments and thermogravimetric analysis. Furthermore, chemisorbed CO2 species formed on the sorbents under dry and humid conditions are elucidated using in situ Fourier-transform infrared spectroscopy. Ammonium bicarbonate formation and enhancement of CO2 adsorption capacity is observed for all supported hindered amines under humid conditions. Our...

We have identified a hydrated bicarbonate formed by chemisorption of 13CO2 on both dimethylaminopropylsilane (DMAPS) and aminopropylsilane (APS) pendant molecules grafted on SBA-15 mesoporous silica. The most commonly used sequence in solid-state NMR, 13C CPMAS, failed to detect bicarbonate in these solid amine sorbent samples; here, we have employed a Bloch decay ("pulse-acquire") sequence (with 1H decoupling) to detect such species. The water that is present contributes to the dynamic motion of the bicarbonate product, thwarting CPMAS but enabling direct 13C detection by shortening the spin-lattice relaxation time. Since solid-state NMR plays a major role in characterizing chemisorption reactions, these new insights that allow for the routine detection of previously elusive bicarbonate species (which are also challenging to observe in IR spectroscopy) represent an important advance. We note that employing this straightforward NMR technique can reveal the presence of bicarbonate that has often otherwise been overlooked, as demonstrated in APS, that has been thought to only contain adsorbed CO2 as carbamate and carbamic acid species. As in other systems (e.g., proteins), dynamic species that sample multiple environments tend to broaden as their motion is frozen out. Here, we show two distinct bicarbonate species upon freezing, and coupling to different protons is shown through preliminary 13C-1H HETCOR measurements. This work demonstrates that bicarbonates have likely been formed in the presence of water but have gone unobserved by NMR due to the nature of the experiments most routinely employed, a perspective that will transform the way the sorption community will view CO2 capture by amines.

The conventional synthesis of metal-organic frameworks (MOFs) through soluble metal-salt precursors provides little control over the growth of MOF crystals. The use of alternative metal precursors would provide a more flexible and cost-effective strategy for direction- and shape-controlled MOF synthesis. Here, we demonstrate for the first time the use of insoluble metal-carbon matrices to foster directed growth of MOFs. Aluminum carbide was implemented as both the metal precursor and growth-directing agent for the generation of MIL-53(Al). A unique needle-like morphology of the MOF was grown parallel to the bulk surface in a layer-by-layer manner. Importantly, the synthesis scheme was found to be transferrable to the production of different linker analogues of the MOF and other topologies. Given the variety of metal carbides available, these findings can be used as a blueprint for controlled, efficient, and economical MOF syntheses and set a new milestone toward the industrial use of MOFs at large-scale.

Materials composed of high-porosity solid supports, such as SBA-15, containing amine-bearing moieties inside the pores, such as 3-aminopropylsilane (APS), are envisioned for carbon dioxide capture; solid-state 15N NMR can be highly informative for studying chemisorption reactions. Two 15N-enriched samples with different APS loadings were studied to probe the identity of the pendant molecules and structure of the chemisorbed CO2 species. 15N cross-polarization magic-angle spinning NMR provides unique information about the amines, whether they are rigid or dynamic, by measuring contact time curves and rotating frame, T1ρ(15N), relaxation. Both carbamate and carbamic acid are formed; carbamic acid is shown to be less stable than carbamate. After desorption, a steady state for the chemisorbed reaction product is reached, leaving behind carbamate. 15N NMR monitors the evolution of the species over time. During desorption, APS is regenerated, but the ammonium propylsilane intensity does not change, leading us t...

Metal–organic frameworks (MOFs), such as MOF-74, can have open metal sites to which adsorbates such as CO2 preferentially bind. 13C NMR of 13CO2 is highly informative about the binding sites present in Mg-MOF-74. We used this technique to investigate loadings between ∼0.88 and 1.15 molecules of CO2 per metal in Mg-MOF-74 at 295 K. 13C lineshapes recorded as a function of loading can be understood in terms of the dependence of the CO2 NMR frequency on the angle (θ) with respect to the CO2 axis and the channel of the MOF, reflected in the Legendre polynomial, P2. In the fast motion limit, the NMR spectra reveal the time-averaged value of P2, where θ is the angle between the instantaneous CO2 axis and the channel axis. DFT calculations were used to determine a weighted average of P2 in this regime and are in good agreement with experimental data. Static variable temperature 13C NMR from cryogenic temperatures to room temperature was used to investigate 13CO2 binding in Mg-MOF-74 loaded at two levels (∼0.88 a...

Multiple chemisorption products are found from the interaction of CO2 with the solid-amine sorbent, 3-aminopropyl silane (APS), bound to mesoporous silica (SBA15) using solid-state NMR and FTIR spectroscopy. We employed a combination of both 15N{13C} rotational-echo double-resonance (REDOR) NMR and 13C{15N} REDOR to determine the chemical identity of these products. 15N{13C} REDOR measurements are consistent with a single 13C–15N pair and distance of 1.45 A. In contrast, both 13C{15N} REDOR and 13C CPMAS are consistent with multiple 13C products. 13C CPMAS shows two neighboring resonances, whose chemical shifts are consistent with carbamate (at 165 ppm) and carbamic acid. The 13C{15N} REDOR experiments resonant at 165 ppm show an incomplete buildup of the REDOR data to ∼90% of the expected maximum. We conclude this 10% missing intensity corresponds to a 13C NMR species that resonates at the identical chemical shift but that is not in dipolar contact with 15N. These data are consistent with the presence of...

Carbon dioxide (CO 2 ) injection into olivine-rich mafic and ultramafic rocks is expected to result in the precipitation of divalent metal carbonate minerals, permanently storing the CO 2 underground. Previous experiments that used unconsolidated forsterite (Mg 2 SiO 4 ) particles in experimental investigations of reactions with water and carbon dioxide have been useful for determining the identity, rates of formation, and spatial location of carbonate mineral reaction products. However there remains a need for information regarding the influence of the internal pore structure and grain boundary surfaces on the extent and locations of these reactions in dense aggregates. We conducted several experiments at 100 °C and 100 bar CO 2 using sintered San Carlos olivine (Fo 90 ) and pure forsterite (Fo 100 ) cylinders, and we documented the type and spatial distribution of the reaction products. Timing of carbonation was measured using in-situ 13 C NMR spectroscopy without removing the sample from the reactor. Ex-situ solid-state NMR spectroscopy, Raman spectroscopy, and electron microscopy were used to examine reacted samples and precipitates. Within 15 days, magnesite is observed only on the surface of Fo 90 . After 53 and 102 days of reaction, magnesite and amorphous silica are observed as a crust around the entire Fo 100 cylinder and as isolated layers within the sample. The spatial transition from an amorphous silica layer to the host Fo 100 indicates that the development of amorphous silica did not impede further forsterite dissolution. While earlier studies documented localized reactions at the grain scale, the development of distinct zones of magnesite and amorphous silica suggest that divalent metal cations are mobile during carbonation of olivine. Grain boundaries, pore structure, and geochemical gradients strongly influence the locations of silicate mineral dissolution and carbonate mineral precipitation even in the absence of advective transport or confinement. The clear spatial distribution of precipitates observed in this study indicates that carbonation in heterogeneous reservoirs may be strongly affected by grain-scale microstructure.

An in-depth study on the etching process for producing carbide-derived carbons from Al 4 C 3 has been performed. These materials were investigated at a range of etching temperatures from 300 to 900 °C and a range of times from 15 min to 6 h. By altering the etching time and temperature, the surface area, residual aluminum content, and pore size distribution can be tuned. A maximum surface area of 1126 m 2 g −1 was observed for materials etched at 500 °C for 1 h. The pore size has shown to be tunable from ≤0.7 to 8 nm. Interestingly, aluminum-based nanoparticles were observed via TEM and SEM for partially etched samples, with evidence of tunable metal species on the surface of the Al 4 C 3 -CDC samples at different etching temperatures between 300 and 700 °C. Characterization of the aluminum species present over this temperature range took place using solid-state 27 Al NMR. The formation of crystalline α-Al 2 O 3 was observed at etching temperatures of 700 °C. The results of this work provide detailed synthesis strategies for controlling not only the porosity and surface area of a carbide-derived carbon, but also the extent and type of residual metal nanoparticles embedded in the final structure.

We have measured the 75As signals arising from the interface region of single-crystal semi-insulating GaAs that has been coated and passivated with an aluminum oxide film deposited by atomic layer deposition (ALD) with optically pumped NMR (OPNMR). Using wavelength-selective optical pumping, the laser restricts the volume from which OPNMR signals are collected. Here, OPNMR signals were obtained from the interface region and distinguished from signals arising from the bulk. The interface region is highlighted by interactions that disrupt the cubic symmetry of the GaAs lattice, resulting in quadrupolar satellites for nuclear [Formula: see text] isotopes, whereas NMR of the "bulk" lattice is nominally unsplit. Quadrupolar splitting at the interface arises from strain based on lattice mismatch between the GaAs and ALD-deposited aluminum oxide due to their different coefficients of thermal expansion. Such spectroscopic evidence of strain can be useful for measuring lattice distortions at heterojunction boundaries and interfaces.

Polymers of intrinsic microporosity (PIMs) can be functionalized with nitrogen-bearing groups, such as a nitrile group for PIM-1 and a methylated tetrazole group for MTZ-PIM, to physisorb CO2. Static 13C NMR spectroscopy was used to investigate CO2 dynamics by analysis of onedimensional spectra and T2 relaxation times at temperatures ranging from 6 to 295 K. Each polymer had two different loadings of CO2 to determine the dominating relaxation mechanism at lower temperatures and deduce the identity of the weaker secondary adsorption site on the rigid polymer backbone. Both polymers, with a high loading of CO2, experience a narrowing of the 13C NMR line width as the samples are warmed to 80 K, which is the onset of the weakly adsorbed CO2 hopping on and off the polymer backbone.

Solid-state 71Ga NMR was used to characterize a series of [Ga13(μ3-OH)6(μ2-OH)18(H2O)](NO3)15 “Ga13” molecular clusters synthesized by multiple methods. These molecular clusters are precursors to thin film electronics and may be employed in energy applications. The synthetic routes provide varying levels of impurities in the solid phase, and these impurities often elude traditional characterization techniques such as powder X-ray diffraction and Raman spectroscopy. Solid-state NMR can provide a window into the gallium species even in amorphous phases. This information is vital in order to prevent the impurities from causing defect sites in the corresponding thin films upon gelation and condensation (polymerization) of the Ga13 clusters. This work demonstrates the resolving power of solid-state NMR to evaluate structure and synthetic quality in the solid state, and the application of high-field NMR to study quadrupolar species, such as 71Ga.

Solid-state NMR measurements coupled with density functional theory (DFT) calculations demonstrate how hydrogen positions can be refined in a crystalline system. The precision afforded by rotational-echo double-resonance (REDOR) NMR to interrogate

Most studies exploring the capture of CO

We have identified a hydrated bicarbonate formed by chemisorption of (13)CO(2) on both dimethylaminopropylsilane (DMAPS) and aminopropylsilane (APS) pendant molecules grafted on SBA-15 mesoporous silica. The most commonly-used sequence in solid-state NMR, (13)C CPMAS, failed to detect bicarbonate in these solid amine sorbent samples; here, we have employed a Bloch decay (“pulse-acquire”) sequence (with (1)H decoupling) to detect such species. The water that is present contributes to dynamic motion of the bicarbonate product, thwarting CPMAS but enabling direct (13)C detection by shortening the spin-lattice relaxation time. Since solid-state NMR plays a major role in characterizing chemisorption reactions, these new in-sights that allow for the routine detection of previously elusive bicarbonate species (which are also challenging to observe in IR spectroscopy) represents an important advance. We note that employing this straightforward NMR technique can reveal the presence of bicarbonate that has often otherwise been overlooked, as demonstrated in APS, that has been thought to only contain adsorbed CO(2) as carbamate and carbamic acid species. As in other systems (e.g. proteins), dynamic species that sample multiple environments tend to broaden as their motion is frozen out. Here, we show two distinct bicarbonate species upon freezing, and coupling to different protons is shown through preliminary (13)C-(1)H HETCOR measurements. This work demonstrates that bicarbonates have likely been formed in the presence of water but have gone unobserved by NMR due to the nature of the experiments most routinely employed, perspective that will transform the way the sorption community will view CO(2) capture by amines.

Hyperbranched amine polymers (HAS) grown from the mesoporous silica SBA-15 (hereafter "SBA-15-HAS") exhibit large capacities for CO2 adsorption. We have used static in situ and magic-angle spinning (MAS) ex situ (13)C nuclear magnetic resonance (NMR) to examine the adsorption of CO2 by SBA-15-HAS. (13)C NMR distinguishes the signal of gas-phase (13)CO2 from that of the chemisorbed species. HAS polymers possess primary, secondary, and tertiary amines, leading to multiple chemisorption reaction outcomes, including carbamate (RnNCOO(-)), carbamic acid (RnNCOOH), and bicarbonate (HCO3(-)) moieties. Carbamates and bicarbonate fall within a small (13)C chemical shift range (162-166 ppm), and a mixture was observed including carbamic acid and carbamate, the former disappearing upon evacuation of the sample. By examining the (13)C-(14)N dipolar coupling through low-field (B0 = 3 T) (13)C{(1)H} cross-polarization MAS NMR, carbamate is confirmed through splitting of the (13)C resonance. A third species that is either bicarbonate or a second carbamate is evident from bimodal T2 decay times of the ∼163 ppm peak, indicating the presence of two species comprising that single resonance. The mixture of products suggests that (1) the presence of amines and water leads to bicarbonate being present and/or (2) the multiple types of amine sites in HAS permit formation of chemically distinct carbamates.

We have developed an approach for determining pH at elevated pressures and temperatures by using (13)C NMR measurements of inorganic carbon species together with a geochemical equilibrium model. The approach can determine in situ pH with precision better than 0.1 pH units at pressures, temperatures, and ionic strengths typical of geologic carbon sequestration systems. A custom-built high pressure NMR probe was used to collect (13)C NMR spectra of (13)C-labeled CO2 reactions with NaOH solutions and Mg(OH)2 suspensions at pressures up to 107 bar and temperatures of 80 °C. The quantitative nature of NMR spectroscopy allows the concentration ratio [CO2]/[HCO3(-)] to be experimentally determined. This ratio is then used with equilibrium constants calculated for the specific pressure and temperature conditions and appropriate activity coefficients for the solutes to calculate the in situ pH. The experimentally determined [CO2]/[HCO3(-)] ratios agree well with the predicted values for experiments performed with three different concentrations of NaOH and equilibration with multiple pressures of CO2. The approach was then applied to experiments with Mg(OH)2 slurries in which the change in pH could track the dissolution of CO2 into solution, rapid initial Mg(OH)2 dissolution, and onset of magnesium carbonate precipitation.

We report an apparatus for in-situ nuclear magnetic resonance (NMR) studies of chemical reactions of dissolved

Instrumentation for optically-pumped and optically-detected nuclear magnetic resonance (OPNMR and ODNMR) has been developed and implemented as a single experimental apparatus to study semiconductors such as GaAs and CdTe. These two measurement schemes use many of the same components for experiments. Here we describe, in two parts, the apparatus that can record such measurements and give examples of representative data. In Part 1, the radio-frequency probe and low-temperature cryostat are described, including single-channel and two-channel static cryogenic probes that both incorporate a modified solenoid coil that permits better optical access. In Part 2, the optical bench is described in detail, which uses a set of experiments (magneto-photoluminescence, photoluminescence excitation, detection of polarized photoluminescence) as important input for ODNMR. We are able to portray a robust design that encompasses multiple measurement modalities, along with the ability to change many experimental parameters with ease.

In the conversion of CO2 to mineral carbonates for the permanent geosequestration of CO2, there are multiple magnesium carbonate phases that are potential reaction products. Solid-state (13)C NMR is demonstrated as an effective tool for distinguishing magnesium carbonate phases and quantitatively characterizing magnesium carbonate mixtures. Several of these mineral phases include magnesite, hydromagnesite, dypingite, and nesquehonite, which differ in composition by the number of waters of hydration or the number of crystallographic hydroxyl groups. These carbonates often form in mixtures with nearly overlapping (13)C NMR resonances which makes their identification and analysis difficult. In this study, these phases have been investigated with solid-state (13)C NMR spectroscopy, including both static and magic-angle spinning (MAS) experiments. Static spectra yield chemical shift anisotropy (CSA) lineshapes that are indicative of the site-symmetry variations of the carbon environments. MAS spectra yield isotropic chemical shifts for each crystallographically inequivalent carbon and spin-lattice relaxation times, T1, yield characteristic information that assist in species discrimination. These detailed parameters, and the combination of static and MAS analyses, can aid investigations of mixed carbonates by (13)C NMR.

Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

Solid-state 71Ga and 69Ga NMR was used to probe the structure of the hydroxo-aquo cluster, [Ga13(μ3-OH)6(μ2-OH)18(H2O)24](NO3)15, envisioned as a solution-processable material for thin film electronics. This species, termed Ga13, is made up of three types of 6-coordinate gallium sites, with bridging OH groups and H2O species decorating the outer edges. Solid-state NMR at two magnetic fields (13.9 and 21.1 T) of these quadrupolar nuclei, in conjunction with modeling, demonstrates that these sites are best represented as distorted octahedra, exhibiting a wide range of distinct quadrupolar couplings and asymmetry parameters. This information is critical for analyses of the local coordination environment for gallium in related gallium-oxide films, and this work adds to the growing body of evidence that gallium solid-state NMR is a useful tool for structural analyses.

1H and 27Al NMR is used to reveal the motions of AlH4 anions in KAlH4. Line-narrowing from rotations and from translational diffusion is observed in the NMR of both nuclei. Unlike the anions in NaAlH4 and LiAlH4 that are not rotating on the NMR time scale at room temperature, the KAlH4 anions are already rotating rapidly at 23 °C. Based on the onset of rotation-induced line narrowing, the 1H T1 minimum, and the low- temperature hydrogen T1ρ minimum associated with reorientations, the rotational activation energy Erot,act = 0.28 eV is determined. Similarly, we use the onset temperature of translational motion-induced line narrowing and the high-temperature T1ρ minimum to determine the diffusion activation energy Ediff,act = 0.70 eV. Lack of sharp structure in the first-order quadrupole pattern and the absence of second-order quadrupole structure in the 27Al NMR data suggest asymmetry (η ≠ 0) and/or variations in the anion electric field gradients from structural disorder.

The CO2 adsorption in a polymer of intrinsic microporosity (PIM) functionalized by tetrazole (TZPIM) has been studied with in situ 13C nuclear magnetic resonance (NMR) spectroscopy at variable temperature and loading conditions. The CO2 molecules are seen to interact with tetrazole sites through physisorption. The adsorbed system was studied from 8 to 385 K at two loadings of CO2. The 13C NMR resonance lineshapes and relaxation times have been analyzed to give insights into the adsorption process. The CO2 molecules undergo site to site hopping with accompanying CO2 reorientations while adsorbed on TZPIM, resulting in line narrowing starting near 100 K. Correspondingly, the spin echo T2 passes through a minimum at 100 K. The analysis indicates that two kinds of adsorption sites are available.

The nature of the surface species formed through the adsorption of CO2 on amine-grafted mesoporous silica is investigated through in situ FTIR spectroscopy with the aid of 15N dynamic nuclear polarization (DNP) and 13C NMR spectroscopy. Primary, secondary, and tertiary amines are functionalized onto a mesoporous SBA-15 silica. Both isotopically labeled 13CO2 and natural-abundance CO2 are used for accurate FTIR peak assignments, which are compared with assignments reported previously. The results support the formation of monomeric and dimeric carbamic acid species on secondary amines that are stabilized differently to the monocarbamic acid species on primary amines. Furthermore, the results from isotopically labelled 13CO2 experiments suggest the existence of two carbamate species on primary amines, whereas only one species is observed predominantly on secondary amines. The analysis of the IR peak intensities and frequencies indicate that the second carbamate species on primary amines is probably more asymmetric in nature and forms in a relatively smaller amount. Only the formation of bicarbonate ions at a low concentration is observed on tertiary amines; therefore, physisorbed water on the surface plays a role in the hydrolysis of CO2 even if water is not added intentionally and dry gases are used. This suggests that a small amount of bicarbonate ions could be expected to form on primary and secondary amines, which are more hydrophilic than tertiary amines, and these low concentration species are difficult to observe on such samples.

In our efforts to study photodimerizations in the solid state, we present data on the influence of the position of aromatic substitution by bromine on the photodimerization rate in cinnamic acid de...

We have investigated rarely observed 77 Se J-couplings (spin-spin couplings) in the mixed-metal face-capped octahedral clusters [Re 5 OsSe 8 (CN) 6 ] 3- and [Re 4 Os 2 Se 8 (CN) 6 ] 2- at natural abundance. To the best of our knowledge, these are the first observations of Se-Se spin-spin interactions between μ 3 -Se sites, important for stereochemical assignments in hexarhenium analogues, Chevrel phase materials, and similar cluster materials. NMR techniques such as COSY, INADEQUATE, and 2D J-resolved spectroscopy have been used in conjunction to study these interactions. The two isomers (cis and trans) of [Re 4 Os 2 Se 8 (CN) 6 ] 2- were distinguishable, and selective isotopic labeling of [Re 5 OsSe 8 (CN) 6 ] 3- with 13 CN ligands enabled resonances to be assigned by observing the 2 J (Se-M-C) couplings. For [Re 5 OsSe 8 (CN) 6 ] 3- , two different 2 J (Se-M-Se) couplings were measurable on a single cluster, and these are related to one another through spin-spin interactions across a face diagonal or along an edge of the cube of inner selenium ligands. A rigorous analysis based on combinatorial math has been invoked to assign the couplings on the basis of the probability of multiple-spin interactions. The face diagonal association is found to result in a J-coupling interaction larger in magnitude than that from coupling along an edge of the cube-information critical for making stereochemical assignments of selenium sites.

Solid-state (71)Ga NMR was used to investigate the structures of several heterometallic Group 13 hydroxo-aquo clusters, [Ga13-xInx (μ3-OH)6(μ2-OH)18(H2O)24](NO3)15 which are envisioned for thin film transistors. The characterization of these clusters in the solid state provides additional information in understanding the synthesis, structure and speciation of these precursors for high-quality, ultrasmooth thin films. Yet important structural information regarding these clusters - including the exact composition, isomeric structure, and coordination environments - were unknown prior to this precise NMR spectroscopy study. These molecular species, termed "Ga13-xInx", contain three types of six-coordinate metal sites, with bridging OH(-) groups and H2O as capping ligands, and we report results on Ga7In6, Ga8In5, Ga10In3, Ga11In2, Ga12In1, and Ga13. Utilizing two magnetic fields (13.9 T and 21.1 T), the solid-state NMR spectra were interpreted in conjunction with computational modeling (using CASTEP) and simulation of spectral lineshapes (using Dmfit). The metal sites are best represented as distorted octahedra, and they exhibit a range of quadrupolar couplings and asymmetry parameters, which can be addressed using longitudinal strain analysis. Until now, there has been speculation about the sites for transmetallation within the synthetic cluster community. Here, we show that Ga NMR is a powerful technique to monitor the transmetallation of In for Ga in the Ga13-xInx clusters, specifically substituting in the "outer ring" sites, and not the "core" or "middle ring".

This Perspective article highlights some of the traditional and non-traditional analytical tools that are presently used to characterize aqueous inorganic nanoscale clusters and polyoxometalate ions. The techniques discussed in this article include nuclear magnetic resonance spectroscopy (NMR), small angle X-ray scattering (SAXS), dynamic and phase analysis light scattering (DLS and PALS), Raman spectroscopy, and quantum mechanical computations (QMC). For each method we briefly describe how it functions and illustrate how these techniques are used to study cluster species in the solid state and in solution through several representative case studies. In addition to highlighting the utility of these techniques, we also discuss limitations of each approach and measures that can be applied to circumvent such limits as it pertains to aqueous inorganic cluster characterization.

We have developed an approach for determining pH at elevated pressures and temperatures by using (13)C NMR measurements of inorganic carbon species together with a geochemical equilibrium model. The approach can determine in situ pH with precision better than 0.1 pH units at pressures, temperatures, and ionic strengths typical of geologic carbon sequestration systems. A custom-built high pressure NMR probe was used to collect (13)C NMR spectra of (13)C-labeled CO2 reactions with NaOH solutions and Mg(OH)2 suspensions at pressures up to 107 bar and temperatures of 80 °C. The quantitative nature of NMR spectroscopy allows the concentration ratio [CO2]/[HCO3(-)] to be experimentally determined. This ratio is then used with equilibrium constants calculated for the specific pressure and temperature conditions and appropriate activity coefficients for the solutes to calculate the in situ pH. The experimentally determined [CO2]/[HCO3(-)] ratios agree well with the predicted values for experiments performed with three different concentrations of NaOH and equilibration with multiple pressures of CO2. The approach was then applied to experiments with Mg(OH)2 slurries in which the change in pH could track the dissolution of CO2 into solution, rapid initial Mg(OH)2 dissolution, and onset of magnesium carbonate precipitation.

The present work focuses on the topochemical photoconversion process in which alpha-trans-cinnamic acid becomes alpha-truxillic acid. This solid-state [2 + 2] cycloaddition reaction has previously been studied with X-ray diffraction, atomic force microscopy, and vibrational spectroscopy. However structural and kinetic details about the reaction are still debated. We present results from (13)C cross-polarization magic angle spinning solid-state NMR experiments that suggest that the Johnson, Mehl, Avrami, and Kolmogorov model of phase transformation kinetics can be applied to this system. The model elucidates parameters of the reaction, such as the nucleation rate, diffusion rate, and dimensionality of the reaction. From our data, it is concluded that this reaction follows one-dimensional growth with a decreasing nucleation rate.

13C-labelled trans-cinnamic acid (3-phenyl-2-propenoic acid) has been synthesized in one step using benzaldehyde-carbonyl-13C and malonic acid-2-13C in the presence of ammonium acetate under microwave irradiation and solvent-free conditions. Copyright © 2004 John Wiley & Sons, Ltd.

Electrochemical insertion of lithium into pyrolyzed amorphous carbons prepared from polymeric precursors of methacrylonitrile and divinylbenzene has been investigated by 7Li variable temperature static and magic angle spinning (MAS) NMR. This method is able to characterize the chemical inventory of lithium, differentiating between reversible species that are truly inserted into the carbon and irreversible species that are lost to traps and parasitic processes. Furthermore, large chemical shift effects indicate that the structural and electronic properties of the inserted reversible lithium species are sensitively dependent on the extent of loading. At loading levels ≤90% relative capacity, the trend is monotonic, whereas in more highly charged samples, two types of electrochemically relevant sites are observed, distinguishable from one another only at lower temperatures. At higher temperatures, dynamic exchange effects between them are evident on the NMR time scale. In the initially prepared state, these ...