Solid-state Nuclear Magnetic Resonance Techniques Research Articles

Cross-Polarization Solid-State NMR Quantification of Species within Pores of Metal-Organic Frameworks: A Case Study of α-Mg3(HCOO)6.

The quantitative measurement of adsorbed guest species within Metal-organic framework (MOF) pores is of fundamental importance for evaluating the adsorption performance of MOFs. However, routine analytic techniques such as thermogravimetric analysis cannot distinguish the contribution from species adsorbed within pores, species adsorbed on the surface, and gas phase or liquid phase encapsulated in the inter-crystalline space. Herein, we developed a new quantification method based on the cross-polarization (CP) solid-state nuclear magnetic resonance (SSNMR) technique, in which only the species within MOF pores are selectively probed due to the dramatically reduced mobility. Using the commercialized MOF α-Mg3(HCOO)6 as an example, a good linear correlation between Areaguest/Areaframework (i.e., the integrated area of guest and framework 13C NMR signals, respectively) and guest loading can be observed for several representative molecules such as benzene, tetrahydrofuran (THF), and 1,4-dioxane, clearly revealing the feasibility of CP quantification approach. The effects of guest molecule and corresponding residual mobility on the CP quantification are further discussed by varying the geometry and size of guest molecules. This methodology thus provides an effective and irreplaceable route to evaluate the adsorption performance of porous materials in-depth, especially for liquid-phase adsorption and gas-phase adsorption in which the capillary condensation is not negligible.

Effects of erosion on macroaggregation, aggregate associated organic carbon sources and compositions in a Mollisol agricultural landscape

Macroaggregation is widely recognized as an important soil carbon (C) stabilization mechanism. However, in eroding landscapes, the relationships among soil aggregation, organic carbon (OC) sources, and chemical composition are poorly understood. In this study, we aimed to explore the effects of erosion and deposition on macroaggregation, OC sources, and chemical compositions in topsoil (0–20 cm) versus subsoil (80–100 cm) in a Mollisol agricultural landscape. The bulk soil was fractionated into macroaggregates (0.25–2 mm), microaggregates (0.053–0.25 mm), and clay and silt (<0.053 mm) using a wet sieving procedure. The plant sources of soil OC were quantified based on the stable isotope 13C (δ13C), and the chemical composition of macroaggregate associated OC (MaOC) was determined by solid-state nuclear magnetic resonance techniques. The results indicated that macroaggregates and MaOC comprised 45–72% of soil mass and 50–66% of soil OC, respectively. There was a reduction in macroaggregate-associated C3-derived C (C3-C) in the eroding position compared to that in the non-eroding position. However, similar amounts of C4-derived C (C4-C) were detected among three topographical areas, indicating the re-macroaggregation of eroded materials in the depositional position and preferential protection of C3-C. In the up-slope positions, topsoil MaOC was composed primarily of O-alkyl C (52%). Compared with the up-slope position, there was a considerable increase in the amount of aromatic C in the erosional macroaggregate fraction. However, at the eroding position, there was a marked increase in the proportion of substituted alkyl-C in the topsoil material, and deposition resulted in an increase in aromatic C in the subsoil. Overall, erosion and deposition change soil aggregation, and sources and composition of OC in different functional pools have important implications for the stabilization of organic matter along an eroding Mollisol hillslope.

Valorisation of microalga Chlorella sp. into furans in the presence of Nb2O5 catalysts

Despite the interest in niobia-based catalysts and the importance of biomass valorisation, studies on these catalysts typically utilize model substrates like simple sugars. In this study, a series of niobium oxide-based catalysts was prepared for the application in aqueous phase catalytic conversion of sugars extracted from Chlorella sp. microalga into value-added furans. The solid catalysts were firstly characterized by various techniques including X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Raman and X-ray photoelectron (XPS) spectroscopy as well as low-temperature N2 physisorption. Moreover, the acidity of the catalysts was assessed by using the temperature-programmed NH3 desorption (NH3-TPD), by titration of water suspended catalyst with NaOH solution, and by P-bearing molecular probes loaded catalysts through 31P and 1H solid-state nuclear magnetic resonance (NMR) techniques. Herein, we focused on the catalytic transformation of Chlorella sp. and glucose solution as model molecule into furans. The best Nb2O5 catalysts for valorizing Chlorella sp. into furans exhibited a larger number of Brønsted acid sites, achieving conversion yields to 5-HMF and furfural of ca. 20–22 % with respect to the extracted sugars from algae. The results showed a discernible dependence of the conversion yields to 5-HMF and furfural on catalyst acidity, specific surface area, and the presence of the Brønsted acid sites. Conversely, when using the glucose solution as substrate is concerning, the highest yield to 5-HMF was reached by using a catalyst that showed also the presence of Lewis acid sites. A systematic investigation of the structure–activity relationships in niobium oxide application for aqueous phase dehydration using real biomass substrates to obtain furanic derivatives has not been documented thus far. Therefore, the current research is significant as it demonstrates the feasibility of transforming the carbohydrate content in microalgal biomass into furans by identifying the best catalyst to use.

Structural Characteristics and Cementitious Behavior of Magnesium Slag in Comparison with Granulated Blast Furnace Slag.

Magnesium slag is a type of industrial solid waste produced during the production of magnesium metal. In order to gain a deeper understanding of the structure of magnesium slag, the composition and microstructure of magnesium slag were investigated by using characterization methods such as X-ray fluorescence, particle size analysis, X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. In addition, the state of Si occurrence in magnesium slag was analyzed using a solid-state nuclear magnetic resonance technique in comparison with granulated blast furnace slag. An inductively coupled plasma-optical emission spectrometer and scanning electron microscope with energy dispersive X-ray spectroscopy were used to characterize their cementitious behavior. The results show that the chemical composition of magnesium slag mainly includes 54.71% CaO, 28.66% SiO2 and 11.82% MgO, and the content of Al2O3 is much lower than that of granulated blast furnace slag. Compared to granulated blast furnace slag, magnesium slag has a larger relative bridging oxygen number and higher [SiO4] polymerization degree. The cementitious activity of magnesium slag is lower compared to that of granulated blast furnace slag, but it can replace part of the cement to obtain higher compressive strength. Maximum compressive strength can be obtained when the amount of magnesium slag replacing cement is 20%, where the 28-day compressive strength can be up to 45.48 MPa. This work provides a relatively comprehensive analysis of the structural characteristics and cementitious behavior of magnesium slag, which is conducive to the promotion of magnesium slag utilization.

A Novel Strategy for the Characterization of Self-Assembled Structures Using the Static Solid-State Phosphorus Nuclear Magnetic Resonance Technique.

Structural characterization of assemblies in solutions is essential for understanding the relationship between the structure and material properties. In this study, we introduce a novel approach to investigate amphiphilic self-assemblies in solutions using the phospholipid molecule 1-palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine (Lyso PC) as a 31P NMR probe. The high natural abundance and gyromagnetic ratio of 31P make it one of the most sensitive nuclei in the low-frequency region, enabling efficient detection even in dilute solutions. Lyso PC can readily co-assemble with amphiphilic molecules and ions in aqueous solutions, forming various structures, such as hexagonal, lamellar, and micellar assemblies. The characteristic line shapes of these assemblies reflect the chemical environment around the probe and provide insights into the different phase states of the assemblies. This strategy offers a simple, cost-effective, and static method for obtaining structural information about various assemblies. Our work not only introduces a sensitive probe for characterizing assemblies in a solvent environment but also inspires new ideas for the development of similar spectroscopic probes.

Peptides as Model Systems for Biofunctionalizations of Cellulose─Synthesis and Structural Characterization by Advanced Solid-State Nuclear Magnetic Resonance Techniques

Peptides as Model Systems for Biofunctionalizations of Cellulose─Synthesis and Structural Characterization by Advanced Solid-State Nuclear Magnetic Resonance Techniques

Probing Molecular Packing of Amorphous Pharmaceutical Solids Using X-ray Atomic Pair Distribution Function and Solid-State NMR.

The structural investigation of amorphous pharmaceuticals is of paramount importance in comprehending their physicochemical stability. However, it has remained a relatively underexplored realm primarily due to the limited availability of high-resolution analytical tools. In this study, we utilized the combined power of X-ray pair distribution functions (PDFs) and solid-state nuclear magnetic resonance (ssNMR) techniques to probe the molecular packing of amorphous posaconazole and its amorphous solid dispersion at the molecular level. Leveraging synchrotron X-ray PDF data and employing the empirical potential structure refinement (EPSR) methodology, we unraveled the existence of a rigid conformation and discerned short-range intermolecular C-F contacts within amorphous posaconazole. Encouragingly, our ssNMR 19F-13C distance measurements offered corroborative evidence supporting these findings. Furthermore, employing principal component analysis on the X-ray PDF and ssNMR data sets enabled us to gain invaluable insights into the chemical nature of the intermolecular interactions governing the drug-polymer interplay. These outcomes not only furnish crucial structural insights facilitating the comprehension of the underlying mechanisms governing the physicochemical stability but also underscore the efficacy of synergistically harnessing X-ray PDF and ssNMR techniques, complemented by robust modeling strategies, to achieve a high-resolution exploration of amorphous structures.

Enhanced room-temperature Na+ ionic conductivity in Na4.92Y0.92Zr0.08Si4O12

Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage. A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability. Herein, we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure. Optimized substitution of Y3+ with Zr4+ in Na5YSi4O12 introduced Na+ ​ion vacancies, resulting in high bulk and total conductivities of up to 6.5 and 3.3 ​mS ​cm−1, respectively, at room temperature with the composition Na4.92Y0.92Zr0.08Si4O12 (NYZS). NYZS shows exceptional electrochemical stability (up to 10 ​V vs. Na+/Na), favorable interfacial compatibility with Na, and an excellent critical current density of 2.4 ​mA ​cm−2. The enhanced conductivity of Na+ ​ions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations, revealing two migration routes facilitated by the synergistic effect of increased Na+ ​ion vacancies and improved chemical environment due to Zr4+ substitution. NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable, low-cost Na+ ion silicate electrolytes.

Structural analysis of non-stoichiometric lithium cuprates, Li2+2xCu1-2xO2-x. Effects of lithium content and thermal treatments

Lithium cuprate (Li2CuO2) is being used for a wide range of applications due to its high lithium diffusion through the layer structure. Moreover, Li2+2xCu1-xO2-x non-stoichiometric material shows enhanced physicochemical properties. Therefore, lithium location understanding is highly important for lithium cuprate applications. This paper reports the structural coherence analysis, local and long atomic arrangement of Li2+2xCu1-xO2-x using X-ray diffraction (XRD), pair distribution function (PDF) and solid-state nuclear magnetic resonance (NMR) techniques. Li2CuO2, containing different excess quantities of lithium (from 0 to 60 at%), were synthesized by solid-state reaction. The synthesized ceramics presented nonstoichiometric structures, with Li2CuO2 type-structure. Two structural models were proposed to explain the high enhancement physicochemical properties of these ceramics; (i) the extra lithium atoms substitute copper sites, and (ii) lithium species occupy interstitial sites in the crystalline structure. Additionally, further thermal treatments rearrange the non-stoichiometric crystalline structures into the stable Li2CuO2 phase.

Internal Interactions within the Complex Type-II Heterojunction of a Graphitic Carbon Nitride/Black Phosphorus Hybrid Decorated with Graphene Quantum Dots: Implications for Photooxidation Performance

In this study, Fermi levels of graphitic carbon nitride (CN), black phosphorus (BP), and graphene quantum dots (GQDs) were rationally combined and tuned through a band engineering approach. The structure–activity relationship of the resulting heterojunction was characterized by using a combination of X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and solid-state nuclear magnetic resonance techniques. The results revealed that CN and BP were in contact through the formed P–N bridges, while the polar functional groups of GQDs interacted with BP and CN via P–O and N–O interactions, respectively. The superior degradation efficiency is attributed to the synergistic effect of the strong coupling at the interfaces where GQDs@CNBP was tested in removal of organic pollutants [methyl orange (MO) and tetracycline (TC)]. The degradation intermediates in both cases were enlightened by NMR experiments showing no trace of either pollutant or photocatalyst in wastewater. The photogenerated charge migration mechanism was experimentally elucidated as a complex-type-II, which is based on the usage of the farthest charges on the band edges. Scavenger experiments and photooxidation of glucose confirmed the in situ generation of oxidative species of •O2–, H2O2, and •OH, which played a vital role in the photooxidation reactions. A GQDs@CNBP heterojunction with the kinetic rate constants of 0.1415 min–1 (30 min) for MO and 0.0371 min–1 (120 min) for TC is one of the highest kinetics that has been reported in the literature so far.

Mechanism underlying the weakening effect of β-glucan on the gluten system

The high β-glucan content in barley disrupts the gluten network in dough. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (NMR) techniques were used to clarify how β-glucan affected the quality of the gluten network structure with β-glucan contents of 0–2%. The results suggest that the physical hindrance of the β-glucan gel destroyed the formation of the gluten network structure. When 1.0–2.0% β-glucan was added, the percentage of α-helical structures increased significantly. When the added amount of β-glucan reached 2.0%, the sulfhydryl group (SH) content increased from 8.06 to 10.27 µmol/g, and the disulfide bond (SS) content decreased from 240.09 to 217.38 µmol/g. The interaction between β-glucan and gluten mainly resulted from the interaction of electron-withdrawing groups, such as carbonyl groups (CO) and double bond carbons (CC), and carbon atoms on the side chains of β-glucan, which play an important role in the central structure of glutenin.

Vat Photopolymerization of Nanocellulose-Reinforced Vegetable Oil-Based Resins: Synergy in Morphology and Functionalization

With the advancement of additive manufacturing (AM) and the mass adoption of 3D printing technology, it is essential to shift focus to environmentally and economically sustainable materials. As the utilization of renewable feedstocks is quite limited in this context, the utilization of more bio-based raw materials in the ongoing development of AM represents an essential means of achieving this shift. In this work, vat photopolymerization 3D printing has been used to process vegetable oil-based (VO) resins with an ultralow concentration of 0.07 vol % nanocellulose fibrils (NFC) and crystals (NCC). The developed nanocellulose containing bio-based vat photopolymerization resin shows excellent shelf stability, enabling high-resolution printing. Compatibilization of the nanocellulose with the polymer matrix was achieved through the introduction of isocyanate or acrylate groups via reactions of acryloyl chloride (AC) and hexamethylene diisocyanate (HMDI) with cellulose surface hydroxyls. Surface functionalization results in ∼20–30% increases in interfacial adhesion and stress transfer, yielding significant improvements in mechanical performance (4× higher toughness, 2.4× higher tensile strength, and 2× higher tensile strain) in 3D-printed specimens. Fourier-transformation infrared (FTIR) spectroscopy complemented by solid-state nuclear magnetic resonance (NMR) techniques enabled a more detailed study of the chemical structure of these materials as well. Tensile performance comparison with literature data on VO-based natural fiber-reinforced resins showed that this work brought bio-based resins one step closer to competing with petroleum-based resins. The prepared VO/nanocellulose resins are promising candidates for high-performance bio-based resins derived from completely renewable feedstocks.

Histone H3 core domain in chromatin with different DNA linker lengths studied by 1H-Detected solid-state NMR spectroscopy.

Chromatin, a dynamic protein-DNA complex that regulates eukaryotic genome accessibility and essential functions, is composed of nucleosomes connected by linker DNA with each nucleosome consisting of DNA wrapped around an octamer of histones H2A, H2B, H3 and H4. Magic angle spinning solid-state nuclear magnetic resonance (NMR) spectroscopy can yield unique insights into histone structure and dynamics in condensed nucleosomes and nucleosome arrays representative of chromatin at physiological concentrations. Recently we used J-coupling-based solid-state NMR methods to investigate with residue-specific resolution the conformational dynamics of histone H3 N-terminal tails in 16-mer nucleosome arrays containing 15, 30 or 60 bp DNA linkers. Here, we probe the H3 core domain in the 16-mer arrays as a function of DNA linker length via dipolar coupling-based 1H-detected solid-state NMR techniques. Specifically, we established nearly complete assignments of backbone chemical shifts for H3 core residues in arrays with 15-60 bp DNA linkers reconstituted with 2H,13C,15N-labeled H3. Overall, these chemical shifts were similar irrespective of the DNA linker length indicating no major changes in H3 core conformation. Notably, however, multiple residues at the H3-nucleosomal DNA interface in arrays with 15 bp DNA linkers exhibited relatively pronounced differences in chemical shifts and line broadening compared to arrays with 30 and 60 bp linkers. These findings are consistent with increased heterogeneity in nucleosome packing and structural strain within arrays containing short DNA linkers that likely leads to side-chains of these interfacial residues experiencing alternate conformations or shifts in their rotamer populations relative to arrays with the longer DNA linkers.

Sulfonic Acid-Grafted Hybrid Porous Polymer Based on Double-Decker Silsesquioxane as Highly Efficient Acidic Heterogeneous Catalysts for the Alcoholysis of Styrene Oxide.

β-Alkoxyalcohols generated from epoxide ring-opening reactions are significant due to their enormous value as pharmaceutical intermediates and fine chemicals. Using a phenyl-substituted double-decker-type silsesquioxane as the precursor, a hybrid porous material (PCS-DDSQ) was synthesized through a Scholl coupling reaction with an AlCl3 catalyst. Then, novel excellent Brønsted acid-derived silsesquioxane solid catalysts (PCS-DDSQ-SO3H-x) were successfully obtained through an electrophilic aromatic substitution reaction of chlorosulfonic acid on phenyl rings of PCS-DDSQ, fully characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, powder X-ray diffraction, temperature-programmed desorption, water contact angle, Brunauer-Emmett-Teller model, thermogravimetric analysis, and solid-state 13C and 29Si nuclear magnetic resonance techniques. The catalytic behavior of the PCS-DDSQ-SO3H-x with different SO3H loadings for the methanolysis of styrene oxide was compared and evaluated. The presence of SO3H groups endows them with excellent catalytic abilities, achieving the highest values from PCS-DDSQ-SO3H-1 (the acid site of its catalyst is 1.84 mmol/g) as 99% conversion and 100% selectivity for the methanolysis of styrene oxide in 30 min, which shows superior catalytic properties of low dosage and high efficiency. Furthermore, the PCS-DDSQ-SO3H-1 catalyst can maintain high activity and selectivity after three cycles. This study provides a feasible method for the preparation of Brønsted solid acid catalysts with different acid loadings by introducing the sulfonic group into PCS-DDSQ.

Vibrational Spectroscopic Analysis of 1,3-Dianiline Squarate: Infrared, Normal Raman, Surface-Enhanced Raman Scattering, and Density Functional Theory Calculations

1,3-Dianiline squarate (DSQ) is an interesting squaraine frequently used as an intermediary reactant in organic synthesis aiming products 1,3-(R1R2)-squarate type, as well as a building block of photoinitiators under visible light widely used in photopolymerization reactions. In this work, structural investigations of DSQ were performed using spectroscopic methods such as solid-state 13C nuclear magnetic resonance and several vibrational techniques. Therefore, a detailed vibrational spectroscopic analysis of DSQ was carried out by infrared, normal Raman, and surface-enhanced Raman scattering (SERS) combined with density functional theory calculations. SERS data suggest two preferential interactions between squaraine and the silver nanoparticle. It is proposed that squaraine is adsorbed mainly through a regular Ag–O interaction involving the carbonyl group; that connection impacts the oscillators around them and consequently their vibrational spectra. In addition, the silver atoms may perturb the DSQ planarity by interacting with the phenyl rings; they promote the molecule to adopt a non-planar tilted orientation on the metal nanoparticle surface.

Structural Characterization of Phosphorous Slag Regarding Occurrence State of Phosphorus in Dicalcium Silicate.

Phosphorous slag is a solid waste generated in the process of yellow phosphorus production. In order to deeply understand the structural and cementitious characteristics of phosphorous slag, comprehensive characterizations, including X-ray fluorescence spectrometry, X-ray diffraction, thermogravimetry, Fourier transform infrared spectrometry, Raman, scanning electron microscope, and inductively coupled plasma mass spectrometry were adopted to investigate the composition, thermal stability, microstructure, and cementitious activity of phosphorous slag. In addition, scanning electron microscope with energy dispersive X-ray spectroscopy, electron microprobe analysis, and solid-state nuclear magnetic resonance techniques were used to analyze the occurrence state of P in phosphorous slag. The results show that phosphorous slag is mostly vitreous with good thermal stability. Its chemical composition mainly comprises 43.85 wt % CaO, 35.87 wt % SiO2, and 5.57 wt % Al2O3, which is similar to that of blast furnace slag, but it presents lower cementitious activity than blast furnace slag. P is uniformly distributed in the phosphorous slag with P2O5 content of 3.75 wt %. The distribution pattern of P is extremely similar to that of Si. P is mainly existing in orthophosphate of 3CaO·P2O5, which forms solid solution with dicalcium silicate (2CaO·SiO2). This work specifically clarifies the occurrence state of P in dicalcium silicate within the phosphorous slag. It is theoretically helpful to solve the retarding problem of phosphorous slag in cement and concrete.

Understanding the molecular origin of the superior toughness of polyamide-6/polyketone blends by solid-state NMR spectroscopy

Polymer blending is a typical and conventional approach for integrating the excellent physical/chemical properties of individual polymer components. Specifically, the mechanical toughness and strength of polyamide-6 (PA6)/polyketone (PK) blend are substantially enhanced compared to either PA6 or PK individual component. Nevertheless, there are few atomic-level insights into such mechanical property enhancement. In this study, solid-state nuclear magnetic resonance (NMR) is utilized as a main tool to understand the molecular origin of the mechanical enhancement of PA6/PK blends. The proton relaxation times are used to evaluate the miscibility and domain sizes in PA6/PK blends, and to determine the crystallinity of each component, where both conventional DSC and WAXD experiments fail because of similar crystallization/melting behaviors of PA6 and PK components. 2D 1 H– 13 C WISE (wideline separation) and HETCOR (heteronuclear correlation) solid-state NMR spectroscopy were performed to further reveal the nano-heterogeneous structures and hydrogen bonding interactions in PA6/PK blend. With further combination with FTIR and SEM results, the previous characteristic morphological model for elucidating the toughening mechanism for PA6/PK blends is refuted, and it is proposed that the superior performance of PA6/PK blend is resulted from the synergistic effects of enhanced interfacial adhesion and interconnected interphase percolated in the bulk PA6/PK blends via hydrogen bonds. We envisage the detailed molecular level insights provided by solid-state NMR spectroscopy could assist in the bottom-up design of high performance polymer blend materials. • The locations of hydrogen bonding between PA6 and PK are precisely determined. • The strength of hydrogen bonding interactions is semi-quantitatively characterized. • A complementary approach for studying crystallization of polymer blends is provided. • Insights into the toughening mechanism via solid-state NMR techniques are obtained.

Multilevel Hollow Phenolic Resin Nanoreactors with Precise Metal Nanoparticles Spatial Location toward Promising Heterogeneous Hydrogenations.

Hollow nanostructures with fascinating properties have inspired numerous interests in broad research fields. Cell-mimicking complex hollow architectures with precise active components distributions are particularly important, while their synthesis remains highly challenging. Herein, a "top-down" chemical surgery strategy is introduced to engrave the 3-aminophenol formaldehyde resin (APF) spheres at nanoscale. Undergoing the cleavage of (Ar)CN bonds with ethanol as chemical scissors and subsequent repolymerization process, the Solid APF transform to multilevel hollow architecture with precise nanospatial distribution of organic functional groups (e.g., hydroxymethyl and amine). The transformation is tracked by electron microscopy and solid-state nuclear magnetic resonancetechniques, the category and dosage of alcohol are pivotal for constructingmultilevel hollow structures. Moreover, it is demonstrated the evolution of nanostructures accompanied with unique organic microenvironments is able to accurately confine multiple gold (Au) nanoparticles, leading to the formation of pomegranate-like particles. Through selectively depositing palladium (Pd) nanoparticles onto the outer shell, bimetallic Au@APF@Pd catalysts are formed, which exhibit excellent hydrogenation performance with turnover frequency (TOF) value up to 11257h-1 . This work provides an effective method for precisely manipulating the nanostructure and composition of polymers at nanoscale and sheds light on the design of catalysts with precise spatial active components.

Recent advances in solid-state NMR of zeolite catalysts.

Zeolites are important inorganic crystalline microporous materials with a broad range of applications in the areas of catalysis, ion exchange, and adsorption/separations. Solid-state nuclear magnetic resonance (NMR) spectroscopy has proven to be a powerful tool in the study of zeolites and relevant catalytic reactions because of its advantage in providing atomic-level insights into molecular structure and dynamic behavior. In this review, we provide a brief discussion on the recent progress in exploring framework structures, catalytically active sites and intermolecular interactions in zeolites and metal-containing ones by using various solid-state NMR methods. Advances in the mechanistic understanding of zeolite-catalysed reactions including methanol and ethanol conversions are presented as selected examples. Finally, we discuss the prospect of the solid-state NMR technique for its application in zeolites.

On the use of cross polarization in solid-state NMR: 1H spin-lock versus adiabatic demagnetization in the rotating frame

Cross polarization (CP) is a widely used solid-state nuclear magnetic resonance (NMR) technique for enhancing the polarization of dilute S spins from much larger polarization of abundant I spins such as 1H. To achieve such a polarization transfer, the I spin should either be spin-locked or be converted to the dipolar ordered state through adiabatic demagnetization in the rotating frame. In this work, we analyze the spin dynamics of the Hartmann-Hahn CP (HHCP) utilizing the 1H spin-locking, and the dipolar-order CP (DOCP) having the 1H adiabatic demagnetization. We further propose an adiabatic demagnetization CP (ADCP) where a constant radio-frequency pulse is applied on the S spin while 1H is adiabatically demagnetized. Our analyses indicate that ADCP utilizes the adiabatic passage to effectively achieve the polarization transfer from the 1H to S spins. In addition, the dipolar ordered state generated during the 1H demagnetization process could also be converted into the observable S polarization through DOCP, further enhancing the polarized signals. It is shown by both static and magic-angle-spinning (MAS) NMR experiments that ADCP has dramatically broadened the CP matching condition over the other CP schemes. Various samples have been used to demonstrate the polarization transfer efficiency of this newly proposed ADCP scheme.