Tunneling Interpenetrative Lithium Ion Conduction Channels in Polymer-in-Ceramic Composite Solid Electrolytes.

Polymer-in-ceramic composite solid electrolytes (PIC-CSEs) provide important advantages over individual organic or inorganic solid electrolytes. In conventional PIC-CSEs, the ion conduction pathway is primarily confined to the ceramics, while the faster routes associated with the ceramic-polymer interface remain blocked. This challenge is associated with two key factors: (i) the difficulty in establishing extensive and uninterrupted ceramic-polymer interfaces due to ceramic aggregation; (ii) the ceramic-polymer interfaces are unresponsive to conducting ions because of their inherent incompatibility. Here, we propose a strategy by introducing polymer-compatible ionic liquids (PCILs) to mediate between ceramics and the polymer matrix. This mediation involves the polar groups of PCILs interacting with Li+ ions on the ceramic surfaces as well as the interactions between the polar components of PCILs and the polymer chains. This strategy addresses the ceramic aggregation issue, resulting in uniform PIC-CSEs. Simultaneously, it activates the ceramic-polymer interfaces by establishing interpenetrating channels that promote the efficient transport of Li+ ions across the ceramic phase, the ceramic-polymer interfaces, and the intervening pathways. Consequently, the obtained PIC-CSEs exhibit high ionic conductivity, exceptional flexibility, and robust mechanical strength. A PIC-CSE comprising poly(vinylidene fluoride) (PVDF) and 60 wt % PCIL-coated Li3Zr2Si2PO12 (LZSP) fillers showcasing an ionic conductivity of 0.83 mS cm-1, a superior Li+ ion transference number of 0.81, and an elongation of ∼300% at 25 °C could be produced on meter-scale. Its lithium metal pouch cells show high energy densities of 424.9 Wh kg-1 (excluding packing films) and puncture safety. This work paves the way for designing PIC-CSEs with commercial viability.

17O solid-state NMR study on exposed facets of ZnO nanorods with different aspect ratios.

The physical and chemical properties of metal oxide nanocrystals are closely related to their exposed facets, so the study on facet structures is helpful to develop facet/morphology-property relationships and rationally design nanostructures with desired properties. In this study, wurtzite ZnO nanorods with different aspect ratios were prepared by controlling the Zn2+/OH- ratio, temperature and time in hydrothermal processes. An 17O solid-state NMR study was performed on these nanorods, after surface 17O labeling, to explore the relationship of the 17O NMR signals with the local surface structure of different exposed facets, i.e., nonpolar (101̄0) and polar (0002) facets. It is observed that, one of the signals, the sharp component of a peak at -18.8 ppm, comprises the contribution from the oxygen ions on the polar (0002) facets, in addition to that from nonpolar (101̄0) facets, which is confirmed by 17O NMR spectra of ZnO nanorods with controlled aspect ratios and different thermal treatment conditions. This is important for accurately interpreting the 17O NMR signal of ZnO-containing materials, especially when studying the facet-related mechanisms. The method applied here can also be extended to study the facet-dependent properties of other faceted oxide nanocrystals.

Unveiling the Surface Structure of ZnO Nanorods and H2 Activation Mechanisms with 17O NMR Spectroscopy.

ZnO plays a very important role in many catalytic processes involving H2, yet the details on their interactions and H2 activation mechanism are still missing, owing to the lack of a characterization method that provides resolution at the atomic scale and follows the fate of oxide surface species. Here, we apply 17O solid-state NMR spectroscopy in combination with DFT calculations to unravel the surface structure of ZnO nanorods and explore the H2 activation process. We show that six different types of oxygen ions in the surface and subsurface of ZnO can be distinguished. H2 undergoes heterolytic dissociation on three-coordinated surface zinc and oxygen ions, while the formed hydride species migrate to nearby oxygen species, generating a second hydroxyl site. When oxygen vacancies are present, homolytic dissociation of H2 occurs and zinc hydride species form from the vacancies. Reaction mechanisms on oxide surfaces can be explored in a similar manner.

Enhanced Fluoride Uptake by Layered Double Hydroxides under Alkaline Conditions: Solid-State NMR Evidence of the Role of Surface >MgOH Sites.

Layered double hydroxides (LDHs) are potential low-cost filter materials for use in fluoride removal from drinking water, but molecular-scale defluoridation mechanisms are lacking. In this research, we employed 19F solid-state NMR spectroscopy to identify fluoride sorption products on 2:1 MgAl LDH and to reveal the relationship between fluoride sorption and the LDH structure. A set of six 19F NMR peaks centered at -140, -148, -156, -163, -176, and -183 ppm was resolved. Combining quantum chemical calculations based on density function theory (DFT) and 19F{27Al} transfer of populations in double resonance (TRAPDOR) analysis, we could assign the peaks at -140, -148, -156, and -163 ppm to Al-F (F coordinated to surface Al) and those at -176 and -183 ppm to Mg-F (F coordinated to surface Mg only). Interestingly, the spectroscopic data reveal that the formation of Al-F is the predominant mode of F- sorption at low pH, whereas the formation of Mg-F is predominant at high pH (or a higher Mg/Al ratio). This finding supports the fact that the F- uptake of 2:1 MgAl LDH was nearly six times that of activated alumina at pH 9. Overall, we explicitly revealed the different roles of the surface >MgOH and >AlOH sites of LDHs in defluoridation, which explained why the use of classic activated alumina for defluoridation is limited at high pH. The findings from this research may also provide new insights into material screening for potential filters for F- removal under alkaline conditions.

TM LDH Meets Birnessite: A 2D-2D Hybrid Catalyst with Long-Term Stability for Water Oxidation at Industrial Operating Conditions.

Efficient noble-metal free electrocatalyst for oxygen evolution reaction (OER) is critical for large-scale hydrogen production via water splitting. Inspired by Nature's oxygen evolution cluster in photosystem II and the highly efficient artificial OER catalyst of NiFe layered double hydroxide (LDH), we designed an electrostatic 2D-2D assembly route and successfully synthesized a 2D LDH(+)-Birnessite(-) hybrid. The as-constructed LDH(+)-Birnessite(-) hybrid catalyst showed advanced catalytic activity and excellent stability towards OER under a close to industrial hydrogen production condition (85 °C and 6 M KOH) for more than 20 h at the current densities larger than 100 mA cm-2 . Experimentally, we found that besides the enlarged interlayer distance, the flexible interlayer NiFe LDH(+) also modulates the electronic structure of layered MnO2 , and creates an electric field between NiFe LDH(+) and Birnessite(-), wherein OER occurs with a greatly decreased overpotential. DFT calculations confirmed the interlayer LDH modulations of the OER process, attributable to the distinct electronic distributions and environments. Upshifting the Fe-3d orbitals in LDH promotes electron transfer from the layered MnO2 to LDH, significantly boosting up the OER performance. This work opens a new way to fabricate highly efficient OER catalyst for industrial water oxidation.

Interactions of Oxide Surfaces with Water Revealed with Solid-State NMR Spectroscopy.

Hydrous materials are ubiquitous in the natural environment and efforts have previously been made to investigate the structures and dynamics of hydrated surfaces for their key roles in various chemical and physical applications, with the help of theoretical modeling and microscopy techniques. However, an overall atomic-scale understanding of the water-solid interface, including the effect of water on surface ions, is still lacking. Herein, we employ ceria nanorods with different amounts of water as an example and demonstrate a new approach to explore the water-surface interactions by using solid-state NMR in combination with density functional theory. NMR shifts and relaxation time analysis provide detailed information on the local structure of oxygen ions and the nature of water motion on the surface: the amount of molecularly adsorbed water decreases rapidly with increasing temperature (from room temperature to 150 °C), whereas hydroxyl groups are stable up to 150 °C, and dynamic water molecules are found to instantaneously coordinate to the surface oxygen ions. The applicability of dynamic nuclear polarization for selective detection of surface oxygen species is also compared to conventional NMR with surface selective isotopic-labeling: the optimal method depends on the feasibility of enrichment and the concentration of protons in the sample. These results provide new insight into the interfacial structure of hydrated oxide nanostructures, which is important to improve performance for various applications.

Crystal-Facet Modulated CrOx/γ-Al2O3: Quasi-Liquid Surface Modification by Bonded Polydimethylsiloxane for Catalytic Oxidation of Propene.

The crystal-facet effect of catalytic supports plays a crucial role in tailoring the physicochemical properties of active sites and the surface chemically bonded polymer can also regulate the local environment around active sites for optimizing catalytic performance. Herein, we report the effect of exposed facets of γ-Al2O3 supports and further modification by surface bonded long-chain polydimethylsiloxane (PDMS) on the properties of CrOx/γ-Al2O3 catalysts for selective oxidation of propene. The {111} facets of γ-Al2O3 stabilize "non-redox Cr3+" and promote the overall oxidation rates compared with catalysts on {110} facets of γ-Al2O3. The surface bonded PDMS, with grafting density being about 0.13 chains/nm2, endows a hydrophobic environment to facilitate the enrichment of the hydrophobic substrate and the desorption of hydrophilic products and occupies some acid sites on catalysts to limit acid-catalyzed side reactions. The inherent liquidlike nature of bonded PDMS also forms a setting that can regulate the redox ability of surface Cr species, that lead to modified activation of oxygen toward more surface adsorbed species. As a result, the modified catalysts enhance the whole oxidation process with favorable formation of epoxide product at low reaction temperatures (<225 °C). Our findings highlight the impact of surface chemically bound polydimethylsiloxane (PDMS) upon tailoring the surroundings of the catalyst surface, and that combined with facet-effect of supports can tune the reaction process toward selective ones.

Morphology-Reserved Synthesis of Discrete Nanosheets of CuO@SAPO-34 and Pore Mouth Catalysis for One-Pot Oxidation of Cyclohexane.

Discrete nanosheets of silicon-doped AlPO4 molecular sieves (SAPO-34) with a thickness of ≈7 nm have been prepared through morphology-reserved synthesis with a lamellar aluminum phosphate as precursor. Cages of the nanosheets are in situ incorporated with copper oxide clusters. The CuO@SAPO-34 nanosheets exhibit a large external surface area with a high number of (010) channel pores on the surface. Due to the thin morphology, copper oxide clusters occupy the outmost cages with a probability >50 %. The distinctive configuration facilitates a new concept of pore mouth catalysis, i.e., reactant molecules larger than the pores cannot enter the interior of the molecular sieves but can interact with the CuO clusters at "the mouth" of the pore. In heterogeneous catalysis, CuO@SAPO-34 nanosheets have shown top performance in one-pot oxidation of cyclohexane to adipic acid by O2 , a key compound for the manufacture of nylon-66, which is so far produced using non-green nitric acid oxidation.

Modulating Lattice Oxygen in Dual-Functional Mo-V-O Mixed Oxides for Chemical Looping Oxidative Dehydrogenation.

Oxygen chemistry plays a pivotal role in numerous chemical reactions. In particular, selective cleavage of C-H bonds by metal oxo species is highly desirable in dehydrogenation of light alkanes. However, high selectivity of alkene is usually hampered through consecutive oxygenation reactions in a conventional oxidative dehydrogenation (ODH) scheme. Herein, we show that dual-functional Mo-V-O mixed oxides selectively convert propane to propylene via an alternative chemical looping oxidative dehydrogenation (CL-ODH) approach. At 500 °C, we obtain 89% propylene selectivity at 36% propane conversion over 100 dehydrogenation-regeneration cycles. We attribute such high propylene yield-which exceeds that of previously reported ODH catalysts-to the involvement and precise modulation of bulk lattice oxygen via atomic-scale doping of Mo and show that increasing the binding energy of V-O bonds is critical to enhance the selectivity of propylene. This work provides the fundamental understanding of metal-oxygen chemistry and a promising strategy for alkane dehydrogenation.

Antimony-doped tin oxide nanoparticles as peroxidase mimics for paper-based colorimetric detection of glucose using smartphone read-out.

Antimony-doped tin oxide nanoparticles (ATO NPs) were loaded on a filter paper where they act as a peroxidase mimic without electrochemical or photochemical assistance. The peroxidase mimicking activity is distinctly improved compared to most known nanomaterials and to natural horseradish peroxidase. The catalytic properties depend on the amount of antimony doped into the ATO NPs. A glucose assay was worked out that is based on (a) the oxidation of glucose by glucose oxidase under formation of H2O2, (b) the oxidation of 3,3,5,5-tetramethybenzidine (TMB) catalyzed by ATO NPs to form blue-green colored oxidized TMB on the surface of the paper. The coloration was analyzed with a smartphone. The method has a 21 µM limit of detection and a linear range that extends from 0.5 to 80 mM. Graphical abstract Antimony-doped tin oxide nanoparticles (ATO NPs) combined with 3,3,5,5-tetramethybenzidine (TMB) and triethylamine were coated on the filter paper. After addition of sample solution, the blue-green colored oxidized TMB was generated and recorded by a digital camera.

Direct Conversion of Syngas into Methyl Acetate, Ethanol, and Ethylene by Relay Catalysis via the Intermediate Dimethyl Ether.

Selective conversion of syngas (CO/H2 ) into C2+ oxygenates is a highly attractive but challenging target. Herein, we report the direct conversion of syngas into methyl acetate (MA) by relay catalysis. MA can be formed at a lower temperature (ca. 473 K) using Cu-Zn-Al oxide/H-ZSM-5 and zeolite mordenite (H-MOR) catalysts separated by quartz wool (denoted as Cu-Zn-Al/H-ZSM-5|H-MOR) and also at higher temperatures (603-643 K) without significant deactivation using spinel-structured ZnAl2 O4 |H-MOR. The selectivity of MA and acetic acid (AA) reaches 87 % at a CO conversion of 11 % at 643 K. Dimethyl ether (DME) is the key intermediate and the carbonylation of DME results in MA with high selectivity. We found that the relay catalysis using ZnAl2 O4 |H-MOR|ZnAl2 O4 gives ethanol as the major product, while ethylene is formed with a layer-by-layer ZnAl2 O4 |H-MOR|ZnAl2 O4 |H-MOR combination. Close proximity between ZnAl2 O4 and H-MOR increases ethylene selectivity to 65 %.

One-Pot Synthesis of Zeolitic Strong Solid Bases: A Family of Alkaline-Earth Metal-Containing Silicalite-1.

Fabricating stable strong basic sites in well-preserved crystallized zeolitic frameworks still remains a difficult issue. Here, we reported a family of MFI-type metallosilicate zeolites, AeS-1 (Ae: alkaline-earth metal ions of Mg, Ca, Sr or Ba; S-1: silicalite-1) through a direct one-pot hydrothermal method involving the acidic co-hydrolysis/condensation of the silica precursor with the Ae salts. Step-by-step full characterizations were designed and conducted for in-depth discussion of the Ae status in AeS-1. Strong basicity (H_≈22.5-26.5) was detected in AeS-1. The basicity was further confirmed by CO2 sorption measurements, (13) C NMR spectra of chloroform-adsorbed samples, and (1) H→(13) C and (1) H→(29) Si cross-polarization magic-angle spinning NMR spectra of ethyl cyanoacetate-adsorbed samples. The results of Knoevenagel condensations demonstrated the excellent solid base catalysis of AeS-1, which showed high activity, reusability, and shape-selectivity, all of which are explained by Ae-derived zeolitic intracrystalline strong basic sites.

MoO2@carbon hollow microspheres with tunable interiors and improved lithium-ion battery anode properties.

MoO2 hollow microspheres with tunable inner space have been synthesized through a hydrothermal process using MoO3 microbelts instead of bulk MoO3 as the precursor. It is found that the reactant morphology has a great impact on the product morphology and the inner space can be tuned by changing the amount of NaOH aqueous solution. An interesting evolutional process from MoO3 microbelts through a rose-like intermediate to MoO2 hollow microspheres has been clearly observed, and thus the possible formation mechanism is revealed. One layer of amorphous carbon has been subsequently coated on the surface of MoO2 hollow microspheres through a simple hydrothermal approach followed by annealing in argon. As the anode material for lithium ion batteries, MoO2@C hollow microspheres manifest excellent lithium-storage properties, such as high capacity (677 mA h g(-1)) and good cycling stability (negligible capacity fading even after 80 cycles). The significantly enhanced performance of MoO2@C hollow microspheres can be attributed to its unique structures, such as nanoscaled primary building blocks, carbon coating, hollow structure, and especially the synergy between the carbon coating and hollow structure.

Oxygen dynamic exchange and diffusion characteristics of ZnO nanorods from 17O MAS NMR.

Interactions of ZnO nanorods with water and the dynamic migration characteristic of surface oxygen species are important in controlling its structure and catalytic properties. Here, we apply 17O solid-state NMR spectroscopy to investigate the interactions, as well as oxygen ion diffusion properties of ZnO nanorods under different conditions.

Fine control for the preparation of ceria nanorods (111).

The morphologies and exposed surfaces of ceria nanocrystals are important factors in determining their performance. In order to establish a structure-property relationship for ceria nanomaterials, it is essential to have materials with well-defined morphologies and specific exposed facets. This is also crucial for acquiring high resolution 17O solid-state NMR spectra. In this study, we explore the synthesis conditions for preparing CeO2 nanorods with exposed (111) facets. The effects of alkali concentration, hydrothermal temperature and time, cerium source and oxidation agent are investigated and optimal synthesis conditions are found. The resulting CeO2 nanorods show very narrow 17O NMR peaks for the oxygen ions in the first, second and third layers, providing a foundation for future research on mechanisms involving ceria materials using 17O solid-state NMR spectroscopy.

Flexible-in-rigid polycrystalline titanium nanofibers: a toughening strategy from a macro-scale to a molecular-scale.

TiO2 nanomaterials, especially one-dimensional TiO2 nanofibers fabricated by electrospinning, have received considerable attention in the past two decades, for a variety of basic applications. However, their safe use and easy recycling are still hampered by the inherently subpar mechanical performance. Here, we toughened polycrystalline TiO2 nanofibers by introducing Al3+-species at the very beginning of electrospinning. The resultant long-and-continuous TiO2 nanofibers achieved a Young's modulus of 653.8 MPa, which is ca. 25-fold higher than that of conventional TiO2 nanofibers. Within each nanofiber, amorphous Al2O3-based oxide effectively hindered the coalescence of TiO2 nanocrystals and potentially repaired the surface groves. The solid-state 17O-NMR spectra further revealed the toughening strategy on a molecular scale, where relatively flexible Ti-O-Al bonds replaced rigid O-Ti-O bonds at the interfaces of TiO2 and Al2O3. Moreover, the modified TiO2 nanofibers exhibited superb sinter-resistance, without cracking over 900 °C, which was dynamically monitored by TEM. Therefore, flexible-in-rigid TiO2 fibrous mats can be facilely folded into 3D sponges through origami art. As a potential showcase, the TiO2 sponges were demonstrated as a duarable and renewable filtrator with a high filtration efficiency of 99.97% toward PM2.5 and 99.99% toward PM10 after working for 300 min. This work provides a rational strategy to produce flexible oxide nanofibers and gives an in-depth understanding of the toughening mechanism from the macro-scale to the molecular-scale.

COx hydrogenation to methanol and other hydrocarbons under mild conditions with Mo3S4@ZSM-5.

The hydrogenation of CO2 or CO to single organic product has received widespread attentions. Here we show a highly efficient and selective catalyst, Mo3S4@ions-ZSM-5, with molybdenum sulfide clusters ([Mo3S4]n+) confined in zeolitic cages of ZSM-5 molecular sieve for the reactions. Using continuous fixed bed reactor, for CO2 hydrogenation to methanol, the catalyst Mo3S4@NaZSM-5 shows methanol selectivity larger than 98% at 10.2% of carbon dioxide conversion at 180 °C and maintains the catalytic performance without any degeneration during continuous reaction of 1000 h. For CO hydrogenation, the catalyst Mo3S4@HZSM-5 exhibits a selectivity to C2 and C3 hydrocarbons stably larger than 98% in organics at 260 °C. The structure of the catalysts and the mechanism of COx hydrogenation over the catalysts are fully characterized experimentally and theorectically. Based on the results, we envision that the Mo3S4@ions-ZSM-5 catalysts display the importance of active clusters surrounded by permeable materials as mesocatalysts for discovery of new reactions.

Solid-state MAS NMR studies of Brønsted acid sites in zeolite H-Mordenite.

(17)O-(1)H double resonance NMR spectroscopy was used to study the local structure of zeolite H-Mordenite. Different contact times were used in cross-polarization magic angle spinning (CPMAS) NMR, CP rotational-echo double resonance (CP-REDOR) NMR, and heteronuclear correlation (HETCOR) NMR spectroscopy to distinguish between Brønsted acid sites with different O-H distances. The accessibility of the various Brønsted acid sites was quantified by adsorbing the basic probe molecule trimethylphosphine in known amounts. On the basis of these experiments, locations of different Brønsted acid sites in H-Mordenite (H-MOR) were proposed. The use of (17)O chemical shift correlations to help assign sites is discussed.

Insights into memory effect mechanisms of layered double hydroxides with solid-state NMR spectroscopy.

Layered double oxides (LDOs) can restore the parent layered double hydroxides (LDHs) structure under hydrous conditions, and this "memory effect" plays a critical role in the applications of LDHs, yet the detailed mechanism is still under debate. Here, we apply a strategy based on ex situ and in situ solid-state NMR spectroscopy to monitor the Mg/Al-LDO structure changes during recovery at the atomic scale. Despite the common belief that aqueous solution is required, we discover that the structure recovery can occur in a virtually solid-state process. Local structural information obtained with NMR spectroscopy shows that the recovery in aqueous solution follows dissolution-recrystallization mechanism, while the solid-state recovery is retro-topotactic, indicating a true "memory effect". The amount of water is key in determining the interactions of water with oxides, thus the memory effect mechanism. The results also provide a more environmentally friendly and economically feasible LDHs preparation route.

Identification of CO2 adsorption sites on MgO nanosheets by solid-state nuclear magnetic resonance spectroscopy.

The detailed information on the surface structure and binding sites of oxide nanomaterials is crucial to understand the adsorption and catalytic processes and thus the key to develop better materials for related applications. However, experimental methods to reveal this information remain scarce. Here we show that 17O solid-state nuclear magnetic resonance (NMR) spectroscopy can be used to identify specific surface sites active for CO2 adsorption on MgO nanosheets. Two 3-coordinated bare surface oxygen sites, resonating at 39 and 42 ppm, are observed, but only the latter is involved in CO2 adsorption. Double resonance NMR and density functional theory (DFT) calculations results prove that the difference between the two species is the close proximity to H, and CO2 does not bind to the oxygen ions with a shorter O···H distance of approx. 3.0 Å. Extensions of this approach to explore adsorption processes on other oxide materials can be readily envisaged.