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Background: Non-small cell lung cancer (NSCLC) is the most prevalent cancer in the world. Chemotherapy resistance is a major obstacle to NSCLC therapy. This study aimed to explore the role and molecular mechanism of circular RNA 0011292 (circ_0011292) in tumorigenesis and chemoresistance of NSCLC. Methods: The levels of circ_0011292, miR-379-5p, and tripartite motif-containing protein 65 (TRIM65) were measured by quantitative real-time polymerase chain reaction or Western blot assay. Cell proliferation was assessed by Cell Counting Kit-8 (CCK-8) assay. Cell apoptosis was monitored by flow cytometry. Cell migration and invasion were detected by transwell assay. The levels of apoptosis-related and epithelial-mesenchymal transition-related proteins were examined by Western blot. The half-inhibition concentration (IC50) of paclitaxel (PTX) was evaluated by CCK-8 assay. Xenograft model was established to analyze the effect of circ_0011292 on PTX resistance of NSCLC in vivo. The interaction among circ_0011292, miR-379-5p, and TRIM65 was verified by dual-luciferase reporter assay and RNA immunoprecipitation assay. Results: Circ_0011292 and TRIM65 were upregulated, while miR-379-5p was downregulated in NSCLC tissues and cells. Circ_0011292 knockdown hindered NSCLC progression and enhanced PTX sensitivity of NSCLC. Circ_0011292 silencing reduced PTX resistance in vivo. Besides, miR-379-5p potentiated PTX sensitivity by targeting TRIM65. Also, circ_0011292 increased PTX resistance by sponging miR-379-5p. Conclusion: Circ_0011292 facilitated tumorigenesis and PTX resistance in NSCLC by regulating the miR-379-5p/TRIM65 axis, suggesting that circ_0011292 was a promising therapeutic target for NSCLC chemotherapy.

Given the limited product variety of electrocatalytic CO2 reduction reactions solely from CO2 and H2O as the reactants, it is desirable to expand the product scope by introducing additional reactants that provide elemental diversity. The integration of inorganic heteroatom-containing reactants into electrocatalytic CO2 reduction could, in principle, enable the sustainable synthesis of valuable products, such as organonitrogen compounds, which have widespread applications but typically rely on NH3 derived from the energy-intensive and fossil-fuel-dependent Haber-Bosch process for their industrial-scale production. In this Perspective, research progress toward building C-N bonds in N-integrated electrocatalytic CO2 reduction is highlighted, and the electrosyntheses of urea, acetamides, and amines are examined from the standpoints of reactivity, catalyst structure, and, most fundamentally, mechanism. Mechanistic discussions of C-N coupling in these advances are emphasized and critically evaluated, with the aim of directing future investigations on improving the product yield and broadening the product scope of N-integrated electrocatalytic CO2 reduction.

The development of benign methylation reactions utilizing CO2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, we report the first electrochemical reductive N-methylation reaction with CO2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO2, with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO2 and nitro-compounds are reduced concurrently to yield N-methylamines with high monomethylation selectivity via the overall transfer of 12 electrons and 12 protons.

Lithium titanium oxide (Li2TiO3) tritium breeder ceramic plates with nano- and coarse-grain size were fabricated. The preparation methods contained CTAB-modifying precursor, combining dry-pressing with isostatically cold-pressing, and calcinating at optimized sintering temperature in turn. Then their properties were characterized after radiation by 280 keV helium (He+) ion. Extensive characterization analyses were performed to reveal the changes in nano-grained and coarse-grained Li2TiO3 after radiation. They contained glancing angle X-ray diffraction (GIXRD), atomic force microscopy (AFM), electron spin resonance (ESR), and scanning electron microscopy (SEM). The results showed as follows, GIXRD peak position of the nano-grained Li2TiO3 was more stable than the coarse-grained Li2TiO3 after radiation. Nano-grained Li2TiO3 was less rough and swollen than the coarse-grained one after radiation. Nano-grained Li2TiO3 had more excellent structural stability and less defect concentration of Eʹ-center after radiation. As a result, nano-grained Li2TiO3 might have much better radiation tolerance than the coarse-grained one by comparing characterization results.

Na metal anode receives increasing attention as a low-cost alternative to Li metal anode for the application in high energy batteries. Despite extensive research efforts to improve the reversibility and cycle life of Na metal electrodes, their rate performance, i.e. electrochemical plating and stripping of Na metal at high current, is underexplored. Herein, we report that Na metal electrodes, unlike the more widely studied Li metal electrodes which survive high current density up to 20 mA/cm2, cannot be fast charged or discharged in common ether electrolyte. The fast charging, namely metal plating, is comprised by severe side reactions that decompose electrolyte into electrochemically inactive Na(I) solid species. The fast discharging, namely metal stripping, is disabled by local Na removal that deteriorates the electrical contact with the current collector. While the fast charging failure is permanent, the capacity loss from fast discharging can be recovered through a restructuring process at a low discharging current which rebuilds the electrical connection. We further reveal that the unsatisfactory rate performance of Na metal electrodes is associated with intrinsic physicochemical properties of Na. This study delineates the mechanistic origins of Na's limitation in fast plating and stripping, and demonstrates the necessity of improving the charging and discharging rate performance of Na metal electrodes.

In perovskite solar cells, doped organic semiconductors are often used as charge-extraction interlayers situated between the photoactive layer and the electrodes. The π-conjugated small molecule 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9-spirobifluorene (spiro-OMeTAD) is the most frequently used semiconductor in the hole-conducting layer1-6, and its electrical properties considerably affect the charge collection efficiencies of the solar cell7. To enhance the electrical conductivity of spiro-OMeTAD, lithium bis(trifluoromethane)sulfonimide (LiTFSI) is typically used in a doping process, which is conventionally initiated by exposing spiro-OMeTAD:LiTFSI blend films to air and light for several hours. This process, in which oxygen acts as the p-type dopant8-11, is time-intensive and largely depends on ambient conditions, and thus hinders the commercialization of perovskite solar cells. Here we report a fast and reproducible doping method that involves bubbling a spiro-OMeTAD:LiTFSI solution with CO2 under ultraviolet light. CO2 obtains electrons from photoexcited spiro-OMeTAD, rapidly promoting its p-type doping and resulting in the precipitation of carbonates. The CO2-treated interlayer exhibits approximately 100 times higher conductivity than a pristine film while realizing stable, high-efficiency perovskite solar cells without any post-treatments. We also show that this method can be used to dope π-conjugated polymers.

The electrochemical reduction of carbon dioxide is an appealing technology that stores renewable electricity in the chemical form and has the potential to transform the way carbon fuels are utilized today. While there have been successes in the electrosynthesis of alkanes, alkenes and alcohols, access to organonitrogen molecules such as alkylamines remains largely beyond the reach of current electrocatalysis. Here we report the first electrochemical reaction that converts carbon dioxide and nitrate to methylamine in aqueous media under ambient conditions catalysed by a cobalt β-tetraaminophthalocyanine molecular catalyst supported on carbon nanotubes. The overall reaction, involving the transfer of 14 electrons and 15 protons to form each methylamine molecule, is an eight-step catalytic cascade process enabled by the coupling of two reactive intermediates near the catalyst surface. The key C–N bond-forming step is found to be the spillover of hydroxylamine from nitrate reduction and its subsequent condensation with formaldehyde from carbon dioxide reduction. This study provides a successful example of sustainable alkylamine synthesis from inorganic carbon and nitrogen wastes, which could contribute to greenhouse gas mitigation for a carbon-neutral future. The electroreduction of CO2 provides a sustainable pathway to value-added fuels and chemicals. Here the authors show a cascade reaction that yields methylamine from CO2 and nitrate. With detailed insight into the multistep catalytic process, the current findings further push the boundaries of this technology.

Wastewater treatment is one of the focuses in current society, and the removal of heavy metal ions from it is crucial in wastewater treatment. Polyvinyl alcohol (PVA) nanofibers play a certain role in the adsorption of heavy metal ions, but their adsorption capacity is limited. In this work, maleic anhydride (MAH) was first grafted onto the molecular chain of PVA. Then through the condensation of the carboxyl group and the amino group, the octaamino-POSS was successfully grafted on the PVA molecular chain. Two kinds of nanofibers, PVA/octaamino-POSS nanofibers as well as PVA-g-POSS nanofibers, were fabricated by electrospinning technology for the adsorption of Pb2+ and Cu2+ in wastewater. The preparation of PVA/octaamino-POSS was used to compare which metal ion adsorption process was more stable, physical blending or chemical grafting. With the increase of contact time, the adsorption capacity of PVA/octaamino-POSS nanofibers to Cu2+ increased at first and then decreased. It was observed that the adsorption capacity of PVA-g-POSS to heavy metal ions was higher than that of PVA/octaamino-POSS. With the increase of octaamino-POSS content, the equilibrium adsorption of Pb2+ and Cu2+ on PVA-g-POSS nanofibers was significantly improved, with prominent adsorption effect for Cu2+. Based on the analysis of quasi-first-order and quasi-second-order dynamic equation, it was deduced that the chemical adsorption and physical adsorption worked together in the adsorption process of Pb2+ and Cu2+ by PVA-g-POSS, and chemical adsorption played a major role.

Li1.5Al0.5Ge1.5(PO4)3 (LAGP) is a solid-state electrolyte with high ionic conductivity and air stability but poor chemical stability and high interfacial impedance when directly contacted with Li metal. In this work, we develop an inorganic/polymer hybrid interlayer composed of Li bis(trifluoromethylsulfonyl)imide/poly(vinylene carbonate) polymer electrolyte and SiO2 submicrospheres to stabilize the Li/LAGP interface. The polymeric component renders high ionic conductance and low interfacial resistance, whereas the inorganic component imparts flame retardancy and a physical barrier to the known Li-LAGP side reaction, together enabling stable Li stripping/plating for more than 1,500 h at room temperature. With this interlayer at both electrodes, all-solid-state Li∥LiFePO4 full cells with stable cycling performance are also demonstrated.

Electrochemical reduction of CO2 is a promising route for sustainable production of fuels. A grand challenge is developing low-cost and efficient electrocatalysts that can enable rapid conversion with high product selectivity. Here we design a series of nickel phthalocyanine molecules supported on carbon nanotubes as molecularly dispersed electrocatalysts (MDEs), achieving CO2 reduction performances that are superior to aggregated molecular catalysts in terms of stability, activity and selectivity. The optimized MDE with methoxy group functionalization solves the stability issue of the original nickel phthalocyanine catalyst and catalyses the conversion of CO2 to CO with >99.5% selectivity at high current densities of up to −300 mA cm−2 in a gas diffusion electrode device with stable operation at −150 mA cm−2 for 40 h. The well-defined active sites of MDEs also facilitate the in-depth mechanistic understandings from in situ/operando X-ray absorption spectroscopy and theoretical calculations on structural factors that affect electrocatalytic performance. Widespread deployment of electrochemical CO2 reduction requires low-cost catalysts that perform well at high current densities. Zhang et al. show that methoxy-functionalized nickel phthalocyanine molecules on carbon nanotubes can operate as high-performing molecularly dispersed electrocatalysts at current densities of up to −300 mA cm–2.

Cu is a well-known electrocatalyst for reducing CO2 to various products. However, unmodified Cu exhibits poor selectivity and activity for formate production. Our in situ Raman spectroscopy study d...

The local pH variation near the surface of CO2 reduction electrodes is important but hard to study. We develop a continuous-flow Raman electrochemical cell that enables the first experimental study of the local pH near a CO2 reduction gas diffusion electrode under reaction conditions. At zero current, CO2 chemically reacts with the 1 M KOH electrolyte at the interface to form HCO3- and CO32-. The local pH on the cathode surface is 7.2, and the HCO3- concentration profile extends a distance of 120 μm into the electrolyte, which verifies that the nominal overpotential reduction from using alkaline electrolyte originates from the Nernst potential of the pH gradient layer at the cathode/electrolyte interface. The CO2-OH- neutralization reaction and the pH gradient layer still persist, albeit to a reduced extent, at CO2 reduction current densities up to 150 mA/cm2.

Bismuth layer-structured BaBi2Nb2O9 (BBN) and BaBi2Ta2O9 (BBT) relaxor ferroelectric ceramics were explored as potential energy storage materials. Remarkable energy storage performances were obtained in both BBN and BBT ceramics, featured by large recoverable energy storage density (~0.84 J/cm3 and ~0.68 J/cm3) and high energy storage efficiency (~90% and ~94%), respectively. Furthermore, both the two ceramics exhibit good thermal and frequency stabilities. Delightedly, both the BBN and BBT ceramics can complete the discharge process within 0.15 μs, resulting in ultrahigh current density of 195 A/cm2 and 234 A/cm2 and excellent power density of 10.74 MW/cm3 and 12.89 MW/cm3, respectively. The obtained results suggest that BaBi2Nb2O9 and BaBi2Ta2O9 ceramics could have a promising future in energy storage applications. This study also demonstrates that the bismuth layer-structured relaxor ferroelectric ceramic can be considered as a novel potential lead-free energy storage materials, in addition to the widely studied pervoskite-structured relaxor ferroelectric ceramics.

Developing electrolytes compatible with efficient and reversible cycling of electrodes is critical to the success of rechargeable Li metal batteries (LMBs). The Coulombic efficiencies and cycle lives of LMBs with ethylene carbonate (EC), dimethyl carbonate, ethylene sulfite (ES), and their combinations as electrolyte solvents show that in a binary-solvent electrolyte the extent of electrolyte decomposition on the electrode surface is dependent on the solvent component that dominates the solvation sheath of Li+ . This knowledge led to the development of an EC-ES electrolyte exhibiting high performance for Li||LiFePO4 batteries. Carbonate molecules occupy the solvation sheath and improve the Coulombic efficiencies of both the anode and cathode. Sulfite molecules lead to desirable morphology and composition of the solid electrolyte interphase and extend the cycle life of the Li metal anode. The cooperation between these components provides a new example of electrolyte optimization for improved LMBs.

A novel mass production method of lithium titanite (Li2TiO3) tritium breeder ceramic pebbles using polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) assisted granulation method (APG) was proposed. A binder solution of polyvinyl alcohol (PVA) was used to modify the Li2TiO3 precursor powder. The powders with adhesive properties were prilled to form green pebbles (GPs) by spheronization at a low rotation speed and spraying with polyvinyl pyrrolidone (PVP), in several cycles. Then, the density and the crush load of the GPs were improved by high-speed rolling. Finally, the ceramic pebbles were produced by sintering. The phase, the microstructure, and the crush load of the ceramic pebbles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and with a universal tester, respectively.

Polysaccharide has been considered as an important bioactive compound in Codonopsis lanceolata. High fat/high sucrose (HFHS) diet-induced insulin resistance is implicated in multiple metabolic diseases, such as type 2 diabetes mellitus (T2DM) and nonalcoholic fatty liver disease (NAFLD), these metabolic diseases has become epidemic health issue worldwide. In this study, the effect of C. lanceolata polysaccharide (CLPS) on improving insulin sensitivity in chronic HFHS diet-fed mice was investigated. Our data indicates that CLPS significantly reduced fasting blood glucose (FBG), fasting serum insulin (FINS) and insulin resistance index, in parallel with improved glucose and insulin tolerance impaired by HFHS diet. Impaired phosphorylation of PKB/Akt and hyperphosphorylation of IRS-1 at Ser307 were observed in the mice fed with HFHS diet, and those defects were also rescued by CLPS administration. In addition, CLPS caused a significant decrease in the level of malondialdehyde (MDA), and an increase in reduced glutathione (GSH)/oxidised glutathione (GSSG) ratio; concurrent with enhanced expression of antioxidant enzymes including superoxide dismutase (SOD) and catalase (CAT), and activated Nrf2 signaling. In summary, these findings suggest that CLPS ameliorates HFHS diet-induced insulin resistance through activating anti-oxidative signaling pathway, providing new insights into the protective effects of C. lanceolata polysaccharide in metabolic disease.

Here, we report the quantitative electroreduction of CO2 to CO by a PNP-pincer iridium(i) complex bearing amino linkers in DMF/water. The electrocatalytic properties greatly depend on the choice of linker within the ligand. The complex 3-N is far superior to the analogues with methylene and oxygen linkers, showing higher activity and better selectivity for CO2 over proton reduction.

Electrochemical carbon dioxide (CO2) reduction can in principle convert carbon emissions to fuels and value-added chemicals, such as hydrocarbons and alcohols, using renewable energy, but the efficiency of the process is limited by its sluggish kinetics1,2. Molecular catalysts have well defined active sites and accurately tailorable structures that allow mechanism-based performance optimization, and transition-metal complexes have been extensively explored in this regard. However, these catalysts generally lack the ability to promote CO2 reduction beyond the two-electron process to generate more valuable products1,3. Here we show that when immobilized on carbon nanotubes, cobalt phthalocyanine—used previously to reduce CO2 to primarily CO—catalyses the six-electron reduction of CO2 to methanol with appreciable activity and selectivity. We find that the conversion, which proceeds via a distinct domino process with CO as an intermediate, generates methanol with a Faradaic efficiency higher than 40 per cent and a partial current density greater than 10 milliamperes per square centimetre at −0.94 volts with respect to the reversible hydrogen electrode in a near-neutral electrolyte. The catalytic activity decreases over time owing to the detrimental reduction of the phthalocyanine ligand, which can be suppressed by appending electron-donating amino substituents to the phthalocyanine ring. The improved molecule-based electrocatalyst converts CO2 to methanol with considerable activity and selectivity and with stable performance over at least 12 hours. Individual cobalt phthalocyanine derivative molecules immobilized on carbon nanotubes effectively catalyse the electroreduction of CO2 to methanol via a domino process with high activity and selectivity and stable performance.

Lithium metatitanate (Li2TiO3) ceramic pebbles were fabricated from the powder synthesised via low-temperature solid-state precursor method. Solid H2TiO3 and LiOH·H2O react chemically during ball milling process to form a nano-sized precursor powder. Pure β-Li2TiO3 powder can be obtained by calcining the precursor powder at 500 °C, which is half the temperature of conventional solid-state method. The synthesis process is simple and low-cost, which would be more available to achieve batch production among all feasible techniques. The low-temperature calcination will effectively avoid hard particle aggregates and poor sinterability caused by high-temperature heat treatment, which is conducive to prepare ceramics with good properties. The results show that the powder exhibits high sinterability with small particle size of 19 nm. The Li2TiO3 ceramic pebbles sintered at 800 °C have small grain size (470 nm), high relative density (83%) and good crush load (45 N), which has great potential as tritium breeding materials for fusion reactors.

Carbon-based CsPbI3 perovskite solar cells (CsPbI3 C-PSCs) without hole-transporting materials have been attracting much attention because of their high stability. However, the electron transport l...

Water splitting is an efficient strategy to produce purity hydrogen and convert intermittent electricity from renewable wind and solar sources. In this work, dense NiMoO4 micro-pillars arrays (MPAs) were in-situ grown on nickel foam (NF) through facile hydrothermal method, then the NiMoO4/NF were converted into NiMoO4–P/NF and NiFe/NiMoO4/NF via phosphating and electrodeposition method, respectively. The NiMoO4–P/NF electrode required small overpotentials of 34 mV@10 mA cm−2 and 130 mV@100 mA cm−2 for hydrogen evolution reaction (HER). The NiFe/NiMoO4/NF electrode exhibited excellent oxygen evolution reaction (OER) activity with overpotentials of 210 mV@10 mA cm−2 and 300 mV@100 mA cm−2. The overall water splitting using the anode-cathode couple of NiFe/NiMoO4/NF||NiMoO4–P/NF only consumes low voltages of 1.47 V@10 mA cm−2 for 100 h and 1.66 V@100 mA cm−2 for 50 h in 1 M KOH. The electronic modification and the well-designed hierarchical structure contribute the high energy-efficient and stabile overall water splitting.

A single device combining the functions of a CO2 electrolyzer and a formate fuel cell is a new option for carbon-neutral energy storage but entails rapid, reversible and stable interconversion between CO2 and formate over a single catalyst electrode. We report a new catalyst with such functionalities based on a Pb-Pd alloy system that reversibly restructures its phase, composition, and morphology and thus alters its catalytic properties under controlled electrochemical conditions. Under cathodic conditions, the catalyst is relatively Pb-rich and is active for CO2 -to-formate conversion over a wide potential range; under anodic conditions, it becomes relatively Pd-rich and gains stable catalytic activity for formate-to-CO2 conversion. The bifunctional activity and superior durability of our Pb-Pd catalyst leads to the first proof-of-concept demonstration of an electrochemical cell that can switch between the CO2 electrolyzer/formate fuel cell modes and can stably operate for 12 days.

The tritium release behavior of the Li4SiO4 pebbles and Li4SiO4 + 5 mol% TiO2 pebbles with small grain sizes was investigated. The tritium release results of Li4SiO4 pebbles with different grain sizes (0.3 μm and 1.5 μm) indicated that the grain size had little effect on the tritium release regardless of the difference in gas composition of purge gas. Moreover, the tritium release of small grained pebbles was dominated by the desorption process, since the addition of H2 to purge gas substantially affected the release behavior. The modified Li4SiO4 pebbles with addition of TiO2 exhibited enhanced water formation capacity due to the increased concentration of active point as the oxygen supplier. Obvious tritiated water release peaks around 690 °C could be observed from the Li4SiO4 + 5 mol% TiO2 pebbles under 0.1%H2+He purge gas. The modified Li4SiO4 pebbles also showed improved tritium release behavior, the tritium release peaks shifted to lower temperatures compared to Li4SiO4 pebbles.

Multi-component materials are a new trend in catalyst development for electrochemical CO2 reduction. Understanding and managing the chemical interactions within a complex catalyst structure may unlock new or improved reactivity, but is scientifically challenging. We report the first example of capping ligand-dependent metal–oxide interactions in Au/SnO2 structures for electrocatalytic CO2 reduction. Cetyltrimethylammonium bromide capping on the Au nanoparticles enables bifunctional CO2 reduction where CO is produced at more positive potentials and HCOO− at more negative potentials. With citrate capping or no capping, the Au–SnO2 interactions steer the selectivity toward H2 evolution at all potentials. Using electrochemical CO oxidation as a probe reaction, we further confirm that the metal–oxide interactions are strongly influenced by the capping ligand.

The development of lead-free ceramics with appropriate energy storage properties is essential for the successful practical application of advanced electronic devices. In this study, a site engineering strategy was proposed to concurrently decrease grain size, increase the band-gap, and enhance the relaxor nature in Ta-doped tungsten bronze ceramics (Sr2NaNb5-xTaxO15) for the improvement of the dielectric breakdown strength and the polarization difference. As a result, the ceramic with x = 1.5, that is, Sr2NaNb3.5Ta1.5O15, exhibited superior energy density (∼3.99 J/cm3) and outstanding energy efficiency (∼91.7%) (@380 kV/cm) as well as good thermal stability and remarkable fatigue endurance. In addition, the ceramic demonstrated an ultrashort discharge time (τ0.9 < 57 ns), a high discharge current density (925.8 A/cm2) along with a high power density (78.7 MW/cm3). The energy storage properties in combination with good stability achieved in this work indicate the powerful potential of Sr2NaNb5-xTaxO15 tungsten bronze ceramics for high-performance capacitor applications. This material can be considered as a complement to the widely studied perovskite-based relaxor ceramics and should be further investigated in the future.

Many transition metal sulfides and phosphides are susceptible to surface oxidation under ambient conditions. The formed surface oxidation layer, which is likely to further restructure under reaction conditions, alters the chemical properties of the pristine material but has not been well studied. In this work, we for the first time use X-ray photoelectron spectroscopy to quantify the natural surface oxidation of transition metal phosphide and sulfide nanoparticles and employ a simplified Deal-Grove model to analyze the kinetics. We show that CoS2 oxidizes faster than CoS whereas CoP2 is more difficult to oxidize compared to CoP, and there exists an inverse correlation between the surface oxidation rate and the Co-S/P distance in the pristine structure. More inclusive investigation unveils different types of surface oxidation behavior: CoS, NiS and FeS are limited by their reactivity with oxygen; CoS2 is the most reactive and its oxidation is governed by oxygen diffusion; CoP2 is influenced by both reactivity and diffusion; CoP, Ni2P, Cu3P and MoP exhibit high initial oxidation degrees and the kinetics are not well-defined; MoS2 is largely stable against oxidation.

Molecular catalysts for electrochemical CO2 reduction have traditionally been studied in their dissolved states. However, the heterogenization of molecular catalysts has the potential to deliver much higher reaction rates and enable the reduction of CO2 by more than two electrons. In light of the recently discovered reactivity of heterogenized cobalt phthalocyanine molecules to catalyze CO2 reduction into methanol, direct comparison is needed to uncover the distinct catalytic activity and selectivity in homogeneous catalysis versus heterogeneous catalysis. Herein, soluble cobalt phthalocyanine derivatives were synthesized, and their catalytic activities in the homogeneous solutions were evaluated. The results show that the observed catalytic activities for both CO2 -to-CO and CO-to-methanol conversions in aqueous solutions of the cobalt phthalocyanines are predominantly heterogeneous in nature through the adsorbed species on the electrode.

Hetero-element doped lithium orthosilicates have been considered as advanced tritium breeders due to the superior performances. In this work, Li4Si1−xTixO4 ceramics were prepared by proprietary hydrothermal process and multistage reactive sintering. The reaction mechanism of Li4Si1−xTixO4 was put forward. XRD and SEM analyses indicate that insertion of Ti leads to lattice expansion, which promotes the grain growth and changes the fracture mode. The compressive tests show that the crush load increases almost four times by increasing x from 0 to 0.2. However, the thermal conductivity and ionic conductivity are the best when x = 0.05 and x = 0.1, respectively. Thermal cycling stability of Li4Si1−xTixO4 pebbles was further appraised through investigating the changes of microstructure and crush load. After undergoing thermal cycling, the Li4Si1−xTixO4 still show higher crush load compared with Li4SiO4, despite Ti segregation in some samples. The x = 0.05 sample exhibits excellent thermal cycling stability. In summary, proper amount of Ti doping can improve the crush load, thermal and ionic conductivity, and thermal cycling stability of Li4SiO4.

Catalytic electrodes with the capability to directly convert atmospheric CO 2 into value‐added products are of potential environmental and economic benefit, but entail an effective CO 2 selection strategy to impede the competing O 2 reduction reaction. In this work, we have developed a new generation of hybrid electrodes with improved O 2 tolerance and unprecedented capability of CO 2 conversion to liquid products in the presence of O 2 . We introduce aniline molecules into the pore structure of a polymer of intrinsic microporosity to expand its gas separation functionality beyond pure physical sieving. The chemical interaction between the acidic CO 2 molecule and the basic amino group of aniline renders enhanced CO 2 separation from O 2 . Loaded with a cobalt phthalocyanine‐based cathode catalyst, our hybrid electrode achieves a CO Faradaic efficiency of 71% with 10% O 2 in the CO 2 feed gas. The electrode can still perform CO production at an O 2 /CO 2 ratio as high as 9:1. Switching to a Sn‐based catalyst, we for the first time realize O 2 ‐tolerant CO 2 electroreduction to liquid products, generating formate with nearly 100% selectivity and a current density of 56.7 mA/cm 2 in the presence of 5% O 2 .

Constructing Schottky junction and multiheterostructure is considered a promising modification strategy to enhance reaction kinetics and prolong cycle life for alkali ion batteries, especially for potassium-ion batteries (KIBs) with sluggish kinetics and huge volume expansion. Herein, a well-designed multiheterostructure of SnS@C@MoS2@NC micronflower is successfully synthesized, which consists of SnS, intermediate carbon, MoS2 and N-doped carbon from interior to exterior. The Schottky junction with built-in electric-field induced by phase boundaries and the double carbon layers (intermediate carbon and N-doped carbon coating layer) significantly improve the electrons transfer rate, and simultaneously the multiheterostructure affords rapid K+ diffusion, strong K absorption and boosted electronic conductivity, resulting in superior charge transfer kinetics, which is explicitly unraveled by experimental results and first-principles calculations. Moreover, this multilayered structure with double carbon layers can effectively buffer the volumetric variation and maintain structural stability. Benefiting from these merits, the SnS@C@MoS2@NC anode delivers remarkable reversible capacity (471 mAh g−1 at 50 mA g−1 after 100 cycles), outstanding rate performance (305 mAh g−1 at 1000 mA g−1) and ultralong lifespan (253 mAh g−1 at 1000 mA g−1 after 3000 cycles) for KIBs. This work sheds a light on fabricating advanced electrodes by utilizing the Schottky junction and multiheterostructure.

Understanding how remarkable properties of materials emerge from complex interactions of their constituents and designing advanced material structures to render desired properties are grand challenges. Metal–oxide interactions are frequently utilized to improve catalytic properties but are often limited to situations where only one component is facilitated by the other. In this work, we demonstrate highly cooperative win-win metal–oxide interactions that enable unprecedented catalytic functionalities for electrochemical CO2 reduction reactions. In a single SnOx/Ag catalyst, the oxide promotes the metal in the CO production mode, and meanwhile the metal promotes the oxide in the HCOOH production mode, achieving potential-dependent bifunctional CO2 conversion to fuels and chemicals with H2 evolution suppressed in the entire potential window. Spectroscopic studies and computational simulations reveal that electron transfer from Ag to SnOx and dual-site cooperative binding for reaction intermediates at the Sn...

Lithium metatitanate (Li2TiO3) ceramic pebbles were successfully fabricated by microwave sintering using the powders synthesized via solid state reaction. Nano-size Li2TiO3 powders with an average particle size of 45 nm were synthesized by solid state reaction, and wet process was employed to fabricate Li2TiO3 pebbles with good sphericity. The pebbles were sintered by microwave process with rapid heating rate. Due to the volumetric heating and enhanced diffusion of microwave sintering, the sintered Li2TiO3 ceramic pebbles show high density (>85%T.D.), high crush load and uniform microstructure with small grain size (100 nm–1 μm), which might hold good potential in tritium release and long-term stability. The results show that the microwave sintering is a promising process for the fabrication of Li2TiO3 pebbles with fine microstructure and good mechanical property.

Photosynthetic CO2 fixation is mediated by the enzyme RuBisCo, which employs a nonredox-active metal (Mg2+) to bind CO2 adjacent to an organic ligand that provides reducing equivalents for CO2 fixa...

Background Objective The cerebral ischemia/reperfusion greatly influences brain metabolism. Remote ischemia preconditioning (RIPC) is reported to confer neuroprotective effects against cerebral ischemia in animal models and human. This study aims to investigate the metabolomic profiles of cerebrospinal fluid (CSF) in patients treated with repetitive lower limb RIPC and provides an insight into possible mechanism underlying RIPC-induced neuroprotection. Method Fifty healthy patients undergoing minor surgery under spinal anesthesia were randomly allocated to 2 groups: control group (Group C, n = 25) and RIPC treatment group (Group T,n = 25). Repetitive limb RIPC were performed 3 sessions, consisting of three 5-min cycles per session from the day before surgery to the morning on the surgery day. The CSF samples were collected from 48 patients before intrathecal injection of local anesthetic. A proton nuclear magnetic resonance (1H NMR)-based metabonomics approach was used to obtain the CSF metabolic profiles of the samples (n = 24 each). The acquired data were processed with MestReNova and followed by statistical analysis with SIMCA-P. Results The model obtained with the orthogonal partial least-squares discriminant analysis (OPLS-DA) identified difference of metabolite profiles between two groups. The validation of the discriminant analysis showed that the accuracy of the OPLS-DA model was 81.3%. Sixteen metabolites including glucose, amino-acids and organic acids et al. were identified as the most influential CSF biomarkers for the discrimination between two groups, which are involved in pathways of energy metabolism and amino-acids metabolism. Conclusion 1H NMR spectra combined with pattern recognition analysis offers a new and promising platform to investigate metabolic signatures in patients treated with RIPC. Our results suggest repetitive RIPC mainly changes energy metabolism and amino-acid metabolism in brain, which provides a potential mechanistic understanding of RIPC-induced tolerance to cerebral ischemia.

Structure and electrocatalytic reactivity of cobalt mono-phosphosulfide nanoparticles supported on carbon nanotubes are investigated. Employing two different synthetic methods, we successfully synthesize cobalt mono-phosphosulfide nanoparticles adopting either the CoP crystal structure (CoP|S with the S/P ratio

Discovering new chemistry and materials to enable rechargeable batteries with higher capacity and energy density is of paramount importance. While Li metal is the ultimate choice of a battery anode, its low efficiency is still yet to be overcome. Many strategies have been developed to improve the reversibility and cycle life of Li metal electrodes. However, almost all of the results are limited to shallow cycling conditions (e.g., 1 mAh cm −2 ) and thus inefficient utilization ( −2 with average Coulombic efficiency >98% in a commercial LiPF 6 /carbonate electrolyte. The high performance is enabled by slow release of LiNO 3 into the electrolyte and its subsequent decomposition to form a Li 3 N and lithium oxynitrides (LiN x O y )-containing protective layer which renders reversible, dendrite-free, and highly dense Li metal deposition. Using the developed Li metal electrodes, we construct a Li-MoS 3 full cell with the anode and cathode materials in a close-to-stoichiometric amount ratio. In terms of both capacity and energy, normalized to either the electrode area or the total mass of the electrode materials, our cell significantly outperforms other laboratory-scale battery cells as well as the state-of-the-art Li ion batteries on the market.

Developing Na metal anodes that can be deeply cycled with high efficiency for a long time is a prerequisite for rechargeable Na metal batteries to be practically useful despite their notable advantages in theoretical energy density and potential low cost. Their high chemical reactivity with the electrolyte and tendency for dendrite formation are two major issues limiting the reversibility of Na metal electrodes. In this work, we introduce for the first time potassium bis(trifluoromethylsulfonyl)imide (KTFSI) as a bifunctional electrolyte additive to stabilize Na metal electrodes, in which the TFSI- anions decompose into lithium nitride and oxynitrides to render a desirable solid electrolyte interphase layer while the K+ cations preferentially adsorb onto Na protrusions and provide electrostatic shielding to suppress dendritic deposition. Through the cooperation of the cations and anions, we have realized Na metal electrodes that can be deeply cycled at a capacity of 10 mAh cm-2 for hundreds of hours.

Flexibile high hydrolysis degree poly(vinyl alcohol) (PVA) films with different polyol plasticizers were obtained by melt processing in the presence of water, and the plasticizing effect of polyols was studied. The results showed that with the incorporation of polyols, the torque decreased, suggesting the improved melt flowing ability of PVA. Higher molecular weight polyols with more –OH groups exhibited higher efficiency to improve the melt flowing ability. The incorporation of polyol plasticizers did not change the crystalline structure of PVA but decreased crystalline degrees. The transmittance decreased with the increase in plasticizer content. The flexibility of PVA films was dramatically enhanced after being plasticized with polyols. The polyols with higher molecular weight possessed a higher stablity in PVA films and resulted in less weight loss during the thermal degradation process. It was suggested that a combination of different polyol plasticizers would be a better choice to obtain the PVA films with overall excellent properties.

Probing and understanding surface restructuring-induced electrocatalytic reactivity is an essential but challenging step toward rational prediction of electrocatalytic properties and design of high-performance catalysts. Cobalt phosphide (CoP) nanoparticles are state-of-the-art electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). However, the structure–reactivity correlations are not straightforward because the nanoparticles will restructure under working conditions. Employing a protective sample transfer procedure, we use simple lab XPS to unveil the changes in oxidation state and composition of the nanoparticle surface induced by electrochemical reaction conditions. CoP nanoparticles are naturally oxidized on their surface. In alkaline electrolyte under HER conditions, a Co-rich phosphide surface is generated as a result of polyphosphate dissolution and reduction of the oxidized P and Co species. In alkaline electrolyte under OER conditions, an oxidati...

Chemistry at the cathode/electrolyte interface plays an important role for lithium-sulfur batteries in which stable cycling of the sulfur cathode requires confinement of the lithium polysulfide intermediates and their fast electrochemical conversion on the electrode surface. While many materials have been found to be effective for confining polysulfides, the underlying chemical interactions remain poorly understood. We report a new and general lithium polysulfide-binding mechanism enabled by surface oxidation layers of transition-metal phosphide and chalcogenide materials. We for the first time find that CoP nanoparticles strongly adsorb polysulfides because their natural oxidation (forming Co-O-P-like species) activates the surface Co sites for binding polysulfides via strong Co-S bonding. With a surface oxidation layer capable of confining polysulfides and an inner core suitable for conducting electrons, the CoP nanoparticles are thus a desirable candidate for stabilizing and improving the performance of sulfur cathodes in lithium-sulfur batteries. We demonstrate that sulfur electrodes that hold a high mass loading of 7 mg cm

The application of CsPbI3 inorganic perovskite in carbon-based perovskite solar cells without hole transporter (C-PSCs) is expected to enhance device stability. However, due to the lower hole selectivity of carbon electrode than that of hole transporter, the efficiency of CsPbI3 C-PSCs is significantly suppressed. Herein, size mismatch-induced cation segregation in CsPbI3 is studied and employed to solve the problem. After treating CsPbI3 with CsX (X Br, Cl and F) ethanol solutions, the larger size mismatch between X- and I- ions would induce the more obvious cation segregation. The moderate size mismatch between I- and Cl- ions allows a partial substitution of I- ions with Cl- ions in CsPbI3 to form energy level gradient, and the CsCl residue on the surface tends to react with CsPbI3 to generate 2D Cs2PbI2Cl2 nanosheets, serving as an electron blocking layer. The synergistic effect of the energy level gradient and the electron blocking layer well improves hole selectivity at CsPbI3/carbon interface to reduce carrier recombination loss. As a result, the C-PSCs based on the CsCl-treated CsPbI3 achieve an efficiency of 15.23%, a record value for inorganic C-PSCs.

Although ceramic-based oxygen transport membranes (OTMs) have irreplaceable advantages over traditional oxygen production technologies, their oxygen permeability and stability need to be further improved. Based on the theoretical starting point of increasing the three-boundary reaction zone and reducing blocking effect, a set of new dual-phase membranes 75wt%Ce0.8Sm0.1Cu0.1O2-δ-25wt%-Sm0.8Sr0.2Co0.8Fe0.2O3-δ (CSC-8282) and 75wt%Ce0.8Sm0.1Cu0.1O2-δ-25wt%Sm0.3Sr0.7Co0.8Fe0.2O3-δ (CSC-3782) with different strontium contents were prepared by a one-pot sol-gel method ensuring that each element has the same chemical potential. The surface morphology, crystal structure and element distribution are systematically studied by SEM, XRD and EDS, which confirms that the synthesized membranes have an obvious dual-phase structure and excellent compactness. The results of the oxygen permeability experiment show that the oxygen permeability of CSC-3782 is always higher than that of CSC-8282 under any conditions due to the inducing effect of strontium on oxygen vacancies, and flow rate of CSC-3782 at 960°C reached 0.64 and 0.22mL⋅cm-2⋅min-1 for He and CO2 as a sweep gas, respectively. The final long-term stability test confirmed that the dual-phase composite membrane with great prospects for development has high temperature stability and CO2-tolerant property, and the doping of strontium to A-site of perovskite contributes to the improvement of its performance.