Langmuir-Blodgett Film Formed by Amphiphilic Molecules for Facile and Rapid Construction of Zinc-Iodine Cell.

Zinc-iodine batteries (ZIBs) are promising candidates for ecofriendly, safe, and low-cost energy storage systems, but polyiodide shuttling and the complex cathode fabrication procedures have severely hindered their broader commercial usage. Herein, a protocol is developed using phospholipid-like oleylamine molecules for scalable production of Langmuir-Blodgett films, which allows the facile preparation of ZIB cathodes in less than 1 min. The resulting inhomogeneous cathode allows for the continuous conversion of iodine. Moreover, the amine group of the oleylamine molecule at the cathode is capable of producing [OA*I+]I3- charge-transfer complexes with iodine, which facilitates the rapid migration of iodine and results in a highly reversible iodine conversion process. Consequently, the as-prepared ZIBs can deliver over 2000 cycles at 0.5 mA cm-2 with a capacity retention of 75.3%. This work presents a novel, straightforward, and efficient method for the rapid construction of ZIBs.

Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia.

The electrocatalytic nitrate (NO3-) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe0.9M0.1O3-δ (M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO3-δ (LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe0.9Cu0.1O3-δ (LF0.9Cu0.1) submicrofibers with a stronger Fe-O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 µg h-1 mg-1cat. and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOL Multiphysics simulations demonstrate that the more positive surface of LF0.9Cu0.1 submicrofibers can induce NO3- enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situ characterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton-electron coupling step (*NO3 + H+ + e- → *HNO3) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.

Bio-Inspired Aerobic-Hydrophobic Janus Interface on Partially Carbonized Iron Heterostructure Promotes Bifunctional Nitrogen Fixation.

Competition from hydrogen/oxygen evolution reactions and low solubility of N2 in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe3 C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe3 C/Fe@PCNF-F away from water infiltration and endow a N2 molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust "quasi-solid-gas" state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe3 C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH3 yield rate up to 29.2 µg h-1 mg-1 cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO3 - yield rate up to 15.7 µg h-1 mg-1 cat. and FE up to 3.4 % in nitrogen oxidation reaction).

Sulfur-Deficient Bismuth Sulfide/Nitrogen-Doped Carbon Nanofibers as Advanced Free-Standing Electrode for Asymmetric Supercapacitors.

The use of free-standing carbon-based hybrids plays a crucial role to help fulfil ever-increasing energy storage demands, but is greatly hindered by the limited number of active sites for fast charge adsorption/desorption processes. Herein, an efficient strategy is demonstrated for making defect-rich bismuth sulfides in combination with surface nitrogen-doped carbon nanofibers (dr-Bi2 S3 /S-NCNF) as flexible free-standing electrodes for asymmetric supercapacitors. The dr-Bi2 S3 /S-NCNF composite exhibits superior electrochemical performances with an enhanced specific capacitance of 466 F g-1 at a discharge current density of 1 A g-1 . The high performance of dr-Bi2 S3 /S-NCNF electrodes originates from its hierarchical structure of nitrogen-doped carbon nanofibers with well-anchored defect-rich bismuth sulfides nanostructures. As modeled by density functional theory calculation, the dr-Bi2 S3 /S-NCNF electrodes exhibit a reduced OH- adsorption energy of -3.15 eV, compared with that (-3.06 eV) of defect-free bismuth sulfides/surface nitrogen-doped carbon nanofiber (df-Bi2 S3 /S-NCNF). An asymmetric supercapacitor is further fabricated by utilizing dr-Bi2 S3 /S-NCNF hybrid as the negative electrode and S-NCNF as the positive electrode. This composite exhibits a high energy density of 22.2 Wh kg-1 at a power density of 677.3 W kg-1 . This work demonstrates a feasible strategy to construct advanced metal sulfide-based free-standing electrodes by incorporating defect-rich structures using surface engineering principles.

Bionanofiber Assisted Decoration of Few-Layered MoSe2 Nanosheets on 3D Conductive Networks for Efficient Hydrogen Evolution.

Molybdenum diselenide (MoSe2 ) has emerged as a promising electrocatalyst for hydrogen evolution reaction (HER). However, its properties are still confined due to the limited active sites and poor conductivity. Thus, it remains a great challenge to synergistically achieve structural and electronic modulations for MoSe2 -based HER catalysts because of the contradictory relationship between these two characteristics. Herein, bacterial cellulose-derived carbon nanofibers are used to assist the uniform growth of few-layered MoSe2 nanosheets, which effectively increase the active sites of MoSe2 for hydrogen atom adsorption. Meanwhile, carbonized bacterial cellulose (CBC) nanofibers provide a 3D network for electrolyte penetration into the inner space and accelerate electron transfer as well, thus leading to the dramatically increased HER activity. In acidic media, the CBC/MoSe2 hybrid catalyst exhibits fast hydrogen evolution kinetics with onset overpotential of 91 mV and Tafel slope of 55 mV dec-1 , which is much more outstanding than both bulk MoSe2 aggregates and CBC nanofibers. Furthermore, the fast HER kinetics are well supported by theoretical calculations of density-functional-theory analysis with a low activation barrier of 0.08 eV for H2 generation. Hence, this work highlights an efficient solution to develop high-performance HER catalysts by incorporating biotemplate materials, to simultaneously achieve increased active sites and conductivity.

Biomass-Derived Nitrogen-Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel-Cobalt Layered Double Hydroxide Nanosheets as High-Performance Asymmetric Supercapacitor Electrode.

The development of biomass-based energy storage devices is an emerging trend to reduce the ever-increasing consumption of non-renewable resources. Here, nitrogen-doped carbonized bacterial cellulose (CBC-N) nanofibers are obtained by one-step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio-template for further deposition of ultrathin nickel-cobalt layered double hydroxide (Ni-Co LDH) nanosheets. The as-obtained CBC-N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g(-1) at a discharge current density of 1 A g(-1) , based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g(-1) and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC-N@LDH composites as positive electrode materials and CBC-N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC-N@LDH composites and 3D nitrogen-doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg(-1) at the power density of 800.2 W kg(-1) . Therefore, this work presents a novel protocol for the large-scale production of biomass-derived high-performance electrode materials in practical supercapacitor applications.

Hierarchical ZnCo2 O4 @NiCo2 O4 Core-Sheath Nanowires: Bifunctionality towards High-Performance Supercapacitors and the Oxygen-Reduction Reaction.

Increasing energy demands and worsening environmental issues have stimulated intense research on alternative energy storage and conversion systems including supercapacitors and fuel cells. Here, a rationally designed hierarchical structure of ZnCo2 O4 @NiCo2 O4 core-sheath nanowires synthesized through facile electrospinning combined with a simple co-precipitation method is proposed. The obtained core-sheath nanostructures consisting of mesoporous ZnCo2 O4 nanowires as the core and uniformly distributed ultrathin NiCo2 O4 nanosheets as the sheath, exhibit excellent electrochemical activity as bifunctional materials for supercapacitor electrodes and oxygen reduction reaction (ORR) catalysts. Compared with the single component of either ZnCo2 O4 nanowires or NiCo2 O4 nanosheets, the hierarchical ZnCo2 O4 @NiCo2 O4 core-sheath nanowires demonstrate higher specific capacitance of 1476 F g(-1) (1 A g(-1) ) and better rate capability of 942 F g(-1) (20 A g(-1) ), while maintaining 98.9 % capacity after 2000 cycles at 10 A g(-1) . Meanwhile, the ZnCo2 O4 @NiCo2 O4 core-sheath nanowires reveal comparable catalytic activity but superior stability and methanol tolerance over Pt/C as ORR catalyst. The impressive performance may originate from the unique hierarchical core-sheath structures that greatly facilitate enhanced reactivity, and faster ion and electron transfer.

Plasmonic liquid marbles: a miniature substrate-less SERS platform for quantitative and multiplex ultratrace molecular detection.

Inspired by aphids, liquid marbles have been studied extensively and have found application as isolated microreactors, as micropumps, and in sensing. However, current liquid-marble-based sensing methodologies are limited to qualitative colorimetry-based detection. Herein we describe the fabrication of a plasmonic liquid marble as a substrate-less analytical platform which, when coupled with ultrasensitive SERS, enables simultaneous multiplex quantification and the identification of ultratrace analytes across separate phases. Our plasmonic liquid marble demonstrates excellent mechanical stability and is suitable for the quantitative examination of ultratrace analytes, with detection limits as low as 0.3 fmol, which corresponds to an analytical enhancement factor of 5×10(8). The results of our simultaneous detection scheme based on plasmonic liquid marbles and an aqueous-solid-organic interface quantitatively tally with those found for the individual detection of methylene blue and coumarin.

Highly Porous Yet Transparent Mechanically Flexible Aerogels Realizing Solar-Thermal Regulatory Cooling.

The demand for highly porous yet transparent aerogels with mechanical flexibility and solar-thermal dual-regulation for energy-saving windows is significant but challenging. Herein, a delaminated aerogel film (DAF) is fabricated through filtration-induced delaminated gelation and ambient drying. The delaminated gelation process involves the assembly of fluorinated cellulose nanofiber (FCNF) at the solid-liquid interface between the filter and the filtrate during filtration, resulting in the formation of lamellar FCNF hydrogels with strong intra-plane and weak interlayer hydrogen bonding. By exchanging the solvents from water to hexane, the hydrogen bonding in the FCNF hydrogel is further enhanced, enabling the formation of the DAF with intra-layer mesopores upon ambient drying. The resulting aerogel film is lightweight and ultra-flexible, which possesses desirable properties of high visible-light transmittance (91.0%), low thermal conductivity (33 mW m-1 K-1), and high atmospheric-window emissivity (90.1%). Furthermore, the DAF exhibits reduced surface energy and exceptional hydrophobicity due to the presence of fluorine-containing groups, enhancing its durability and UV resistance. Consequently, the DAF has demonstrated its potential as solar-thermal regulatory cooling window materials capable of simultaneously providing indoor lighting, thermal insulation, and daytime radiative cooling under direct sunlight. Significantly, the enclosed space protected by the DAF exhibits a temperature reduction of 2.6 °C compared to that shielded by conventional architectural glass.

Thermal-Rectified Gradient Porous Polymeric Film for Solar-Thermal Regulatory Cooling.

Solar-thermal regulation concerning thermal insulation and solar modulation is pivotal for cooling textiles and smart buildings. Nevertheless, a contradiction arises in balancing the demand to prevent external heat infiltration with the efficient dissipation of excess heat from enclosed spaces. Here, a concentration-gradient polymerization strategy is presented for fabricating a gradient porous polymeric film comprising interconnected polymeric microspheres. This method involves establishing an electric field-driven gradient distribution of charged crosslinkers in the precursor solution, followed by subsequent polymerization and freeze-drying processes. The resulting porous film exhibits a significant porosity gradient along its thickness, leading to exceptional unidirectional thermal insulation capabilities with a thermal rectification factor of 21%. The gradient porous film, with its thermal rectification properties, effectively reconciles the conflicting demands of diverse thermal conductivity for cooling unheated and spontaneously heated enclosed spaces. Consequently, the gradient porous film demonstrates remarkable enhancements in solar-thermal management, achieving temperature reductions of 3.0 and 4.1 °C for unheated and spontaneously heated enclosed spaces, respectively, compared to uniform porous films. The developed gradient-structured porous film thus holds promise for the development of thermal-rectified materials tailored to regulate solar-thermal conditions within enclosed environments.

Pseudolaric acid B triggers ferritinophagy and ferroptosis via upregulating NCOA4 in lung adenocarcinoma cells.

BACKGROUND: Ferroptosis is a novel subtype of programmed cell death caused by iron-dependent lipid peroxidation and excessive reactive oxygen species (ROS) production. Small-molecule ferroptotic drugs have the probability of selectively targeting the specific features of aggressive tumor cells. In particular, pseudolaric acid B (PAB) triggered ferroptosisin breast cancer cells. The aim of this study is to explore the antitumor effect of PAB on A549 cells and provide a theoretical basis for the further development and clinical application of PAB. METHODS: First, relevant databases were used to predict of target genes related to PAB, Then, EdU proliferation assay, colony formation and wound-healing assays were applied to calculate A549 cells proliferative abilities. Measurement of ferrous iron, lipid peroxidation, ROS, malondialdehyde (MDA) and glutathione (GSH) were utilized to explore the relevant mechanism. RESULTS: We showed that PAB decreased the viability of lung adenocarcinoma cells in vitro, which was accompanied by abnormally elevated levels of intracellular ferrous iron and overproduction of lipid reactive oxidate species (L-ROS). In turn, deferoxamine (DFO) significantly rescued PAB-induced lipid peroxidation. PAB also improved the intracellular labile iron pool by promoting ferritin autophagy via the upregulation of the nuclear receptor coactivator 4 (NCOA4). Moreover, silencing of NCOA4 alleviated PAB-inducedferroptotic death and reduced the levels of intracellular ferrous iron. CONCLUSIONS: In summary, PAB-triggered ferroptosis in lung adenocarcinoma cells by enhancing ferritinophagy. thus, PAB is a potential therapeutic agent for lung adenocarcinoma.

Visible-Light Transparent, Ultrastretchable, and Self-Healable Semicrystalline Fluorinated Ionogels for Underwater Strain Sensing.

The development of ultrastretchable ionogels with a combination of high transparency and unique waterproofness is central to the development of emerging skin-inspired sensors. In this study, an ultrastretchable semicrystalline fluorinated ionogel (SFIG) with visible-light transparency and underwater stability is prepared through one-pot copolymerization of acrylic acid and fluorinated acrylate monomers in a mixed solution of poly(ethylene oxide) (PEO) and fluorinated ionic liquids. Benefiting from the formation of the PEO-chain semicrystalline microstructures and the abundant noncovalent interactions (reversible hydrogen bonds and ion-dipole interactions) in an ionogel, SFIG is rendered with room-temperature stable cross-linking structures, providing high mechanical elasticity as well as high chain segment dynamics for self-healing and efficient energy absorption during the deformation. The resultant SFIG exhibits excellent stretchability (>2500%), improved mechanical toughness (7.4 MJ m-3), and room-temperature self-healability. Due to the high compatibility and abundance of hydrophobic fluorinated moieties in the ionogel, the SFIG demonstrates high visible-light transparency (>97%) and excellent waterproofness. Due to these unique advantages, the as-prepared SFIG is capable of working as an ultrastretchable ionic conductor in capacitive-type strain sensors, demonstrating excellent underwater strain-sensing performances with high sensitivity, large detecting range, and exceptional durability. This work might provide a straightforward and efficient method for obtaining waterproof ionogel elastomers for application in next-generation underwater sensors and communications.

Recent advances and perspectives of 3D printed micro-supercapacitors: from design to smart integrated devices.

3D-printed micro-supercapacitors (MSCs) have emerged as the ideal candidates for energy storage devices owing to their unique characteristics of miniaturization, structural diversity, and integration. Exploring the 3D printing technology for various materials and architectures of MSCs is key to realizing customization and optimizing the performance of 3D-printed MSCs. In this review, we summarize the latest progress in 3D-printed MSCs with regards to general printing approaches, printable materials, and rational design considerations. Specifically, several general types of 3D printing techniques (their working principles, available materials, resolutions, advantages, and disadvantages) and their applications to fabricate electrodes with different energy storage mechanisms, and various electrolytes, are summarized. We further discuss research directions in terms of integrated systems with other electronics. Finally, future perspectives on the research and development directions in this important field are further discussed.

MiR-579 Inhibits Lung Adenocarcinoma Cell Proliferation and Metastasis via Binding to CRABP2.

Background: Lung cancer is the cancer with the highest morbidity and mortality. Lung adenocarcinoma (LUAD) is a subtype of lung cancer. The aim of this study is to explore the functions of miR-579 and CRABP2 in lung adenocarcinoma. Methods: Cell counting kit-8 (CCK-8) and colony formation assays were applied to calculate cell proliferative abilities. Transwell assay was utilized to measure cell invasive ability. Results: MiR-579 is low expressed in LUAD tissues and cell lines. MiR-579 inhibits cell viability and invasion of lung adenocarcinoma. Knockdown of CRABP2 inhibits cell proliferation and invasion of Calu-3 cells. MiR-579 suppresses cell proliferation and invasion by regulating CRABP2 in Calu-3 cells. Conclusion: Our study reveals that miR-579 acts as a tumor suppressor in LUAD and miR-579 can target and regulate the expression of CRABP2 to mediate cell proliferation and invasion. This study indicates that miR-579 has a potential to be a candidate biomarker for the treatment of LUAD.

Homogeneous electric field and Li+ flux regulation in three-dimensional nanofibrous composite framework for ultra-long-life lithium metal anode.

Lithium (Li) metal is considered as the best anode candidate for next-generation high-energy batteries due to its ultralow electrochemical potential and extremely high theoretical capacity. However, issues arising from the undesired growth of lithium dendrites and infinite volumetric change have seriously hindered the practical application of lithium metal batteries (LMBs). Here, we designed a super-lithiophilic amorphous zinc oxide-doped carbon nanofiber framework with uniformly-distributed and parallel multichannels (MCCNF@ZnO) to achieve the homogeneous distribution of electric field and Li+ flux. By the assistances of COMSOL Multiphysics simulations and ex-situ scanning electron microscopy, we reveal that the Li metal preferentially deposits into the porous nanochannels inside the nanofibers, followed by its even distribution on the lithiophilic surface of MCCNF@ZnO. Furthermore, the conductive multichannels of the carbon nanofiber skeleton can effectively minimize the partial current density, thereby effectively avoiding the electrochemical polarization and assisting the uniform metallic deposition. As a result, MCCNF@ZnO exhibits a stable CE over 99.2% as the substrate after 500 cycles at the current density of 1 mA cm-2. The symmetrical cell of lithium-loaded MCCNF@ZnO composite electrodes can stably operate over 3300 h at 0.5 mA cm-2, indicating the great potential of MCCNF@ZnO for stabilizing lithium metal anodes in practical applications of LMBs.

A Universal Spinning-Coordinating Strategy to Construct Continuous Metal-Nitrogen-Carbon Heterointerface with Boosted Lithium Polysulfides Immobilization for 3D-Printed LiS Batteries.

Constructing intimate coupling between transition metal and carbon nanomaterials is an effective means to achieve strong immobilization of lithium polysulfides (LiPSs) in the applications of lithium-sulfur (LiS) batteries. Herein, a universal spinning-coordinating strategy of constructing continuous metal-nitrogen-carbon (MNC, M = Co, Fe, Ni) heterointerface is reported to covalently bond metal nanoparticles with nitrogen-doped porous carbon fibers (denoted as M/MN@NPCF). Guided by theoretical simulations, the Co/CoN@NPCF hybrid is synthesized as a proof of concept and used as an efficient sulfur host material. The polarized CoNC bridging bonds can induce rapid electron transfer from Co nanoparticles to the NPCF skeleton, promoting the chemical anchoring of LiPSs to improve sulfur utilization. Hence, the as-assembled LiS battery presents a remarkable capacity of 781 mAh g-1 at 2.0 C and a prominent cycling lifespan with a low decay rate of only 0.032% per cycle. Additionally, a well-designed Co/CoN@NPCF-S electrode with a high sulfur loading of 7.1 mg cm-2 is further achieved by 3D printing technique, which demonstrates an excellent areal capacity of 6.4 mAh cm-2 at 0.2 C under a lean-electrolyte condition. The acquired insights into strongly coupled continuous heterointerface in this work pave the way for rational designs of host materials in LiS systems.

Correlation Study on the Expression of INSR, IRS-1, and PD-L1 in Nonsmall Cell Lung Cancer.

Objective: To study the expression and correlation of insulin receptor (INSR), insulin receptor substrate-1 (IRS-1), and programmed cell death ligand-1 (PD-L1) in nonsmall cell lung cancer (NSCLC). Methods: 45 lung cancer tissues and 30 adjacent normal tissues of NSCLC patients diagnosed in the Second Affiliated Hospital of Shandong First Medical University from June 2019 to August 2020 were selected. The expressions of INSR, IRS-1, and PD-L1 proteins in tumor tissues and adjacent tissues of NSCLC were detected by immunohistochemical staining. Results: The expression of INSR and IRS-1 in NSCLC was significantly higher than that in adjacent normal lung tissue (P < 0.05). INSR expression had statistical significance with the degree of pathological differentiation of nonsmall cell carcinoma (P = 0.031), but had no significant association with age, gender, pathological type, TNM stage, and lymph node metastasis status (P > 0.05). There was no significant correlation between IRS-1 positive expression and NSCLC patients' age, gender, pathological typing, degree of differentiation, TNM stage, and lymph node metastasis (P > 0.05). PD-L1 positive expression was correlated with lymph node metastasis of NSCLC (P = 0.028), while there was no significant correlation with gender, age, pathological type, TNM stage, and pathological differentiation degree of NSCLC patients (P > 0.05). Spearman correlation analysis showed that PD-L1 protein expression had a significant positive correlation with IRS-1 protein expression (r = 0.373), but was not correlated with the expression of INSR protein. Conclusion: IRS-1 may be involved in the regulation of PD-L1 expression and mediate the occurrence of tumor immune escape, which is expected to become a new target for NSCLC immunotherapy and provide new clinical evidence for immunosuppressive therapy.

Semicrystalline Conjugated Polymers with Well-Defined Active Sites for Nitrogen Fixation in a Seawater Electrolyte.

Faradaic efficiency for the nitrogen reduction reaction (NRR) is often limited by low N2 solubility in the electrolyte, while a large number of intimate contacts between the electrolyte and solid catalyst can also inevitably sacrifice many active sites for the NRR. Here, it is reported that a "quasi-gas-solid" interface formed in donor-acceptor-based conjugated polymers (CPs) is beneficial to boosting the NRR process and at the same time suppressing the competing hydrogen evolution reaction. Of particular interest, it is found that a semicrystalline CP catalyst, SC-PBDT-TT, exhibits a high Faradaic efficiency of up to 60.5% with a maximum NH3 production rate of 16.8 µg h-1 mg-1 in a neutral-buffered seawater electrolyte. Molecular dynamics and COMSOL Multiphysics simulations reveal the origin of the observed high NRR performance arising from the presence of desirable crystal regions to resist the penetration of H2 O molecules, leading to the formation of a "quasi-gas-solid" interface inside the catalyst for a favorable direct-contact between the catalyst and N2 molecules. Furthermore, high-throughput computations, based on density functional theory, reveal the actual real active site for N2 adsorption and reduction in SC-PBDT-TT. This work provides a new framework for optimizing NRR performance of metal-free catalysts by controlling their crystallinities.

Soluble porous organic cages as homogenizers and electron-acceptors for homogenization of heterogeneous alloy nanoparticle catalysts with enhanced catalytic activity.

The creation of ultrafine alloy nanoparticles (<5 nm) that can maintain surface activity and avoid aggregation for heterogeneous catalysis has received much attention and is extremely challenging. Here, ultrafine PtRh alloy nanoparticles imprisoned by the cavities of reduced chiral covalent imine cage (PtRh@RCC3) are prepared successfully by an organic molecular cage (OMC) confinement strategy, while the soluble RCC3 can act as a homogenizer to homogenize the heterogeneous PtRh alloy in solution. Moreover, the X-ray absorption near-edge structure (XANES) results show that the RCC3 can act as an electron-acceptor to withdraw electrons from Pt, leading to the formation of higher valence Pt atoms, which is beneficial to improving the catalytic activity for the reduction of 4-nitrophenol. Attributed to the synergistic effect of Pt/Rh atoms and the unique function of the RCC3, the reaction rate constants of Pt1Rh16@RCC3 are 49.6, 8.2, and 5.5 times than those of the Pt1Rh16 bulk, Pt@RCC3 and Rh@RCC3, respectively. This work provides a feasible strategy to homogenize heterogeneous alloy nanoparticle catalysts in solution, showing huge potential for advanced catalytic application.

Asymmetric Sodiophilic Host Based on a Ag-Modified Carbon Fiber Framework for Dendrite-Free Sodium Metal Anodes.

Sodium (Na) metal is considered a promising anode material for high-energy Na batteries due to its high theoretical capacity and abundant resources. However, uncontrollable dendrite growth during the repeated Na plating/stripping process leads to the issues of low Coulombic efficiency and short circuits, impeding the practical applications of Na metal anodes. Herein, we propose a silver-modified carbon nanofiber (CNF@Ag) host with asymmetric sodiophilic features to effectively improve the deposition behavior of Na metal. Both density functional theory (DFT) calculations and experiment results demonstrate that Na metal can preferentially nucleate on the sodiophilic surface with Ag nanoparticles and uniformly deposit on the whole CNF@Ag host with a "bottom-up growth" mode, thus preventing unsafe dendrite growth at the anode/separator interface. The optimized CNF@Ag framework exhibits an excellent average Coulombic efficiency of 99.9% for 500 cycles during Na plating/stripping at 1 mA cm-2 for 1 mAh cm-2. Moreover, the CNF@Ag-Na symmetric cell displays stable cycling for 500 h with a low voltage hysteresis at 2 mA cm-2. The CNF@Ag-Na//Na3V2(PO4)3 full cell also presents a high reversible specific capacity of 102.7 mAh g-1 for over 200 cycles at 1 C. Therefore, asymmetric sodiophilic engineering presents a facile and efficient approach for developing high-performance Na batteries with high safety and stable cycling performance.