Manipulating the selectivity-determining step in the hydrogenation of nitrogen-containing intermediates is critical to achieving high ammonia selectivity in electrocatalytic nitrate reduction. Here, we propose a molecular interface engineering strategy that functionalized with thiol-anchored aromatic ligands to regulate the interfacial binding affinity and activation of key nitrogen-containing intermediates on silver nanocube surfaces. By systematically varying the electronic properties of the substituents, we identify 4-(methylthio)benzaldehyde as the most effective ligand, increasing the ammonia Faradaic efficiency from 50.8% to 98.9% and achieving a yield rate of 14,366.1 μg h-1 cmgeo-2 at -0.63 V versus reversible hydrogen electrode. In situ electrochemical characterizations combined with theoretical simulations further reveal that 4-(methylthio)benzaldehyde modification promotes the activation of weakly hydrogen-bonded water molecules and accelerates the hydrogenation of *HNO intermediates. This targeted modulation of interfacial binding affinity offers an effective strategy for selectivity control in electrocatalytic nitrate reduction. The enhanced performance is further validated in a membrane electrode assembly electrolyser, underscoring the practical viability of this molecular design strategy for selective nitrate conversion.

Introducing ES into 1 H ,1 H ,5 H -perfluoropentyl-1,1,2,2-tetrafluoroethyl (OTE)-based electrolyte creates SO⋯C–F interactions that weaken the fluorine effect, reduce anion aggregation, and promote loose solvation and fast kinetics.

Abstract Lithium metal batteries (LMBs) are regarded as promising next-generation energy-storage systems; however, their practical application is hindered by unstable lithium deposition and severe interfacial side reactions. While extensive efforts have focused on electrolyte design and interfacial engineering, the role of commercial Cu current collectors, particularly their intrinsic structure mechanics characteristics remain largely overlooked. Herein, commercial Cu foils with distinct intrinsic properties are systematically investigated to elucidate how their mechanical–microstructural characteristics govern lithium nucleation and growth behavior. By establishing a direct correlation between intrinsic properties, Li deposition morphology, and electrochemical performance, we reveal that tensile properties, defect structures, and surface homogeneity collectively regulate the interfacial energy landscape, Li+ flux distribution, and local current density. Among the investigated samples, the 8+ Cu foil achieves an optimal balance between mechanical strength, ductility, and structural uniformity, enabling reduced nucleation overpotential and uniform, dense lithium deposition with suppressed dendrite formation. Consequently, it delivers superior electrochemical performance, including symmetric-cell voltage hysteresis/polarization of 32.2 mV at 1 mA cm–2 and 1 mAh cm–2, stable symmetric-cell cycling over 800 h, and stable cycling for more than 100 cycles at 0.5 C in LiFePO4 full cells. This work demonstrates that optimizing the intrinsic mechanical-performance-related characteristics of commercial Cu current collectors offers a practical and scalable strategy for regulating lithium deposition and improving LMB stability.

Lithium metal batteries (LMBs) are hindered by dendrite growth and volume expansion. While 3D hosts offer solutions, uniform lithiophilicity often leads to surface-preferred deposition and internal space wastage. Herein, we report amorphous carbon-coated ferroferric oxide (Fe3O4@C) nanospheres designed with a radial lithiophilicity gradient. The strong lithiophilic Fe3O4/C core and weaker lithiophilic carbon shell create a thermodynamic driving force, guiding Li ions to penetrate the outer layer and achieve "bottom-up" or "inside-out" deposition. This gradient mechanism, coupled with the robust solid core and flexible shell, effectively suppresses Li dendrite growth and accommodates volume expansion through synergistic mechanical stress. As a result, the half-cell achieves a stable Coulombic efficiency of 97.17% at 1 mAh cm-2, while the symmetrical cell demonstrates long-term cycling stability over 2000 h. Furthermore, the LFP full-cell retains a 93.4% capacity after 150 cycles at 1 C. This work highlights the critical role of radial gradient lithiophilicity in ensuring uniform, deep-level Li deposition for practical LMBs.

Metallic Li is considered a promising anode material for high-energy batteries due to its extremely high theoretical capacity and lowest electrochemical potential. However, the commercialization of lithium metal batteries faces significant challenges, primarily due to uncontrollable growth of lithium dendrites and substantial volume changes during charge and discharge, which result in poor safety, low stability, and limited cycle life. Here, a spinel-type Li4Ti5O12 (LTO) coating was prepared by a simple high-temperature solid-phase method and attached to the separator surface of lithium metal batteries as a coating through a mechanical coating approach. Benefiting from its improved electrolyte wettability and high ionic conductivity of the modified coating, it exhibited a low interfacial resistance, enabling lithium ions to rapidly penetrate the coating and maintaining a uniform lithium-ion flux at the electrode interface. It alleviated the growth of Li dendrites caused by the uneven distribution of lithium ions and mitigated the volume change. This composite coating achieves excellent cycling performance in half-cells, symmetric cells and button-type full cells. At a current density of 0.5 mA cm-2 and a capacity of 1 mAh cm-2, the Li/PP@LTO||Cu battery achieves stable cycling for over 180 cycles with a Coulombic efficiency maintained at 98%. At current densities of 1 mA cm-2 and capacity of 1 mAh cm-2, the Li/PP@LTO||Li/PP@LTO composite symmetric battery can stably cycle for 900 h with a polarization voltage stabilized at 25 mV. This work demonstrates a straightforward approach to develop dendrite-free lithium metal anodes, addressing the critical challenges of interface instability in lithium metal batteries.

Abstract Despite their ultrahigh theoretical energy density of 2600 Wh kg−1, the practical application of lithium−sulfur (Li−S) batteries is severely hindered by a kinetic dilemma: traditional electrolytes fail to balance the conflicting demands of the sulfur cathode (which requires strong solvation for polysulfide conversion) and the lithium anode (which requires weak solvation for stability). To address this, we propose a rational electrolyte design by introducing 1,2-dimethoxyethane (DME) as a “molecular trigger” into a weakly solvating THF/TTE baseline electrolyte. Multiscale characterizations and molecular dynamics simulations reveal that the precise incorporation of DME reconstructs the primary Li+ solvation sheath into an anion-participating configuration. This optimized structure not only effectively activates the deep conversion kinetics of polysulfides at the cathode but also thermodynamically drives the formation of a robust, dense, and inorganic-rich (LiF/Li2S) solid electrolyte interphase (SEI) at the anode. Consequently, the optimized electrolyte enables dendrite-free lithium deposition with a Coulombic efficiency of >99% at a high current density of 4 mA cm−2, achieving stable cycling for over 1000 h in symmetric cells. Furthermore, the corresponding Li−S full cells deliver a high reversible capacity of ∼600 mAh g−1 (∼800 mAh g−1 with LiNO3 additives) and excellent rate capability. This study provides deep fundamental insights into solvation-structure-regulated interfacial chemistry, presenting a viable strategy for developing high-energy, long-lifespan Li−S batteries.

Cemented carbides, known for their exceptional hardness, thermal stability, and wear resistance, serve as vital components across various industries, including mechanical manufacturing, aerospace, and chemical engineering. Despite their advantageous properties, poor machinability restricts the application of cemented carbides in manufacturing complex-shaped components. However, 3D printing technology offers a novel solution, enabling the production of cemented carbide parts with intricate geometries, on-demand manufacturing, and a reduction in material waste and scrap compared to traditional methods. This paper presents a comprehensive review of the latest advancements in cemented carbides 3D printing technology. It outlines the raw materials and preparation methods utilized for cemented carbides, examines the principles and characteristics of cemented carbides 3D printing, and highlights recent technological innovations. Additionally, the paper analyzes metallurgical defects that may occur during the printing process and discusses various detection methods, alongside post-processing techniques for 3D-printed cemented carbide substrates. Finally, the review explores future development directions in cemented carbides 3D printing, considering potential trends in manufacturing processes.

We reported a novel approach to the synthesis of hierarchically structured nitrogen-doped carbon nanotubes (NCNTs) via chemical vapor deposition using anodic aluminum oxides as templates and the following annealing in ammonia. The ruthenium (Ru) nanoparticles with low content of 1.6 wt% were embedded in NCNTs, and the molybdenum carbide (Mo2C) nanoparticles were decorated on outer surfaces of NCNTs. Thanks to the combined contributions of doped N, Ru and Mo2C, the Ru@NCNT/Mo2C composites exhibited a low overpotential of 22 mV at a current density of 10 mA cm- 2 and a small Tafel slope of 26 mV dec- 1 for hydrogen evolution reaction (HER) in 1 M KOH. After further constructing anion exchange membrane electrolyzers using Ru@NCNT/Mo2C composites as electrocatalysts in cathodes, the electrolyzers delivered a low cell voltage of 1.86 V at industry-level current density of 1 A cm- 2 as well as superior durability. Moreover, Ru@NCNT/Mo2C composites also demonstrated a low overpotential of 38 mV at 10 mA cm- 2, a small Tafel slope of 36 mV dec- 1 and good stability for HER in 0.5 M H2SO4. This work may pave a new way for the synthesis of high performance HER electrocatalysts in both alkaline and acid electrolytes.

Coal-based hard carbon is regarded as the most commercially promising anode material for sodium-ion batteries (SIBs) due to its abundant production and ultrahigh carbonization yield. However, due to the stacking and rearrangement of carbon layers during high-temperature carbonization, coal-based hard carbon has a high degree of graphitization, which seriously limits its sodium storage capacity. Therefore, we adopted a carbon-carbon composite carbonization method, using carbohydrates (glucose, starch, and sucrose) mixed with bituminous coal for carbonization. The rich oxygen functional groups in carbohydrates undergo strong cross-linking reactions with bituminous coal during high-temperature carbonization, inhibiting the graphitization process of carbon layers and achieving a synergistic optimization effect through mixed carbonization. The prepared composite hard carbon exhibits more excellent sodium storage performance. Additionally, the optimal addition ratios of bituminous coal mixed with three carbohydrates for carbonization were explored, and the reasons for the performance differences were revealed from the perspective of carbonization behavior. Benefiting from the rational regulation of graphitization degree, when glucose is used as the carbon source, the sodium storage capacity of BC-Glu-73 significantly increases from 253.6 to 297.2 mAh g-1, with an initial Coulombic efficiency (ICE) as high as 82.7%, and it shows the most excellent sodium storage kinetics in all samples. Finally, the optimal addition amounts of glucose, starch, and sucrose were determined to be 30, 50, and 70%, respectively. The collaborative carbonization strategy adopted in this study offers a possible path for the development of advanced coal-based anode materials suitable for commercial sodium-ion batteries.

Gel polymer electrolytes (GPEs) are of great interest for their ability to provide good interfacial contact and high ionic conductivity. However, the lower electrochemical stabilization window (ESW) and poor long-cycle performance of gel electrolytes are the main barriers to their commercial application. In this paper, GPEs with a wide ESW and high long-cycle performance were obtained by thermal in-situ polymerization of Poly(ethylene glycol) diacrylate (PEGDA) monomer and Ethoxylated trimethylolpropane triacrylate (ETPTA) cross-linker inside the cell. Raman, NMR and DFT theoretical calculations were performed to determine the contribution of the dimer formed by PEGDA and ETPTA under thermal initiation to the ESW, as well as the binding energy for lithium ions. The optimal gel electrolyte PE31 exhibited a molecular weight of 249,8 kDa, Li+ migration number of 0.564 and a wide ESW up to 5.18 V. The GPE cell had a high discharge specific capacity of 138.72 mAh g 1 at 2C and a capacity retention of 84.27 % after 550 cycles at 2C. This work explains the respective roles of PEGDA and ETPTA for lithium-ion transfer after polymerization and provides a long-cyclable gel electrolyte system with high ESW and high discharge specific capacity.

Halogen bonding interactions are crucial in the design of 2D supramolecular assemblies. In this study, we introduce the N-oxide moiety as a halogen-bonding acceptor for the formation of 2D coassemblies. The monomers 4,4'-bipyridine N,N'-dioxide (BPYD) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1,3,5-TFTIB) coassemble into well-ordered, close-packed nanoarchitectures on HOPG surfaces. BPYD forms both halogen and hydrogen bonds with 1,3,5-TFTIB, resulting in pentameric structural units. At high concentrations, these units pack into dense ordered structures. When octanoic or nonanoic acid is used as a solvent, the formation of a 3-component linear structure with the interdigitated solvent molecules between the linear-arranged pentameric units is observed at low concentrations of reactants.

In aqueous zinc-ion batteries, uncontrolled dendrite growth at the anode and corrosion of the zinc electrode lead to poor cycle stability and low coulombic efficiency. To mitigate these side reactions, this study employs an in-situ growth approach to create a copper phosphate coating (CP@Zn) on the zinc anode. The uniformly grown copper phosphate reduces the nucleation energy barrier of Zn2+, offers uniform nucleation sites for the deposition of Zn2+, guides the deposition of Zn2+ in a 2D diffusion manner, enhances the deposition kinetics of Zn2+, Hydrophobic structures reduce electrode contact with water improving corrosion resistance, and increases the diffusion coefficient of charge carriers. The symmetric cell utilizing this anode can stably cycle for 2000 h at a current density of 5 mA cm-2 and a fixed areal capacity of 1 mAh cm-2, achieving high reversibility and a coulombic efficiency of 99.8% over 1800 cycles at a current density of 2 mA cm-2. It is capable of powering an LED lamp in a button cell with MnO2 as the cathode material. This approach provides an effective method for improving the performance of zinc anodes.

The slow dynamics on the air cathode side of zinc-air batteries and the high overpotential severely hinder their commercial development. This urgently requires a significant improvement in the kinetics of the cathodic oxygen reduction reaction (ORR) and enhancement of the catalyst's ORR/OER catalytic performance. Here, a novel ORR/OER bifunctional catalyst, CoCu-NC with excellent hydrophobicity, is reported to address these issues. Cu-modified Co nanoparticles (Co/Cu) are encapsulated in a leaf-like porous nitrogen-doped carbon material. The Co/Cu heterophase modulates the electronic states of the CoCu-NC catalyst, thus optimising its ORR/OER performance. On the other hand, the CoCu-NC catalyst with abundant voids and hydrophobic microstructures on lotus leaf-like surfaces enhances the kinetic process of the electrocatalytic reaction. Therefore, the CoCu-NC catalyst exhibits excellent electrocatalytic activity with an ORR half-wave potential of 0.89 V, an oxygen evolution overpotential of 180 mV, and a potential gap Delta E of 0.52 V. The corresponding liquid ZAB achieves a high peak power density of 198 mW cm-2, while the quasi-solid ZAB also demonstrates a peak power density of up to 513 mW cm-2. The CoCu-NC catalyst shows great potential in the ZAB field, providing new material design concepts for the development of high-power density zinc-air batteries.

Three highly ordered nanostructures consisting of different oligomers are exclusively obtained via a surface assembly-directed approach. It is suggested that this high selectivity is induced by the adsorption and assembly of specific oligomers at different temperatures, highlighting the self-sorting process in dynamic covalent reactions on surfaces.

Despite the exceptional theoretical capacity of lithium metal anodes (3860 mAh g-1), their practical implementation in high-energy-density batteries remains severely hampered by two persistent challenges: uncontrolled dendritic lithium growth and inherent cyclic volume fluctuations during plating/stripping processes. These intertwined issues not only compromise both operational safety and long-term cyclability but also undermine the electrochemical performance and commercial viability of lithium metal batteries. This study demonstrates a rational strategy to suppress lithium dendrite growth through the construction of a lithiophilic MXene/Germanium (Ge) hybrid substrate. A dense Ge layer with homogeneous distribution was successfully integrated onto layered MXene films via magnetron sputtering, forming a synergistic interface architecture. The optimized MXene/Ge-Li anode exhibits exceptional cycling stability, maintaining stable operation for over 1300 h at 1 mA cm-2 with minimal voltage hysteresis. Remarkably, the composite anode demonstrates temperature-adaptive performance, showing consistent cycling behavior. When paired with a LiFePO4 cathode, the full cell delivers a capacity retention of 132.46 mAh g-1 after 100 cycles at 1 C rate. This work provides fundamental insights into the design principles of lithiophilic substrates for metal anodes, offering a viable pathway toward safe and high-performance lithium metal batteries through interfacial engineering.

Lithium-ion batteries derived from single-crystal LiNixCoyMnzO2(x >= 0.8, y <= 0.2, x + y + z = 1) cathode materials are gaining growing attention owing to their enhanced structural stability and reliable safety in comparison with polycrystalline NCM. However, the sluggish kinetic behavior, interfacial side reactions, and intragranular cracking remain major bottlenecks restricting their widespread applications. In this work, the particle size was modulated and the composite coating layer was deposited on the single-crystal LiNi0.83-Co0.12Mn0.05O2 by introducing Wand B in the multi-step calcination process, aiming to simultaneously enhance the Li+ kinetics and structural stability. Notably, the as-obtained modified single-crystal LNCM-WWB cathode exhibited excellent capacity retention (93.67 % after 100 cycles, 1 C) and rate performance (144.7 mAh g-1, 5 C) with Li metal anode. Furthermore, the LNCM-WWB/graphite pouch-type full cell achieved a capacity retention of 84.45 % after 2000 cycles. Comprehensive multi-scale in situ/ex situ characterizations ascertained that the improvement mechanism of W/B modification is ascribed to the synergistic contributions of boosted mechanical stability, reinforced interfacial stability, and ameliorated reaction heterogeneity. This study underscores the significance of an integrated optimization strategy and provides critical design guidelines for the future development of Ni-rich single-crystal cathode materials.

Vanadium-based materials are recognized as promising cathodes for high-energy-density aqueous zinc-ion batteries (AZIBs). However, their inherent low intrinsic conductivities and sluggish reaction kinetics curtail their capacity release. Here, we enhanced the electron and ion transport properties of vanadium-based cathodes through heterojunction engineering, coupled with in situ electrochemical activation, significantly enhancing an unprecedented zinc-ion storage capacity and rapid kinetic performance. A heterostructured V2O3/g-C3N4 (V2O3/CN) precursor was synthesized via a calcination process firstly. When employed as a cathode in AZIBs, this precursor undergoes an in situ phase transformation into Zn3(OH)2V2O7·2H2O/C3N4 (ZVOH/CN) during the inaugural charging process, while retaining its heterojunction structure. Both electrochemical assessments and theoretical calculations revealed that ZVOH/CN exhibits superior zinc-ion adsorption and migration capabilities compared to conventional vanadium-based cathodes. The formation of the heterojunction amplifies the material’s electronic conductivity and ion diffusion kinetics. As a result, the optimal ZVOH/CN composite electrode showcases a remarkable capacity of 518.5 mAh g−1 at 0.5 A g−1, superior rate performance of 177.8 mAh g−1 at 20 A g−1, and impressive cycling stability. This work offers a novel design strategy for vanadium-based composite materials as high-performance AZIB cathodes.

Surface-catalyzed polymerization is crucial in both chemical science and industrial manufacturing, yet achieving regioselective radical polymerization on the surface remains challenging. Here, we demonstrate the regioselective Ullmann polymerization of nonsymmetrical 2,8-dibromoquinoline (DBQ) on an Au(111) surface. By combining scanning tunneling microscopy, density functional theory calculations, and kinetic modeling, we reveal the regioselectivity and its evolution with surface temperature at the molecular level. At 348-368 K, DBQ monomers primarily form covalent dimers through energetically favored head-to-head (HtH) coupling. As the temperature increases to 390-473 K, oligomers and long polymer chains are formed, with less favored head-to-tail (HtT) linkages emerging and eventually dominating over HtH linkages. Such regioselectivity evolution from HtH to HtT is suggested to be related to a sequential monomer addition mode and a shift in the distribution of reactive sites at the end and tail of the polymer chains during polymerization. This result provides molecular-level mechanistic insights into the regiochemistry of surface-catalyzed polymerization.

Lithium metal anodes suffer from dendrites, unstable solid electrolyte interface (SEI), and volume changes. Three-dimensional conductive hosts, particularly lightweight carbon cloth (CC), mitigate these by homogenizing Li+ flux and buffering expansion. While cobalt oxide (Co3O4) modification enhances CC lithiophilicity, the roles of specific surface area (SSA) and nanostructure geometry (nanoparticles vs. nanosheets) in lithium deposition behavior remain less understood. This study bridges this gap by fabricating two architecturally distinct Co3O4modified CCs via controlled synthesis: one with dense Co3O4 nanoparticles and another with high-SSA Co3O4 nanosheet arrays. Both significantly reduce nucleation overpotential versus pristine CC and exhibit a two-stage deposition mechanism. Crucially, dense nanoparticles on CC induce uniform, compact Li deposition, enhance SEI stability, and suppress dead Li formation, whereas high SSA proves less effective. Consequently, the CC with dense nanoparticles anode delivers exceptional stability: an average coulombic efficiency (CE) of 99.24 % over 200 cycles (2 mA cm- 2, 4 mAh cm- 2), symmetric cell operation for 1200 h at 1 mA cm- 2/1 mAh cm- 2, and full cells with LiFePO4 retaining 91 % capacity after 180 cycles at 2C. This work establishes fundamental correlations between host nanostructure geometry, SSA, and Li deposition behavior, providing vital design principles for practical lithium metal batteries.

Nitrogen-doped carbon nanotubes (NCNTs) that encapsulate PtRu alloy nanoparticles were fabricated by performing chemical vapor deposition using anodic aluminum oxide templates and subsequent annealing in ammonia. Pt and Ru had low contents of 0.8 wt% and 4.2 wt%, respectively, but their combined contributions with nitrogen doping resulted in excellent electrocatalytic activity of the PtRu@NCNT composites for the hydrogen evolution reaction in alkaline, acid and neutral electrolytes.