Abstract Aqueous Zn‒I2 batteries based on four-electron conversion chemistry have been extensive explored due to their high voltage and large specific capacity. However, the intrinsic instability of I+ generated during the high-voltage conversion process and the severe electrochemical corrosion of Zn anode in aqueous electrolyte primarily hinder the construction of high-performance Zn‒I2 batteries. Herein, trimethylammonium bromide (TMBr) with functional cation and anion has been selected as a dual-side shielding electrolyte additive to concurrently resolve these problems. On the one hand, Br− in TMBr could incorporate into the electrolyte solvation structure and reconstitute the hydrogen-bond (H-bond) network, suppressing the activity of free H2O molecules and consequently enhancing the Zn anode stability. On the other hand, the Br− could electrochemically activate I+, followed by the stabilization of I+ via complexation interactions with trimethylamine cations (TM+) and Br−, synergistically achieving facile high-voltage conversion chemistry of I2 cathode. As a result, the TMBr additive enables the four-electron conversion-type Zn‒I2 batteries to demonstrate a remarkable capacity of 250 mAh g−1 coupled with stable cycling exceeding 15000 cycles at 3 A g−1. Additionally, the 160 mAh pouch cell delivers an energy density of 367.4 Wh kg−1 (based on I2 mass) with a lifetime of over 300 cycles.

Ammonia (NH3) is one of the important chemicals in human society. Conversion of air and water to NH3 by plasma treatment and electrocatalytic reduction is a prospective approach. Herein, a self-supported CuCo/Cu nanowires (NWs) catalyst is prepared through simple electrochemical methods, achieving exceptional eNO(x)(-)RR performance: 99.8 % Faradaic efficiency and 230.3 mg h(-1) cm(-2) NH3 yield rate at -0.7 V vs. RHE in 1 M NaOH with 0.2 M NOx-. The 3D NWs architecture provides abundant exposed active sites, significantly improving the catalyst's NOx- reduction activity. Besides, the introduction of Co modulates the electronic structure of Cu while serving as a complementary site for active hydrogen (*H) supply, thereby synergistically promoting the eNO(x)(-)RR process. Finally, CuCo/Cu NWs serve as a bifunctional catalyst coupled with the anodic hydrazine oxidation reaction (HzOR) instead of the oxygen evolution reaction (OER), effectively reducing the energy consumption of the eNO(x)(-)RR system and achieving a greener and energy conservation route for the synthesis of NH3.

Ammonia (NH3) is seen to be promising hydrogen carrier, but its decomposition into hydrogen (H2) has been plagued by high operating temperature (400-700 degrees C) and long start-up time. Here, we present that directly electrochemical liquid NH3 decomposition (ELADH) method could realize efficient onsite H2 generation at room-temperature, whereas active and stable electrocatalytic system is challenging. Through rationally optimizing the electrolysis system with Ru catalysts, we achieved an active and durable ELADH into H2 under ambient temperature. It was found that Ru nanoparticles (Ru NPs) with (101) facet could effectively promote the favorable N-H dissociation and hydrogen desorption, and thus accelerate the slow reaction kinetics. The as-prepared Ru NPs on nitrogen carbon exhibit lower potential of -1.01 V vs. NHE at -10 mA cm-2 and larger current density of -910 mA cm-2 at -1.47 V vs. NHE, superior to Ru single atoms and commercial Pt/C. Importantly, this system affords stable H2 evolution under 100 h continuous electrolysis without apparent degradation, far beyond the reported catalysts. This work paves the new way of room-temperature onsite H2 production and presents insightful understanding of the electrochemical liquid ammonia splitting process.

Abstract Ammonia (NH3), an essential chemical in the contemporary world, is emerged as a promising carbon-free energy carrier. Herein, plasma-electrocatalytic synthesis of ammonia (PESA), by combining plasma N2 fixation (PNF) with electrochemical nitrate/nitrite (NOx−) reduction reaction (eNOxRR), is integrated with an ammonia capture system to achieve NH3 synthesis and its further conversion into high-purity solid NH4Cl. Accordingly, we report a spinel-structured CuCo2O4/Fe3O4 catalyst that significantly boosts the overall PESA process. In the PNF step, theoretical analysis reveals that N2 and O2 exhibit stronger adsorption and more facile dissociation on CuCo2O4/Fe3O4, accounting for the enhanced NOx− yield rate (297.0 mmol h−1). For eNOxRR, the catalyst delivers an NH3 yield rate of 322.5 mg h−1 cm−2 and a Faradaic efficiency (FE) of 98.6%. Theoretical analysis further indicates that the key intermediate NO2* binds strongly to the active site on CuCo2O4/Fe3O4, while the reduced energy barrier facilitates the NH3 formation. The integrated capture unit allows virtually 100% recovery of NH3 from the catholyte within 20 min, enabling direct formation of high‑purity solid NH4Cl. Overall, this work provides an efficient plasma-electrocatalytic route for the integrated synthesis, separation, and upgrading of nitrogen products from air and water.

The electrocatalytic reduction of CO2 to formic acid (HCOOH) is a promising route toward carbon neutrality, offering high selectivity and Faradaic efficiency. However, the essential mechanism governing the reduction of CO2 to HCOOH remains elusive, as the reaction intermediates have not been conclusively identified. Herein, we discovered that the hydroxylated metallic Bi (OH-Bi) achieves a formate FE of up to 99.9%, markedly surpassing the 5% FE of commercial Bi powder. In situ Raman spectroscopy revealed that OH-Bi promotes the formation of carbonate intermediates during the CO2 reduction reaction (CO2 RR). Isotopic labeling experiments with O-18 in online differential electrochemical mass spectrometry (DEMS) confirmed that the oxygen atoms from surface hydroxyl groups actively participate in formate production. Density functional theory calculations proposed a feasible pathway from CO2 to HCOOH, demonstrating that the hydroxylated Bi surface lowers the free energy change for CO2 hydrogenation from 6.40 to 0.72 eV by facilitating elongation of C=O bonds in CO2 molecules and blocking the hydrogen evolution reaction, which enables the OH-Bi catalyst exhibiting near-unity formate selectivity and enhanced stability. This study clarifies the essential mechanism of HCOOH production by electrocatalytic CO2 reduction, providing theoretical guidance for the rational design of efficient catalysts.

1, 3-Dioxolane (DOL), as an ideal electrolyte solvent for lithium metal batteries, exhibits excellent lowtemperature performance and fast-charging potential. However, its practical application is severely hindered by Lewis acid-catalyzed ring-opening polymerization. Herein, a theoretical framework is established to evaluate the ring-opening polymerization tendency of cyclic ethers. The results reveal that the pronounced susceptibility of DOL to such polymerization stems from its combination of high ring-opening strain energy and strong nucleophilicity. Therefore, we propose an "Lewis acid trapping" strategy and synthesize a strongly Lewis-basic lithium salt additive, lithium tetrakis[(1,3-dioxolan-4-yl)methoxy]aluminate (LAD). It sequesters Lewis acids to suppress polymerization while regulating the solvation structure to induce a LiF-rich, polyether-free solid electrolyte interphase (SEI). This enables lithium metal anodes to deliver a high Coulombic efficiency of 99.30%, and the symmetric cell further exhibits stable plating/stripping over 4000 h at 0.5 mA cm- 2. Consequently, Li/ LE-LAD/LiFePO4 full cells demonstrate superior low-temperature (-30 degrees C) and rate performance (20C). As a practical validation, a 1.3 Ah Li// LiFePO4 pouch cell retains 97.9% capacity over 120 cycles following 30 days of storage. The theoretical prediction framework and active inhibition strategy proposed in this work offer a solution to uncontrolled polymerization in cyclic-ether-based electrolytes.

ABSTRACT Ammonia is a promising carbon‐free energy carrier, offering advantages in storage, transport, and infrastructure compatibility. Its application in anion exchange membrane‐based direct ammonia fuel cells (AEM‐DAFCs) represents a promising approach to sustainable energy conversion. However, the development of AEM‐DAFCs is critically limited by noble‐metal dependence. Although powder‐based non‐noble metal catalysts have been widely investigated, devices assembled with them still deliver low power density and poor durability. Here, we present an activated nickel phosphorus on Ni foam (A‐Ni 3 P@NF) as an efficient integrated non‐noble anode. Through a P doping strategy that introduces tunable defect centers, the electronic structure of nickel is tuned to regulate the adsorption of reaction intermediates. This modulation enables a new ammonia oxidation reaction (AOR) pathway, which is validated through in situ characterization, synchrotron Ni K ‐edge X‐ray absorption spectroscopy (XAS), and theoretical calculation. The optimized A‐Ni 3 P@NF‐III exhibits outstanding ammonia oxidation activity, remarkable N 2 selectivity (96.4%), and record‐long durability (>320 h). Integrated into AEM‐DAFCs, the catalyst achieves peak power densities of 166.83 in O 2 and 123.69 mW cm −2 in air, the highest value reported for non‐noble anodes. This work establishes a universal strategy for non‐noble integrated anodes, advancing AEM‐DAFCs toward practical application.

Ambient electrosynthesis urea using NO3-, CO2, and H2O has emerged as an alternative to the current energy-intensive industrial synthesis process while storing renewable energy. Unfortunately, C-N coupling reaction kinetics are sluggish due to difficult CO2 activation/conversion, along with strong side reactions, leading to high overpotential, low selectivity, and consequently low yield. Here, to avoid the competitive CO2 and NO3- reduction and the high overpotential of CO2 reduction in the traditional Langmuir-Hinshelwood route via C/N intermediates, we developed an effective C-N coupling strategy via the Eley-Rideal route, wherein prioritized NO3- reduction intermediates directly assisted CO2 fixation. Using bimetallic CuZn catalysts, we achieved efficient urea production at an ultralow operating potential of -0.1 V vs RHE. The CuZn catalyst reached a maximum Faradaic efficiency of 55.2% at -0.2 V vs RHE and a considerable yield rate of 37.9 mmol h(-1) g(cat.)(-1) at -0.3 V vs RHE, surpassing its counterparts. Utilizing in/ex situ experiments and theoretical calculations, we found that favorable C-N bond formation proceeds through the direct interaction of free CO2 with *NO intermediates on reconstructed metallic CuZn sites. This work highlights that rationally regulating C-N coupling is compelling for facilitating high-efficiency urea synthesis and other important C-N reactions.

Neutral zinc-iron flow batteries (ZIFBs) are promising candidates for grid-scale energy storage due to their safety, low cost, and sustainability. However, their cycle stability and energy density are restricted by zinc dendrite growth, hydrogen evolution, and more positive Zn anode potential in neutral media compared to alkaline conditions. Herein, we propose a ligand-coordination strategy using tetrasodium iminodisuccinate (IDs) to rationally tune the redox behavior of Zn2+. The formation of a stable [H4Zn(C8H7NO8)2]2- complex converts the conversional Zn(H2O)6 2+ structure into a chelate-dominated configuration, inducing an outer-sphere electron transfer pathway by preventing direct Zn-electrode interactions. Meanwhile, it results in a significant negative shift in redox potential of 350 mV (from -0.814 to -1.164 V vs. SHE), enabling a record-high cell voltage of 1.63 V in neutral ZIFBs. The stabilized coordination environment facilitates highly reversible Zn plating/stripping while suppressing hydrogen evolution, dendrite formation and other side reactions. As a result, such high-voltage ZIFB demonstrates a remarkable energy efficiency of 88.77% at 40 mA cm-2 and excellent cycling stability over 320 cycles, advancing durable and high-performance neutral ZIFBs.

In this work, an effective catalyst of Cu/MnOOH has been successfully constructed for electrochemical nitrate reduction reaction (eNO3RR) for synthesis of ammonia (NH3) under ambient conditions. The substrate of MnOOH plays an important role on the size and electronic structure of Cu nanoparticles, where Cu has the ultrafine size of 2.2 nm and positive shift of its valence states, which in turn causes the increased number of Cu active sites and enhanced intrinsic activity of every active site. As a result, this catalyst realizes an excellent catalytic performance on eNO3RR with the maximal NH3 Faraday efficiency (FE) (96.8%) and the highest yield rate (55.51 mg h−1 cm−2) at a large NH3 partial current density of 700 mA/cm2, which could help to promote the industrialization of NH3 production under ambient conditions.

Neither single electrolyte design nor solid electrolyte interface (SEI) engineering alone can effectively resolve the dual challenges of sluggish reaction kinetics and unstable interfaces in polymer-based lithium metal batteries (LMBs). Herein, a rational integrated design strategy is adopted to simultaneously fabricate poly(trifluoroethyl methacrylate-co-4-oxo-5,8,11-trioxa-3-azatridec-12-en-1-yl acrylate)-based gel polymer electrolyte (PTDA-GPE) and stable composite SEI during the thermal-induced in situ polymerization process. The resulting PTDA-GPE demonstrates superior Li+ transport kinetics (1.34 mS cm-1 at 30 °C), enhanced mechanical strength and flame retardancy, and an expanded electrochemical window of up to 4.8 V (vs. Li+/Li). Notably, the SEI constructed using the differentiated adsorption forces and redox kinetics between various components and lithium metal has a unique organic-inorganic composite structure. Ultimately, Li/PTDA-GPE/LiFePO4 batteries can achieve over 1000 stable cycles at -20 °C and 60 °C (capacity retention of 95 % and 80 %, respectively)，and Li/PTDA-GPE/LiCoO2 demonstrates high capacity retention of 98 % after 200 cycles. In addition, the 1.2 Ah Li/PTDA-GPE/LiFePO4 pouch cell can guarantee enhanced safety features and constant output voltage under abuse conditions. This work demonstrates a facile and universal strategy for in situ integrated fabrication of composite SEI/GPE.

Electrochemical nitrite (NO2-) reduction offers a sustainable route for ammonia (NH3) synthesis while simultaneously removing contaminants in wastewater. However, its efficiency is often limited by low catalytic efficiency and the competitive hydrogen evolution reaction at low NO2-concentrations. Herein, we report an intermittent pulsed electrolysis (IPE) strategy using copper oxide (CuxO) nanowires, which significantly enhances the NH3 yield rate and Faradaic efficiency (FE) at lower reactant concentrations. In situ experiments and theoretical calculations reveal that alternating between open-circuit and cathodic potentials modulates the copper oxidation states, stabilizing the catalytically active cuprous oxide (Cu2O). Consequently, the IPE approach provides an outstanding NH3 yield rate of 115.10 mgh-1cm-2 and FE of 91.14% in the of 25 mM conventional constant

Electricity driven nitrogen (N2) reduction (eNRR) presents one green and ambient alternative to Haber-Bosch ammonia (NH3) synthesis. However, NH3 yield rate and selectivity are extremely low due to failures in sufficient N2 activation and suppressing robust competitive reaction. Herein, efficient plasma N2 activation is matched with thermodynamically favorable electrocatalytic hydrogenation in the specially integrated system and achieves sustainable and ambient NH3 synthesis directly using air and water. Through this well-designed reactor with an optimal Cu mesh electrode, high NH3 Faradaic efficiency of 91.42% and yield rate of 14.01 mg h-1 cm-2 are achieved, largely surpassing eNRR and sole nitrite (NO2 -) electroreduction in a similar electrolyte. Using in situ experiments and theoretical calculations, it is found that NH3 synthesis mainly goes through plasma N2 oxidation into gaseous nitric oxide (NO) and aqueous NO2 -, followed by the electroreduction of these intermediates to NH3. The slightly oxidized Cu species with low coordination state and high NO affinity, which are stabilized by plasma treatment, account for the accelerated reaction kinetics of *NO hydrogenation and the suppressed combination of *H into hydrogen. This work highlights the possibility of sustainable NH3 synthesis directly from ambient air and water beyond the fossil fuel-driven synthesis process.

Passive ammonia fuel cells (PAFCs) offer modular adaptability but face dual challenges: limited power density and dependency on noble metals. Here, a comprehensive strategy is presented to address these issues through coordinated materials and system design. Pre‐oxidized nickel substrates direct the formation of β‐phase NiOOH/Ni 3 P (β‐NiOOH/Ni 3 P) heterointerfaces in anode, significantly enhancing ammonia oxidation reaction (AOR) kinetics with a high current density of 171 mA cm −2 at 0.7 V. A spinel‐structured MnCo 2 O 4 /C cathode catalyst demonstrates remarkable ammonia tolerance and outperforms Pt/C in stability. A polytetrafluoroethylene/layered double hydroxide (PTFE/LDH) composite membrane is also introduced, which effectively reduces ammonia crossover. Their integration with an optimized graphite prototype further enhances PAFCs' efficiency and stability. This synergistic multi‐phase optimization enables record‐breaking performance for non‐noble metal‐based PAFCs, achieving a peak power density (PPD) of 61 mW cm −2 and an open circuit voltage (OCV) of 0.87 V (outperforming Pt‐based PAFCs). Stable discharge can be sustained by the present PAFC for 9 h by replenishing the ammonia supply. This work establishes a prototype‐to‐performance strategy for cost‐effective PAFC, highlighting the potential of non‐noble metal catalysts in ammonia electrochemical energy conversion.

The inherent coupling between lithium salt concentration and mechanical robustness, along with inadequate anode compatibility, constrain the practical application of "polymer-in-salt electrolytes" (PISEs). Inspired by biomimetic design principles, a sea cucumber mimetic multifunctional poly(vinyl chloride-co-2-(((2,2,3,3-tetrafluoropropoxy) carbonyl) amino) ethyl acrylate)-based solid polymer electrolyte (PVCTF-SPE) is developed through hydrogen-bond engineering, achieving liquid to solid phase transition via a solvent-free tape casting approach. The introduced multi -NH-OC- hydrogen-bond interactions decouple the intrinsic trade-off in PISEs, endowing PVCTF-SPE with an ionic conductivity of 1.21 x 10(-4) S cm(-1), exceptional stretchability (1380 % strain), and autonomous self-healing capability. Furthermore, the superior elastic deformation behavior and strong Li-PVCTF interfacial adhesion effectively mitigate interfacial impedance and suppress tip-induced Li dendrite growth, enabling stable Li deposition/stripping for 3800 h in Li/Li symmetric cells. The strategically engineered molecular structure also delivers an expanded electrochemical window (>4.8 V) and flame-retardant characteristics. A 1.5 Ah Li/LiFePO4 pouch cell demonstrates stable cycling performance (100 cycles, 70 % capacity retention) even under 7.5 % tensile strain and passes rigorous safety tests. This hydrogen bond engineering provides a universal paradigm for developing solid electrolytes with synergistically enhanced ion transport and mechanical stability.

Plasma-electrocatalytic ammonia (NH3) synthesis using renewable energy as an input is an ideal and sustainable method for NH3 production. However, its practical application is hindered by the inferior performance of the plasma nitrogen oxidation reaction (pNOR) and its inability to proceed synchronously with the electrochemical nitrate-nitrite reduction reaction (eNOx-RR) process. Herein, a bifunctional Co-P catalyst supported on Ni foam (Co-P/NF) achieves outstanding performance in both pNOR (NOx- yield: 171.3 mmol h-1) and eNOx-RR (NH3 yield: 319.2 mg h-1 cm-2; Faraday efficiency: 99.2%). More importantly, an integrated scaled-up device is further constructed, enabling gram-scale NH3 production (1.53 g h-1) directly from air and water. Experimental studies reveal that P-doping modulates the catalyst structure, facilitates N2 adsorption, and accelerates the pNOR rate-determining step. Meanwhile, it optimizes H2O dissociation to supply abundant H* species for the hydrogenation process in the eNOx-RR. This synergistic mechanism collectively enables the remarkable NH3 yield.

Gel polymer-based lithium batteries exhibit a unique combination of advantageous properties, including the favorable interfacial contact characteristic of liquid-state batteries and the inherent stability of solid-state batteries. For Li-air batteries operated in the semi-open atmosphere, implementing in situ synthesized gel polymer electrolytes (GPEs) is effective in mitigating the environment-induced challenges. In this study, a dimethyl sulfoxide (DMSO)-based GPE in situ initiated by the toluene-2,4-diisocyanate (TDI) and 1,4-benzenediboronic acid (BDBA) is designed to enable the stable operation of lithium-air batteries. The integration of in situ polymerization and polyvinyl alcohol's functional group engineering not only brings benefits to the interfacial contact and electrochemical stability of the battery but also mitigates the moisture sensitivity and volatility of the DMSO electrolyte in the ambient environment. In addition, the GPE can promote the formation of a robust protection film on the lithium surface. As a result, the designed GPE makes the batteries fully leverage their outstanding cycling stability in the ambient environment (241 cycles at 500 mA g-1 and 1000 mAh g-1). Moreover, an optimized Li-air pouch cell structure incorporating the GPE achieves a boasted energy density of 757.5 Wh kg-1, providing a significant technical pathway to bring Li-O2 batteries to practical Li-air batteries. An advanced DMSO-based gel polymer electrolyte is designed to conquer the challenges of electrolyte evaporation and lithium anode corrosion faced by the semi-open Li-air battery systems, realizing comprehensive performance improvement in the ambient environment, especially the cycling lifetime and energy density. image

Recently, hydrazine borane (HB, N2H4BH3) is recognized as an ideal chemical hydrogen storage material due to its high efficiency in storing hydrogen and excellent stability. However, finding an efficient, stable, and low-cost catalyst is still a challenge. In this study, CoPt nanoparticles (NPs) supported on carbon nanotubes (CNTs) are prepared at room temperature. The Co0.4Pt0.6/CNTs catalyst exhibits optimal catalytic performance for hydrogen production from HB at ambient conditions, achieving a total turnover frequency (TOF) value of 1525.4 h(- 1 )and 100% H-2 selectivity. The well-dispersed CoPt NPs on CNTs and the synergistic effect between Co and Pt further enhance the decomposition efficiency of HB. This high-performance catalyst has significant implications for the advancement of hydrogen storage materials, particularly in relation to HB.