Zinc-iodine batteries (ZIBs) have long struggled with the uncontrolled spread of polyiodide in aqueous electrolytes, despite their environmentally friendly, inherently safe, and cost-effective nature. Here, we present an integral redesign of ZIBs that encompasses both the electrolyte and cell structure. The developed self-sieving polyiodide-capable liquid-liquid biphasic electrolyte can achieve an impressive polyiodide extraction efficiency of 99.98%, harnessing a meticulously iodine-containing hydrophobic solvated shell in conjunction with the salt-out effect. This advancement facilitates a membrane-free design with a Coulombic efficiency of similar to 100% at 0.1C, alongside an ultra-low self-discharge rate of similar to 3.4% per month and capacity retention of 83.1% after 1300 cycles (iodine areal loading: 22.2 mg cm-2). Furthermore, the integrated cell structure, paired with the low-cost electrolyte ($4.6 L-1), enables rapid assembly into A h-level batteries within hours (1.18 A h after 100 cycles with a capacity retention of 86.7%), supports electrolyte regeneration with similar to 100% recycling efficiency, and extends to ZIBs with a two-electron iodine conversion reaction. This endeavor establishes a novel paradigm for the development of practical zinc-iodine batteries.

Electrocatalytic nitrate reduction to ammonia (eNRA) is a promising route toward environmental sustainability and clean energy. However, its efficiency is often limited by the slow conversion of intermediates due to spin-forbidden processes. Here, we introduce a novel A-site high-entropy strategy to develop a new perovskite oxide (La0.2Pr0.2Nd0.2Ba0.2Sr0.2)CoO3-δ (LPNBSC) for eNRA. The LPNBSC possesses a higher concentration of high-spin (HS) cobalt-active centers, resulting from an increased concentration of [CoO5] structural motifs compared to conventional LaCoO3. Consequently, this material exhibits a significantly improved electrocatalytic performance toward ammonia (NH3) production, resulting in a 3-fold increase in yield rate (129 μmol h-1 mgcat.-1) and a 2-fold increase in Faradaic efficiency (FE, 76%) compared to LaCoO3 at the optimal potential. Furthermore, the LPNBSC-based Zn-nitrate battery reaches a maximum FE of 82% and an NH3 yield rate of 57 μmol h-1 cm-2. Density functional theory calculations reveal that A-site high-entropy management in perovskites facilitates nitrate activation and potentially optimizes the thermodynamic rate-determining step of the eNRA process, namely, *HNO3 + H+ + e- → *NO2 + H2O. This work presents an efficient concept for modulating the spin state of the B-site metal in perovskites and offers valuable insights for the design of high-performance eNRA catalysts.

Cobalt single atoms on nitrogen-doped carbon (CoSAs/N-C) were successfully synthesized through the pyrolysis of metal-organic supramolecular self-template. Only 0.12 wt% metal-doped CoSAs/N-C anodes bring a rate capacity enhancement of 195 mAh g(-1) compared to the blank group of nitrogen-doped carbon electrodes at 0.1 A g(-1). In addition, the CoSAs/N-C anodes exhibit remarkable sodium-ion storage capacities of 285 mAh g(-1) after 2000 cycles at 1.0 A g(-1) and 133 mAh g(-1) with an exceptional cycling stability for 10,000 cycles at an ultra-high current density of 20 A g(-1), thereby showcasing excellent Na ion storage performance. Ex-situ X-ray photoelectron spectroscopic study demonstrates that some N atoms in CoSAs/N-C can reversibly store and release Na ions during discharge and charge cycles. The full cell assembled with CoSAs/N-C anode and Na3V2(PO4)(3) cathode displays Coulombic efficiency of >99.7 % after 200 cycles at 0.5 A g(-1). Density functional theory (DFT) calculations further reveal that the presence of single-atom Co results in a decrease in the Na binding energy surrounding pyrrolic-N and pyridinic-N structures. This moderate binding energy may be beneficial for Na ion adsorption and desorption. This study opens up new possibilities of fabricating advanced metal single atom anodes for high-performance sodium-ion batteries.

Functionalizing sp(3) C-H bonds in toluene through photocatalysis poses a significant challenge in organic synthesis, garnering substantial research attention. Nevertheless, the inert nature of the C-H bond restricts the photocatalytic conversion efficiency. Here, we construct bismuth defect modified ultrathin Bi2WO6 nanosheets (BT-48) for the conversion of toluene into benzaldehyde under light irradiation. Density functional theory (DFT) calculations validate the effectiveness of Bi defects in Bi2WO6 in activating the C-H bond in toluene. Moreover, a comprehensive physiochemical analysis shows that the introduction of bismuth defects in ultrathin Bi2WO6 nanosheets could promote the separation of photoexcited charge carriers. As a result, the optimal BT-48 sample exhibits an impressive benzaldehyde formation (6781 mu mol g(-1) h(-1)) with a high selectivity of 96%, which is 6 times higher than that of Bi2WO6 (1109 mu mol g(-1) h(-1)) and surpasses those of all the previously reported Bi2WO6-based photocatalysts. It is expected that this work could enhance our understanding of designing efficient photocatalysts for the activation of C-H bonds under light illumination.

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+]I-3(-) 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.

High-entropy perovskite fluoride (HEPF) has gradually attracted attention in the field of electrocatalysis due to its unique properties. Although traditional co-precipitation methods can efficiently produce HEPF, the resulting catalysts often lack regular morphology and tend to aggregate extensively. Here, nanocubic K(CuMgCoZnNi)F3 HEPF (HEPF-2) was successfully prepared on a gram-scale by a polyvinylpyrrolidone (PVP)-confined nucleation strategy. Benefiting from its large electrochemically active surface area and well-exposed active sites, the HEPF-2 demonstrates dramatically enhanced electrocatalytic activity in electrocatalytic nitrate reduction to ammonia, leading to an improved ammonia yield rate (7.031 mg h-1 mgcat.-1), a high faradaic efficiency (92.8%), and excellent long-term stability, outperforming the irregular HEPF nanoparticles (HEPF-0) prepared without the assistance of PVP. Our work presents an efficient and facile method to synthesize perovskite fluorides with a well-defined structure, showing great promise in the field of high-performance electrocatalysis.

Metal nanoparticle (NP) cocatalysts are widely investigated for their ability to enhance the performance of photocatalytic materials; however, their practical application is often limited by the inherent instability under light irradiation. This challenge has catalyzed interest in exploring high-entropy alloys (HEAs), which, with their increased entropy and lower Gibbs free energy, provide superior stability. In this study, 3.5 nm-sized noble-metal-free NPs composed of a FeCoNiCuMn HEA are successfully synthesized. With theoretic calculation and experiments, the electronic structure of HEA in augmenting the catalytic CO2 reduction has been uncovered, including the individual roles of each element and the collective synergistic effects. Then, their photocatalytic CO2 reduction capabilities are investigated when immobilized on TiO2. HEA NPs significantly enhance the CO2 photoreduction, achieving a 23-fold increase over pristine TiO2, with CO and CH4 production rates of 235.2 and 19.9 µmol g-1 h-1, respectively. Meanwhile, HEA NPs show excellent stability under simulated solar irradiation, as well high-energy X-ray irradiation. This research emphasizes the promising role of HEA NPs, composed of earth-abundant elements, in revolutionizing the field of photocatalysis.

The dissolution of iodine species into the aqueous electrolyte is an inevitable issue in zinc-iodine (Zn-I2) battery, leading to its fading capacity and inferior cycle life. Herein, the porous oxidized salt-templated carbon (OSTC) with abundant carbonyl groups is prepared by using H2O and ZnCl2 as gasification agent/oxidant and salttemplate, respectively. The synergistic effect of oxygen-containing functional group and unique pore structure in OSTC makes it a promising host to confine iodine tightly, resulting in the extraordinary cycling stability (a high capacitance retention of 85.04% after 10,000 cycles) and excellent rate performance for the as-assembled Zn-I2 battery. Experimental ex-situ and in-situ characterizations, and theoretical calculations (density functional theory calculation and COMSOL Multiphysics simulation) are conducted jointly to reveal its dual energy storage mechanisms: (1) only one-step redox reaction between I2 and I- can be observed without any appearance of I3intermediates that is beneficial to increasing the utilization of iodine; (2) the abundant C=O groups on the OSTC surface can also react with the Zn2+ ions to form C-O-Zn group and provide extra pseudocapacity for Zn-I2 battery. This work not only presents a high-performance cathode for Zn-I2 battery, but also sheds light on possible strategies for other metal-I2 batteries.

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).

The development of a 3D carbon assembly with a combination of extraordinary electrochemical and mechanical properties is desirable yet challenging. Herein, an ultralight and hyperelastic nanofiber-woven hybrid carbon assembly (NWHCA) is fabricated by nanofiber weaving of isotropic porous and mechanical brittle quasi-aerogels. Upon subsequent pyrolysis, metallogel-derived quasi-aerogel hybridization and nitrogen/phosphorus co-doping are integrated into the NWHCA. Finite element simulation indicates that the 3D lamella-bridge architecture of NWHCA with the quasi-aerogel hybridization contributes to resisting plastic deformation and structural damage under high compression, experimentally demonstrated by complete deformation recovery at 80% compression and unprecedented fatigue resistance (>94% retention after 5000 cycles). Due to the superelasticity and quasi-aerogel integration, the zinc-air battery assembled based on NWHCA shows excellent electrochemical performance and flexibility. A proof-of-concept integrated device is presented, in which the flexible battery powers a piezoresistive sensor, using the NWHCA as the air cathode and the elastic conductor respectively, which can detect full-range and sophisticated motions while attached to human skin. The nanofiber weaving strategy allows the construction of lightweight, superelastic, and multifunctional hybrid carbon assemblies with great potential in wearable and integrated electronics.

The electrocatalytic carbon–nitrogen (CN) coupling, facilitating one‐step urea synthesis under ambient conditions, holds great promise as a viable alternative to conventional protocols. However, developing efficient and low‐cost electrocatalysts for CN coupling remains a great challenge. Herein, a “bottom‐up” strategy is proposed to synthesize multidimensional hybrid materials of ultrathin NiCu layered double hydroxide (LDH) nanosheets on carbon nanofiber (u‐NiCu‐LDH/CNF) through an ultrasonic‐assisted solvothermal method. The NiCu‐LDH nanosheets in the u‐NiCu‐LDH/CNF composite exhibit a significantly thinner morphology compared to NiCu‐LDH/CNF prepared by conventional solvothermal without ultrasonic assistance. Leveraging its large specific surface area and well‐exposed active sites, the u‐NiCu‐LDH/CNF demonstrates dramatically improved electrocatalytic activity in CN coupling for urea production, leading to a satisfactory urea yield rate (19.43 mmol g−1 h−1) and a high Faradaic efficiency (13.95%). Density functional theory calculations reveal that the CN coupling step on the NiCu‐LDH model starts through the reaction between *NO2 and *CO2 intermediates. This spontaneous CN coupling process is beneficial in promoting high levels of urea yield. This work presents a facile approach for preparing 2D ultrathin LDH, showcasing tremendous prospects in electrocatalytic urea synthesis.

High‐entropy alloys (HEAs) made up of multiple metallic elements have gained attention for their excellent electrocatalytic performance. However, their application in the field of nitrogen (N 2 ) oxidation reaction (NOR) remains underexplored. In this study, a “pomegranate‐like” carbon embedded with ultrafine AuPdPtRhIr HEA (HEA@C) is synthesized using a polymer‐confined pyrolysis strategy. Molecular dynamics (MD) simulations show that small‐sized metal nanoparticles formed by the confinement of polyvinyl alcohol (PVA) during the hydrothermal process can easily form a single‐phase HEA through a thermodynamically‐driven solid‐phase diffusion process during subsequent pyrolysis. Additionally, a porous carbon layer which in situ converted from the PVA shell can effectively inhibit the agglomeration of HEA nanoparticles and confine the surrounding N 2 . Experimentally, the HEA@C nanohybrid demonstrates a satisfactory NO 3 − yield rate of 23.8 µg h −1 mg cat. −1 and a high Faraday efficiency of 13.8% for the NOR process. By using operando Fourier Transform Infrared spectroscopy, online differential electrochemical mass spectrometry (DEMS), and density functional theory calculations, potential efficient active sites (Rh–Ir–o) and pathways for the electrochemical conversion of inert N 2 to NO 3 − are revealed. This research provides an effective strategy for producing highly dispersed ultrafine HEA nanoparticles, showing a wide range of applications in advanced electrocatalysis.

Ambient electrocatalytic nitrogen fixation is an emerging technology for green ammonia synthesis, but the absence of optimized, stable and performant catalysts can render its practical application challenging. Herein, bimetallic NiCo boride nanoparticles confined in MXene are shown to accomplish high-performance nitrogen reduction electrolysis. Taking advantage of the synergistic effect in specific compo-sitions with unique electronic d and p orbits and typical architecture of rich nanosized particles embed-ded in the interconnected conductive network, the synthesized MXene@NiCoB composite demonstrates extensive improvements in nitrogen molecule chemisorption, active area exposure and charge transport. As a result, optimal NH3 yield rate of 38.7 lg h-1 mgcat.-1 and Faradaic efficiency of 6.92% are acquired in 0.1 M Na2SO4 electrolyte. Moreover, the great catalytic performance can be almost entirely maintained in the cases of repeatedly-cycled and long-term electrolysis. Theoretical investigations reveal that the nitro-gen reduction reaction on MXene@NiCoB catalyst proceeds according to the distal pathway, with a distinctly-reduced energy barrier relative to the Co2B counterpart. This work may inspire a new route towards the rational catalyst design for the nitrogen reduction reaction.(c) 2022 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

AbstractDie überwältigende Konkurrenz durch Wasserstoff/Sauerstoff‐Entwicklungsreaktionen und die geringe Löslichkeit von N2 in wässrigen Systemen beeinträchtigen die Selektivität und Aktivität bei der Stickstofffixierungsreaktion. Hier entwerfen wir eine aerob‐hydrophobe Janus‐Struktur, indem wir eine fluorierte Modifikation auf porösen Kohlenstoff‐Nanofasern einführen, die in teilweise karbonisierte Eisen‐Heterokontakte (Fe3C/Fe@PCNF‐F) eingebettet sind. Die Simulationen zeigen, dass die Janus‐Struktur die interne Fe3C/Fe@PCNF‐F vor Wassereindringung schützen und einen N2‐Molekül‐konzentrierenden Effekt verleihen kann. Dadurch werden konkurrierende Reaktionen unterdrückt und die Massentransferbeschränkungen überwunden, um einen robusten “quasi‐fest‐gasförmigen” Mikrobereich um die Katalysatoroberfläche herum zu bilden. In diesem Proof‐of‐Concept‐System zeigt Fe3C/Fe@PCNF‐F eine hervorragende elektrokatalytische Leistung für die Stickstofffixierung (NH3‐Ausbeute von bis zu 29.2 μg h−1 mg−1Kat. und faradayscher Wirkungsgrad (FE) von bis zu 27.8 % im NRR; NO3− Ausbeute bis zu 15.7 μg h−1 mg−1Kat. und FE bis zu 3.4 % in NOR).

Rechargeable aqueous zinc-iodine batteries (ZIBs) are considered a promising newly-developing energy-storage system, but the corrosion and dendritic growth occurring on the anode seriously hinder their future application. Here, the corrosion mechanism of polyiodide is revealed in detail, showing that it can spontaneously react with zinc and cause rapid battery failure. To address this issue, a sulfonate-rich ion-exchange layer (SC-PSS) is purposely constructed to modulate the transport and reaction chemistry of polyiodide and Zn2+ at the zinc/electrolyte interface. The resulting ZIBs can work properly over 6000 cycles with high-capacity retention (90.2%) and reversibility (99.89%). Theoretical calculations and experimental characterization reveal that the SC-PPS layer blocks polyiodide permeation through electrostatic repulsion, while facilitating desolvation of Zn(H2O)(6)(2+) and restricting undesirable 2D diffusion of Zn2+ by chemisorption.

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.

This review details past attempts, breakthroughs, and computational/characterization methods in developing metal–iodine batteries along with their key innovations, deficiencies, and possible solutions.

Aqueous rechargeable multivalent metal-ion batteries (ARMMBs) have attracted considerable attention due to their high capacity, high energy density, and low cost. However, their performance is often limited by low temperature operation, which requires the development of anti-freezing electrolytes. In this review, we summarize the anti-freezing mechanisms and optimization strategies of anti-freezing electrolytes for aqueous batteries (especially for Zn-ion batteries). Besides, we investigate the possible interactions and side reactions between electrolytes and electrodes. We also analyze the problems between electrolytes and electrodes at low temperature, and propose possible solutions. The research progress in the field of low temperature energy storage for aqueous Mg-ion, Ca-ion, and Al-ion batteries, and the challenges faced in their anti-freezing electrolytes are investigated in detail. Last but not least, the outlook on the energy storage applications of ARMMBs is provided to guide the future research.

AbstractThe development of aqueous rechargeable zinc‐iodine (Zn‐I2) batteries is still plagued by the polyiodide shuttle issue, which frequently causes batteries to have inadequate cycle lifetimes. In this study, quaternization engineering based on the concept of “electric double layer” is developed on a commercial acrylic fiber skeleton ($1.55–1.7 kg−1) to precisely constrain the polyiodide and enhance the cycling durability of Zn‐I2 batteries. Consequently, a high‐rate (1 C–146.1 mAh g−1, 10 C–133.8 mAh g−1) as well as, ultra‐stable (2000 cycles at 20 C with 97.24% capacity retention) polymer‐based Zn‐I2 battery is reported. These traits are derived from the strong electrostatic interaction generated by quaternization engineering, which significantly eliminates the polyiodide shuttle issue and simultaneously realizes peculiar solution‐based iodine chemistry (I−/I3−) in Zn‐I2 batteries. The quaternization strategy also presents high practicability, reliability, and extensibility in various complicated environments. In particular, cutting‐edge Zn‐I2 batteries based on the concept of derivative material (commercially available quaternized resin) demonstrate ≈100% capacity retention over 17 000 cycles at 20 C. This work provides a general and fresh insight into the design and development of large‐scale, low‐cost, and high‐performance zinc‐iodine batteries, as well as, other novel iodine storage systems.

Hybrid capacitors exhibit promise to bridge the gap between rechargeable high-energy density batteries and high-power density supercapacitors. This separation is due to sluggish ion/electron diffusion and inferior structural stability of battery-type materials. Here, a topochemistry-driven method for constructing expanded 2D rhenium selenide intercalated by nitrogen-doped carbon hybrid (E-ReSe2@INC) with a strong-coupled interface and weak van der Waals forces, is proposed. X-ray absorption spectroscopy analysis dynamically tracks the transformation from Re-O into Re-C bonds. The bridging bonds act as electron transport channels to enable improved conductivity and accelerated reaction kinetics. The expanded interlayer-spacing of ReSe2 layer by INC facilitates ion diffusion and ensures structural stability. As expected, the E-ReSe2@INC achieves an improved rate capability (252.5 mAh g(-1) at 20 A g(-1)) and long-term cyclability (89.6% over 3500 cycles). Moreover, theoretical simulations reveal the favorable Na+ storage kinetics can be ascribed to its low bonding energy of -0.06 eV and diffusion barrier of 0.08 eV for sodium ions. Additionally, it is demonstrated that 3D printed sodium-ion hybrid capacitors deliver high energies/power densities of 81.4 Wh kg(-1)/0.32 mWh cm(-2) and 9992.1 W kg(-1)/38.76 mW cm(-2), as well as applicability in a wide temperature range.