Acute ultraviolet exposure disrupts the epidermal barrier, induces oxidative stress, and accelerates extracellular matrix degradation, necessitating effective strategies for photodamage repair. Here, we establish a molecular-weight-graded agarose system-Aga-U, Aga-H, Aga-M, and Aga-L-to assess the effect of molecular weight on the physicochemical and biological properties of agarose. Controlled hydrolysis generated agarose fractions with progressively reduced molecular weight, resulting in enhanced solubility, hydrophilicity, fluidity, and antioxidant capacity. All fractions exhibited good cytocompatibility and promoted zebrafish caudal-fin regeneration, with Aga-L demonstrating the strongest bioactivity. In vitro and in vivo evaluations, including fibroblast assays and zebrafish and UV-induced acute photodamage mouse models, revealed that Aga-L most effectively restored the epidermal barrier, reduced oxidative stress, and enhanced collagen deposition. Molecular analyses showed that Aga-L downregulated MMP-1, MMP-2, MMP-9, p-c-Fos, and p-c-Jun and upregulated Nrf2, HO-1, Col I and Col III. These findings identify low-molecular-weight agarose as a potent bioactive polysaccharide for repairing UV-induced skin injury and provide a basis for developing agarose-based therapeutic strategies.

The electrocatalytic reduction of carbon dioxide represents a pivotal strategy for mitigating greenhouse gas emissions and producing value-added chemicals. Two-dimensional organic framework materials (e.g., 2D-MOFs and 2D-COFs) have emerged as promising catalysts due to their high specific surface area, tunable structures, surface modification capabilities, and accessible active sites. This review systematically summarizes recent advances in 2D organic framework materials for CO2RR, categorizing discussions by target products: carbon monoxide, methane, formic acid, and multi-carbon compounds. Key structural design strategies-including metal center engineering, ligand modification, layer number tuning, and catalytic system optimization -are critically evaluated to elucidate their impact on activity, selectivity, and stability. Despite progress, challenges persist in long-term stability, low-concentration CO2 operation, and cost efficiency. Future directions emphasize "self-healing" frame materials, composite frame materials, and machine learning-guided design to advance industrial deployment.

ABSTRACT Although acidic CO 2 electroreduction to multicarbon products offers superior carbon utilization compared to alkaline/neutral routes, its performance is severely hampered by proton‐enrichment‐induced hydrogen evolution (HER). To address this issue, we propose a host‐guest cooperative catalysis strategy by constructing a structurally well‐defined Ionic Liquid functionalized Metal‐covalent organic framework (IL@MCOF). Within this architecture, the confined ionic liquid creates a localized high‐concentration CO 2 microenvironment and induces interfacial water restructuring, thereby effectively suppressing HER caused by proton enrichment. Meanwhile, non‐covalent interactions between the π‐conjugated framework of MCOF and the IL cations promote directional transport of adsorbed CO 2 toward copper active sites. Mechanistic studies further reveal that the MCOF catalytic sites synergize with the guest IL to lower the formation energy barriers of the key C 2+ intermediates *COCO and *OCCOH. Consequently, IL@MCOF achieves a record 56.5% Faradaic efficiency with −162 mA cm −2 for C 2+ products at −1.8 V versus RHE in acidic media, surpassing all reported MOF‐based acidic catalysts. This work provides a host‐guest molecular engineering approach for highly selective acidic CO 2 electroreduction.

Electrochemical N2 fixation, including N2-to-NH3 (NRR) and N2-to-NO3-(NOR) conversions, represents sustainable alternative to the energy-intensive Harbor-Bosch and Ostwald processes for ammonia and nitrate production, respectively. The key to efficient nitrogen fixation lies in the adsorption and activation of N2. The heterogenous dual perimeter active sites exhibit higher energetic activity of N2 activation in favor of the subsequent processes. Herein, we present an Au/TiO2 catalyst with heterogenous dual Au-Ti perimeter sites for electrochemical N2 fixation under ambient conditions. The catalyst demonstrates excellent performance in both NH3 and NO3-production with an NH3 yield of 9.4 mu mol cm-2 h-1 (FE: 32.2 %), and a NO3-yield of 1.4 mu mol cm-2 h-1 (FE: 33.0 %), along with impressive electrochemical stability, outperforming most reported catalysts. In situ characterizations and theoretical calculations reveal that the N2 molecules preferentially adsorb on the Au/TiO2 perimeter, bridging Au and Ti sites in a sloped orientation to form a unique Au-N-N-Ti structure. This configuration significantly activates the adsorbed N2 molecules by extending the N-N bond length and decreasing its energy, thereby facilitating the narrowed span energies to produce NH3 and NO3-. Our work establishes a novel approach utilizing heterogeneous dual perimeter sites to designing high-performance catalysts for nitrogen fixation.

Ammonia (NH 3 ) is a crucial chemical in modern industry, serving as a key component in fertilizers and emerging as a potential energy carrier. However, traditional NH 3 synthesis via the Haber‐Bosch process is highly energy‐intensive and contributes significantly to global CO 2 emissions. Electrochemical nitrate reduction reaction (NO 3 RR) has emerged as a sustainable alternative for NH 3 production, leveraging renewable electricity to reduce nitrate (NO 3 −) under ambient conditions. Among various electrocatalysts, 3d‐block transition metal‐based materials have shown remarkable potential due to their low cost, electronic structures, redox flexibility, and tunable catalytic properties. This review provides a comprehensive analysis of recent advances in 3d‐block transition metal‐based catalysts for NO 3 RR, highlighting catalyst design, performance metrics, mechanistic insights, and challenges. Furthermore, strategies such as alloying, single‐atom catalysts, and high‐entropy alloys are reviewed to enhance efficiency and selectivity. Finally, we discuss future perspectives on catalyst development and practical application in green NH 3 production, aiming to bridge the gap between fundamental research and industrial applications.

The electrochemical nitrate reduction reaction (eNO3RR) is hindered by poor selectivity and sluggish kinetics due to competing hydrogen evolution and complex multi-electron/proton transfers. Here, a bimetallic CuCo-MOF （Metal-Organic Framework） is reported catalyst that undergoes in situ electrochemical reconstruction to form copper nanoparticles embedded within a cobalt-MOF matrix, establishing spatially coupled active sites for tandem catalysis. Mechanistic investigations reveal that the in situ-generated Cu nanoparticles selectively catalyze the nitrate-to-nitrite conversion, while the adjacent cobalt sites in the MOF framework facilitate water dissociation to provide reactive hydrogen species (*H) for subsequent nitrite hydrogenation to ammonia. The confined MOF architecture ensures efficient intermediate transfer, effectively preventing nitrite accumulation. This unique relay catalysis mechanism enables the reconstructed CuCo-DHTA catalyst to achieve remarkable NO3RR performance, including a Faradaic efficiency exceeding 95% across a wide potential window (-0.8 to -1.0 V vs RHE) and a record-high ammonia production rate of 20.02 mg h-1 cm-2, surpassing state-of-the-art MOF-based catalysts. The pre-catalyst's reconstruction strategy in this work provides a flexible design for high-performance nitrate reduction catalysts.

Electrochemical nitrate reduction (NO3RR) to ammonia is a promising method for treating nitrate pollutant and potentially replacing the Haber-Bosch process for ammonia production. High-entropy nanoalloys (HEAs) show significant potential in catalyzing NO3RR due to their compositional diversity, which results in a unique "cocktail" effect beneficial for the multistep NO3RR process. Herein, a high-entropy alloy catalyst consisting of Co, Ni, Cu, Mn, and Fe elements is prepared through the pyrolysis of a high-entropy Prussian blue precursor. After optimizing the elemental proportions, the Fe HEA catalyst exhibits exceptional NO3RR activity with an NH3 Faradaic efficiency (FE) of 92% and a yield rate of 3.25 mg h-1 cm-2. Moreover, the electrochemical hydrazine oxidation reaction (HzOR) is applied to construct a NO3RR-HZOR flow cell. This cell system not only produces NH3, but also generates electricity, achieving a peak power density of 1.32 mW cm-2. Theoretical investigations show that the excellent performance of HEA can be attributed to the "cocktail" effect induced by multi-element composition, which results in a lower work function and a negative shifting of the d band center, thus favoring the charge transfer and hydrogenation process of NO3RR. This work highlights the remarkable potential of HEAs for multistep chemical production and expands their applications in energy conversion and electrosynthesis.

Cu-based electrocatalysts exhibit superior reduction kinetics in the electrochemical nitrate reduction reaction (NO3RR) and suppress competing hydrogen evolution reaction, making NO3RR an alternative to the traditional Haber-Bosch process in NH3 production. However, the NO3RR in NH3 production involves a nine-proton and eight-electron process, and its performance is constrained by the poor capacity to generate protons. In this study, frustrated Lewis pairs (FLPs) were introduced into Cu-based catalysts to create La-doped Cu2O, in which the FLPs [Cu-O-La-Ov] (where v denotes vacancy) formed by the Lewis acidic sites Ov and Lewis basic sites O in the Cu-O-La motif served as active sites. These active sites facilitated H2O dissociation, providing ample protons for the NO3RR hydrogenation. The La9-CuOx catalyst exhibited an ultralow NH3 production overpotential of only 290 mV, achieving an NH3 current density of 1.76 A cm-2 at -0.4 V vs the reversible hydrogen electrode, with an NH3 yield rate of 139.5 mg h-1 cm-2 and Faradaic efficiency of 98.9%. Due to the superior NO3RR performance of La9-CuOx, a La9-CuOx-based Zn-NO3- battery achieved a remarkable power density of 80.6 mW cm-2, with an NH3 yield rate of 21.4 mg h-1 cm-2. This study clarifies the role of FLPs in facilitating the NO3RR and achieves an efficient Zn-NO3- battery to accomplish electricity generation and NH3 production simultaneously.

The pursuit of advanced anode materials to address inferior conductivity and slow ion diffusion has driven the development of fast‐charging sodium‐ion batteries (SIBs). Herein, a promising anode material of KCu 7 S 4 nanowires with a tunnel structure is proposed for SIBs. The Na + (de)insertion mechanisms of the KCu 7 S 4 anode are comprehensively elucidated through a combination of in situ TEM/SAED/XRD analyses and theoretical calculations. The detailed intermediates (Na 3 Cu 4 S 4 , NaCuS) and final products (CuS, Cu) during (de)sodiation processes are identified, revealing that the highly mobile Cu + ion can facilitate the formation of tunnel‐structured Na 3 Cu 4 S 4 and layer‐structured NaCuS during the electrochemical reaction process. The reaction dynamics indicate that the formation of Na 3 Cu 4 S 4 and NaCuS intermediates facilitates electron transfer and ion diffusion during Na + (de)insertion. Moreover, the KCu 7 S 4 anode exhibits a high discharge capacity of 337 mAh g −1 at 10 A g −1 , and the corresponding Na 3 V 2 (PO 4 ) 3 //KCu 7 S 4 full cell delivers a high energy density of 303 Wh kg −1 at 375 W kg −1 , demonstrating its excellent application prospect. This work opens a new avenue for fast‐charging electrode materials for advanced SIBs.

Electrochemical CO2 reduction has been considered a promising approach to neutralizing the global CO2 level. As an intriguing technique, metal-CO2 battery devices can not only capture CO2 into valuable carbonaceous chemicals and reduce the CO2 concentration in the atmosphere but enable energy conversion. Among metal-CO2 batteries, aqueous Zn-CO2 batteries, especially rechargeable systems, exhibit flexible CO2 electrochemistry in terms of multi-carbon chemicals, which are gaseous or water-soluble, in favor of rechargeability and cycling durability of aqueous battery systems. Despite the increasing number of publications on Zn-CO2 batteries in the past three years, this field is still in its beginning stage and facing many challenges considering the capability of CO2 fixation and battery performance. Herein, we present a timely and overall summary of the recent progress in Zn-CO2 batteries, including fundamental mechanisms, affecting factors on electrochemical performance, catalyst cathodes, and electrolytes (catholytes and anolytes). Besides, we assess the application potential of Zn-CO2 batteries and compare this with those of alkali metal-CO2 batteries based on CO2 fixation and battery performance. Finally, we point out some current challenges for the further development of Zn-CO2 batteries and put forward perspectives of the research directions for practical applications of Zn-CO2 batteries in the future.

Ammonia (NH3) is an important feedstock for industry, an ideal energy carrier, and a perspective storage media for hydrogen. Recently, electrochemical nitrate (NO3-) reduction under acidic conditions has received considerable attention but it suffers from limited efficiency especially under low NO3- concentration. Here, we report an in situ formed positively charged polyethyleneimine-modified Cu under acidic conditions as a catalyst-electrolyte interface (CEI) for electrochemical NO3- reduction to NH3. Such CEI can effectively accumulate NO3- anions via static interactions and accelerate *NO hydrogenation to *NOH by weakening *NO intermediate adsorption on Cu site, thereby facilitating NO3--to-NH3 conversion. Such CEI delivers an increased NH3 Faradaic efficiency (FE) of 83.5% and an impressive half-cell energy efficiency (EE) of 37.1% in 10 mM NO3- solution (pH = 1). The NH3 FE and EE can further increase to 90.2% and 44.1% in 0.5 M NO3-, respectively. The high EE of CEI surpasses previously reported catalyst performances for NO3- reduction. Finally, we demonstrate the feasibility of a novel NO3--furfural battery, showcasing a self-power electrocatalytic system capable of simultaneously treating NO3- pollutants, generating value-added NH3 and upgrading biomass. This work offers valuable insights into the construction of a CEI to enhance the efficiency of NH3 synthesis.

Introducing a built-in electric field/external stimuli is an efficient strategy to promote the nitrate reduction reaction for ammonia production.

The participation of high-energy hot electrons generated from the non-radiative decay of localized surface plasmons is an important mechanism for promoting catalytic processes. Herein, another vital mechanism associated with the localized surface plasmon resonance (LSPR) effect, significantly contributing to the nitrogen reduction reaction (NRR), is found. That is to say, the LSPR-induced strong localized electric fields can weaken the intermolecular hydrogen bonds and regulate the arrangement of water molecules at the solid-liquid interface. The AuCu pentacle nanoparticles with excellent light absorption ability and the capability to generate strong localized electric fields are chosen to demonstrate this effect. The in situ Raman spectra and theoretical calculations are employed to verify the mechanism at the molecular scale in a nitrogen fixation process. Meanwhile, due to the promoted electron transfer at the interface by the well-ordered interfacial water, as well as the participation of high-energy hot electrons, the optimal catalyst exhibits excellent performance with an NH3 yield of 52.09 µg h-1 cm-2 and Faradaic efficiency (FE) of 45.82% at ─0.20 V versus RHE. The results are significant for understanding the LSPR effect in catalysis and provide a new approach for regulating the reaction process.

Ammonia (NH3) is an ideal green fuel with high energy density and plays an indispensable role in fertilizer production. Electrochemical reduction of nitrate (NO3–), a toxic pollutant in groundwater, has shown promising as a viable approach to converting waste into valuable NH3 under ambient conditions, offering an alternative to the energy-intensive Haber-Bosch process. Due to their high efficiency, copper (Cu)-based materials have shown great potential as electrocatalysts for the NO3– reduction reaction (NO3–RR) to NH3. In this review, we provide a comprehensive summary of the fundamental principles underlying nitrate reduction over Cu-based electrocatalysts and discuss various strategies to enhance the performance of NO3– reduction, including facets, morphologies, size, surface functionalization, compositional engineering, and defect engineering. We also delve into the relationship between the electrocatalytic performance and structure characteristics of electrocatalysts and thoroughly examine the reaction mechanism involved in NO3–RR. Furthermore, we highlight the existing challenges and prospective paths forward in this area of study. This review offers valuable insights and guidance for the strategic design and optimization of Cu-based electrocatalysts for NO3–RR applications.

Electrochemical conversion of nitrate to ammonia is an appealing route to efficiently synthesize ammonia under ambient conditions while reducing environmental nitrate pollutants. However, this approach is obstructed by the limited yield and selectivity of ammonia because the electrochemical nitrate-to-ammonia conversion involves multi-electron/proton transfer and faces competition from the hydrogen evolution reaction. Here, we demonstrate a plasmon-assisted strategy to improve the performance of nitrate-to-ammonia electrochemical conversion by constructing plasmonic antenna-reactor catalysts, where Au and Pd nanoparticles/hydrogen substituted graphdiyne (Pd/HsGDY) work as the light antenna and reaction site, respectively. Plasmonic excitation of Au-Pd/HsGDY catalysts can remarkably accelerate the nitrate reduction, with the yield rate, selectivity, and Faradaic efficiency of ammonia respectively increased by 14.3, 2.1, and 1.8 times under optimal conditions. Mechanistic investigations unveil that Au plasmon-induced hot electrons facilitate nitrate-to-ammonia reaction by regulating the adsorption of reaction intermediates on Pd/HsGDY, wherein the rate-determining step was shifted from nitrate adsorption to *NH protonation and the overall apparent activation was reduced. Moreover, hot electrons suppress the competing hydrogen evolution by enlarging the Gibbs free energy of hydrogen formation. These results open a way to develop desirable catalysts for producing value-added ammonia from environmentally hazardous nitrate by a synergistic combination of electricity and light.

Ammonia, as a high-energy-density carrier for hydrogen storage, is in great demand worldwide. Electrocatalytic nitrate reduction reaction (NO3RR) provides a green NH3 production process. However, the complex reaction pathways for NO3RR to NH3 and the difficulty in controlling intermediate products limit the reduction process. Herein, by incorporating atomic-level bismuth (Bi) into CuCo2O4 hollow carbon nanofibers, the catalytic activity of the electrocatalyst for NO3RR is enhanced. The maximum Faradaic efficiency of Bi-1-CuCo2O4 is 95.53%, with an NH3 yield of 448.74 mu mol h(-1) cm(-2) at -0.8 V versus RHE. Density Functional Theory calculations show that the presence of Bi lowers the reaction barrier for the hydrogenation step from *NO2 to *NO2H, while promoting mass transfer on the release of *NH3 and the reactivation of surface-active sites. Differential charge density calculations also show that after Bi doping, the charge supplied by the catalyst to NO3- increases from 0.62 to 0.72 e(-), thus reasoned for enhanced NO3RR activity. The established nitrate-Zn battery shows an energy density of 2.81 mW cm(-2), thus implying the potential application.

Directly electrochemical conversion of nitrate (NO 3 − ) is an efficient and environmentally friendly technology for ammonia (NH 3 ) production but is challenged by highly selective electrocatalysts. High-entropy alloys (HEAs) with unique properties are attractive materials in catalysis, particularly for multi-step reactions. Herein, we first reported the application of HEA (FeCoNiAlTi) for electrocatalytic NO 3 − reduction to NH 3 (NRA). The bulk HEA is active for NRA but limited by the unsatisfied NH 3 yield of 0.36 mg h −1  cm −2 and Faradaic efficiency (FE) of 82.66 %. Through an effective phase engineering strategy, uniform intermetallic nanoparticles are introduced on the bulk HEA to increase electrochemical active surface area and charge transfer efficiency. The resulting nanostructured HEA (n-HEA) delivers enhanced electrochemical NRA performance in terms of NH 3 yield (0.52 mg h −1  cm −2 ) and FE (95.23 %). Further experimental and theoretical investigations reveal that the multi-active sites (Fe, Co, and Ni) dominated electrocatalysis for NRA over the n-HEA. Notably, the typical Co sites exhibit the lowest energy barrier for NRA with *NH 2 to *NH 3 as the rate-determining step.

Anionic redox reactions would achieve a higher capacity than typical transition -metal -oxide cathodes, offering low-cost chemistry for advanced lithium -ion batteries. Li-Cl2 chemistry using anionic redox reactions of Cl0/-1 shows superior operation voltage (-3.8 V) and capacity (756 mAh g-1). However, a redox-active and reversible chlorine cathode has not been developed in organic electrolyte based lithium -ion batteries. Chlorine ions bonded by ionic bonding hardly dissolve in organic electrolytes, imposing a thermodynamic barrier for redox reactions. Meanwhile, chlorine gas is easily formed during oxidation. Herein, we report an interhalogen compound, iodine trichloride (ICl3), as the cathode to address these two issues. In situ and ex situ spectroscopy data and calculations reveal that reduced Cl- ions are partially dissolved in the electrolyte, and oxidized Cl0 is anchored by forming interhalogen bonds. A reversible Li-Cl2 delivers a specific capacity of 302 mAh g-1 at 425 mA g-1 and 73.8% capacity retention at 1,250 mA g-1.

Compared to sp 2 -hybridized graphene, graphdiynes (GDYs) composed of sp and sp 2 carbon are highly promising as efficient catalysts for electrocatalytic oxygen reduction into oxygen peroxide because of the high catalytic reactivity of the electron-rich sp -carbon atoms. The desired catalytic capacity of GDY, such as catalytic selectivity and efficiency, can theoretically be achieved by strategically steering the sp -carbon contents or the topological arrangement of the acetylenic linkages and aromatic bonds. Herein, we successfully tuned the electrocatalytic activity of GDYs by regulating the sp -to- sp 2 carbon ratios with different organic monomer precursors. As the active sp -carbon atoms possess electron-sufficient π orbitals, they can donate electrons to the lowest unoccupied molecular orbital (LUMO) orbitals of O 2 molecules and initiate subsequent O 2 reduction, GDY with the high sp -carbon content of 50 at % exhibits excellent capability of catalyzing O 2 reduction into H 2 O 2 . It demonstrates exceptional H 2 O 2 selectivity of over 95.0 % and impressive performance in practical H 2 O 2 production, Faraday efficiency (FE) exceeding 99.0 %, and a yield of 83.3 nmol s −1  cm −2 . Our work holds significant importance in effectively steering the inherent properties of GDYs by purposefully adjusting the sp -to- sp 2 carbon ratio and highlights their immense potential for research and applications in catalysis and other fields.