Electrochemical removal of nitrate in high-salt wastewater with low-cost iron electrode modified by phosphate.

Nitrate (NO3-) is a widespread pollutant in high-salt wastewater and causes serious harm to human health. Although electrochemical removal of nitrate has been demonstrated to be a promising treatment method, the development of low-cost electro-catalysts is still challenging. In this work, a phosphate modified iron (P-Fe) cathode was prepared for electrochemical removal of nitrate in high-salt wastewater. The phosphate modification greatly improved the activity of iron, and the removal rate of nitrate on P-Fe was three times higher than that on Fe electrode. Further experiments and density functional theory (DFT) calculations demonstrated that the modification of phosphoric acid improved the stability and the activity of the zero-valent iron electrode effectively for NO3- removal. The nitrate was firstly electrochemically reduced to ammonium, and then reacted with the anodic generated hypochlorite to N2. In this study, a strategy was developed to improve the activity and stability of metal electrode for NO3- removal, which opened up a new field for the efficient reduction of NO3- removal by metal electrode materials.

In Situ Construction of SnS2@SnO2 Heterostructure for Photo-Assisted Electrocatalysis of Oxygen Evolution Reaction.

Photo-assisted electrocatalysis has arisen as a promising approach for hydrogen generation by incorporating photocatalysts into electrocatalysts. 2D SnS2 is a photocatalyst that absorbs visible light. However, the rapid recombination of photo-generated electron-hole pairs significantly reduces the overall photocatalytic efficiency of SnS2, limiting its practical application. Thus, this study prepares an in situ heterojunction SnS2@SnO2 using a one-step hydrothermal method. The degradation efficiency of methyl orange (MO) using SnS2@SnO2 is measured, achieving a degradation rate of 92.75% within 1 h, which is 1.9 times higher than that of pure SnS2. Additionally, FeNiS/SnS2@SnO2 is synthesized and exhibited significant improvements in the photo-assisted oxygen evolution reaction (OER). It achieves an overpotential of 260 mV and a Tafel slope of 65.1 mV dec-1 at 10 mA cm-2, showing reductions of 11.8% and 31.8%, respectively, compared to FeNiS alone. These enhancements highlight the strong photo-response capability of SnS2@SnO2. Under the internal electric field of SnS2@SnO2, the photogenerated electrons in the conduction band of SnS2 quickly move toward SnO2, facilitating efficient photocatalytic reactions. FeNiS, with a lower Fermi energy level (EF), facilitates electron transfer from SnS2@SnO2 and enhances OER performance by efficiently participating in the reaction. This study paves a new path for 2D photocatalyst materials.

Topologically Close-Packed Frank-Kasper C15 Phase Intermetallic Ir Alloy Electrocatalysts Enables High-Performance Proton Exchange Membrane Water Electrolyzer.

Chemical synthesis of unconventional topologically close-packed intermetallic nanocrystals (NCs) remains a considerable challenge due to the limitation of large volume asymmetry between the components. Here, a series of unconventional intermetallic Frank-Kasper C15 phase Ir2M (M = rare earth metals La, Ce, Gd, Tb, Tm) NCs is successfully prepared via a molten-salt assisted reduction method as efficient electrocatalysts for hydrogen evolution reaction (HER). Compared to the disordered counterpart (A1-Ir2Ce), C15-Ir2Ce features higher Ir-Ce coordination number that leads to an electron-rich environment for Ir sites. The C15-Ir2Ce catalyst exhibits excellent and pH-universal HER activity and requires only 9, 16, and 27 mV overpotentials to attain 10 mA cm-2 in acidic, alkaline, and neutral electrolytes, respectively, representing one of the best HER electrocatalysts ever reported. In a proton exchange membrane water electrolyzer, the C15-Ir2Ce cathode achieves an industrial-scale current density of 1 A cm-2 with a remarkably low cell voltage of 1.7 V at 80 °C and can operate stably for 1000 h with a sluggish voltage decay rate of 50 µV h-1. Theoretical investigations reveal that the electron-rich Ir sites intensify the polarization of *H2O intermediate on C15-Ir2Ce, thus lowering the energy barrier of the water dissociation and facilitating the HER kinetics.

Efficient cleavage of CαCß bonds in lignin using tetrabutylammonium tetrafluoroborate as both the catalyst and auxiliary electrolyte.

Lignin is a promising alternative to fossil resources due to its abundance of benzene ring monomers. However, the stability of the CαCß bond in lignin has hindered its efficient depolymerization. Electrochemical methods for breaking this bond are not well-studied. This paper presents a novel approach for catalytic depolymerization of lignin to produce acetals under mild conditions, without the need for additional catalysts. Under room temperature and in an air atmosphere, the combination of tetrabutylammonium tetrafluoroborate (TBABF4) as an auxiliary electrolyte and methanol (MeOH) as a solvent has shown high selectivity in catalyzing the cleavage of CαCß bonds in lignin. Over 90.0 % of the resulting products are acetals, with the optimal conditions being a substrate concentration of 0.02 M, TBABF4 concentration of 0.008 M, a constant current of 30 mA, and a reaction time of 3 h. This led to a substrate conversion rate of 95.8 % and a product yield of 98.0 % for benzaldehyde dimethyl acetal (Bda). The mechanism study reveals that the tributyl ammonium radical cation decomposed by TBABF4 is adsorbed on the electrode surface. Subsequently, the adsorbed O2 is activated to form superoxide anion radical active species through single electron transfer, which plays a crucial catalytic role. TBABF4 acts as both an auxiliary electrolyte and a catalyst in this process. This research introduces a novel approach for electrocatalytic depolymerization of inert CαCß bonds in lignin, leading to the selective conversion into acetal chemicals.

Recent Advances in Bonding Regulation of Metalloporphyrin-Modified Carbon-Based Catalysts for Accelerating Energy Electrocatalytic Applications.

Metalloporphyrins modified carbon-based materials, owing to the excellent acid-base resistance, optimal electron transfer rates, and superior catalytic performance, have shown great potential in energy electrocatalysis. Recently, numerous efforts have concentrated on employing carbon-based substrates as platforms to anchor metalloporphyrins, thereby fabricating a diverse array of composite catalysts tailored for assorted electrocatalytic processes. However, the interplay through bonding regulation of metalloporphyrins with carbon materials and the resultant enhancement in catalyst performance remains inadequately elucidated. Gaining an in-depth comprehension of the synergistic interactions between metalloporphyrins and carbon-based materials within the realm of electrocatalysis is imperative for advancing the development of innovative composite catalysts. Herein, the review systematically classifies the binding modes (i.e., covalent grafting and non-covalent interactions) between carbon-based materials and metalloporphyrins, followed by a discussion on the structural characteristics and applications of metalloporphyrins supported on various carbon-based substrates, categorized according to their binding modes. Additionally, this review underscores the principal challenges and emerging opportunities for carbon-supported metalloporphyrin composite catalysts, offering both inspiration and methodological insights for researchers involved in the design and application of these advanced catalytic systems.

The AUREX cell: a versatile operando electrochemical cell for studying catalytic materials using X-ray diffraction, total scattering and X-ray absorption spectroscopy under working conditions.

Understanding the structure-property relationship in electrocatalysts under working conditions is crucial for the rational design of novel and improved catalytic materials. This paper presents the Aarhus University reactor for electrochemical studies using X-rays (AUREX) operando electrocatalytic flow cell, designed as an easy-to-use versatile setup with a minimal background contribution and a uniform flow field to limit concentration polarization and handle gas formation. The cell has been employed to measure operando total scattering, diffraction and absorption spectroscopy as well as simultaneous combinations thereof on a commercial silver electrocatalyst for proof of concept. This combination of operando techniques allows for monitoring of the short-, medium- and long-range structure under working conditions, including an applied potential, liquid electrolyte and local reaction environment. The structural transformations of the Ag electrocatalyst are monitored with non-negative matrix factorization, linear combination analysis, the Pearson correlation coefficient matrix, and refinements in both real and reciprocal space. Upon application of an oxidative potential in an Ar-saturated aqueous 0.1 M KHCO3/K2CO3 electrolyte, the face-centered cubic (f.c.c.) Ag gradually transforms first to a trigonal Ag2CO3 phase, followed by the formation of a monoclinic Ag2CO3 phase. A reducing potential immediately reverts the structure to the Ag (f.c.c.) phase. Following the electrochemical-reaction-induced phase transitions is of fundamental interest and necessary for understanding and improving the stability of electrocatalysts, and the operando cell proves a versatile setup for probing this. In addition, it is demonstrated that, when studying electrochemical reactions, a high energy or short exposure time is needed to circumvent beam-induced effects.

Stabilization of High-Valent Molecular Cobalt Sites through Oxidized Phosphorus in Reduced Graphene Oxide for Enhanced Oxygen Evolution Catalysis.

Heterogeneous molecular cobalt (Co) sites represent one type of classical catalytic sites for electrochemical oxygen evolution reaction (OER) in alkaline solutions. There are dynamic equilibriums between Co2+, Co3+ and Co4+ states coupling with OH-/H+ interaction before and during the OER event. Since the emergence of Co2+ sites is detrimental to the OER cycle, the stabilization of high-valent Co sites to shift away from the equilibrium becomes critical and is proposed as a new strategy to enhance OER. Herein, phosphorus (P) atoms were doped into reduced graphene oxide to link molecular Co2+ acetylacetonate toward synthesizing a novel heterogeneous molecular catalyst. By increasing the oxidation states of P heteroatoms, the linked Co sites were spontaneously oxidized from 2+ to 3+ states in a KOH solution through OH- ions coupling at an open circuit condition. With excluding the Co2+ sites, the as-derived Co sites with 3+ initial states exhibited intrinsically high OER activity, validating the effectiveness of the strategy of stabilizing high valence Co sites.

Unveiling electron transfer and radical transformation pathways in coupled electrocatalysis and persulfate oxidation reactions for complex pollutant removal.

The degradation of multiple organic pollutants in wastewater via advanced oxidation processes might involve different radicals, of which the types and concentrations vary upon interacting with different pollutants. In this study, electrochemical activation of peroxymonosulfate (E/PMS) using advanced activated carbon cloth (ACC) as electrode was applied for simultaneous degradation of mixed pollutants, e.g., metronidazole (MNZ) and p-chloroaniline (PCA). 92.5 % of MNZ and 91.4 % of PCA can be degraded at the cathode and anode at a low current density and PMS concentration, respectively. The rate constants for the simultaneous removal of MNZ and PCA in the E/PMS/MNZ(PCA) system were 118 times and 6 times higher than those in the sole PMS system, and 2.5 times and 1.6 times higher than those in the E/Na2SO4/MNZ(PCA) system, respectively. Different electrochemical characteristics, EPR spectra and radical quenching tests verified that the degradation of MNZ and PCA in the optimal system proceeded primarily through non-radical-dominated oxidation, involving electron transfer and 1O2 effect. The system also exhibited low energy consumption (0.215 kWh/m-3·order-1), broad operational pH range, excellent removal efficiency for water matrix, and low by-products toxicity, indicating its strong potential for practical applications. The ACC, with its super stable, low cost, and electrochemical activity, make it as a promising materials applicable in the E/PMS system for degradation of multiple pollutants. The study further elucidated the mechanism of pollutant interaction with electrode materials in terms of radical and non-radical transformation, providing fundamental insight into the application of this system for treatment of complex wastewater.

Amorphous Nanobelts for Efficient Electrocatalytic Ammonia Production.

One-dimensional (1D) amorphous nanomaterials combine the advantages of high active site concentration of amorphous structure, high specific surface area and efficient charge transfer and mass transport of 1D materials, so they present promising opportunities for catalysis. However, a significant challenge involves achieving a balance between the high orientation of 1D morphology and the isotropy of amorphous structure, which severely obstructs the controllable preparation of 1D amorphous materials. Guided by the hard-soft acids-bases theory, here we develop a general strategy for preparing 1D amorphous nanomaterials through the precise modulation of bond strength between metal ions and organic ligands for a moderated fastness. The soft base dodecanethiol (DT) is multifunctionally served as both structure-regulating agent and morphology-directing agent. Compared with the borderline acids (e.g. Fe2+, Co2+, Ni2+) to construct amorphous structure, soft acid of Cu+ which produced crystalline nanobelts can still be amorphized by reducing the hardness of Cu ions through redox reaction to weak Cu-SR bond. Due to the combined advantages of amorphous structure and one-dimensional morphology, amorphous CuDT nanobelts exhibited excellent electrocatalytic activity in electrochemical nitrate reduction, outperformed the most of the reported Cu-based catalysts. This work will effectively bridge the gap between traditional 1D crystalline nanomaterials and amorphization preparation.

Recent Achievements in Heterogeneous Bimetallic Atomically Dispersed Catalysts for Zn-Air Batteries: A Minireview.

Rechargeable Zn-air batteries (ZABs) hold promise as the next-generation energy-storage devices owing to their affordability, environmental friendliness, and safety. However, cathodic catalysts are easily inactivated in prolonged redox potential environments, resulting in inadequate energy efficiency and poor cycle stability. To address these challenges, anodic active sites require multiple-atom combinations, that is, ensembles of metals. Heterogeneous bimetallic atomically dispersed catalysts (HBADCs), consisting of heterogeneous isolated single atoms and atomic pairs, are expected to synergistically boost the cyclic oxygen reduction and evolution reactions of ZABs owing to their tuneable microenvironments. This minireview revisits recent achievements in HBADCs for ZABs. Coordination environment engineering and catalytic substrate structure optimization strategies are summarized to predict the innovation direction for HBADCs in ZAB performance enhancement. These HBADCs are divided into ferrous and nonferrous dual sites with unique microenvironments, including synergistic effects, ion modulation, electronic coupling, and catalytic activity. Finally, conclusions and perspectives relating to future challenges and potential opportunities are provided to optimise the performance of ZABs.

Conversion of Nitrate to Ammonia by Amidinothiourea-Coordinated Metal Molecular Electrocatalysts with d-π Conjugation.

The electrochemical reduction of nitrate to ammonia (NO3RR) provides a desired alternative of the traditional Haber-Bosch route for ammonia production, igniting a research boom in the development of electrocatalysts with high activity. Among them, molecular electrocatalysts hold considerable promise for the NO3RR, suppressing the competing hydrogen evolution reaction. However, the complicated synthesis procedure, usage of environmentally unfriendly organic solvents, and poor stability of Cu-based molecular electrocatalysts greatly limit their employment in NO3RR, and the development of desired Cu-based molecular catalysts remains challenging. Herein, a simple nonorganic solvent involving a one-step strategy was proposed to synthesize d-π-conjugated molecular electrocatalysts metal-amidinothiourea (M-ATU). Cu-ATU is composed of Cu coordinated with two S and two N atoms, whereas Ni-ATU is formed by Ni with four N atoms from two ATU ligands. Remarkably, Cu-ATU with a Cu-N2S2 coordination configuration exhibits superior NO3RR activity with a NH3 yield rate of 159.8 mg h-1 mgcat-1 (-1.54 V) and Faradaic efficiency of 91.7% (-1.34 V), outperforming previously reported molecular catalysts. Compared to Ni-ATU, Cu-ATU transfers more electrons to the *NO intermediate, effectively breaking the strong sp2 hybridization system and weakening the energy of N═O bonds. The increase in free energy of *NO reduced the energy barriers of the rate-determining step, facilitating the further hydrogenation process over Cu-ATU. Our work opened up a new horizon for exploring molecular electrocatalysts for nitrate activation and paved a way for the in-depth understanding of catalytic behaviors, aligning more closely with industrial demands.

Deciphering electrocatalytic hydrogen production in water through a bioinspired water-stable copper(II) complex adorned with (N2S2)-donor sites.

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H2 generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-LN2S2]ClO4, featuring the N,S-type ligand, LN2S2 (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H2 production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by H2O during electrochemical conditions yielding [H2O-Cu-LN2S2]2+ as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.75 s-1 for hydrogen generation. Controlled potential electrolysis at -1.2 V vs. Ag/AgCl for 1.6 h reveals a high turnover number of 73.06 with a commendable Faradic efficiency of 94.2%. A comprehensive analysis encompassing electrochemical, spectroscopic, and analytical methods reveals an insignificant degradation of the molecular catalyst. However, the post-CPE electrocatalyst, present in the solution domain, signifies the coveted stability and effective activity under the specified electrochemical conditions. The synergy of electrochemical, spectroscopic, and computational studies endorses the proton-electron coupling mediated catalytic pathways, affirming the viability of sustainable hydrogen production.

Precise Electrocatalysis on Fe-Porphyrin Conjugated Networks Achieves Energy-Efficient Extraction of Uranium.

Electrochemical extraction has the potential to enhance uranium (U) extraction capacity and rates, but thus far, high selectivity and energy efficiency have not been achieved through the design of electrode materials. Herein, a precise electrocatalysis strategy is developed using a Ferrum (Fe) porphyrin-phenanthroline conjugated network (Fe@PDACN) for energy-efficient uranium extraction. The phenanthroline provides specific binding sites for selective enrichment of U(VI) at active sites (Kd = 2.79 × 105 mL g-1 in multi-ion solution). The Fe(II) sites have strong trap-redox activity for U(VI) and act as dynamic electron donors to rapidly mediate electrocatalytic U(VI) extraction through the redox reaction of Fe(0/II)/Fe(III). Moreover, the Fe-porphyrin blocks support sustained electron donation for U(VI) electrocatalysis by pre-storing electrons. These features enable selective uranium capture and a high electroextraction capacity of 24 646.3 mg g-1 from simulated nuclear wastewater in 280 h at a low voltage of -1.5 V. An ultra-high Faraday efficiency of 90.1% is achieved, and the energy cost is 3.22 × 10-2 $ kg-1 U, significantly lower than the previously reported materials. This work provides a highly efficient strategy for uranium extraction from water.

Molten Salt-Assisted Synthesis of Ferric Oxide/M-N-C Nanosheet Electrocatalysts for Efficient Oxygen Reduction Reaction.

Efficient, stable, and low-cost oxygen reduction catalysts are the key to the large-scale application of metal-air batteries. Herein, high-dispersive Fe2O3 nanoparticles (NPs) with abundant oxygen vacancies uniformly are anchored on lignin-derived metal-nitrogen-carbon (M-N-C) hierarchical porous nanosheets as efficient oxygen reduction reaction (ORR) catalysts (Fe2O3/M-N-C, M═Cu, Mn, W, Mo) based on a general and economical KCl molten salt-assisted method. The combination of Fe with the highly electronegative O induces charge redistribution through the Fe-O-M structure, thereby reducing the adsorption energy of oxygen-containing substances. The coupling effect of Fe2O3 NPs with M-N-C expedites the catalytic activity toward ORR by promoting proton generation on Fe2O3 and transfer to M-N-C. Experimental and theoretical calculation further revealed the remarkable electronic structure evolution of the metal site during the ORR process, where the emission density and local magnetic moment of the metal atoms change continuously throughout their reaction. The unique layered porous structure and highly active M-N4 sites resulted in the excellent ORR activity of Fe2O3/Cu-N-C with the onset potential of 0.977 V, which is superior to Pt/C. This study offers a feasible strategy for the preparation of non-noble metal catalysts and provides a new comprehension of the catalytic mechanism of M-N-C catalysts.

Spin-dependent electrocatalysis.

The shift towards sustainable energy requires efficient electrochemical conversion technologies, emphasizing the crucial need for robust electrocatalyst design. Recent findings reveal that the efficiency of some electrocatalytic reactions is spin-dependent, with spin configuration dictating performance. Consequently, understanding the spin's role and controlling it in electrocatalysts is important. This review succinctly outlines recent investigations into spin-dependent electrocatalysis, stressing its importance in energy conversion. It begins with an introduction to spin-related features, discusses characterization techniques for identifying spin configurations, and explores strategies for fine-tuning them. At the end, the article provides insights into future research directions, aiming to reveal more unknown fundamentals of spin-dependent electrocatalysis and encourage further exploration in spin-related research and applications.

Electrochemical Enantioselective Nickel-Catalyzed Cross-Coupling of Aldehydes with Aryl Iodides.

The preparation of enantioenriched diarylmethanol derivatives is described using nickel-catalyzed electrochemical cross-couplings between various alkyl/aryl aldehydes and aryl iodides. Performed in an electrochemical cell equipped with an iron anode and a nickel cathode, this electrocatalytic variant led to the scalemic targeted products in the presence of 2,2-bis((4R,5S)-4,5-diphenyl-4,5-dihydrooxazol-2-yl)acetonitrile (L2), as enantiopure cyano-bis(oxazoline) ligand. X-ray structure analysis of a pre-catalyst, for instance the [Ni(II)(L2)2] complex, with L2 as an anionic bisoxazolinate ligand, confirms the chemical formulation of one nickel surrounded by two ligands. The redox behavior of the new Ni complexes generated in situ was first assessed by cyclic voltammetry showing a redox wave at ca. -1.5 V that can be assigned to the two-electron reduction of the Ni(II) center to the Ni(0) state. Oxidative addition between the electrogenerated Ni(0) complex and aryl iodide was evidenced. An intense current was observed in presence of a mixture of the two substrates pertaining an electrocatalytic process. Interestingly, we found that the sacrificial iron anode plays a crucial role in the catalytic mechanism.

Hydrogen-Bond-Assisted Electrocatalytic Semi-Oxidation of 5-Hydroxymethylfurfural into 2,5-Diformylfuran by Operando Dissociated N-Oxyl Mediator.

The conversion of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a promising approach for enhancing biomass utilization. Nevertheless, traditional methods using noble metal catalysts face challenges due to high costs and poor selectivity towards DFF. Herein, we developed a novel catalytic electrode integrating N-hydroxyphthalimide (NHPI) into a metal-organic framework on a hydrophilic carbon cloth. This design significantly enhances the selective adsorption of HMF due to stronger hydrogen-bond interaction between the electrode's hydrophilic surface and the C(sp3)-OH group in HMF compared to the C(sp2)=O in DFF. Additionally, the electro-driven dissociation of the NHPI-linker generates stabilized N-Oxyl radicals that promote selective semi-oxidation of HMF under neutral conditions. As a result, this approach achieves a high yield rate of 138.2 mol molcat-1 h-1 with a selectivity of 96.7% for the HMF-to-DFF conversion. This work introduces a novel strategy for designing catalytic electrodes with stabilized N-Oxyl radicals, and offers a promising method for electrocatalytic DFF synthesis, leveraging hydrogen-bond interaction between electrode surface and HMF.

Construction of One-Dimensional Covalent-Organic Framework Coordinated with Main Group Metals for Selective Electrochemical Synthesis of H2O2.

Covalent-organic frameworks (COFs) are promising electrocatalysts for the selective synthesis of H2O2 through the two-electron oxygen reduction reaction (2e- ORR). However, the design and synthesis of efficient and stable COF-based electrocatalysts is still challenging. In this work, a predesigned 1,10-phenanthroline-based one-dimensional COF (PYTA-PTDE-COF) was constructed to anchor main group metal (In, Sn, and Sb) as electrocatalysts toward 2e- ORR. The catalysts are featured with fully exposed metalated side chains. Structural characterization revealed that PYTA-PTDE-M's (M = In, Sn, and Sb) are all quite similar, except for the coordinated metal ions with the maintenance of good crystallinity. They all exhibited satisfying activity and selectivity toward 2e- ORR under alkaline conditions. Among them, PYTA-PTDE-Sb exhibited the best performance (Eonset is 0.765 V, the H2O2 selectivity is 96%, and the yield rate is 209.2 mmol gcat-1 h-1). Moreover, it also delivered superior stability with almost no attenuation of current density during the long-time test. Theoretical calculations revealed that the Sb metal site in the COFs has the lowest adsorption strength of *OOH, which could be the main reason for its superior selectivity. The PYTA-PTDE-Sb assembled zinc-air battery realizes not only the supply of clean energy but also the production of green chemicals, showing it is highly promising in practical applications. This work offers an example for designing main group metal-coordinated 1D COFs and reveals fundamental structure-activity relationship toward 2e- ORR.

Co2P/CoP embedded in N, P, S triply-doped hollow carbon towards enhanced oxygen electrocatalysis.

Simultaneously dispersing phosphide crystallites and multiple heteroatoms in hollow carbon is a significant yet challenging task for achieving high-performance oxygen electrocatalysts of zinc-air batteries. Herein, a simple wrapping-pyrolysis strategy is proposed to prepare Co2P/CoP embedded in N, P, S triply-doped hollow carbon (Co2P/CoP@NPS-HC). Co2P/CoP@NPS-HC composite features hollow polyhedral structure populated with numerous catalytically active Co2P/CoP nanoparticles and N, P, S heteroatoms. This optimized catalyst exhibits excellent activity for oxygen reduction reaction, with a half-wave potential of 0.82 V vs. RHE, and impressive enhancement for oxygen evolution reaction, indicated by an overpotential of 400 mV at 10 mA cm-2. Moreover, Co2P/CoP@NPS-HC catalyst exhibits greater durability and superior methanol tolerance compared to commercial Pt/C. The excellent bifunctional electrocatalytic performance of Co2P/CoP@NPS-HC catalyst is attributed to the synergistic effect of uniformly dispersed Co2P/CoP nanoparticles and N, P, S triply-doped hollow carbon structure. The former provides abundant catalytically active sites, while the latter offers a high accessible specific surface area, as well as enhances catalytic activity and electronic conductivity due to its altered charge distribution.

Defects trigger redox reactivities between metal and lattice oxygen in high-entropy layered double hydroxide for boosting oxygen evolution in alkaline.

The oxygen evolution reaction (OER) at the anode undergoes a sluggish multi-step process, thereby impeding overall water splitting. As the classical adsorbate evolution mechanism (AEM) involves multiple oxygen-containing intermediates, such as *OH, *O and *OOH, breaking the linear relationship of the adsorption energies between *OH and *OOH is the key to efficient oxygen evolution. Herein, we report a high-entropy FeCoNiAlZn layered double hydroxide decorated with defects (E-FeCoNiAlZn LDH) for boosting oxygen evolution in alkaline. The product exhibits high OER activity with a low overpotential of 220 at 10 mA cm-2 and outstanding stability with negligible decline after 100 h operation. The defects in E-FeCoNiAlZn LDH not only enhance the adsorption of *OH by metal sites but also foster the release of oxygen from lattice, which triggers the coupled oxygen evolution mechanism (COM). This mechanism has only *OH and *OO intermediates, perfectly avoiding the obstacles of linear relationship between *OH and *OOH. Theoretical calculations demonstrate that the introduction of defects enhances the adsorption of *OH due to the presence of unsaturated bonds. Additionally, it is evidence that the O 2p band is elevated, leading to a weakening of the metal-O bond and a reduction of the energy barrier for OO coupling.