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2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.
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With the utilization of nitrophenols in manufacturing various materials and the expansion of industry, nitrophenols have emerged as water pollutants that pose significant risks to both humans and the environment. Therefore, it is imperative to convert nitrophenols into aminophenols, which are less toxic. This conversion process is achieved through the use of noble metal nanoparticles, such as gold, silver, copper, and palladium. The primary challenge with noble metal nanoparticles lies in their accumulation and deactivation, leading to a decrease in catalyst activity. Covalent organic frameworks (COFs) are materials characterized by a crystalline structure, good stability, and high porosity with active sites. These properties make them ideal substrates for noble metal nanoparticles, enhancing catalytic activity. This overview explores various articles that focus on the synthesis of catalysts containing noble metal nanoparticles attached to COFs as substrates to reduce nitrophenols to aminophenols.
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Developing efficient Pd-based electrocatalysts is of vital importance for the application of direct alcohol fuel cells. Designing the core-shell architecture of Pd-based nanomaterials rationally has emerged as an effective strategy to promote the sluggish kinetics of anodic reactions. Herein, the PdAg alloy is reduced on a non-noble metal oxide surface for the formation of a core-shell nanostructure. The optimized SnO2@PdAgh nanospheres deliver the optimal catalytic performance compared with other counterparts and commercial Pd/C. The structural investigation reveals that the introduction of Ag and formation of a PdAg/SnO2 heterointerface effectively regulate the electronic structure of Pd, making SnO2@PdAgh a highly active catalyst for methanol and ethylene glycol oxidation reactions. Impressively, the strong interaction between the PdAg shell and SnO2 core stabilizes the metal-oxide heterointerface, contributing to the improved stability of SnO2@PdAgh in electrocatalytic reactions. This study proposes the use of non-noble metal oxides as the core to suppress the dissolution of the catalysts and highlights the rational design of core@shell nanoarchitectures.
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The hetero and homo metal exchange of Au25(SR)18 - and Ag25(SR)18 - nanoclusters with metal-thiolate (M-SR) complexes (AuI(SR), AgI(SR), CuI(SR), and CuII(SR)2) are studied using ab initio molecular dynamics (AIMD) simulations. The AIMD simulation results unveil that the M-SR complexes directly displace Au(SR) or Ag(SR) units on the gold or silver core surface through an "anchoring effect". The whole process of metal-exchange reactions can be divided into three steps, including the adsorption of M-SR complexes on clusters, the formation of new staple motif, and the displacement of Au(SR) or Ag(SR) units by M-SR complexes. The key role of sulfur atoms in metal exchange reactions in M-SR complexes is revealed, which facilitates formation of new staple motifs and doping of M-SR complexes into gold and silver cores. This work provides a theoretical basis for further exploring the metal exchange reaction between noble metal nanoclusters and metal-thiolate complexes, as well as the isotope exchange reactions.
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The direct one-step hydrogenation of toluene to methylcyclohexane facilitated by a proton-exchange membrane water electrolyzer driven by renewable energy has garnered considerable attention for stable hydrogen storage and safe hydrogen transportation. However, a persistent challenge lies in the crossover of toluene from the cathode to the anode chamber, which deteriorates the anode and decreases its energy efficiency and lifetime. To address this challenge, the catalyst-poisoning mechanism is systematically investigated using IrO2 and high-entropic non-noble-metal alloys as anodes in acidic electrolytes saturated with toluene and toluene-oxidized derivatives, such as benzaldehyde, benzyl alcohol, and benzoic acid. Benzoic acid plays an important role in polymer-like carbon-film formation by blocking the catalytically active sites on the anode surface. Moreover, Nb and the highly entropic state on the surface of the multi-element alloy lower the adsorbing ability of toluene and prevent polymer-like carbon film formation. This study contributes to the design of catalyst-poisoning-resistant anodes for organic hydride technology, advanced fuel cells, and batteries.
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Two-dimensional layered semiconductor materials as a distinctive class of materials are comprehensively explored for widespread applications due to narrow bandgap, controllable morphology, and tunable metal cation composition. Herein, we constructed a sensing platform of surface enhanced Raman spectroscopy (SERS) by combination of nickelcobalt layered double hydroxide (NiCo-LDH) microurchins and plasmonic silver nanoparticles (Ag NPs) for fungicide detection of thiabendazole (TBZ). The NiCo-LDHs/Ag-NPs microcomposites consist of NiCo-LDHs microurchins having a large number of nanoneedles deposited with photoreduced Ag NPs. The SERS platform with NiCo-LDHs/Ag-NPs shows an excellent SERS performance for TBZ detection, including an ultra-low detection limit of 1.49 × 10-11 M, a sublime enhancement factor of 1.71 × 109, high uniformity, good reproducibility, and long-term storage stability. The ultrahigh SERS activity of NiCo-LDH/Ag-NPs can be attributed to strong electromagnetic enhancement in the nanoscale gaps between Ag NPs, massive charge transfer through large-area NiCo-LDH/Ag-NPs interfaces, and the synergistic action of electromagnetic and charge transfer mechanisms. Besides, the unique morphology of NiCo-LDHs/Ag-NPs microcomposite provides a broad surface area for adsorption of TBZ molecules for further Raman signal enhancement. The practicability of the proposed SERS platform is confirmed by detecting TBZ in the real samples of apple juice and river water. The exceptional self-cleaning capability of the NiCo-LDHs/Ag-NPs microcomposite with an retention rate of 81.97 % even after the fifth degradation cycle underscores its impressive sustainable reusability and cost-effectiveness. The findings in this work lay the foundation for the development of high-performance SERS platforms to ensure food safety and environmental protection.
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Renewable energy-driven proton exchange membrane water electrolyzer (PEMWE) attracts widespread attention as a zero-emission and sustainable technology. Oxygen evolution reaction (OER) catalysts with sluggish OER kinetics and rapid deactivation are major obstacles to the widespread commercialization of PEMWE. To date, although various advanced electrocatalysts have been reported to enhance acidic OER performance, Ru/Ir-based nanomaterials remain the most promising catalysts for PEMWE applications. Therefore, there is an urgent need to develop efficient, stable, and cost-effective Ru/Ir catalysts. Since the structure-performance relationship is one of the most important tools for studying the reaction mechanism and constructing the optimal catalytic system. In this review, the recent research progress from the construction of unsaturated sites to gain a deeper understanding of the reaction and deactivation mechanism of catalysts is summarized. First, a general understanding of OER reaction mechanism, catalyst dissolution mechanism, and active site structure is provided. Then, advances in the design and synthesis of advanced acidic OER catalysts are reviewed in terms of the classification of unsaturated active site design, i.e., alloy, core-shell, single-atom, and framework structures. Finally, challenges and perspectives are presented for the future development of OER catalysts and renewable energy technologies for hydrogen production.
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The urgent need to develop efficient, durable, and cost-effective oxygen evolution reaction (OER) catalysts for energy conversion and storage has prompted extensive research. Currently available commercial noble metal-based OER catalysts are expensive and exhibit limited long-term stability. In this study, boron-doped diamond composites (BDDCs) consisting of CoFe and CoFe2C nanoparticles supported by boron-doped diamond (BDD) particles have been prepared. The BDDC catalyst, prepared through a straightforward annealing process, exhibits exceptional durability (up to 72 h at 10 mA cm-2), a low overpotential (306 mV at 10 mA cm-2), and modest Tafel slope (58 mV dec-1). The coherent interfaces between CoFe/CoFe2C nanoparticles and the BDD substrate are essential for enhancing the OER performance. The fabrication method and composite structures presented in this study may facilitate the design and production of promising catalysts.
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The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO2 reduction, nitrogen fixation, and metal-air batteries. Among various water electrolysis techniques, proton exchange membrane (PEM)-based water electrolysis devices offer numerous advantages, including high current densities, exceptional chemical stability, excellent proton conductivity, and high-purity H2. Nevertheless, the prohibitive cost associated with Ir/Ru-based OER electrocatalysts poses a significant barrier to the broad-scale application of PEM-based water splitting. Consequently, it is crucial to advance the development of non-noble metal OER catalysis substance with high acid-activity and stability, thereby fostering their widespread integration into PEM water electrolyzers (PEMWEs). In this review, a comprehensive analysis of the acidic OER mechanism, encompassing the adsorbate evolution mechanism (AEM), lattice oxygen mechanism (LOM) and oxide path mechanism (OPM) is offered. Subsequently, a systematic summary of recently reported noble-metal-free catalysts including transition metal-based, carbon-based and other types of catalysts is provided. Additionally, a comprehensive compilation of in situ/operando characterization techniques is provided, serving as invaluable tools for furnishing experimental evidence to comprehend the catalytic mechanism. Finally, the present challenges and future research directions concerning precious-metal-free acidic OER are comprehensively summarized and discussed in this review.
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Direct lignin fuel cells (DLFC) are one of the important forms of high value-added utilization of lignin. In this study, lignin was studied not only as a fuel but also as a catalyst. Specifically, Kraft lignin was modified with ZnCl2, KOH and THF (Tetrahydrofuran) respectively, and added to the catalyst after activation. The results of scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive spectrometer (EDS), Brunauer - Emmett - Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR) and Raman spectra shown that AL/FePc-NrGO (activated lignin/iron phthalocyanine/nitrogen-doped reduction of graphene oxide) three-dimensional composite catalyst has been synthesized. The results showed that KOH-activated Kraft lignin had the best performance as an oxygen reduction reaction (ORR) catalyst, with a half-wave potential (E1/2) of 0.73 V and a limiting diffusion current density of 4.3 mA cm-1. The THF-modified catalyst showed similar stability and methanol resistance to 20 % Pt/C at ORR. The ORR catalyst applied to the DLFC has the best electrical performance with an open circuit voltage (OCV) was 0.53 V and the maximum power density it could reach 95.29 mW m-2 when the catalyst was modified with THF. It is encouraging that the AL/FePc-NrGO catalyst has better-generated electricity performance than 20 % Pt/C. This work has provided a new idea for developing non-noble metal catalysts and studying direct biomass liquid fuel cells.
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Plasmonic nanomaterials such as Au, Ag, and Cu are widely recognized for their strong light-matter interactions, making them promising photothermal materials for solar steam generation. However, their practical use in water evaporation is significantly limited by the trade-off between high costs and poor stability. In this regard, we introduce a novel, nonmetallic dual plasmonic TiN/MoO3-x composite. This composite features a three-dimensional, urchin-like biomimetic structure, with plasmonic TiN nanoparticles embedded within a network of plasmonic MoO3-x nanorods. As a solar absorber, the TiN/MoO3-x composite achieves a high evaporation rate of â¼2.05 kg m-2 h-1 with an energy efficiency up to 106.7% under 1 sun illumination, outperforming the state-of-the-art plasmonic systems. The high photothermal stability and unique dual plasmonic nanostructure of the TiN/MoO3-x composite are demonstrated by advanced in situ laser-heating transmission electron microscopy and photon-induced near-field electron microscopy/electron energy-loss spectroscopy, respectively. This work provides new inspiration for the design of plasmonic materials.
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As a widely used support, TiO2 has often been combined with Pd to form highly sensitive gas-chromic materials. Herein, we prepared a series of Pd/TiO2 catalysts with different Pd content (from 0.1 to 5 wt.%) by the impregnation method for their utilization in fast room-temperature CO detection. The detection was simply based on visible color change when the Pd/TiO2 was exposed to CO. The sample with 1 wt.% Pd/TiO2 presented an excellent CO gasochromic character, associated with a maximum chromatic aberration value of 90 before and after CO exposure. Systematic catalyst characterizations of XPS, FT-IR, CO-TPD, and N2 adsorption-desorption and density functional theory calculations for the CO adsorption and charge transfer over the Pd and PdO surfaces were further carried out. It was found that the interaction between CO and the Pd surface was strong, associated with a large adsorption energy of -1.99 eV and charge transfer of 0.196 e. The color change was caused by a reduction in Pd2+ to metallic Pd0 over the Pd/TiO2 surface after CO exposure.
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They have achieved a significant breakthrough in the preparation and development of two-dimensional nanocomposites with P-N heterojunction interfaces as efficient cathode catalysts for electrochemical hydrogen evolution reaction (HER) and iodide oxidation reaction (IOR). P-type acid-doped polyaniline (PANI) and N-type exfoliated molybdenum disulfide (MoS2) nanosheets can form structurally stable composites due to formation of P-N heterojunction structures at their interfaces. These P-N heterojunctions facilitate charge transfer from PANI to MoS2 structures and thus significantly enhance the catalytic efficiency of MoS2 in the HER and IOR. Herein, by combining efficient sodium-functionalized chitosan-assisted MoS2 exfoliation, electropolymerization of PANI on nickel foam (NF) substrate, and electrochemical activation, controllable and scalable Na-Chitosan/MoS2/PANI/NF electrodes are successfully constructed as non-noble metal-based electrochemical catalysts. Compared to a commercial platinum/carbon (Pt/C) catalyst, the Na-Chitosan/MoS2/PANI/NF electrode exhibits significantly lower resistance and overpotential, a similar Tafel slope, and excellent catalytic stability at high current densities, demonstrating excellent catalytic performance in the HER under acidic conditions. More importantly, results obtained from proton exchange membrane fuel cell devices confirm the Na-Chitosan/MoS2/PANI/NF electrode exhibits a low turn-on voltage, high current density, and stable operation at 2 V. Thus, this system holds potential as a replacement for Pt/C with feasibility for applications in energy-related fields.
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The straightforward synthesis of noble-metal-nanoparticle-decorated ordered mesoporous transition metal oxides remains a great challenge due to the difficulty of balancing the interactions between precursors and templates. Herein, a solvent-pair-enabled multicomponent coassembly (SPEMC) strategy is developed for straightforward synthesis of noble-metal-nanoparticle-decorated nitrogen-doped ordered mesoporous tungsten oxide (abbreviated as NM/N-mWO3, NM = Pt, Rh, Pd). The amphiphilic poly(ethylene oxide)-block-polystyrene (PEO-b-PS) copolymers coassemble with ammonium metatungstate (AMT) clusters and different kinds of hydrophilic noble metal precursors without phase separation. SPEMC synthesis requires no direct interaction between PEO-b-PS and AMT, thus the assembly equilibriums between noble metal precursors and PEO-b-PS can be readily controlled. The obtained NM/N-mWO3 nanocomposites possess ordered mesopores, abundant oxygen vacancies, and metal-metal oxide interfaces. As a result, the Pt/N-mWO3 sensors exhibit superior ammonia sensing performances with high sensitivity, an ultralow limit of detection (51.2 ppb), good selectivity, and long-term stability. Spectroscopic analysis reveals that ammonia is oxidized stepwise to NO, NO2 -, and NO3 - during the sensing process. Moreover, a portable wireless module based on Pt/N-mWO3 sensor can recognize ppm-level concentration of ammonia, which lays a solid foundation for its application in various fields.
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The seawater electrolysis technology powered by renewable energy is recognized as the promising "green hydrogen" production method to solve serious energy and environmental problems. The lack of low-cost and ampere-level current OER (oxygen evolution reaction) and HER (hydrogen evolution reaction) catalysis limits their industrial application. In this work, a unique tri-metal (Co/Fe/Ni) layered double hydroxide hollow array anode catalyst (CFN-LDH/NF) and the CoP/FeNi2P heterojunction hollow array cathode are successfully prepared via one in-situ growth of Co-MOF on nickel foam (Co-MOF/NF) precursor, which exhibits excellent catalytic performance. The η1000 values of 352 and 392 mV are achieved for CFN-LDH/NF (OER catalyst) in 1.0 M KOH and alkaline seawater solution, respectively. The CFNP/NF with a low overpotential of 281 mV is required to reach 1000 mA cm-2 current density for HER in 1.0 M KOH solution, while the η1000 in alkaline seawater solution is 312 mV. The CFN-LDH/NF||CFNP/NF electrolyzer exhibits excellent long-term durability over 100 h, achieving current density of 500 mA cm-2 at 1.825 V in 1.0 M KOH solution. The construction of hollow tri-metal LDH and phosphides heterostructures may open a new and relatively unexplored path for fabricating high performance seawater splitting catalysis.
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The utilization of seawater for hydrogen production via water splitting is increasingly recognized as a promising avenue for the future. The key dilemma for seawater electrolysis is the incompatibility of superior hydrogen- and oxygen-evolving activities at ampere-scale current densities for both cathodic and anodic catalysts, thus leading to large electric power consumption of overall seawater splitting. Here, in situ construction of Fe4N/Co3N/MoO2 heterostructure arrays anchoring on metallic nickel nitride surface with multilevel collaborative catalytic interfaces and abundant multifunctional metal sites is reported, which serves as a robust bifunctional catalyst for alkaline freshwater/seawater splitting at ampere-level current density. Operando Raman and X-ray photoelectron spectroscopic studies combined with density functional theory calculations corroborate that Mo and Co/Fe sites situated on the Fe4N/Co3N/MoO2 multilevel interfaces optimize the reaction pathway and coordination environment to enhance water adsorption/dissociation, hydrogen adsorption, and oxygen-containing intermediate adsorption, thus cooperatively expediting hydrogen/oxygen evolution reactions in base. Inspiringly, this electrocatalyst can substantially ameliorate overall freshwater/seawater splitting at 1000 mA cm-2 with low cell voltages of 1.65/1.69 V, along with superb long-term stability at 500-1500 mA cm-2 for over 200 h, outperforming nearly all the ever-reported non-noble electrocatalysts for freshwater/seawater electrolysis. This work offers a viable approach to design high-performance bifunctional catalysts for seawater splitting.
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All-vanadium redox flow batteries (VRFB) have the advantages of high safety and long life, and have broad application prospects in the field of large-scale power energy storage. Low energy density is the main factor restricting its development. In this study, the carbon felt used as the electrode was pretreated in various ways to improve the performance of the vanadium redox flow battery. The pretreatment conditions of carbon felt were compared to the performance of carbon felt after treatment at different temperatures and different times. The properties of the pretreated carbon felt were investigated and their effect on cell performance was tested.Next, by introducing a noble metal catalyst into the carbon felt, the characteristics of the carbon felt were studied and the effect on the performance of the vanadium redox flow battery was investigated. It was found that Carbon felt thermal-treated at 500 °C for 2 h showed the best characteristics and had the longest charge/discharge time and the lowest resistance. The results also show that Carbon felt with catalyst introduced without PTFE(Polytetrafluoroethylene) binder showed larger BET(Brunauer-Emmett-Teller) surface area and electrical conductivity compared to PTFE mixed, and cell performance was also excellent.
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We developed multiwavelength evanescent scattering microscopy (MWESM), which can acquire plasmonic nanoparticle images at the particle level using the evanescent field as the incident source and distinguish different LSPR (localized surface plasmon resonance) spectral peaks among four wavelengths. Our microscope could be easily and simply built by modifying a commercial total internal reflection fluorescence microscope (TIRFM) with the substitution of a beamsplitter and the addition of a semicircular stop. The ultrathin depth of illumination and rejection of the reflected incident source together contribute to the high sensitivity and contrast of single nanoparticle imaging. We first validated the capability of our imaging system in distinguishing plasmonic nanoparticles bearing different LSPR spectral peaks, and the results were consistent with the scattering spectra results of hyperspectral imaging. Moreover, we demonstrated high imaging quality from the aspects of the signal/noise ratio and point spread function of the single-particle images. Meaningfully, the system can be utilized in rapidly determining the concentration of toxic lead ions in environmental and biological samples with good linearity and sensitivity, based on single-particle evanescent scattering imaging through the detection of the alteration of the LSPR of silver nanoparticles. This system holds the potential to advance the field of nanoparticle imaging and foster the application of nanomaterials as sensors.
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Benefiting from the ultrahigh specific surface areas, massive exposed surface atoms, and highly tunable microstructures, the two-dimensional (2D) noble metal nanosheets (NSs) have presented promising performance for various electrocatalytic reactions. Nevertheless, the heteroatom doping strategy, and in particular, the electronic structure tuning mechanisms of the 2D noble metal catalysts (NMCs) yet remain ambiguous. Herein, we first review several effective strategies for modulating the electrocatalytic performance of 2D NMCs. Then, the electronic tuning effect of hetero-dopants for boosting the electrocatalytic properties of 2D NMCs is systematically discussed. Finally, we put forward current challenges in the field of 2D NMCs, and propose possible solutions, particularly from the perspective of the evolution of electron microscopy. This review attempts to establish an intrinsic correlation between the electronic structures and the catalytic properties, so as to provide a guideline for designing high-performance electrocatalysts.
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Transition metal sulfides, particularly heterostructures, represent a promising class of electrocatalysts for two electron oxygen reduction (2e- ORR), however, understanding the dynamic structural evolution of these catalysts during alkaline ORR remains relatively unexplored. Herein, NiS2/In2.77S4 heterostructure was synthesized as a precatalyst and through a series of comprehensive ex-situ and in-situ characterizations, including X-ray absorption spectroscopy, Raman spectroscopy, transient photo-induced voltage measurements, electron energy loss spectroscopy, and spherical aberration-corrected electron microscopy, it was revealed that nickel/indium (oxy)hydroxides (NiOOH/In(OH)3) could be evolved from the initial NiS2/In2.77S4 via both electrochemical and chemical-driven methods. The electrochemical-driven phase featured abundant bridging oxygen-deficient [NiO6]-[InO6] units at the interfaces of NiOOH/In(OH)3, facilitating a synergistic effect between active Ni and In sites, thus enabling an enhanced alkaline 2e- ORR capability than that of chemical-driven process. Remarkably, electrochemically induced NiOOH/In(OH)3 exhibited exceptional performance, achieving H2O2 selectivity of >90% across the wide potential window (up to 0.4 V) with a peak selectivity of >99%. Notably, within the flow cell, a current density exceeding 200 mA cm-2 was sustained for over 20 h, together with an impressive Faradaic efficiency of approximately 90% and a hydrogen peroxide production rate surpassing 4 mol g-1 h-1.