Superior Catalytic Performance Research Articles

Comparative Study of Porous High‐entropy Oxides as Low‐temperature Catalysts for CO2 Methanation

High‐entropy oxides (HEOs) are an emerging class of materials whose compositional complexity has garnered attention because of their tailorable chemistries and unique properties arising from extreme configurational entropy. Solid‐state methods are often employed to synthesize HEOs, but such methods result in poor material properties for catalytic processes, leaving HEOs less studied for catalysis. Here we utilize different wet‐synthesis strategies to produce porous HEOs and investigate their performance in heterogeneous CO2 hydrogenation to methane. Specifically, HEOs were synthesized using hydrothermal, co‐precipitation, and solvothermal methods, resulting in different morphologies like platelets or spheres. Of the tested materials, HEOs with 2‐D platelets derived from hydrothermally‐synthesized high‐entropy layered double hydroxides had superior catalytic performance, especially in low‐temperature regimes (<300°C). K‐edge XANES indicated that metallic sites (Ni0‐Co0) were formed during the reaction, and these metallic sites are dispersed into the HEO matrix which is confirmed by STEM/elemental mapping. This facile synthesis approach allows for realized synergy between the metallic sites and the HEO support, leading to superior performance for CO2 methanation compared to low‐entropy counterparts. Finally, this study illustrates how HEOs offer new avenues of tailorability in terms of the interplay between support, active site and reaction temperatures for heterogeneous catalysis.

A comparative study for the efficiency of Pd (II) and Fe (III) complexes as efficient catalysts for synthesis of dihydro‐7H‐5‐thia‐hexaaza‐s‐indacen‐6‐one derivatives supported with DFT approach

Two novel complexes were synthesized by the reaction of benzothiazol‐pyrimidin‐2‐ylidene ligand (BTP) with Pd (II) and Fe (III) ions. A variety of various spectral and analytical methods (infrared, 1H/NMR, 13C/NMR, electronic spectra, CHN analyses, mass spectra, thermogravimetric analysis, and magnetic susceptibility) were used to characterize the investigated BTP ligand and its complexes. Correlation of experimental results with density functional theory calculation proves that the geometry of BTP‐Fe complex is octahedral, whereas BTP‐Pd complex is square planner. The catalytic effectiveness of BTP complexes were tested for three‐component condensation process under moderate and environmentally friendly reaction conditions. Moreover, the effects of different Lewis acid, basic, and ionic liquid catalysts, as well as solvent and catalyst dose on the catalytic reaction were investigated. Both catalysts demonstrated strong catalytic capability in the carefully regulated ideal reaction circumstances. Heterogeneous catalyst BTP‐Pd exhibited superior catalytic performance compared to homogeneous catalyst BTP‐Fe. All products were obtained in high TOF (turnover frequency) numbers in the presence of these catalysts, which indicate the high efficiency of these catalysts in the synthesis of dihydro‐7H‐5‐thia‐hexaaza‐s‐indacen‐6‐one derivatives. Moreover, the two catalysts' recycling and reusability in reactions were also investigated. Heterogeneous BTP‐Pd catalyst could be reused up to seven times with high efficiency, but the homogeneous catalyst (BTP‐Fe) could only be recycled up to four times. Furthermore, the mechanism of catalytic reaction was suggested and supported by DFT calculation. The simplicity, safety, stability, use of commercially available catalysts, quick reaction times, and excellent yields make it promising for future industrial use.

Plasma-catalytic direct oxidation of methane to methanol over Cu-MOR: Revealing the zeolite-confined Cu2+ active sites

Efficient methane conversion to methanol remains a significant challenge in chemical industry. This study investigates the direct oxidation of methane to methanol under mild conditions, employing a synergy of non-thermal plasma and Cu-MOR (Copper-Mordenite) catalysts. Catalytic tests demonstrate that the Cu-MOR IE-3 catalyst (i.e., prepared by three cycles of ion exchange) exhibits superior catalytic performance (with 51 % methanol selectivity and 7.9 % methane conversion). Conversely, the Cu-MOR catalysts prepared via wetness impregnation tend to over-oxidize CH4 to CO and CO2. Through systematic catalyst characterizations (XRD, TPR, UV–Vis, HRTEM, XPS), we elucidate that ion exchange mainly leads to the formation of zeolite-confined Cu2+ species, while wetness impregnation predominantly results in CuO particles. Based on the catalytic performance, catalyst characterizations and in-situ FTIR spectra, we conclude that zeolite-confined Cu2+ species serve as the active sites for plasma-catalytic direct oxidation of methane to methanol.

Solvothermal synthesis of PdCu nanorings with high catalytic performance for alcohol electrooxidation

Two-dimensional (2D) Pd-based nanostructures with a high active surface area and a large number of active sites are commonly used in alcohol oxidation research, whereas the less explored ring structure made of nanosheets with large pores is of interest. In this study, we detail the fabrication of PdCu nanorings (NRs) featuring hollow interiors and low coordinated sites using a straightforward solvothermal approach. Due to increased exposure of active sites and the synergistic effects of bimetallics, the PdCu NRs exhibited superior catalytic performance in both the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR). The mass activities of PdCu NRs for EOR and EGOR were measured at 7.05 A/mg and 8.12 A/mg, respectively, surpassing those of commercial Pd/C. Furthermore, the PdCu NRs demonstrated enhanced catalytic stability, maintaining higher mass activity levels compared to other catalysts during stability testing. This research offers valuable insights for the development of efficient catalysts for alcohol oxidation.

CeCoaOx catalysts derived from metal-organic frameworks for enhancing catalytic toluene oxidation by tuning surface oxygen property

Rod-shaped CeCoaOx catalysts with varying Co doping ratios (a = 0.012, 0.017, 0.022) were synthesized by calcinating the Ce-MOF, prepared using a water bath and trimesic acid as an organic ligand. This method ensured a high degree of elemental mixing, abundant pore channels and a large specific surface area are all beneficial for enhancing toluene catalytic oxidation activity. Raman, XPS, and catalytic activity tests confirmed strong interactions between the Ce and Co oxides, promoting the formation of more Ce3+ and oxygen vacancies. Among these catalysts, CeCo0.012Ox exhibited superior catalytic performance for toluene oxidation under weight hourly space velocity of 40,000 mL·g−1·h−1. The temperature at toluene conversion of 10 %, 50 % and 90 % was 140, 205 and 226 °C, respectively, which was 61, 12 and 14 °C higher than those over pure phase CeO2. CeCo0.012Ox also demonstrated excellent activity stability under high humidity (10 vol%H2O). H2-TPR, O2-TPD and in situ DRIFTS also revealed that surface-absorbed oxygen species played a crucial role in catalytic activity, with CeCo0.012Ox benefiting from abundant oxygen vacancies and effective oxygen species mobility.

Ternary Fe–Ni–B particles supported on Cu(OH)2–Cu foam: A highly efficient and stable catalyst for hydrolysis of ammonia borane

Ammonia borane (NH3BH3) as a solid chemical hydrogen storage material with a high hydrogen content can be hydrolyzed under mild conditions to release hydrogen. In this work, Fe–Ni–B/Cu(OH)2–Cu foam was synthesized by combining in situ growth and electroless plating. Compared with the binary Fe–B/Cu(OH)2–Cu foam and Ni–B/Cu(OH)2–Cu foam prepared by the same method, the ternary Fe–Ni–B/Cu(OH)2–Cu foam has superior catalytic performance. The Fe–Ni–B/Cu(OH)2–Cu foam catalyst was able to achieve a maximum hydrogen production rate of 5.6 ml min−1 cm−2 at 298 K with an activation energy as low as 46.3 kJ mol−1. And more importantly, its catalytic efficiency has hardly decayed after ten cycles. These excellent properties are due to its low activation energy and the large specific surface, multi–site Cu(OH)2–Cu–foam carrier.

Efficient photocatalytic degradation of 24 imidazolium ionic liquids in an N-ZnO/simulated sunlight irradiation system and its mechanism

An efficient nitrogen (N)-ZnO photocatalytic composite was synthesized and well characterized to demonstrate its superior photocatalytic performance as well as the degradation kinetics of 24 ILs in an N-ZnO/Xe lamp irradiation system, as well as the pathways and mechanisms of the photocatalytic degradation (PCD) of typical ionic liquids [OMIm]Br was systematically studied. To investigate the catalytic effect, nitrogen was synthesized from various inorganic and organic nitrogen compounds to ZnO. The NH4NO3-ZnO composite calcined at 300 °C with a molar ratio of NH4NO3 to Zn(NO3)2·6H2O of 10:1 exhibited superior catalytic performance as assessed by SEM, TEM, FT-IR, UVDRS, BET surface area, XPS, and XRD characterizations. After 24 h of exposure to Xe lamp irradiation, all 24 ILs were significantly degraded by the introduction of 0.125 g/L of catalyst, whereas simulated sunlight alone resulted in minimal degradation. The pseudo-first-order rate coefficients (k) for PCD were closely related to the carbon chain length of the alkyl substituents and the type of anion. Multiple linear regression analysis indicated no linear correlation between the parameters E, H°, Eth, and Cv° from the Gaussian calculation and k. Conversely, a positive correlation was observed for EHOMO (B=0.742, β = 1.282, P = 0.011), qH+ (B=1.040, β = 3.284, P = 0.006), and G° (B=0.001, β = 5.400, P = 0.007) with k. Mass spectrometry analysis revealed that the primary PCD pathway for [OMIm]Br involved C-N and/or C-C bond breaking, mono-, di-, and tri-hydroxylation, single and double oxygen transfer, and bromo-substitution reactions.

Low-silica zeolite MTT: Synthesis and efficient catalysis in methanol dehydration

Zeolite MTT features a one-dimensional (1D) 10-membered ring (10 MR) straight channel system. This unique structure provides superior catalytic performance in petrochemical processes such as isomerization, dewaxing, and olefin oligomerization. The conventional synthesis of zeolite MTT typically requires large amounts of organic structure directing agents (OSDA), and the resulting zeolite MTT usually has a Si/Al ratio greater than 20. Herein, we present a facile strategy for synthesizing zeolite MTT possessing a low Si/Al ratio of 12.5 and a greatly improved specific surface area of 308.0 m2/g with the assistance of MTT seeds. This low-silica zeolite MTT demonstrates a higher methanol conversion (84 %) at a low temperature (170 °C) in the methanol dehydration reaction compared to conventionally synthesized zeolite MTT, which achieves less than 70 % conversion.

High valent manganese-oxo species activation of peroxymonosulfate by different phases manganese oxides nanoplates for catalytic water decontamination

Advanced oxidation processes involving high-valent metal-oxo species have garnered increasing attention for their effective pollutant degradation in water. However, less is known about the mechanism of the species in the manganese oxides (MnOx) system. Therefore, it is crucial to design MnOx catalysts to systematically clarify the high-valent metal-oxo species reaction mechanism. In this study, MnOx nanoplates including Mn3O4, Mn5O8, and Mn2O3 were synthesized via a facile thermal treatment of a Mn(OH)2 precursor to activate peroxymonosulfate (PMS) for mechanism studies. The Mn3O4 catalyst exhibited superior catalytic performance and reusability owing to its unique spinel structure and rapid electron transfer properties. The first-order rate constant for Mn3O4 is 0.64 min−1, which is 3.7 and 1.5 times higher than those of Mn5O8 and Mn2O3, respectively. Scavenging experiments, electron paramagnetic resonance, and electrochemical analysis revealed that free radicals played a negligible role, while the formation of high-valent Mn-oxo species was promoted, facilitated by the Mn3O4-PMS* complex. These high-valent Mn-oxo species were highly reactive towards various pollutants. Moreover, the degradation intermediates of bisphenol A (BPA) in the Mn3O4/PMS system were identified, further elucidating the interactions between high-valent Mn-oxo species and BPA. Additionally, the Mn3O4 catalyst exhibited excellent catalytic performance under practical conditions and maintained superior stability over six cycles. This work provides crucial insights into the role of transition metal oxides in activating PMS for the catalytic degradation of emerging pollutants.

Advances in the Development of Dual‐Atom Catalysts: Structural Characterization and Diversified Catalytic Applications

AbstractAtomically dispersed metal atoms on supports exhibit distinctive advantages in maximizing atomic utilization, which plays an indispensable role in the fabrication of cost‐effective catalysts. In particular, dual‐atom catalysts (DACs) containing dual active sites not only retain the merits of single‐atom catalysts (SACs), but also introduce diverse interactions between the two adjacent metal atoms, endowing them with superior catalytic performance and a broad range of applications. With the development of DACs, it is important to identify active sites and establish intrinsic catalytic mechanisms relationship. The general characterization methods for DACs are comprehensively summarized here, especially the structural nature of dual active sites is discussed in detail. Subsequently, the representative scientific research efforts in various applications including thermocatalysis, electrocatalysis, and photocatalysis are described, with emphasis on structure‐property relationships. Finally, a summary and some prospects for the future of advanced DACs are presented.

Activating peroxymonosulfate with MOF-derived NiO-NiCo2O4/titanium membrane for water treatment: A non-radical dominated oxidation mechanism

Traditional peroxymonosulfate (PMS) catalytic membranes dominated by radical pathways often face interference from complex components in water bodies. Herein, we employed a controlled electro-deposition technique to coat a Ni-Co metal–organic framework (MOF) precursor onto titanium hollow fiber membrane (THFM), followed by high-temperature calcination to synthesize a MOF-derived NiO-NiCo2O4/THFM (M−NNCO−THFM) PMS catalytic membrane. Then, the M−NNCO−THFM filtration integrated with PMS activation (MFPA process) for water treatment. Experimental results demonstrated that the M−NNCO−THFM MFPA process successfully achieved complete phenol (PE) removal via a non-radical-dominated degradation pathway, involving singlet oxygen (1O2) and electron transfer, while exhibiting wide pH adaptability and exceptional stability in complex water matrices. Mechanism analysis revealed that the electron transfer process was significantly enhanced by the MOF-derived heterojunction structure, which increased the flat-band potential from 0.39 eV to 0.56 eV, thereby facilitating efficient electron transfer for PE removal. The non-radical 1O2 pathway was primarily due to the cycling of metal valence states (Ni2+/Co3+), leading to the reduction of Co2+ and its reaction with PMS, resulting in the generation of reactive species. Furthermore, electrochemical measurements indicated that the M−NNCO−THFM exhibited lower charge transfer resistance and enhanced charge transfer efficiency compared to non-MOF-derived NNCO-THFM, corresponding to the superior catalytic performance and electrochemically active surface area of M−NNCO−THFM.

Highly selective regulation of non-radical and radical mechanisms by Co cubic assembly catalysts for peroxymonosulfate activation

Peroxymonosulfate (PMS) activation on efficient catalysts is a promising strategy to produce sulfate radical (SO4−) and singlet oxygen (1O2) for the degradation of refractory organic pollutants. It is a great challenge to selectively generate these two reactive oxygen species, and the regulation mechanism from non-radical to radical pathway and vice versa is not well established. Here, we report a strategy to regulate the activation mechanism of PMS for the selective generation of SO4− and 1O2 with 100 % efficiency by sulfur-doped cobalt cubic assembly catalysts that was derived from the Co-Co Prussian blue analog precursor. This catalyst showed superior catalytic performance in activating PMS with normalized reaction rate increased by 87 times that of the commercial Co3O4 nanoparticles and had much lower activation energy barrier for the degradation of organic pollutant (e.g., p-chlorophenol) (18.32 kJ⋅mol−1). Experimental and theoretical calculation results revealed that S doping can regulate the electronic structure of Co active centers, which alters the direction of electron transfer between catalyst and PMS. This catalyst showed a strong tolerance to common organic compounds and anions in water, wide environmental applicability, and performed well in different real-water systems. This study provides new opportunities for the development of metal catalyst with metal-organic frameworks structure and good self-regeneration ability geared specifically towards PMS-based advanced oxidation processes applied for water remediation.

Encapsulated metal-based MOF nanoparticles as efficient catalysts for catalytic transfer hydrodeoxygenation of lignin-derived vanillin to 2-methoxy-4-methylphenol

A range of carbon-encapsulated non-precious metal catalysts (Ni@C, Ce@C, Mo@C, and Zn@C) were prepared using the hydrothermal approach for the catalytic transfer hydrodeoxygenation of vanillin compound derived from lignin. The catalytic efficacy was affected by the level of acid sites, catalyst durability, and the cooperation with H-donor solvents. Analysis indicated that the thin carbon layer enclosing the active sites notably improved catalytic effectiveness and thermodynamic stability compared to alternative catalysts. Notably, Ni@C demonstrated superior catalytic performance, achieving a vanillin conversion rate of 98.72 % and an 87.12 % yield of the major product 2-methoxy-4-methylphenol under specific conditions (240 ℃, 2.0 MPa N2, ethanol as a solvent, 4-hour reaction time). These findings underscore the significant potential of carbon-wrapped MOF catalysts in advancing the sustainable utilization of lignin and fostering the growth of a more eco-friendly bioeconomy.

Constructing Functional Radiation-Resistant Thorium Clusters for Catalytic Redox Reactions.

When catalytic reactions are interfered with by radiation sources, thorium clusters are promising as potential catalysts due to their superior radiation resistance. However, there is currently very little research on the design synthesis and catalytic application of radiation-stable thorium clusters. In this work, we have elaborately engineered and fabricated three high-nuclear thorium cluster catalysts denoted as Th12L3-MA12, Th12L3-MA6-BF6, and Th12L3-Fcc12, which did not undergo any significant alterations in their molecular structures and compositions after irradiation with 690 kGy γ-rays. We systematically investigated the photocatalytic/thermocatalytic properties of these radiation-resistant thorium clusters for the first time and found that γ-rays could not alter their catalytic activities. In addition, it was found that ligand engineering could modulate the catalytic activity of thorium clusters, thus expanding the range of catalytic applications of thorium clusters, including reduction reactions (nitroarene reduction) and some oxidation reactions (N-heterocyclic oxidative dehydrogenation and diphenylmethane oxidation). Meanwhile, all of these organic transformation reactions achieved a >80% conversion and nearly 100% product selectivity. Radiation experiments combined with DFT calculations showed that the synergistic catalysis of thorium-oxo core and ligands led to the generation of specific active species (H+, O2•-, or tBuO/tBuOO•) and activation of substrate molecules, thus achieving superior catalytic performance. This work is not only the first to develop radiation-resistant thorium cluster catalysts to perform efficient redox reactions but also provides design ideas for the construction of high-nuclearity thorium clusters under mild conditions.

Significant Promotional Effect of Nb Doping in Bifunctional Pd/WOx Nanocatalysts on One‐Step Benzene Hydroalkylation

AbstractThe development of high‐efficiency heterogeneous bifunctional metal‐acid catalysts with an appropriate metal‐acid balance for the production of cyclohexylbenzene (CHB) via the one‐step tandem benzene hydroalkylation still faces a dilemma because of the difficulty in inhibiting the over hydrogenation of benzene substrate and cyclohexene intermediate and controlling target product selectivity. In this study, Nb‐doped WOx supported Pd nanocatalysts were developed. It has been shown that doping Nb into WOx supports altered surface properties and microstructures of catalysts, resulting in the generation of more surface acidic sites and defective W−Ov−Nb structures (Ov: oxygen vacancies). As‐constructed Pd‐based nanocatalyst with only 0.1 wt % Pd loading and a Nb/(Nb+W) molar ratio of 0.25 exhibited superior catalytic benzene hydroalkylation performance to undoped supported Pd catalyst, with a much higher yield of CHB (35.6 %) at 220 °C. It was authenticated that highly dispersed Pd sites facilitated the dissociation of hydrogen molecules, defective W−Ov−Nb structures were conductive to the surface transfer of active hydrogen species, a large number of acidic sites favored benzene/cyclohexene intermediate adsorption, and abundant Brønsted acidic sites promoted the alkylation between cyclohexene intermediate formed and benzene. Accordingly, excellent cooperative catalysis between Pd sites, acidic sites, and oxygen vacancies contributed to improved catalytic performance of Nb‐doped WOx supported Pd catalysts in benzene hydroalkylation. This research presents an alternative for the creation of low‐cost practical bifunctional metal‐acid catalysts for highly efficient benzene hydroalkylation.

Facile preparation of alkali metal‐modified hollow nanotubular manganese‐based oxide catalysts and their excellent catalytic soot combustion performance

AbstractThe soot emitted during the operation of diesel engine exhaust seriously threatens the human health and environment, so treating diesel engine exhaust is critical. At present, the most effective method for eliminating soot particles is post‐treatment technology. Preparation of economically viable and highly active soot combustion catalysts is a pivotal element of post‐treatment technology. In this study, different single‐metal oxide catalysts with fibrous structures and alkali metal‐modified hollow nanotubular Mn‐based oxide catalysts were synthesized using centrifugal spinning method. Activity evaluation results showed that the manganese oxide catalyst has the best catalytic activity among the prepared single‐metal oxide catalysts. Further research on alkali metal modification showed that doping alkali metals is beneficial for improving the oxidation state of manganese and generating a large number of reactive oxygen species. Combined with the structural effect brought by the hollow nanotube structure, the alkali metal‐modified Mn‐based oxide catalysts exhibit superior catalytic performance. Among them, the Cs‐modified Mn‐based oxide catalyst exhibits the best catalytic performance because of its rich active oxygen species, excellent NO oxidation ability, abundant Mn4+ ions (Mn4+/Mnn+ = 64.78%), and good redox ability. The T10, T50, T90, and CO2 selectivity of the Cs‐modified Mn‐based oxide catalyst were 267°C, 324°C, 360°C, and 97.8%, respectively.

Engineering Lewis-Acid Defects on ZnO Quantum Dots by Trace Transition-Metal Single Atoms for High Glycerol-to-Glycerol Carbonate Conversion.

Efficient conversion of biomass wastes into valuable chemicals has been regarded as a sustainable approach for green and circular economy. Herein, a highly efficient catalytic conversion of glycerol (Gly) into glycerol carbonate (GlyC) by carbonylation with the commercially available urea is presented using low-cost transition metal single atoms supported on zinc oxide quantum dots (M1-ZnO QDs) as a catalyst without using any solvent. A facile one-step wet chemical synthesis allows various types of metal single atoms to simultaneously dope and introduce Lewis-acid defects in the ZnO QD structure. It is found that doping with a trace amount of isolated metal atoms greatly boosts the catalytic activity with Gly conversion of 90.7%, GlyC selectivity of 100.0%, and GlyC yield of 90.6%. Congruential results from both Density Functional Theory (DFT)and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) studies reveal that the superior catalytic performance can be attributed to the enriched Lewis acid sites that endow optimal adsorption, formation of the intermediate for coupling between urea and Gly, and desorption of GlyC. Moreover, the tiny size of ZnO QDs efficiently promotes the accessibility of these active sites to the reactants.

Tailoring oxygen vacancies by synergy of dual metal cations in LaCo0.8M0.2O3 (M = Cu, Ni, Fe, Mn) towards catalytic oxidation of toluene

Enhancing the catalytic performance of transition metal oxide catalysts is prerequisite for the efficient catalytic oxidation of VOCs. Here the B-site partially substituted LaCoO3 (LaCo0.8M0.2O3, M = Cu, Ni, Fe and Mn) catalysts was synthesized for the catalytic oxidation of toluene. Among these catalysts, LaCo0.8Ni0.2O3 catalyst exhibits remarkable catalytic performance for toluene with T50 = 226 °C and T90 = 239 °C at an initial toluene concentration of 1000 ppm, whose T50 (and T90) reduced by 13 °C (and 34 °C) compared with that of LaCoO3. Confirmed by BET, XPS, and EPR characterizations, Ni substitution improves the specific surface area, Co3+/Co2+ ratio, Oads/Olatt ratio, and oxygen vacancies concentration. This improvement indicates the improvement of adsorption and activation of reactant, mobility of oxygen species, thereby contributing to the superior catalytic performance in toluene oxidation. The B-site of LaCoO3 occupied by dual cations caused the lattice distortion and formation of oxygen vacancies due to the ionic radii difference between Co and Ni cations. Moreover, the apparent activation energy of LaCo0.8Ni0.2O3, as the determining factor for the catalytic oxidation rate, was remarkably reduced. Our findings confirmed the synergy effect of Co and Ni cations at B-site on the enhancement of catalytic activity, which provides a promising strategy for oxygen vacancy engineering.

Electrosynthesis of Transition Metal Coordinated Polymers for Active and Stable Oxygen Evolution

Transition metal coordination polymers (TM‐CP) are promising inexpensive and flexible electrocatalysts for oxygen evolution reaction in water electrolysis, while their facile synthesis and controllable regulation remain challenging. Here we report an anodic oxidation‐electrodeposition strategy for the growth of TM‐CP (TM = Fe, Co, Ni, Cr, Mn; CP = polyaniline, polypyrrole) films on a variety of metal substrates that act as both catalyst supports and metal ion sources. An exemplified bimetallic NiFe‐polypyrrole (NiFe‐PPy) features superior mechanical stability in friction and exhibits high activity with long‐term durability in alkaline seawater (over 2000 h) and anion exchange membrane electrolyzer devices at current density of 500 mA cm−2. Spectroscopic and microscopic analysis unravels the configurations with atomically distributed metal sites induced by d‐π conjugation, which transforms into a mosaic structure with NiFe (oxy)hydroxides embedded in PPy matrix during oxygen evolution. The superior catalytic performance is ascribed to the anchoring effect of PPy that inhibits the metal dissolution, the strong substrate‐to‐catalyst interaction that ensures good adhesion, and the Fe/Ni−N coordination that modulates the electronic structures to facilitate the deprotonation of *OOH intermediate. This work provides a general strategy and mechanistic insight into building robust inorganic/polymer composite electrodes for oxygen electrocatalysis.

Electrosynthesis of Transition Metal Coordinated Polymers for Active and Stable Oxygen Evolution.

Transition metal coordination polymers (TM-CP) are promising inexpensive and flexible electrocatalysts for oxygen evolution reaction in water electrolysis, while their facile synthesis and controllable regulation remain challenging. Here we report an anodic oxidation-electrodeposition strategy for the growth of TM-CP (TM = Fe, Co, Ni, Cr, Mn; CP = polyaniline, polypyrrole) films on a variety of metal substrates that act as both catalyst supports and metal ion sources. An exemplified bimetallic NiFe-polypyrrole (NiFe-PPy) features superior mechanical stability in friction and exhibits high activity with long-term durability in alkaline seawater (over 2000 h) and anion exchange membrane electrolyzer devices at current density of 500 mA cm-2. Spectroscopic and microscopic analysis unravels the configurations with atomically distributed metal sites induced by d-π conjugation, which transforms into a mosaic structure with NiFe (oxy)hydroxides embedded in PPy matrix during oxygen evolution. The superior catalytic performance is ascribed to the anchoring effect of PPy that inhibits the metal dissolution, the strong substrate-to-catalyst interaction that ensures good adhesion, and the Fe/Ni-N coordination that modulates the electronic structures to facilitate the deprotonation of *OOH intermediate. This work provides a general strategy and mechanistic insight into building robust inorganic/polymer composite electrodes for oxygen electrocatalysis.