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To replace the noble metal catalysts for oxygen reduction reaction (ORR), a Ni@C-supported N-doped carbon material (Ni@C/NC) is in-situ prepared via one-step pyrolyzing the polymerizable ionic liquid of vinyl imidazole combined with Ni(NO 3) 2. Systemic investigations demonstrate that these nanosized Ni particles are tightly wrapped with a thin carbon layer to form the core/shell structure, meanwhile carbon capsules are synchronously yielded on the carbon matrix. As a result, both the carbon shell and the carbon capsule jointly increase the active sites of the Ni@C/NC, while the carbon shell also contributes the fast electron-transfer from Ni particle. Compared with the normal Ni-supported carbon catalyst, the Ni@C/NC shows the respectable ORR performance with the onset and half-wave potentials of 0.96 and 0.84 V RHE. After the long-term electrocatalysis (10 h), the Ni@C/NC is found to possess the great structural and electrocatalytic stabilities, which maintains 93 % of the initial current density and the well-dispersed and uniform Ni@C particles. Subsequently, a Zn-Air battery with the Ni@C/NC cathode is assembled and exhibits a peak power density of 200 mW cm−2. Therefore, the as-obtained Ni@C/NC with the high electroactivity and stability can be expected as an ideal candidate to apply in the metal-air batteries and fuel cells in the future. Ni particles wrapped with a thin carbon layer is in-situ formed and supported on a N-doped carbon with many capsules, fabricating the Ni@C/NC catalyst, which exhibit the superior catalytic performance for oxygen reduction. [Display omitted] • A Ni@C-supported N-doped carbon material is in-situ prepared. • Nanosized Ni particles are wrapped with a thin carbon layer. • Carbon capsules are synchronously yielded on the carbon matrix. • The Ni@C/NC shows the respectable ORR performance. • The Ni@C/NC possesses the great structural and electrocatalytic stabilities. [ABSTRACT FROM AUTHOR]

The structural tailoring of Pt‐based catalysts into 1D nanowires for oxygen reduction reactions (ORR) has been a focus of research. Mo(CO)6 is commonly used as a morphological modifier to form nanowires, but it is found that it inevitably leads to Mo doping. This doping introduces unique electrochemical signals not seen in other Pt‐based catalysts, which can directly reflect the stability of the catalyst. Through experiments, it is demonstrated that Mo doping is detrimental to ORR performance, and theoretical calculations have shown that Mo sites that are inherently inactive also poison the ORR activity of the surrounding Pt. Therefore, a novel gas‐assisted technique is proposed to replace Mo(CO)6 with CO, which forms ultrafine nanowires with an order of magnitude increase in length, ruling out the effect of Mo. The catalyst performs at 1.24 A mgPt−1, 7.45 times greater than Pt/C, demonstrating significant ORR mass activity, and a substantial improvement in stability. The proton exchange membrane fuel cell using this catalyst provides a higher power density (0.7 W cm−2). This study presents a new method for the preparation of ultra‐long nanowires, which opens up new avenues for future practical applications of low‐Pt catalysts in PEMFC. [ABSTRACT FROM AUTHOR]

The electrochemical production of hydrogen peroxide (H2O2) using metal‐free catalysts has emerged as a viable and sustainable alternative to the conventional anthraquinone process. However, the precise architectural design of these electrocatalysts poses a significant challenge, requiring intricate structural engineering to optimize electron transfer during the oxygen reduction reaction (ORR). Herein, we introduce a novel design of covalent organic frameworks (COFs) that effectively shift the ORR from a four‐electron to a more advantageous two‐electron pathway. Notably, the JUC‐660 COF, with strategically charge‐modified benzyl moieties, achieved a continuous high H2O2 yield of over 1200 mmol g−1 h−1 for an impressive duration of over 85 hours in a flow cell setting, marking it as one of the most efficient metal‐free and non‐pyrolyzed H2O2 electrocatalysts reported to date. Theoretical computations alongside in situ infrared spectroscopy indicate that JUC‐660 markedly diminishes the adsorption of the OOH* intermediate, thereby steering the ORR towards the desired pathway. Furthermore, the versatility of JUC‐660 was demonstrated through its application in the electro‐Fenton reaction, where it efficiently and rapidly removed aqueous contaminants. This work delineates a pioneering approach to altering the ORR pathway, ultimately paving the way for the development of highly effective metal‐free H2O2 electrocatalysts. [ABSTRACT FROM AUTHOR]

The electrochemical production of hydrogen peroxide (H2O2) using metal‐free catalysts has emerged as a viable and sustainable alternative to the conventional anthraquinone process. However, the precise architectural design of these electrocatalysts poses a significant challenge, requiring intricate structural engineering to optimize electron transfer during the oxygen reduction reaction (ORR). Herein, we introduce a novel design of covalent organic frameworks (COFs) that effectively shift the ORR from a four‐electron to a more advantageous two‐electron pathway. Notably, the JUC‐660 COF, with strategically charge‐modified benzyl moieties, achieved a continuous high H2O2 yield of over 1200 mmol g−1 h−1 for an impressive duration of over 85 hours in a flow cell setting, marking it as one of the most efficient metal‐free and non‐pyrolyzed H2O2 electrocatalysts reported to date. Theoretical computations alongside in situ infrared spectroscopy indicate that JUC‐660 markedly diminishes the adsorption of the OOH* intermediate, thereby steering the ORR towards the desired pathway. Furthermore, the versatility of JUC‐660 was demonstrated through its application in the electro‐Fenton reaction, where it efficiently and rapidly removed aqueous contaminants. This work delineates a pioneering approach to altering the ORR pathway, ultimately paving the way for the development of highly effective metal‐free H2O2 electrocatalysts. [ABSTRACT FROM AUTHOR]

The development of high active and stable Pt−M (M=transition metals) electrocatalysts for oxygen reduction reaction (ORR) is crucial for the commercialization of proton exchange membrane fuel cells (PEMFCs). The main challenge of Pt−M electrocatalysts is their instability, mainly due to the leaching of M. In this study, we report the design of P and O co‐doped octahedral PtCo alloy on Ketjen carbon black (Px‐Oct PtCo/C) through a seed‐mediated synthesis. In‐situ FTIR spectroscopy revealed that P0.61‐Oct PtCo/C has the lowest d‐band center, thereby enhancing the catalytic activity. The strong interaction formed by chemical bond between O and Co in Px‐Oct PtCo/C, observed by EXAFS spectra effectively inhibited the dissolution of Co and improved the ORR stability. The mass activity and specific activity of P0.61‐Oct PtCo/C can reach 0.61 A mgPt−1 and 2.4 mA cm−2, respectively, which is 4.1 times and 10.9 times higher than that of commercial Pt/C. After 50,000 potential cycles, the loss of mass activity is only 25 %, surpassing the DOE 2025 target of less than 40 % loss after 30,000 cycles. This study offers an alternative approach to enhancing the activity and durability of Pt−M electrocatalysts for the ORR. [ABSTRACT FROM AUTHOR]

Activation, break‐in, and/or pre‐treatment protocols are generally applied to energy conversion devices before regular operation to reach stable performance. There remains much to understand about the relationships among physical properties, performance, and electrochemical pre‐treatments. Here, a design‐of‐experiments (DoE) strategy is employed to address this gap by demonstrating the influence of five pre‐treatment parameters for carbon‐supported Pt‐nanoparticle catalysts on the electrocatalytic oxygen reduction reaction (ORR). A subset of pre‐treatments, developed using a central composite design, are tested in a flow cell combined with an inductively‐coupled plasma mass spectrometer (on‐line ICP‐MS). The DoE‐based approach facilitates comprehensive insights from two orders of magnitude fewer experiments than a conventional grid search. The coupled on‐line ICP‐MS setup enables effective catalysis and real‐time catalyst dissolution data. Leveraging insights from DoE for on‐line ICP‐MS and additional characterization, a model is built between the degradation of a multi‐dimensional supported Pt surface, its performance, and applied electrochemical parameters. These investigations identify surface modifications, such as oxidation, and subsequent restructuring of Pt during pre‐treatment as a primary cause of performance deterioration during ORR. By combining DoE with advanced characterization techniques, a powerful approach is demonstrated to gain a mechanistic understanding of pre‐treatment protocols that can be broadly adapted to various reaction chemistries. [ABSTRACT FROM AUTHOR]

Strategies for discovery of high‐performance electrocatalysts are important to advance clean energy technologies. Metastable phases such as low temperature or interfacial structures that are difficult to access in bulk may offer such catalytically active surfaces. We report here that the suboxide Zr3O, which is formed at Zr−ZrO2 interfaces but does not appear in the experimental Zr−O phase diagram exhibits outstanding oxygen reduction reaction (ORR) performance surpassing that of benchmark Pt/C and most transition metal‐based catalysts. Addition of Fe3C nanoparticles to give a Zr−Zr3O−Fe3C/NC catalyst (NC=nitrogen‐doped carbon) gives a half‐wave potential (E1/2) of 0.914 V, outperforming Pt/C and showing only a 3 mV decrease after 20,000 electrochemical cycles. A zinc‐air battery (ZAB) using this cathode material has a high power density of 241.1 mW cm−2 and remains stable for over 50 days of continuous cycling, demonstrating potential for practical applications. Zr3O demonstrates that interfacial or other phases that are difficult to stabilize may offer new directions for the discovery of high‐performance electrocatalysts. [ABSTRACT FROM AUTHOR]

Strategies for discovery of high‐performance electrocatalysts are important to advance clean energy technologies. Metastable phases such as low temperature or interfacial structures that are difficult to access in bulk may offer such catalytically active surfaces. We report here that the suboxide Zr3O, which is formed at Zr−ZrO2 interfaces but does not appear in the experimental Zr−O phase diagram exhibits outstanding oxygen reduction reaction (ORR) performance surpassing that of benchmark Pt/C and most transition metal‐based catalysts. Addition of Fe3C nanoparticles to give a Zr−Zr3O−Fe3C/NC catalyst (NC=nitrogen‐doped carbon) gives a half‐wave potential (E1/2) of 0.914 V, outperforming Pt/C and showing only a 3 mV decrease after 20,000 electrochemical cycles. A zinc‐air battery (ZAB) using this cathode material has a high power density of 241.1 mW cm−2 and remains stable for over 50 days of continuous cycling, demonstrating potential for practical applications. Zr3O demonstrates that interfacial or other phases that are difficult to stabilize may offer new directions for the discovery of high‐performance electrocatalysts. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Facile mass transport channel and accessible active sites are crucial for binder‐free air electrode catalysts in rechargeable flexible zinc‐air battery (ZAB). Herein, a ZnS/NH3 dual‐assisted pyrolysis strategy is proposed to prepare N/S‐doped hierarchical porous bamboo carbon cloth (HP‐NS‐BCC) as binder‐free air electrode catalyst for ZAB. BCC fabric with abundant micropores is firstly used as flexible carbon support to facilitate the heteroatom‐doping and construct the hierarchical porous structure. ZnS nanospheres and NH3 activization together facilitate the electronic modulation of carbon matrix by N/S‐doping and optimize the macro/meso/micropores structure of carbon fibers. Benefiting from the highly‐exposed N/S‐induced sites with enhanced intrinsic activity, the optimized mass transport of biocarbon fibers, as well as the ultra‐large specific surface area of 2436.1 m2·g–1, the resultant HP‐NS‐BCC catalyst exhibits improved kinetics for oxygen reduction/evolution reaction. When applied to rechargeable aqueous ZABs, it achieves a significant peak power density of 249.1 mW·cm−2. As binder‐free air electrode catalyst, the flexible ZAB also displays stable cycling over 500 cycles with a minimal voltage gap of 0.42 V, showcasing promising applications in flexible electronic devices. [ABSTRACT FROM AUTHOR]

Diatomic catalysts (DACs), as a frontier of research on atomically dispersed catalysts, have drawn great attention, especially in electrocatalysis. However, most of the current synthetic strategies for DACs suffer from poor efficiency and high cost. In this work, a novel noncovalent assembly strategy is reported for the efficient synthesis of DACs. By the aid of two kinds of noncovalent intermolecular force, the π–π stacking and Coulomb forces, a pair of metal complex ions with opposite electrical charges is spontaneously loaded onto the carbon substrate and transformed into diatomic sites via thermal treatment. This noncovalent assembly approach shows universal feasibility for a broad spectrum of DACs (Ir–Fe, Pt–Fe, Pt–Co, and Pt–Ni). To prove the practical utility, the as‐prepared PtFe‐DAC is deployed as oxygen reduction reaction catalyst, performing excellent activity with a half‐wave potential of 0.935 V (vs RHE) and a 2.3 times higher turnover frequency than that of the single‐atomic Fe‐SAC. In situ characterization and theoretical calculation indicate that the adjacent Pt sites could endow moderate activation of oxygen molecule on Fe sites by lowering the electron pairing energy as well as the modulation of the d‐band center and spin states of Fe centers propelling the desorption of the intermediates. [ABSTRACT FROM AUTHOR]

We propose an in situ gas etching-thermal assembly strategy to simultaneously create mesopore-dominated carbon cores with ultrathin carbon-layer shells fully decorated with highly dispersed Mn-N 4 single-atom sites, which was used as a highly active and stable ORR catalyst in zinc-air batteries. [Display omitted] Applications of zinc-air batteries are partially limited by the slow kinetics of oxygen reduction reaction (ORR); Thus, developing effective strategies to address the compatibility issue between performance and stability is crucial, yet it remains a significant challenge. Here, we propose an in situ gas etching-thermal assembly strategy with an in situ -grown graphene-like shell that will favor Mn anchoring. Gas etching allows for the simultaneous creation of mesopore-dominated carbon cores and ultrathin carbon layer shells adorned entirely with highly dispersed Mn-N 4 single-atom sites. This approach effectively resolves the compatibility issue between activity and stability in a single step. The unique core–shell structure allows for the full exposure of active sites and effectively prevents the agglomerations and dissolution of Mn-N 4 sites in cores. The corresponding half-wave potential for ORR is up to 0.875 V (vs. reversible hydrogen electrode (RHE)) in 0.1 M KOH. The gained catalyst (Mn-N@Gra-L)-assembled zinc-air battery has a high peak power density (242 mW cm−2) and a durability of ∼ 115 h. Furthermore, replacing the zinc anode achieved a stable cyclic discharge platform of ∼ 20 h at varying current densities. Forming more fully exposed and stable existing Mn-N 4 sites is a governing factor for improving the electrocatalytic ORR activity, significantly cycling durability, and reversibility of zinc-air batteries. [ABSTRACT FROM AUTHOR]

This study introduces a novel combination of sulfur-doped reduced graphene oxide (S-rGO), zinc ferrite (ZnFe 2 O 4) and nickel cobalt layered double hydroxide (NiCoLDH) as an efficient and low-cost electrocatalyst for oxygen reduction reaction (ORR) for the first time. The hydrothermal method is used to synthesize all samples including graphene oxide (GO), S-rGO, NiCoLDH, ZnFe 2 O 4 and S-rGO/ZnFe 2 O 4 /NiCoLDH hybrids. X-ray diffraction (XRD) analysis, field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), energy dispersive x-ray analysis (EDX), electrochemical surface area (ECSA), and fourier transform infrared spectroscopy (FTIR) analysis are used to determine the structure of synthesized electrocatalysts, physical properties, and morphology. The electrochemical measurements are carried out using cyclic voltammetry (CV), linear scanning voltammetry (LSV), chronoamperometry (ChA), and electrochemical impedance spectroscopy (EIS). The results for all samples are compared with the Pt/C commercial catalyst. According to the electrochemical results, the S-rGO/ZnFe 2 O 4 /NiCoLDH electrocatalyst has the best electrochemical performance. Moreover, the nanocomposite exhibited better electrocatalysis, a high diffusion limiting current density of −5.4 mA cm−2 and an onset potential of 0.03 V. Based on the results of this study, the LDH enhances electrical conductivity, electrocatalytic activity, active surface area, and stability of the catalyst for ORR after combining with carbon bases and ferrite. [Display omitted] • An electrochemical method was utilized for NiCo-LDH on S-rGO/ZnFe 2 O 4. • S doped reduced graphene oxide was used in a composite for improving its ORR activity. • NiCo-LDH was used as electrocatalyst for ORR. • S-rGO/ZnFe 2 O 4 /NiCo-LDH hybrid showed better ORR activity. [ABSTRACT FROM AUTHOR]

During the past few years, single‐atom catalysts (SACs) have attracted considerable attention in electrolysis due to their outstanding catalytic performance and efficient atomic utilization. SACs exhibit a simple structure, high catalytic activity, consistent scaling relationships for single sites, and low metal content but their practical applications are still limited. Dual single‐atom catalysts (DACs), which feature excellent selectivity, high atomic utilization efficiency, and remarkable stability, are emerging as new frontiers in heterogeneous electrocatalysis. They increase catalytic activity by promoting synergistic effects between metal‐active sites. In this paper, we present a comprehensive overview of the latest developments in dual‐atom catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In addition, we explore the differences between homonuclear and heteronuclear configurations, the emergence of single/dual‐site metal catalysts, and the methods currently used for their synthesis. Lastly, this review discusses several perspectives for advancing the development of dual‐atom catalysts for OER and ORR electrocatalysis. [ABSTRACT FROM AUTHOR]

We explored two methods for synthesizing Pd nanoparticles using three different carbide-derived carbon (CDC) support materials, one of which was nitrogen-doped. These materials were studied for oxygen reduction reaction (ORR) in 0.1 M KOH solution, and the resulting CDC/Pd catalysts were characterized using TEM, XRD, and XPS. The citrate method and the polyol method using polyvinylpyrrolidone (PVP) as a capping agent were employed to elucidate the impact of the support material on the final catalyst. The N-doping of the CDC material resulted in smaller Pd nanoparticles, but only in the case of the citrate method. This suggests that the influence of support is weaker when using the polyol method. The citrate method with CDC1, which is predominantly microporous, led to a higher degree of agglomeration and formation of larger particles in comparison to supports, which possessed a higher degree of mesoporosity. We achieved smaller Pd particle sizes using citrate and NaBH4 compared to the ethylene glycol PVP method. Pd deposited on CDC2 and CDC3 supports showed similar specific activity (SA), suggesting that the N-doping did not significantly influence the ORR process. The highest SA value was observed for CDC1/Pd_Cit, which could be attributed to the formation of larger Pd particles and agglomerates. [ABSTRACT FROM AUTHOR]

Due to structural complexity and limited understanding, precise chemical modification in atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts requires theoretical calculations to optimize electronic, geometric, and catalytic performance and experimental implementation of learned lessons to improve their catalytic performance towards oxygen reduction reaction (ORR). Herein, we conducted a density functional theory (DFT) investigation to understand the effect of the replacement of O-atoms in Fe–O 4 –C by N-atoms in the first coordination shell of Fe-site (constructing five models: Fe–O 4 –C, Fe–O 3 N–C, Fe–N 2 O 2 –C, Fe–ON 3 –C and Fe–N 4 –C) towards ORR. The geometric and electronic calculations of these models suggested that replacing all the O-atoms with N-atoms around the Fe-site would make it more conducive to the adsorption of ORR intermediates. Moreover, the Gibbs free energy calculations demonstrated that the Fe-site becomes the active centre for 2e− ORR, leading to the dominant generation of H 2 O 2 when Fe is coordinated with four O-atoms (Fe–O 4 –C). Whereas in compounds like Fe–N 2 O 2 –C, Fe–O 3 N–C, and Fe–N 4 –C, where the Fe-site displays 4e− ORR, form water is a preferred product if the O-atoms are replaced by N-atoms, as in Fe–N 2 O 2 –C, Fe–O 3 N–C, and Fe–N 4 –C. This study would provide a fundamental understanding of how atomically dispersed M-N-C catalysts' electrocatalytic activity is affected by changes in the coordination environment of metal sites. [Display omitted] • A theoretical approach was used to construct the models of Fe-NxOy-C-based electrocatalysts. • The models Fe–O 4 –C, Fe–NO 3 –C, M–N 2 O 2 –C, M–N 3 O–C, and M-N4-C, were completely investigated via DFT approaches. • The O 2 adsorption at the Fe–N 4 –C catalyst was the determining step during the associative pathway. • The M-N 4 -C catalytic moel displayed 4e- ORR, while the M-O 4 -C catalyst showed 2e- ORR. [ABSTRACT FROM AUTHOR]

Electrochemical oxygen reduction reaction (ORR) via the 2e− pathway in an acidic media shows great techno-economic potential for the production of hydrogen peroxide. Currently, carbon-based single-atom catalysts (C-SACs) have attracted extensive attention due to their tunable electronic structures, low cost, and sufficient stability in acidic media. This review summarizes recent advances in metal centers and their coordination environment in C-SACs for 2e−-ORR. Firstly, the reaction mechanism of 2e−-ORR on the active sites of C-SACs is systematically presented. Secondly, the structural regulation strategies for the active sites of 2e−-ORR are further summarized, including the metal active center, its species and configurations of nitrogen coordination or heteroatom coordination, and their near functional groups or substitute groups, which would provide available and proper ideas for developing superior acidic 2e−-ORR electrocatalysts of C-SACs. Finally, we propose the current challenges and future opportunities regarding the acidic 2e−-ORR pathway on C-SACs, which will eventually accelerate the development of the distributed H2O2 electrosynthesis process. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) represents a cornerstone for many clean energy conversion technologies such as fuel cells and metal‐air batteries. Nevertheless, the commercialization of these technologies is largely impeded by the slow kinetics of ORR, for which active, durable and cost‐effective ORR catalysts are needed. In recent years, zeolitic imidazolate framework (ZIF) derived carbon materials emerge as a new class of non‐precious metal catalysts (NPMCs) toward ORR, largely benefiting from their high surface area, abundant porosity, tunable chemical/electronic structure, and superior ORR activity which is comparable or even surpasses those state‐of‐the‐art Pt‐based ORR catalysts. This review offers a comprehensive overview of the recent advances in ZIF‐derived carbons for ORR. The synthesis strategies and the key factors affecting the ORR performance of ZIF‐derived carbon materials are discussed. Future research directions and perspectives on exploring ZIF derived carbons as efficient ORR catalysts are highlighted, with a focus on the principles of rationally engineering the coordination structures of active sites. [ABSTRACT FROM AUTHOR]

With respect to the potential of palladium (Pd)‐based nanomaterials in catalyzing typical electrochemical reactions, herein, a strategy that couples the quick Joule‐heating with a solid phase synthesis for producing carbon‐supported Pd–Se nanoparticles with welcome features is reported, e.g., fine sizes, clean surfaces, and controlled crystal phases toward electrocatalysis of oxygen reduction reaction (ORR) and ethanol oxidation reaction (EOR) in an alkaline medium. Principally, the introduction of Se into Pd alters its electronic properties and weakens the adsorption of key reaction intermediates on the Pd–Se nanoparticles during the ORR and EOR process, thus endowing them with better electrocatalysis for the same electrochemical reactions. Impressively, the carbon‐supported Pd–Se nanoparticles exhibit phase‐dependent electrocatalysis toward ORR and EOR. In particular, the cubic Pd17Se15 nanoparticles supported on carbon substrate show mass activity of 0.206 A mgPd−1 and specific activity of 0.546 mA cm−2 at 0.9 V for ORR in 0.1 m KOH electrolyte, while the orthorhombic PdSe2 nanoparticles show a mass activity of 3.79 A mgPd−1 for EOR, higher than that of their cubic counterpart and commercial Pd/C catalyst. The universality of this synthetic strategy in manufacturing carbon‐supported noble metal chalcogenide nanoparticles and highlighting its potential in designing highly efficient electrocatalysts are emphasized. [ABSTRACT FROM AUTHOR]

Pt nanoparticles are electrodeposited on nitrogen-doped graphene nanosheets using different electrodeposition procedures such as cyclic voltammetry, chronoamperometry and pulse deposition while keeping the overall deposition time and precursor concentration constant. A comparison of electrodeposition in Ar-saturated and O2-saturated solutions was also made to study the influence of competing oxygen reduction and hydrogen adsorption/desorption on the electroreduction of Pt ions. Scanning electron microscopy results showed that the surface morphology of the Pt catalysts is dependent on the electrodeposition protocol and nucleation overpotential. The particle size and number density of the electrodeposited Pt nanoparticles vary from sample to sample. Cyclic voltammetry and CO stripping experiments in 0.1 M HClO4 solution showed different surface electrochemistry of the Pt catalysts. Rotating disk electrode measurement revealed that all the catalysts are highly active towards the oxygen reduction reaction in perchloric acid. [ABSTRACT FROM AUTHOR]

Li-O2 batteries are considered a highly promising energy storage solution. However, their practical implementation is hindered by the sluggish kinetics of the oxygen reduction (ORR) and oxygen evolution (OER) reactions at cathodes during discharging and charging, respectively. In this work, we investigated the catalytic performance of Wn+1Cn and Wn+1CnO2 MXenes (n = 1, 2, and 3) as cathodes for Li-O2 batteries using first principles calculations. Both Wn+1Cn and Wn+1CnO2 MXenes show high conductivity, and their conductivity is further enhanced with increasing atomic layers, as reflected by the elevated density of states at the Fermi level. The oxygen functionalization can change the electronic properties of WC MXenes from the electrophilic W surface of Wn+1Cn to the nucleophilic O surface of Wn+1CnO2, which is beneficial for the activation of the Li-O bond, and thus promotes the Li+ deintercalation during the charge–discharge process. On both Wn+1Cn and Wn+1CnO2, the rate-determining step (RDS) of ORR is the formation of the (Li2O)2* product, while the RDS of OER is the LiO2* decomposition. The overpotentials of ORR and OER are positively linearly correlated with the adsorption energy of the RDS LixO2* intermediates. By lowering the energy band center, the oxygen functionalization and increasing atomic layers can effectively reduce the adsorption strength of the LixO2* intermediates, thereby reducing the ORR and OER overpotentials. The W4C3O2 MXene shows immense potential as a cathode catalyst for Li-O2 batteries due to its outstanding conductivity and super-low ORR, OER, and total overpotentials (0.25, 0.38, and 0.63 V). [ABSTRACT FROM AUTHOR]

Bimetallic phosphides are considered as promising electrocatalysts for zinc–air batteries toward oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). To address the semi‐conductor inherent low electronic conductivity and catalytic activity, a polymetal‐chelated strategy is employed to in situ fabricate bimetallic nanophosphides within carbon matrix anchoring by chemical bonding. The employment of biomolecule polydopamine (PDA) efficiently anchors various transition metal ions due to its strong chelating capability via inherent functional groups. Furthermore, the chelation of multi‐metal ion is proved to promote the formation of graphitic nitrogen. The bimetallic FexCoyP phosphides nanoparticles are intimately encapsulated in carbon matrix through in situ carbonization and phosphatization processes. When utilized in Zinc–air batteries, Fe0.20Co0.80P anchored within N, P co‐doped sub‐microsphere (Fe0.20Co0.80P /PNC) exhibit a maximum power density of 167 mW cm−2 and cycle life up to 270 cycles, with a round‐trip voltage of 0.955 V. The mechanisms for catalytic activity passivation are ascribed to the etching of nitrogen and oxidation of phosphorus in carbon matrix, as well as the oxidation of the surface phosphide on the sub‐microspheres. This study presents a promising candidate for advancing the further development of energy conversation catalysis. [ABSTRACT FROM AUTHOR]

Atomically dispersed active sites and hierarchical porosity in Fe–N–C catalyst materials are essential for efficient oxygen reduction reaction (ORR) electrocatalysis and effective mass transport, respectively. However, the majority of these catalysts fail to deliver outstanding electrocatalytic activity and stumble when used as cathode materials in fuel cells. Herein, we developed a catalyst with partially transformed metallic Fe into Fe-N x sites embedded in the carbonaceous matrix, and its excellent electrocatalytic performance is attributed to the hybrid nanoparticles and built-in Fe-N x site structures. The optimized Fe@Fe–N–C catalyst was tested for ORR performance both ex-situ using the rotating (ring)-disk electrode technique and in an anion exchange membrane fuel cell (AEMFC). The Fe@Fe–N–C electrocatalyst exhibited remarkably enhanced ORR activity in alkaline media with a half-wave potential of 0.822 V vs. reversible hydrogen electrode (RHE) and showed the maximum power density (P max) of 242 mW cm−2 in an AEMFC test, surpassing the peak power density obtained from the Pt/C cathode catalyst (P max = 220 mW cm−2) under H 2 –O 2 conditions. Therefore, the study provides a promising prospect for designing improved, cost-effective, and noble metal-free electrocatalysts for achieving high performance in AEMFCs. [Display omitted] • Hybrid Fe–N–C electrocatalysts with metallic Fe nanoparticles was developed. • A new strategy is proposed using melamine and N-hydroxysuccinimide to produce Fe–N–C. • The hybrid electrocatalyst with Fe and FeN x sites jointly promote the ORR activity. • The Fe@Fe–N–C cathode catalyst in AEMFC exhibits a peak power density of 242 mW cm−2. [ABSTRACT FROM AUTHOR]

Carbon nanotubes (CNTs) play vital role in electrocatalysis due to large surface area and unique one-dimensional conductivity, reducing electron scattering. The abundance of the defect sites in CNTs, the catalytically active sites vary based on synthesis methodology. While chemical vapor deposition (CVD) technique has been widely studied, a detailed correlation of the synthetic parameters in the floating catalyst method, with activity is missing. Scalability is also crucial to study as in CVD technique carbon vapor is injected into the furnace but floating catalyst method relies on in-situ vapor generation from solid carbon precursors. We have mapped catalyst dosage and reaction atmosphere's impact on electrocatalytic efficiency for various CNTs produced under different conditions towards the oxygen reduction reaction (ORR) and rationalised the variation in activity by spectroscopic evidences. Optimized CNTs exhibit a high electrocatalytic ORR efficiency with prolonged durability, highlighting the role of the interaction between CNTs and encapsulated iron nanoparticles in response to reaction atmosphere. [Display omitted] • Comprehensive study on floating-catalyst technique to produce bamboo-like CNTs. • Rational portrayal of synthesis parameters affecting catalytic efficiency of CNTs. • Influence of catalyst dosage in determining the conductivity of CNTs. • Synthesis atmosphere dictates synergistic role of encapsulated iron in ORR activity. [ABSTRACT FROM AUTHOR]

Beginning with the mechanism of ORR, this article integrates the preparation and application of Fe/N/C materials, analyzes the mechanism of efficient oxygen reduction electrocatalysis of Fe/N/C materials from the perspective of active sites, and elaborates on the stability issues encountered in the development of high-performance Fe/N/C materials. It further proposes suggestions and prospects for the application of Fe/N/C catalysts in fuel cells, providing references for the future development of Fe/N/C materials. [ABSTRACT FROM AUTHOR]

Recently, theoretical calculations have played an irreplaceable role in the discovery of electrocatalysts as a relatively time‐efficient, cost‐effective, and predictable method. More importantly, theoretical calculations can help screen out the best active reaction sites and modulate them accordingly, which is beneficial for the development of efficient catalysts. In this concept, we focus on the important role of theoretical calculations in determining catalytic active sites and understanding reaction mechanisms, emphasizing its importance in assisting the design and synthesis of efficient oxygen reduction reaction catalysts. Finally, we provide an outlook on the challenges and future development trend in this field. [ABSTRACT FROM AUTHOR]

High-entropy alloys (HEAs) are a class of metal alloys consisting of four or more molar equal or near-equal elements. HEA nanomaterials have garnered significant interest due to their wide range of applications, such as electrocatalysis, welding, and brazing. Their unique multi-principle high-entropy effect allows for the tailoring of the alloy composition to facilitate specific electrochemical reactions. This study focuses on the synthesis of high-purity HEA nanoparticles using the method of femtosecond laser ablation synthesis in liquid. The use of ultrashort energy pulses in femtosecond lasers enables uniform ablation of materials at significantly lower power levels compared to longer pulse or continuous pulse lasers. We investigate how various femtosecond laser parameters affect the morphology, phase, and other characteristics of the synthesized nanoparticles. An innovative aspect of our solution is its ability to rapidly generate multi-component nanoparticles with a high fidelity as the input multi-component target material at a significant yielding rate. Our research thus focuses on a novel synthesis of high-entropy alloying CuCoMn1.75NiFe0.25 nanoparticles. We explore the characterization and unique properties of the nanoparticles and consider their electrocatalytic applications, including high power density aluminum air batteries, as well as their efficacy in the oxygen reduction reaction (ORR). Additionally, we report a unique nanowire fabrication phenomenon achieved through nanojoining. The findings from this study shed light on the potential of femtosecond laser ablation synthesis in liquid (FLASiL) as a promising technique for producing high-purity HEA nanoparticles. [ABSTRACT FROM AUTHOR]

[Display omitted] • 1D zeolitic imidazolate framework-nanorod (ZIF-NR) has been prepared through facet engineering of the parental 2D ZIF-L. • The Co-NCR possesses rod-like morphology, metallic Co nanoparticle, high N content, and hierarchical porous structure. • Co-NCR exhibits superior ORR activity (E onset = 0.96 V, E 1/2 = 0.88 V). • Zinc-air battery assembled with Co-NCR exhibits high performance. The properties of metal–organic framework (MOF) nanocrystals are highly dependent on their sizes, morphologies, and exposed facets. Facet engineering of MOFs offers an efficient strategy to tailor the active sites and optimize the catalytic activity of both MOFs and their derivatives. In this study, we prepared 1D zeolitic imidazolate framework-nanorod (ZIF-NR) through facet engineering of the parental 2D ZIF-L. The introduction of cetyltrimethylammonium bromide (CTABr) surfactant into the synthesis solution hindered the crystal growth along the c -axis of leaf-like ZIF-L, resulting in the formation of 1D ZIF-NR. The derived Co nanoparticle encapsulated N doped carbon nanorod (denoted as Co-NCR) exhibited high activity and stability for electrocatalytic oxygen reduction reactions and Zn-air batteries. Facet engineering of a 2D MOF with a uniquely oriented layered structure demonstrates the possibility of designing novel electrocatalysts. [ABSTRACT FROM AUTHOR]

Anaerobic digestion (AD) was initially evaluated as a potential preprocessing method for preparing biomass-based carbon electrocatalysts in this study. The AD pretreatment succeeded in the structural depolymerization and nitrogen enrichment of Hybrid Pennisetum, which provided favorable conditions to achieve efficient and homogeneous nitrogen introduction due to microorganism community enrichment and provided a porous structure by degradation of the biodegradable components. The resulted biochar exhibited improved physiochemical properties including higher specific surface areas, nitrogen content and graphitization degree than that obtained from pyrolyzing raw biomass. These improvements were positively correlated with the AD time and showed to have enhanced the performance in oxygen reduction reaction and practical microbial fuel cell applications. Amongst the investigated samples, the obtained biochar pretreated by AD for 15 days exhibited the most excellent performance with an onset potential of 0.17 V (VS. saturated calomel electrode) and the maximal power density of 543.2 mW cm−2 assembled in microbial fuel cells. This study suggested applying AD as a new biological pretreatment in the preparation of biomass-based electrocatalysts, and provided a unique pathway for fabricating high-performance biochar-based catalysts by structure optimization and N-containing active sites construction via gentle biological method, thereby providing a cost-effective method to fabricate metal-free catalysts for oxygen reduction reaction. Highlights: Anaerobic digestion pretreatment was conducted to assist electrocatalyst preparation. The biological pretreatment succeeded in carbohydrates decomposition and nitrogen enrichment. Pretreatment derived biochar significantly increased the ORR activity and microbial fuel cell performance. [ABSTRACT FROM AUTHOR]

Single atom catalysts with defined local structures and favorable surface microenvironments are significant for overcoming slow kinetics and accelerating O2 electroreduction. Here, enriched tip‐like FeN4 sites (T−Fe SAC) on spherical carbon surfaces were developed to investigate the change in surface microenvironments and catalysis behavior. Finite element method (FEM) simulations, together with experiments, indicate the strong local electric field of the tip‐like FeN4 and the more denser interfacial water layer, thereby enhancing the kinetics of the proton‐coupled electron transfer process. In situ spectroelectrochemical studies and the density functional theory (DFT) calculation results indicate the pathway transition on the tip‐like FeN4 sites, promoting the dissociation of O−O bond via side‐on adsorption model. The adsorbed OH* can be facilely released on the curved surface and accelerate the oxygen reduction reaction (ORR) kinetics. The obtained T−Fe SAC nanoreactor exhibits excellent ORR activities (E1/2=0.91 V vs. RHE) and remarkable stability, exceeding those of flat FeN4 and Pt/C. This work clarified the in‐depth insights into the origin of catalytic activity of tip‐like FeN4 sites and held great promise in industrial catalysis, electrochemical energy storage, and many other fields. [ABSTRACT FROM AUTHOR]

Single atom catalysts with defined local structures and favorable surface microenvironments are significant for overcoming slow kinetics and accelerating O2 electroreduction. Here, enriched tip‐like FeN4 sites (T−Fe SAC) on spherical carbon surfaces were developed to investigate the change in surface microenvironments and catalysis behavior. Finite element method (FEM) simulations, together with experiments, indicate the strong local electric field of the tip‐like FeN4 and the more denser interfacial water layer, thereby enhancing the kinetics of the proton‐coupled electron transfer process. In situ spectroelectrochemical studies and the density functional theory (DFT) calculation results indicate the pathway transition on the tip‐like FeN4 sites, promoting the dissociation of O−O bond via side‐on adsorption model. The adsorbed OH* can be facilely released on the curved surface and accelerate the oxygen reduction reaction (ORR) kinetics. The obtained T−Fe SAC nanoreactor exhibits excellent ORR activities (E1/2=0.91 V vs. RHE) and remarkable stability, exceeding those of flat FeN4 and Pt/C. This work clarified the in‐depth insights into the origin of catalytic activity of tip‐like FeN4 sites and held great promise in industrial catalysis, electrochemical energy storage, and many other fields. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) are crystalline organic porous polymers that can be precisely integrated by building blocks to achieve pre‐designed composition, components, and functions, making them a powerful platform for the development of molecular devices in the field of electrocatalysis. The precise control of channel/dopant positions and highly ordered network structures of COFs provide an ideal material system for the applications of advanced electrocatalysis. In this paper, the topological structure design and synthesis methods of COFs are reviewed in detail, and their design principles are deeply analyzed. In addition, the applications of COFs and their derivatives in the field of electrocatalysis are systematically summarized and the optimization strategies are proposed. Finally, the application prospects of COFs and their derivatives in electrocatalysis and the challenges that may be encountered in the future are prospected, providing helpful guidance for future research. [ABSTRACT FROM AUTHOR]

Highlights: The advancement and current status of dual-atom catalysts are reported. The synergistic effects exhibited by recent dual-atom catalysts in mechanistic studies are classified and summarized. Challenges and prospects of dual-atom catalysts in synthesis, characterization, applications, and theory are discussed. The exploration of sustainable energy utilization requires the implementation of advanced electrochemical devices for efficient energy conversion and storage, which are enabled by the usage of cost-effective, high-performance electrocatalysts. Currently, heterogeneous atomically dispersed catalysts are considered as potential candidates for a wide range of applications. Compared to conventional catalysts, atomically dispersed metal atoms in carbon-based catalysts have more unsaturated coordination sites, quantum size effect, and strong metal–support interactions, resulting in exceptional catalytic activity. Of these, dual-atomic catalysts (DACs) have attracted extensive attention due to the additional synergistic effect between two adjacent metal atoms. DACs have the advantages of full active site exposure, high selectivity, theoretical 100% atom utilization, and the ability to break the scaling relationship of adsorption free energy on active sites. In this review, we summarize recent research advancement of DACs, which includes (1) the comprehensive understanding of the synergy between atomic pairs; (2) the synthesis of DACs; (3) characterization methods, especially aberration-corrected scanning transmission electron microscopy and synchrotron spectroscopy; and (4) electrochemical energy-related applications. The last part focuses on great potential for the electrochemical catalysis of energy-related small molecules, such as oxygen reduction reaction, CO2 reduction reaction, hydrogen evolution reaction, and N2 reduction reaction. The future research challenges and opportunities are also raised in prospective section. [ABSTRACT FROM AUTHOR]

Engineering the electronic configuration and intermediates adsorption behaviors of high‐performance non‐noble‐metal‐based catalysts for the sluggish oxygen reduction reaction (ORR) kinetics at the cathode is highly imperative for the development of anion exchange membrane fuel cells (AEMFCs), yet remains an enormous challenge. Herein, a rare‐earth metal oxide engineering tactic through the formation of Fe3O4/La2O3 heterostructures in N,O‐doped carbon nanospheres (Fe3O4/La2O3@N,O‐CNSs) for efficient oxygen reduction electrocatalysis is reported. The theoretical calculations reveal that the interfacial bonds formed by the La─O─Fe heterogeneous interface effectively optimize the electronic structure of the Fe d‐band center relative to the Fermi level, which results in a significant reduction of the reaction barriers of rate‐limiting steps during the ORR. The modulation in intermediates chemisorption enables Fe3O4/La2O3@N,O‐CNSs an outstanding ORR performance and improved stability, with a significantly higher half‐wave potential value (0.88 V). More impressively, this integrated catalyst delivers a remarkable power density of 148.7 mW cm−2 in practical AEMFC operating conditions, along with negligible performance degradation over 100 h using an H2‐air atmosphere, which is higher than commercial Pt/C‐coupled electrodes. The results presented here are believed to provide guidelines for fabricating high‐performance AEMFCs electrocatalysts in terms of heterointerface engineering and strong electronic coupling effect induced by rare‐earth oxides. [ABSTRACT FROM AUTHOR]

High‐entropy alloys (HEAs) have offered wide opportunities for materials discovery, property optimization, and application exploration. In spite of some encouraging progress, manipulating HEAs with functional morphology/mesostructure and controlled chemical orderliness remains a big challenge. In this manuscript, a powerful and general strategy to synthesizing libraries of mesoporous high‐entropy intermetallics (MHEIs) with controlled orderliness in both mesoscopic and atomic levels is reported for the first time. Final products feature an ordered polyhedral morphology and double‐gyroid mesostructure as well as long‐range L10 intermetallic phase and HEA composition, delivering multiple advantages for enhancing electrochemical performance in oxygen reduction reaction (ORR) and single rechargeable zinc–air battery. Specifically, MHEI‐PtPdFeCoNi affords remarkable ORR activity (0.63 A mg−1 for mass activity and 1.01 mA cm−2 for specific activity) and superior stability (≈87% activity retained for 50 000 cycles and chronoamperometry tests) compared with the MHEAs with disordered atomic arrangement and commercial Pt/C. The excellent performance comes from the optimized surface HEA multimetallization as well as ordered intermetallic and mesoporous structure that changes the chemisorption of O*/OH* intermediates and lowers the overall energy barrier of oxygen reduction. [ABSTRACT FROM AUTHOR]

Proper regulating morphology and rationally distributing of active sites in a catalyst is crucial for improving its electrocatalytic performance. In this study, we synthesized a series of porous urchin-like NiCo 2 O 4 structures through hydrothermal reaction and adjusted their morphologies and oxygen vacancies concentration by annealing them under different conditions. The resulting structure has interconnected pores that facilitate the fast transport of active species, assembled from many nanoneedles containing nanoparticles. Our results show that the porous urchin-like NiCo 2 O 4 structure obtained after annealing at 400 °C under an argon atmosphere has the largest surface coverage area for redox species and the richest oxygen vacancies. This configuration demonstrates excellent performance in both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline solution. Our findings offer a facile pathway to optimizing active sites on urchin-like NiCo 2 O 4 structures, which could serve as bifunctional electrocatalysts for direct methanol fuel cells (DMFCs). [Display omitted] • Porous urchin-like NiCo 2 O 4 structures were fabricated by the hydrothermal method. • Morphology and oxygen vacancies were tuned by annealing conditions simultaneously. • Optimized structure shows excellent performance in MOR and ORR in alkaline solution. [ABSTRACT FROM AUTHOR]

Electrocatalysts with atomically dispersed metal sites (e.g. metal‐nitrogen‐carbon) have been deemed as promising alternatives for noble‐metal catalysts in couples of electrocatalytic reactions. However, the modulation of such atomic sites and the understanding of their interactions are still highly challenging. Herein, we propose a unique supermolecule assembly‐profile coating strategy to prepare a series of diatomic electrocatalysts by profile coating of eight Prussian blue analogues (PBAs) on supramolecular supports respectively as bimetallic sources. The detailed microstructure analysis revealed that the metal‐nitrogen‐carbon sites with four‐ (Zn−N4) and five‐coordination (Fe−N5) via the nitrogen coordination are similar to the cytochrome c oxidases. For promising electrocatalysis, such unique microstructure is able to activate oxygen molecules due to nitrogen‐bonding coordination with bimetal sites, thus leading to efficient four‐electron oxygen reduction in alkaline, neutral, and acid electrolytes. Especially, zinc group elements (e.g. Zn and Cd) with d10 electron configuration would significantly boost the nitrogen‐bonding coordination with bimetal sites to enhance electrocatalytic activity. The proof‐of‐concept for the general synthesis of advanced electrocatalysts with controllable bimetal active sites and the mechanistic understanding will promote the promising electrocatalysis by applying the similar principles. [ABSTRACT FROM AUTHOR]

Electrocatalysts with atomically dispersed metal sites (e.g. metal‐nitrogen‐carbon) have been deemed as promising alternatives for noble‐metal catalysts in couples of electrocatalytic reactions. However, the modulation of such atomic sites and the understanding of their interactions are still highly challenging. Herein, we propose a unique supermolecule assembly‐profile coating strategy to prepare a series of diatomic electrocatalysts by profile coating of eight Prussian blue analogues (PBAs) on supramolecular supports respectively as bimetallic sources. The detailed microstructure analysis revealed that the metal‐nitrogen‐carbon sites with four‐ (Zn−N4) and five‐coordination (Fe−N5) via the nitrogen coordination are similar to the cytochrome c oxidases. For promising electrocatalysis, such unique microstructure is able to activate oxygen molecules due to nitrogen‐bonding coordination with bimetal sites, thus leading to efficient four‐electron oxygen reduction in alkaline, neutral, and acid electrolytes. Especially, zinc group elements (e.g. Zn and Cd) with d10 electron configuration would significantly boost the nitrogen‐bonding coordination with bimetal sites to enhance electrocatalytic activity. The proof‐of‐concept for the general synthesis of advanced electrocatalysts with controllable bimetal active sites and the mechanistic understanding will promote the promising electrocatalysis by applying the similar principles. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) is of critical significance in the advancement of fuel cells and zinc‐air batteries. The iron‐nitrogen (Fe−Nx) sites exhibited exceptional reactivity towards ORR. However, the task of designing and controlling the local structure of Fe species for high ORR activity and stability remains a challenge. Herein, we have achieved successful immobilization of Fe species onto the highly curved surface of S, N co‐doped carbonaceous nanosprings (denoted as FeNS/Fe3C@CNS). The induction of this twisted configuration within FeNS/Fe3C@CNS arose from the assembly of chiral templates. For electrocatalytic ORR tests, FeNS/Fe3C@CNS exhibits a half‐wave potential (E1/2) of 0.91 V in alkaline medium and a E1/2 of 0.78 V in acidic medium. The Fe single atoms and Fe3C nanoparticles are coexistent and play as active centers within FeNS/Fe3C@CNS. The highly curved surface, coupled with S substitution in the coordination layer, served to reduce the energy barrier for ORR, thereby enhancing the intrinsic catalytic activity of the Fe single‐atom sites. We also assembled a wearable flexible Zn‐air battery using FeNS/Fe3C@CNS as electrocatalysts. This work provides new insights into the construction of highly curved surfaces within carbon materials, offering high electrocatalytic efficacy and remarkable performance for flexible energy conversion devices. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) is of critical significance in the advancement of fuel cells and zinc‐air batteries. The iron‐nitrogen (Fe−Nx) sites exhibited exceptional reactivity towards ORR. However, the task of designing and controlling the local structure of Fe species for high ORR activity and stability remains a challenge. Herein, we have achieved successful immobilization of Fe species onto the highly curved surface of S, N co‐doped carbonaceous nanosprings (denoted as FeNS/Fe3C@CNS). The induction of this twisted configuration within FeNS/Fe3C@CNS arose from the assembly of chiral templates. For electrocatalytic ORR tests, FeNS/Fe3C@CNS exhibits a half‐wave potential (E1/2) of 0.91 V in alkaline medium and a E1/2 of 0.78 V in acidic medium. The Fe single atoms and Fe3C nanoparticles are coexistent and play as active centers within FeNS/Fe3C@CNS. The highly curved surface, coupled with S substitution in the coordination layer, served to reduce the energy barrier for ORR, thereby enhancing the intrinsic catalytic activity of the Fe single‐atom sites. We also assembled a wearable flexible Zn‐air battery using FeNS/Fe3C@CNS as electrocatalysts. This work provides new insights into the construction of highly curved surfaces within carbon materials, offering high electrocatalytic efficacy and remarkable performance for flexible energy conversion devices. [ABSTRACT FROM AUTHOR]

Molecular electrocatalysis requires the immobilization of molecular catalysts on electrode materials for practical uses. Direct adsorption of catalyst molecules on electrode materials is simple, but grafting molecules through chemical bonds can significantly improve electrocatalytic efficiency and durability. However, designing and synthesizing catalyst molecules to simultaneously improve catalytic activities and realize easy grafting on electrodes is challenging. The study herein reports on a one‐pot strategy to graft Co corroles on pyridine‐modified carbon nanotubes (CNTs) for oxygen electrocatalysis. By modifying CNTs with pyridines, the resulting pyridine‐modified CNTs can function as platforms to grab in situ generated Co corroles through the axial pyridine ligation on Co. Such an immobilization strategy combines three effects for the regulation of electrocatalysis, including the axial ligand effect, the electron transfer effect, and the chemical bond effect. The resulting hybrid materials show high efficiency for oxygen electrocatalysis, and the Zn–air battery assembled using these materials displays comparable performance as the Pt/Ir‐based battery. Moreover, the electrocatalytic efficiency of these hybrid materials can be systematically tuned by using different pyridines, highlighting the controllable feature of this strategy. Therefore, this work is significant to present a one‐pot three‐in‐one strategy to immobilize catalyst molecules on CNTs for electrocatalysis. [ABSTRACT FROM AUTHOR]

This article provides an insightful understanding of how the surface property of N, S-co doped graphene can be modulated by the encapsulated Co 8 FeS 8 , resulting in easier OH desorption on the doped graphene surface for efficient alkaline oxygen reduction reaction. Particularly, the constructed interface for N, S-co doped graphene encapsulating Co 8 FeS 8 could evidently raise the catalytic activity through slightly positively-charged C active site, thus simultaneously enhancing electronic conductivity. [Display omitted] • An encapsulated catalyst of Co 8 FeS 8 @NSG has been successfully synthesized. • Surface property of the doped graphene can be modulated by Co 8 FeS 8. • The Co 8 FeS 8 @NSG exhibited superior catalytic activity for oxygen reduction electrocatalysis. • Greatly promoted electron transfer was achieved from the cobalt-rich sulfides to the doped graphene. • The enhanced performance was further unveiled by density functional theory calculations. Similar to proton exchange membrane fuel cell, anion-exchange membrane fuel cell is also a significant energy conversion device for achieving the utilization of clean hydrogen energy. However, the cathodic alkaline oxygen reduction reaction (ORR) is kinetically not favored and usually requires platinum-group metal (PGM) catalysts such as Pt/C to reduce the overpotential. The major challenge in using PGM-free catalysts for ORR is their low efficiency and poor stability, which urgently demands new concepts and strategies to address this issue. Herein, we controllably manufactured a N, S-co doped graphene encapsulating uniform cobalt-rich sulfides (Co 8 FeS 8 @NSG) by a universal synthesis strategy. After encapsulation, electron transfer from the encapsulated cobalt-rich sulfides to the doped graphene was greatly promoted, which effectively optimizes the electronic structure of the doped graphene, thereby enhancing the ORR activity of the doped graphene surface. Consequently, the Co 8 FeS 8 @NSG exhibits enhanced ORR activity with a higher half-wave potential of 0.868 V (versus reversible hydrogen electrode, vs. RHE) when compared with pure NSG (0.765 V vs. RHE). Density functional theory calculations further confirm that the construction of interface for NSG encapsulating cobalt-rich sulfides could conspicuously elevate the ORR activity through slightly positively-charged C active site and thus simultaneously enhancing electronic conductivity. [ABSTRACT FROM AUTHOR]

Shape-controlled metal-based nanomaterials provide a special platform to regulate the surface physicochemical properties for optimizing the electrocatalytic performance, due to their homogeneously arranged surface atomic structures. Accordingly, owing to the solely {100} facets-ended surfaces, highly uniform Pt nanocubes (NCs) are utilized in this study, to probe the effects of synergizing with Ir species (a very effective metal for various electrocatalysis) on the electrocatalytic performance for the oxygen reduction reaction (ORR). Electrochemical results present that carbon-supported Pt 1 Ir 1 NCs with surface Ir–O species (Pt 1 Ir 1 –O NCs/C) have much enhanced electrocatalytic activity and electrochemical stability than both Pt NCs/C and commercial Pt/C. Physicochemical characterization and theoretical calculation analyses further elucidate the mechanism of the improved electrocatalytic performance: the strong electronic interaction between Pt and Ir, the lowered d -band center of the surface metal atoms, and especially the synergistic effect induced by the surface Ir–O species. This study not only develops a highly active and stable ORR electrocatalyst, but also demonstrates an effective and universal research paradigm to explore the surface engineering effects on the electrocatalytic performance, which can be further applied in other crystalline facets for other (electro)catalytic reactions. Alloying with Ir evidently enhances the oxygen-reduction performance of the {100} facets-enclosed Pt nanocubes, through the modified electronic structure and especially the local O–O repulsion caused by the surface Ir–O species. [Display omitted] • Small and highly uniform Pt–Ir alloy NCs with surface Ir–O species are synthesized. • Pt–Ir NCs exhibit evidently higher ORR performance than both Pt NCs and Pt/C. • Ir tunes the electronic structure of Pt{100} facets for lowering the d -band center. • Ir–O species alter the surface chemical environment to form the O–O repulsion. [ABSTRACT FROM AUTHOR]

The chiral‐induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin‐dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well‐known molecular catalyst for this reaction. The FePc complex belongs to the non‐precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self‐assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro‐self‐assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides′ handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D‐enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2/H2O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L‐enantiomers. [ABSTRACT FROM AUTHOR]

The chiral‐induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin‐dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well‐known molecular catalyst for this reaction. The FePc complex belongs to the non‐precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self‐assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro‐self‐assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides′ handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D‐enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2/H2O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L‐enantiomers. [ABSTRACT FROM AUTHOR]

A series of metal‐free imidazole‐benzimidazole catalysts (ImBenz‐H, ImBenz‐NO2, ImBenz‐OCH3) for oxygen reduction reaction (ORR) were prepared. We demonstrate that the electrocatalytic O2 reduction by ImBenz‐NO2 with the electron‐withdrawing group showed high selectivity toward H2O with the number of electrons transferred (n=3.7) in a neutral aqueous solution. The highest ORR selectivity toward H2O2 was achieved using ImBenz‐H (n=2.4) in an alkaline solution. Electrochemical studies of reaction kinetics disclosed that the highest turnover frequencies were obtained from ImBenz‐H in both neutral and alkaline aqueous solutions. The results prove that the ORR selectivity is tunable by modulating the substituent of the ImBenz catalysts. Furthermore, DFT calculations suggested that the ORR mechanism of ImBenz‐H involves the electron transfer from imidazole‐benzimidazole to O2 resulting in the formation of H2O2 which supports the redox active properties of the catalysts ImBenz. [ABSTRACT FROM AUTHOR]

Exploring the high activity of non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) is necessary to reduce the cost of commercial application of fuel cells. In this work, MnO@Sm 2 O 2 CO 3 (MnO@SOC) nanosheets with abundant oxygen vacancies were synthesized by solvothermal method. The nanosheets showed the best ORR performance in 0.1 M KOH solution after annealing at 500 °C. In electron paramagnetic resonance (EPR) results reveal that annealing reduces the number of oxygen vacancies in the catalyst, increases the lattice oxygen, further enhances the ability of transition metals to combine with oxygen atoms during the reaction. Meanwhile, the support Sm 2 O 2 CO 3 is beneficial to accelerate the breaking of O–O bond, thus promoting the complete reduction of O 2 in the electrocatalytic reaction. This work enriches the family of lanthanide metal catalysts and provides a new strategy for the design and improvement of heterogeneous catalysts. • MnO x @SOC nanosheets were prepared by solvothermal method for the first time. • Annealing will affect oxygen vacancy and metal valence on catalyst surface. • The ratio of MnO/Mn 2 O 3 affected the catalytic performance of the catalyst. [ABSTRACT FROM AUTHOR]

The iron-nitrogen co-doped carbon (Fe–N–C) materials have considered one of the oxygen reduction reaction catalysts with the best potential. Unfortunately, their insufficient intrinsic activity and low active sites result in thick cathode catalytic layers of fuel cell, which has limited discharge performance of the Fe–N–C catalysts in the fuel cells. Herein, a supramolecular assembly strategy is designed to prepare accessible Fe-N x sites and ultra-fine Fe 3 C nanoparticles in porous carbon nanosheet with optimized pore structure toward oxygen reduction electrocatalysis. It is found that supramolecular assembly strategy has significantly increased the specific surface area and Fe-N x site content, and induced the formation of highly dispersed Fe 3 C nanoparticles, which contributes to the high electrochemical active surface area and catalytic activity. The obtained FeNC-900-S catalyst exhibits a high half-wave potential of 0.860 V and a current density of up to 8.28 mA/cm2 (J k at 0.85 V) in 0.1 M KOH, outperforming the those of commercial Pt/C. More importantly, when the FeNC-900-S is employed as an air cathode catalyst towards zinc-air batteries, it obtains an open-circuit voltage of 1.548 V, a power density of 188.8 mW/cm2 and a specific capacity of 790.5 mAh/g. A supramolecular assembly strategy is designed to prepare accessible Fe 3 C/Fe-N x sites in porous carbon nanosheet, and it exhibits a half-wave potential of 0.86 V in 0.1 M KOH, with a power density of 188.8 mW/cm2 for zinc-air battery. [Display omitted] • A highly accessible Fe 3 C@Fe-N x active sites in porous carbon nanosheet is prepared via a supramolecular assembly strategy. • The melamine-cyanuric acid supramolecular promoted the formation of highly active sites and porosity. • The FeNC-900-S obtains high ORR activity in 0.1 M KOH, and zinc-air battery exhibits a power density of 188.8 mW cm−2. [ABSTRACT FROM AUTHOR]

The development of highly efficient catalysts for oxygen reduction reaction (ORR) is the key to improve the performance of fuel cells and metal-air batteries. However, ORR is a kinetic slow reaction with high overpotential, which limits the energy conversion efficiency of fuel cells and metal- air batteries. High-entropy alloy is a new kind of alloy, which is consisted of five or more metal ele- ments with (nearly) equimolar ratios. With unique composition and structural advantages, high entro py alloy can effectively accelerate ORR kinetics and lower overpotential, showing remarkable catalytic performance toward ORR. In this paper, the structures, properties, preparation methods and applications of high entropy alloys in catalytic ORR were reviewed, and the challenges and development perspec- tives were proposed. [ABSTRACT FROM AUTHOR]

An oxygen reduction reaction (ORR) is the key half reaction of proton exchange membrane fuel cells (PEMFCs), and is highly dependent on Pt-based nanocrystals as core electrocatalysts. Despite the exceptional ORR activity from adjusting the electronic structures of surface or near-surface atoms, several serious issues, including the corrosion of carbon supports, the preferential leaching of active metal elements, the instability of surface low-coordinated atoms and the sintering/agglomeration of nanocrystals, still exist, challenging the ORR durability of developed Pt-based ORR catalysts. From the point of view of the catalyst structure design, in this review, we summarized the state-of-the-art structural regulation strategies for improving the ORR durability of Pt-based catalysts. The current limitation of Pt-based binary catalysts for ORR electrocatalysis is firstly discussed, and the detailed strategies are further classified into the optimization of supports, metal-doped alloys, core/shell structures, intermetallics and high-entropy alloys, etc. The structure–performance relationship is detailedly explained, especially emphasizing the elimination of the above restrictions. Finally, the existing challenges and future research direction are further presented, aiming at practicing the PEMFC devices of the ultradurable Pt-based catalysts. [ABSTRACT FROM AUTHOR]

While Pt‐based binary alloys hold promising potential as cathode catalysts in proton exchange membrane fuel cells (PEMFCs) due to their desirable properties compared with monometallic counterparts, their weak interactions with carbon support make them challenging for practical cell implementation. Here, the PtFe alloys are uniformly deposited onto the surface of Fe‐Nx‐enriched nanocubes (FeNC) via surface confinement and internal vapor phase etching. The combined action of PtFe alloy and FeNC support acts as the electronic structure modulator resulting in the optimized intermediate adsorption (revealed by density function theory calculations), thereby boosting intrinsic activity to oxygen reduction reaction (ORR) and simultaneously enhancing their interactions. The resultant Pt1Fe1 @ Fe0.5NC‐900 catalyst with a low Pt loading (0.065 mgPt cm−2) exhibits excellent mass activity and stability toward ORR in acidic media. When incorporated into a PEMFC, it delivers a superior peak power density of 1.05 W cm−2 and satisfactory stability performance. [ABSTRACT FROM AUTHOR]