Oxygen Reduction Reaction Activity Research Articles

Sulfate Oxyanion Steered d-Orbital Electronic State of Nickel-Iron Nanoalloy for Boosting Electrocatalytic Performance.

Oxyanion groups recently offer an innovative avenue for improving the sluggish kinetics of electrochemical reactions benefitting from their particular polyanion configurations and large electronegativity. Nevertheless, the exact structure design and deep regulating mechanism of oxyanion species remain poorly understood. Herein, a fresh architecture of the sulfate oxyanion coordinated nickel-iron nanoalloy on nitrogen and sulfur co-doped carbon nanotube (SO4 2--NiFe/NSCT) is newly proposed to study the activity increment effect and mechanism. The SO4 2--NiFe/NSCT displays hierarchical nanostructure with robust-wrinkled surface and highly efficient active sites. Importantly, the SO4 2- group, as a significant manipulation factor, is first evidenced to promote the oxygen reduction reaction (ORR) activity for NiFe nanoalloy under the reductive condition, showcasing outstanding bifunctional properties toward ORR and oxygen evolution reaction (OER), as well as the exceptional performance in non-aqueous Li-O2 battery. Both experimental and theoretical results elucidate that, as an electron bridge, the introduction of SO4 2- downshifts the d-band center of SO4 2--NiFe/NSCT and gives the electron transfer passageway between the H atom in OH* intermediate and the O atom in SO4 2- group, greatly optimizing the metal-intermediate interaction with weaker bond energy. This work provides a deep insight into the activity enhancement mechanism by the sulfate oxyanion.

High-Throughput UV-Induced Synthesis and Screening of Alloy Electrocatalysts.

The combination of different elements in alloy catalysts can lead to improved activity as it provides opportunities to tune the electronic structures of surface atoms. However, the synthesis and performance screening of alloy catalysts through a vast chemical space are cost- and labor-intensive. Herein, a UV-induced, high-throughput method is reported for the synthesis and screening of alloy electrocatalysts in a fast and low-cost manner. A platform that integrates 37 mini-reaction-cells enables simultaneous UV-induced photodeposition of alloy nanoparticles with up to 37 compositions. These mini-reaction-cells further allow a transfer-free, high-throughput electrochemical performance screening. Binary (PtPd, PtIr, PdIr), ternary (PtPdIr, PtRuIr) and quaternary (PtPdRuIr) alloys have been synthesized with the activity of the binary alloys (57 compositions) for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) being screened. The predicted high performance of identified alloy compositions are subsequently validated by standard measurements using a rotating disk electrode configuration. It is found that the as-synthesized alloy nanoparticles are rich in twin boundaries and thus possess lattice strain. Density functional theory calculation implies that the high ORR activity of the screened Pt0.75Pd0.25 alloy originates from the interplay between the differentiated adsorption sites because of alloying and the strain-induced modulation of the d-band center.

Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction

Nanographenes are among the fastest‐growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal‐based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2‐conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes’ ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.

Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction.

Nanographenes are among the fastest-growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal-based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2-conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes' ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.

Machine-Learning-Assisted Screening of Nanocluster Electrocatalysts: Mapping and Reshaping the Activity Volcano for the Oxygen Reduction Reaction.

In computational heterogeneous catalysis, Sabatier's principle-based activity volcano plots provide an intuitive guide to catalyst design but impose a fundamental constraint on the maximum achievable catalytic performance. Recently, subnano clusters have emerged as an exciting platform, offering high noble metal utilization and superior performance for various reactions compared to extended surfaces, reflecting a complex structure-activity relationship in the non-scalable regime. However, understanding their non-monotonic catalytic activity, attributed to the large configurational space and their fluxional identity, poses a formidable challenge. Here, we present a machine learning (ML) framework that captures the non-monotonic trends in oxygen reduction reaction (ORR) activity at the subnanometer scale, attributed to their dynamic fluxional characteristics. We demonstrate a size-dependent shifting and reshaping of the ORR activity volcano, with Au replacing Pt at the peak. Leveraging only upon the non-ab initio geometric and electronic properties, our trained ML model accurately captures the site-specific adsorption energies of intermediates at the subnanometer regime. To account for the inconsistent trend in activity, we analyzed the correlation between electronic and geometric properties. Our findings reveal that the d-filling and coupling matrix of the neighboring metal atom significantly influences the intermediate adsorption on the local chemical environment compared to the d-band center. Following this analysis, we utilized ML to map the catalyst distribution in the activity volcano and identified the five best sub-nano electrocatalysts, demonstrating overpotential values lower than or comparable to the Pt(111) surface for the ORR. This study provides intuitive guidelines for the rational designing of highly efficient electrocatalysts for fuel cell applications while modifying the activity volcano plots for electrocatalysts at the subnanometer regime.

Tailoring ORR Activity in Fe-N-C Catalysts through Phosphorus Incorporation.

Atomically dispersed iron and nitrogen co-doped carbon materials (Fe-N-C) represent promising non-precious metal catalysts for the oxygen reduction reaction (ORR), offering potential alternatives to noble metal-based benchmarks. In our study, we investigated the influence of phosphorus doping on the catalytic activity of Fe-N-C. The experimental research demonstrate that the doping of phosphorus significantly enhances the ORR activity. Specifically, the resulting Fe-NPC exhibits high metal loading and excellent ORR activity in 0.1 M KOH with an onset potential of 1.00 V and a half-wave potential of 0.864 V. Density functional theory (DFT) simulations reveal that phosphorus improves the electrocatalytic activity by activating O2 molecules and reducing the energy barrier (the hydrogenation reaction *OH→H2O) of the rate-determining step. Furthermore, Fe-NPC exhibits promising application prospects as an air cathode in Zn-air batteries, delivering a high maximum discharge power density of 180.3 mW cm-2 and outstanding discharge specific capacity (758.8 mAh g-1Zn) at a discharge current density of 10 mA cm-2.

Fine Engineering of d-Orbital Vacancies of ZnN4 via High-Shell Metal and Nonmetal Single-Atoms for Efficient and Poisoning-Resistant ORR.

Atomically dispersed metal-nitrogen-carbon (M-N-C) materials are active oxygen reduction reaction (ORR) catalysts. Among M-N-C catalysts, ZnN4 single-atom catalysts (SACs) due to a nearly full 3d10 electronic configuration insufficiently activate oxygen and display low ORR activity. To finely engineer d-orbital vacancies of ZnN4, we combine high-shell metal and nonmetal SAs as electronic regulators that are ZnN4Cl and carbon vacancy-hosted -Cl motifs, which show complementary electron-withdrawing capacities versus the ZnN4. Under that, the ZnN4 exhibits significantly enhanced ORR activity with a half-wave potential (E1/2) of 0.912 VRHE relative to the unmodified ZnN4 (E1/2 = 0.822 VRHE) and simultaneously robust durability (negligible activity loss after 10,000 potential cycles). Particularly, the engineered ZnN4 possesses high resistance to SCN- poisoning, which is rarely achieved among M-N-C SACs. Our works show that combining high-shell metal and nonmetal SAs can finely engineer d-orbital vacancies of metal centers to an optimal state, thereby intrinsically enhancing their catalytic performance.

Enhancing Oxygen Reduction Reaction Electrocatalytic Performance of Nickel‐Nitrogen‐Carbon Catalysts through Coordination Environment Engineering†

Comprehensive SummarySingle‐atom catalysts (SACs) have attracted significant attention due to their high atomic utilization and tunable coordination environment. However, the catalytic mechanisms related to the active center and coordination environment remain unclear. In this study, we systematically investigated the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalytic activities of NiN4, NiN3, NiN3H2, NiN4X, NiN3X, and NiN3H2X (X denotes axial ligand) through density functional theory (DFT) calculations. This study unveils two distinct reaction pathways for ORR and OER, involving proton‐electron pairs adsorbed from both the solution and the catalyst surface. The overpotential is the key parameter to evaluate the catalytic performance when proton‐electron pairs are adsorbed from the solution. NiN3 and NiN3H2 show promise as pH‐universal bifunctional electrocatalysts for both ORR and OER. On the other hand, when proton‐electron pairs are adsorbed from the catalyst surface, the reaction energy barrier becomes the crucial metric for assessing catalytic activity. Our investigation reveals that NiN3H2 consistently exhibits optimal ORR activity across a wide pH range, regardless of the source of proton‐electron pair (solvent or catalyst surface).

Consolidating the Oxygen Reduction with Sub-Polarized Graphitic Fe-N4 Atomic Sites for an Efficient Flexible Zinc-Air Battery.

The effectuation of the Zn-air battery (ZAB) is appealing for active and durable catalysts to kinetically drive the sluggish cathodic oxygen reduction reaction (ORR). Atomic metal-Nx-C sites are widely witnessed with Pt-like activity, but their demetalations still severely restrict the durability in ORR. Here we have profiled an ordered hierarchical porous carbon supported Fe-N4 single-atom (FeNC) catalyst by a template derivation method for efficient ORR and flexible ZAB studies. The FeNC structure is observed with a sub-polarized graphitic Fe-N4 coordination with a shortened Fe-N bond for potentially consolidating the ORR, together with the hierarchical porous matrix for kinetical mass transfer. Resultantly, the optimized FeNC catalyst showcases Pt-beyond alkaline ORR activity (E1/2 = 0.95 V) with long-term durability for 100 h, delivering the flexible ZAB device with high power density (251 mW cm-2) and durable cycle life (80 h). This research underscores the criterion in rationalizing active and robust ORR catalysts through metal-nitrogen bond modulation.

Effect of N-Doped Carbon on the Morphology and Oxygen Reduction Reaction (ORR) Activity of a Xerogel-Derived Mn(II)O Electrocatalyst

This work synthesizes a xerogel from a sol–gel synthesis strategy and supports it on N-doped carbon support from spent coffee biomass (Mn(II)O/N-CC, hereafter MnO) as an efficient oxygen reduction reaction (ORR) catalyst in alkaline electrolytes. The effects of N-CC carbon content on MnO nanoparticle size, dispersion, distribution, morphology, and electrochemistry on ORR are discussed. The SEM and TEM measurements show that increasing the N-CC content during the MnO gelation reaction improved MnO dispersion and particle size during thermal treatment, increasing the ORR’s electrochemical active surface area. Several physiochemical and electrochemical characterizations show a clear relationship between N-CC catalysts and ORR activities. The best catalyst, MnO/N-CC-5, had an even distribution of 27 nm MnO nanoparticles on the N-CC support. The MnO/N-CC-5 catalyst had almost identical ORR kinetics and stability to those of the state-of-the-art Pt/C catalyst in 0.1 M KOH electrolytes, losing only 10 mV in half-wave potential after 5000 potential cycles and retaining 96% of current for over 10 h of continuous chronoamperometric stability. By measuring the electrochemical active surface areas of various catalysts by cyclic voltammetry at different scan rates and measuring the double layer capacitance (Cdl) and ECSA, MnO/N-CC-5 catalysts were shown to have enhanced ORR activity. The XPS analysis explains the ORR activity in terms of the Mn3+/Mn4+ ratio, and a mechanism was proposed. These findings suggest that the MnO/N-CC-5 catalyst could be a cathode catalyst in fuel cells, biofuel cells, metal–air batteries, and other energy conversion devices.

Cobalt Phosphide Decorating Metallic Cobalt With a Nitrogen‐Doped Carbon Nano‐Shell Surpasses Platinum Group Metals for Oxygen Electrocatalysis Applications

ABSTRACTIt has been a long‐standing challenge to cultivate capable and resilient oxygen electrocatalysts with higher activity, low price, and long lifetime to replace the commonly used platinum group metals, i.e., Pt for oxygen reduction reaction (ORR) and RuO2/IrO2 for oxygen evolution reaction (OER). This work presents a promising approach to address the challenges associated with oxygen electrocatalysis by introducing a cobalt phosphide/metallic cobalt (Co2P/Co) core wrapped in a nitrogen‐doped conductive carbon (CN) nano‐shell, demonstrated as Co2P/Co@NC. The strong chemical bonding between metallic cobalt and phosphorus, nitrogen and conductive carbon contributes to the enhanced conductivity and stability of the electrocatalyst. The nitrogen doping in the carbon shell provides additional Co–N active sites, which are crucial for ORR activity. Co2P/Co@NC demonstrates promising activity and stability compared to noble metals such as Pt for ORR in an alkaline medium. This suggests its potential as a cost‐effective alternative to Pt‐based catalysts. Further, due to factors such as strong cobalt‐phosphide bonding, high cobalt oxidation states and excellent conductivity of the nitrogen‐doped carbon shell, the Co2P/Co@NC outperforms noble metal oxides like iridium dioxide (IrO2) and ruthenium dioxide (RuO2) for OER. Co2P/Co@NC exhibits a low potential difference of 0.63 V, which is among the lowest reported for bifunctional electrocatalysts capable of both ORR and OER. Overall, the described strategy offers a promising avenue for developing efficient, low‐cost and stable electrocatalysts for oxygen reactions, which are crucial for various electrochemical energy conversion and storage technologies, such as fuel cells and metal–air batteries.

Activating the Mn Single Atomic Center for an Efficient Actual Active Site of the Oxygen Reduction Reaction by Spin-State Regulation.

The ligand engineering for single-atom catalysts (SACs) is considered a cutting-edge strategy to tailor their electrocatalytic activity. However, the fundamental reasons underlying the reaction mechanism and the contemplation for which the actual active site for the catalytic reaction depends on the pyrrolic and pyridinic N ligand structure remain to be fully understood. Herein, we first reveal the relationship between the oxygen reduction reaction (ORR) activity and the N ligand structure for the manganese (Mn) single atomic site by the precisely regulated pyrrolic and pyridinic N4 coordination environment. Experimental and theoretical analyses reveal that the long Mn-N distance in Mn-pyrrolic N4 enables a high spin state of the Mn center, which is beneficial to reduce the adsorption strength of oxygen intermediates by the high filling state in antibond orbitals, thereby activating the Mn single atomic site to achieve a half-wave potential of 0.896 V vs RHE with outstanding stability in acidic media. This work provides a new fundamental insight into understanding the ORR catalytic origin of Mn SACs and the rational design strategy of SACs for various electrocatalytic reactions.

Deep Eutectic Solvent and Molten Salt-Assisted Construction of Wheat Straw-Derived N/O Co-Doped Porous Carbon for Flexible Zinc-Air Batteries.

As a common biomass resource, wheat straw is gradually being derived as carbon materials for oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Herein, the wheat straw-derived carbon was prepared by ball milling and pyrolysis using deep eutectic solvent (DES) as the medium, which avoided the cumbersome procedures. The hydrogen bond of DES was utilized to reconstructed into a hydrogen bond network structure between DES and lignin/cellulose/hemicellulose of wheat straw. The hydrogen bond network structure was converted into N/O co-doped porous carbon (N/O-WSPC) with abundant N/O co-doped sites after high-temperature pyrolysis. Meanwhile, KHCO3 was employed to further generate hierarchical pore structures and increase the specific surface area of the N/O-WSPC. The N/O co-doped sites provided intrinsic ORR activity, while the porous structure facilitates the mass transfer effect. Therefore, the N/O-WSPC exhibited a half-wave potential of 0.87 V (vs. RHE) and a limiting current density of 5.98 mA cm-2 for ORR. The N/O-WSPC-based flexible ZAB displayed an energy density of 652.23 Wh kg-1 and a charging-discharging cycle duration for over 19 h. The DES-assisted strategy facilitates the sustainable and efficient application of wheat straw-derived carbon materials in energy storage and conversion devices.

Heterointerfacial engineering of N,P-doped carbon nanosheets supported Co/Co2P nanoparticles for boosting oxygen reduction and oxygen evolution reactions towards rechargeable Zn-air battery

Transition metal phosphides (TMPs) with high electrocatalytic activity for the oxygen evolution reaction (OER) are reckoned as a substitution of precious group metals catalysts in rechargeable Zn-air battery. In this work, Co/Co2P heterojunction nanoparticles supported N,P-doped carbon nanosheets (Co/Co2P@NPCNS) were designed and prepared via a facile one-step molten salt-assisted pyrolysis process. Density function theory calculations reveal that the heterogeneous interactions of Co/Co2P effectively enhance the bifunctional electrocatalytic activity for oxygen reduction reaction (ORR) and OER. The synergistic interaction between the Co/Co2P heterojunction nanoparticles with highly exposed active sites and excellent catalytic activity and the two-dimensional doped carbon nanosheets with high conductivity contributes to Co/Co2P@NPCNS exhibiting preeminent bifunctional ORR/OER activity and stability with a high half-wave potential for ORR (0.87 V), a low overpotential for OER (302 mV at 10 mA cm−2) and a low potential gap (0.66 V). The homemade rechargeable Zn-air battery performs high peak power density (187 mW cm−2) and exceptional endurance. This heterogeneous interface tactic of integrating TMPs with heteroatom-doped carbon materials may shed light on the research and development of non-precious metal electrocatalysts.

Unique electron-feeding mechanism in CoN3O for enhanced acidic oxygen reduction

Co-centered single-atom catalysts (SACs) have emerged as an increasingly promising non-platinum group candidate for acidic oxygen reduction reaction (ORR) due to their balanced activity and stability. However, the intrinsic ORR activity of present Co-centered SACs remains far below the commercial Pt/C. Herein, a CoN3O-structured SAC is successfully fabricated by a gas-phase strategy and achieves a peak power density of 492.6 mW cm−2 under the 1.0 bar H2/air condition, demonstrating its excellent application potential in practical fuel cells. Unique electron-feeding mechanism is revealed to account for the remarkably enhanced ORR activity inner CoN3O SAC. It is indicated that the electron interaction inner active site governed by both electronegativity in σ bond and d-p back-feeding in π bond reaches balance at CoN3O, thus optimized adsorption of oxygen-containing intermediates. Our work provides multiple insights into the orbital scale laws for higher-performance PGM-free ORR catalysts.

Tailoring the catalytic activity of PrBaFe2O5+δ cathode material with non-transition metal In-doping for solid oxide fuel cells

Double perovskite PrBaFe2O5+δ (PBF) is a promising cathode material for solid oxide fuel cell (SOFCs) due to the favorable catalytic activity and superior electrochemical stability. Herein, to further tailor the oxygen-ion transport kinetics and electrochemical performance, unlike the typical approach through using higher valence, non-transition metal In3+ ion doping is initially investigated to partially replace Fe3+/Fe4+ site, forming the compositions of PrBaFe2−xInxO5+δ (PBFInx, x = 0, 0.05, 0.1, and 0.15). Xray diffraction (XRD) analysis indicates that PBFInx exhibit satisfactory chemical and thermal compatibility with the gadolinia-doped ceria (GDC) electrolyte. Expectedly, the polarization resistance (Rp) of PBFIn0.1 cathode is decreased by approximately 40 % and an anode-supported single cell with PBFIn0.1 cathode yields a 36 % higher peak power density (PPD) at 800 °C compared to that of PBF. Moreover, the single cell using PBFIn0.1 as the cathode can be operated stably at 0.4 A cm−2 for more than 50 h without obvious performance degradation. In addition, the X-ray photoelectron spectroscopy (XPS) results confirm that the low-valence state In3+ introduced into PBF have a positive impact on the oxygen vacancy concentration and boost the oxygen reduction reaction (ORR) activity, thus significantly enhancing the electrochemical performance of the PBF cathode. The results show that the non-transition metal In3+ ion doping is an effective method to improve the performance of the PBF cathode for SOFCs.

Surface segregation on Ag@MNi (M = Pd, Pt, Rh, and Ru) core–shell nanocrystals for enhancing the oxygen reduction performance

Synthesis of cost-effective electrocatalysts for oxygen reduction reaction (ORR) has received wide attention due to their sluggish kinetics, which limits the development and application of fuel cell technique. In this work, we report a versatile synthetic approach to prepare a series of small-sized Ag@MNi (M = Pd, Pt, Rh, Ru) nanocrystals with core–shell structures by a simple solvothermal method. According to characterization analysis, surface segregation of Pd was proved in the outermost layer with the Pd-rich shell layer, which can regulate the adsorption energy of *OH. Electrochemical results show that the onset potential and half-wave potential of Ag@PdNi nanocrystals (Ag@PdNi NCs) are 1.005 and 0.913 V vs. RHE (reversible hydrogen electrode), respectively, with a Tafel slope of 55.31 mV dec-1 and strong ORR catalytic durability, which is similar to Ag@MNi (M = Pt, Rh, Ru) NCs and slightly higher than that of PdAg alloy nanoparticles (PdAg alloy NPs), PdNi alloy nanoparticles (PdNi alloy NPs), commercial Pd black and even commercial Pt/C, in alkaline medium. Density Functional (DFT) calculations show that the presence of Agcore effectively promotes the segregation of Pd atoms to the outer shell surface, where Ni provides better segregated substitution sites for Pd, which significantly improves the ORR activity and durability due to the electronic synergistic effect between Agcore nuclei and Pdshell can reduce the adsorption strength of OHads.

Enhanced bifunctional electrocatalysis of Co5.47N nanocrystals in porous carbon nanofibers for high-efficiency zinc-air batteries

As a promising energy conversion and storage device, recently, rechargeable zinc-air batteries (ZABs) have developed rapidly, and the exploitation of excellent electrode catalysts to improve the energy efficiency and long-term performance of ZABs has become a focus of current research. Herein, the Co5.47N nanocrystals embedded in porous carbon nanofibers (Co5.47N PCNFs) were designed to act as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and iodide oxidation reaction (IOR), which occur on the electrode in the charging-discharging process of ZABs. The electrochemistry results showed that the ORR activity of Co5.47N PCNFs is comparable to the commercial Pt/C electrocatalyst, and the IOR activity and stability are higher than those of the Pt/C electrocatalyst. Importantly, Co5.47N PCNFs electrocatalyst endows ZABs with a low charge–discharge voltage difference (0.49 V), a high round-trip energy efficiency (72.1 %), as well as a large specific capacity (791.5 mAh gZn−1), surpassing the performance of Pt/C electrocatalyst. Density functional theory calculation demonstrates that Co5.47N PCNFs have lower Gibbs free energy for the formation of IOR intermediate species, thereby displaying outstanding IOR catalytic performance compared to that of Pt/C electrocatalyst. These findings offer crucial insights into the rational design of cobalt nitride-based electrocatalysts for application in ZABs with high energy efficiency.

Axial Coordination Engineering on Fe-N-C Materials for Oxygen Reduction: Insights from Theory.

Axial coordination engineering has emerged as an effective strategy to regulate the catalytic performance of metal-N-C materials for oxygen reduction reaction (ORR). However, the ORR mechanism and activity changes of their active centers modified by axial ligands are still unclear. Here, a comprehensive investigation of the ORR on a series of FeN4-L moieties (L stands for an axial ligand) is performed using advanced density functional theory (DFT) calculations. The axial ligand has a substantial effect on the electronic structure and catalytic activity of the FeN4 center. Specially, FeN4-C6H5 is screened as a promising active moiety with superior ORR activity, as further revealed by constant-potential calculations and kinetic analysis. The enhanced activity is attributed to the weakened *OH adsorption caused by the altered electronic structure. Moreover, microkinetic modeling shows that at pH=1, FeN4-C6H5 possesses an impressive theoretical half-wave potential of ~1.01 V, superior to the pristine Fe-N-C catalysts (~0.88 V) calculated at the same level. These findings advance the understanding of the ORR mechanism of FeN4-L and provide guidance for optimizing the ORR performance of single-metal-atom catalysts.

Fe-N catalyst derived from and supported on Lycopodium clavatum sporopollenin exine capsules for the oxygen reduction reaction

A carbon-supported electrocatalyst, featuring carbon nanotubes anchored on 3D porous graphitic carbon, was developed with the aim to perform in the operating conditions of alkaline fuel cells and metal air batteries. The catalyst was developed via two steps: first powders of Sporopollenin exine capsules used as a bio-based carbon support were activated via CO2 gasification to obtain a high specific area and porosity, second the derived porous carbons were impregnated by an iron salt and a nitrogen source, to be carbonised in Nitrogen at high temperature. The prepared catalyst demonstrated an efficient oxygen reduction reaction activity showing a half-wave potential of ~ 0.775 V vs. Reversible hydrogen electrode, comparable with that of commercial 20 wt% Pt/C in alkaline conditions, a good stability after accelerated degradation testing, retaining ~ 86% of the initial limiting current density, and a higher diffusion limited current density (6.3 vs. 5.1 mA cm− 2) than the commercial counterpart. Overall, we show the suitability of Sporopollenin exine capsule as support for electrocatalysis and a promising methodology to develop sustainable catalysts for the oxygen reduction reaction.