Step For Oxygen Reduction Reaction Research Articles

Piezo-photocatalytic Synergetic for H2O2 Generation via Dual-pathway over Z-scheme ZIF-L/g-C3N4 Heterojunction

The constructed ZIF-L/g-C3N4 piezo-photocatalytic system showed exceptional H2O2 production yield. It was primarily attributable to the matched Z-scheme band alignments and the forceful piezoelectric field formed between g-C3N4 and ZIF-L, which was favor of reducing the energy barrier of electron excitation and directional transferring of photo-generated charge carriers. Meanwhile, the composition between ZIF-L and g-C3N4 can alter the H2O2 generation mechanism from single-pathway to dual-pathway. Thus, this mutual promotion significantly elevated the catalytic H2O2 production rate to 1.45mmolg−1 h−1 without any contaminative scavenger. The catalytically produced H2O2 solution can be used to achieve ultrafast degradation of organic pollutants with 100% efficiency through homogeneous Fenton reaction within tens of seconds. The mediating multi-roles of natural organic matter (NOM) in regulating the H2O2 production were systematically investigated. Finite-element-method (FEM) simulations and density functional theory (DFT) calculations conjointly revealed the constructed piezo-photocatalytic system not only markedly accelerated separation of charge carriers, but also facilitated the activation of vital intermediates (O2⁎, OOH⁎ and ⁎OH) for H2O2 synthesis, which were the rate-determining steps for oxygen reduction reaction (ORR) and water oxidation reaction (WOR). This study will provoke the rational design of MOFs-based dual-pathway materials for piezo-photocatalytic H2O2 generation and follow-up applications.

Bimetal organic framework derived CoM@N–C composites as bifunctional oxygen catalysts for Zn-air batteries

Metal-loaded nitrogen-doped carbon (M@N–C) catalysts have shown promise as electrocatalysts for replacing noble metal catalysts in industrial processes. To study the influence on structural and performance caused by different bimetal doping, a family of bimetals CoM@N–C (M = Cu/Ni/Fe) composites with porous surface and abundant C defects were well-designed. After bimetallic doping, more defects are introduced into the carbon frameworks, and the metal-N species are fixed. As such, efficient utilization of active sites and rapid mass transfer make the reaction kinetics process more favorable and stable. Density functional theory calculations indicate that Cu/Ni doping optimizes the electronic environment of the Co–N, resulting in the balanced adsorption and dissociation of oxygen intermediates. While the synergy of FeCo activates the O=O, which promotes the sharp decrease in free energy of ∗OOH to ∗O, shifting the rate-determining step for oxygen reduction reaction. This indicates the adsorption site transfer of CoFe0.05@N–C in oxygen reduction and evolution reactions. The CoFe0.05@N–C catalyst exhibits superior bifunctional catalytic activity (with a potential gap of 0.80 V) than that of Pt catalysts. This work presents a simple strategy to fabricate well-defined bimetals doping in bifunctional oxygen electrocatalysts and it is expected to inspire future work on the role of electronic structure modulation and interface engineering.

Electron redistribution and proton transfer induced by atomically fully exposed Cu-O-Fe clusters coupled with single-atom sites for efficient oxygen electrocatalysis

Single-atom catalysts have garnered significant attention by showing sparkling performance in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the air cathode side of energy devices such as metal-air batteries and fuel cells. This work presents a novel catalyst, AC-CuFe-NC, that incorporates Fe-doped CuO atomic clusters (CuOFe) synergistically with single-atom sites. The AC-CuFe-NC demonstrates outstanding ORR performance (half-wave potential of 0.92 V) and an oxygen overpotential gap between ORR and OER as low as 0.61 V, which is among the top reported performances. Combined with in situ ATR-SEIRAS and DFT calculations, it is shown that the synergistic CuOFe atomic clusters are effective in inducing the electronic structure redistribution of the Fe single-atom site, modulating oxygen adsorption energy, and lowering ORR barriers. More importantly, it is revealed that the synergistic adsorption of clusters and single-atom sites establishes hydrogen bonds between the oxygenated intermediates and the electrolyte H2O molecules. The constructed hydrogen bond can provide a pathway for efficient proton transport as supported by kinetic isotope experiments, leading to a substantial enhancement in reaction kinetics. Additionally, the oxygenated intermediates are stabilized, and the Fe-O bond is elongated during the final step of ORR, thereby facilitating the desorption of OH*. The excellent bifunctional electrocatalytic performance of AC-CuFe-NC enable it to show promising application in rechargeable Zn-air batteries. The innovative catalyst structure and synergistic mechanism demonstrated in this study shed light on the development of high-performance catalysts in energy devices.

Molecular Fe─N4 Moieties Coupled with Atomic Co─N4 Sites Toward Improved Oxygen Reduction Performance

AbstractResearch on high‐efficiency and cost‐efficient catalysts for oxygen reduction reaction (ORR) is still a vital but challenging issue for commercializing metal–air batteries. Herein, a single‐molecule/atom hybrid catalyst is developed to boost the ORR, in which iron phthalocyanine molecules containing molecular Fe─N4 moieties couple with atomic Co─N4 sites on the surface of polyhedral carbon. Density functional theory calculations reveal that face‐to‐face laminated construction of Fe─N4 and Co─N4 in the hybrid catalyst can effectively modulate the electronic structure of active iron atoms and reduce the energy barrier of the rate‐determining step for ORR. As a result, this hybrid catalyst demonstrates excellent ORR performance, featuring a half‐wave potential of 0.904 V, a peak power density of 238.3 mW cm−2 for zinc–air battery, and outstanding electrocatalytic stability. This work offers a distinctive and robust molecular/atomic engineering approach to creating efficient electrocatalysts, advancing the fields of metal–air batteries.

Tailoring Ba0.5Sr0.5FeO3-δ cobalt-free perovskites with zinc as triple-conducting cathodes for protonic ceramic fuel cells

Developing triple-conducting cathode is an available way to enhancing the electrochemical performance of protonic ceramic fuel cells (PCFCs). Here we report a systematical investigation on the performance of cobalt-free perovskites Ba0.5Sr0.5Fe1-xZnxO3-δ (x = 0, 0.1, and 0.2; BSF, BSFZ0.1, and BSFZ0.2) as triple-conducting cathodes for PCFCs. Zn doping improves the hydration capacity, oxygen vacancy concentration, surface exchange coefficient, and bulk diffusion coefficient of BSFZx (x = 0.1 and 0.2) as compared to the bare BSF. Theory calculations show that Zn doping benefits the oxygen vacancy formation, which is conducive to the promotion of cathodic oxygen reduction reaction (ORR). Among materials investigated, the BSFZ0.2 perovskite possesses an abundance of oxygen vacancies, strong hydration capacity and exceptional triple conductivity (H+/O2−/e−), and thus showing the lowest polarization resistance (Rp) of 0.328 Ω cm2 at 700 °C under wet air. At 700 °C, the cell reaches a maximum power density of 497 mW cm−2 in H2 using BSFZ0.2-30 wt% BaZr0.4Ce0.4Y0.15Zn0.05O3-δ (BZCYZ) composite cathode based on 25-μm-thick BZCYZ electrolyte, and there is no obvious deterioration in performance after operation for 100 h. The rate-limiting steps of ORR on BSFZ0.2-BZCYZ composite cathode are determined to be the surface oxygen incorporated into lattice reaction processes. These findings demonstrate that the proposed BSFZ0.2 holds great potential as a cobalt-free triple-conducting cathode for PCFCs.

Unveiling the impact of axial ligands on Fe-N-C complexes through DFT simulation and machine learning analysis

Single-atom catalysts (SACs), featuring isolated metal atoms embedded in graphitic carbon materials, have attracted considerable research interest due to their cost-effectiveness, high catalytic activity, and customizable functionality across various catalytic reactions. Among SACs, the Fe-N4-C class has garnered significant attention. Tailoring the properties of Fe-N4 sites through localized chemical modifications stands as a key strategy for catalyst engineering. Recent experimental and computational investigations have underscored the distinct influence of axial ligands on Fe in modulating the oxygen reduction reaction (ORR) activity. However, the precise quantitative structure-property relationship between ligands and the catalytic properties of the Fe center remains elusive. In this study, we combined the density functional theory (DFT) simulations and machine learning (ML) models to unravel the relationship between the ligand properties and the oxo binding energy. This energy pertains to the binding of an oxygen atom to the Fe center, a fundamental step in ORR. Through the design of 33 ligands and 5 molecular complexes that accommodate the Fe-N4 moiety, we screened a total of 278 oxo binding energies across an array of ligands and host complexes. Harnessing the power of ML models, we achieved an accurate prediction of these oxo binding energies using features collected from DFT simulations. Notably, the predominant features contributing to the oxo binding energy prediction primarily derived from complexes with attached ligands, rather than isolated ligand properties. We formulated an approach that leverages these critical features and identified the isolated ligand properties capable of effectively predicting these features. This methodology can potentially be applied to investigate other ORR intermediates and a comprehensive understanding of the ligand effect for the ORR activity in SACs can be achieved.

A New Catalyst System for the Oxygen Reduction Reaction (ORR) at Fuel Cell Cathodes: P-Block Precious Group Metal-Free Tin and Nitrogen-Doped Carbon (SnNC) Catalyst

The sluggish kinetics of the Oxygen Reduction Reaction (ORR) and the consequently large amount of platinum catalyst required for cathode material in Proton Exchange Membrane Fuel Cell (PEMFC) is today’s primary hurdle for commercializing fuel cell technology in automotive application.1 A class of carbon-doped with metal and nitrogen electrocatalysts (labelled MNC) is promising substitute for platinum-group metals (PGMs) in oxygen reduction reaction (ORR) in PEMFC.2 Particular attention was placed on a specific family of MNC catalysts derived from 3d transition metal precursors with FeNC and CoNC being the most promising for PEMFC applications requiring high power density.3-5 In the present contribution, we report on a new MNC catalyst system, different by its chemical nature from all others catalysts previously reported as ORR-active in acidic medium. The highlights of this work are the successful design and synthesis of SnNC as a non-noble metal catalyst for the first time, and the finding that SnNC hosts Sn-based active sites that can achieve the same turnover frequency as Fe-based active sites in FeNC, and much higher turnover frequency than Co-based active sites in CoNC. FeNC and CoNC materials have, until now, been the state-of-art PGM-free catalysts for ORR in acidic medium. The present SnNC material shows also high and similar selectivity for the four-electron ORR pathway as FeNC, much higher than CoNC materials. The prepared SnNC catalysts meet and exceed the FeNC catalysts in terms of hydrogen-air fuel cell power density. The SnNC-NH3 catalysts displayed a 40-50% higher current density than FeNC-NH3 at cell voltages below 0.7 V. Added benefits include a Fenton-inactive character of Sn. Among other techniques, density functional theory and 119Sn Mössbauer spectroscopy were used in combination to investigate SnNC, providing for the first time insights on the structure of its active sites, their rate-determining step for ORR and selectivity for the four-electron reduction pathway. References Holton, O. T.; Stevenson, J. W., The Role of Platinum in Proton Exchange Membrane Fuel Cells. Platinum Metals Review 2013, 57 (4), 259-271.Luo, F.; Wagner, S.; Ju, W.; Primbs, M.; Li, S.; Wang, H.; Kramm, U. I.; Strasser, P., Kinetic Diagnostics and Synthetic Design of Platinum Group Metal-Free Electrocatalysts for the Oxygen Reduction Reaction Using Reactivity Maps and Site Utilization Descriptors. Journal of the American Chemical Society 2022, 144 (30), 13487-13498.Zitolo, A.; Ranjbar-Sahraie, N.; Mineva, T.; Li, J.; Jia, Q.; Stamatin, S.; Harrington, G. F.; Lyth, S. M.; Krtil, P.; Mukerjee, S.; Fonda, E.; Jaouen, F., Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications 2017, 8 (1), 957.Zitolo, A.; Goellner, V.; Armel, V.; Sougrati, M.-T.; Mineva, T.; Stievano, L.; Fonda, E.; Jaouen, F., Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nature materials 2015, 14 (9), 937-942.Luo, F.; Roy, A.; Silvioli, L.; Cullen, D. A.; Zitolo, A.; Sougrati, M. T.; Oguz, I. C.; Mineva, T.; Teschner, D.; Wagner, S.; Wen, J.; Dionigi, F.; Kramm, U. I.; Rossmeisl, J.; Jaouen, F.; Strasser, P., P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nature materials 2020, 19 (11), 1215-1223.

Density Functional Theory Investigation of Temperature-Dependent Properties of Cu-Nitrogen-Doped Graphene as a Cathode Material in Fuel Cell Applications

In this study, density functional theory (DFT) was used to investigate the influence of temperature on the performance of a novel Cu-nitrogen-doped graphene Cu2-N8/Gr nanocomposite as a catalyst for the oxygen reduction reaction (ORR) in fuel cell applications. Our DFT calculations, conducted using Gaussian 09w with the 3–21G/B3LYP basis set, focus on the Cu-nitrogen-doped graphene nanocomposite cathode catalyst, exploring its behavior at three distinct temperatures: 298.15 K, 353.15 K, and 393.15 K, under acidic conditions. Our analysis of formation energies indicates that the structural stability of the catalyst remains unaffected as the temperature varies within the potential range of 0–7.21 V. Notably, the stability of the ORR steps experiences a marginal decrease with increasing temperature, with the exception of the intermediate OH + H2O (*OH + H + *OH). Interestingly, the optimization reveals the absence of single OH and H2O intermediates during the reactions. Furthermore, the OH + H2O step is optimized to form the OH + H + OH intermediate, featuring the sharing of a hydrogen atom between dual OH intermediates. Free energy calculations elucidate that the catalyst supports spontaneous ORR at all temperatures. The highest recorded maximum cell potential, 0.69 V, is observed at 393.15 K, while the lowest, 0.61 V, is recorded at 353.15 K. In particular, the Cu2-N8/Gr catalyst structure demonstrates a reduced favorability for the H2O2 generation at all temperatures, resulting in the formation of dual OH intermediates rather than H2O2. In conclusion, at 393.15 K, Cu2-N8/Gr exhibits enhanced catalyst performance compared to 353.15 K and 298.15 K, making it a promising candidate for ORR catalysis in fuel cell applications.

Importing Antibonding‐Orbital Occupancy through Pd−O−Gd Bridge Promotes Electrocatalytic Oxygen Reduction

AbstractThe active‐site density, intrinsic activity, and durability of Pd−based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon‐based rare‐earth (RE) oxides (Gd2O3, Sm2O3, Eu2O3, and CeO2) by using RE metal–organic frameworks to tune the ORR performance of the Pd sites through the Pd−RExOy interface interaction. Taking Pd−Gd2O3/C as a representative, it is identified that the strong coupling between Pd and Gd2O3 induces the formation of the Pd−O−Gd bridge, which triggers charge redistribution of Pd and Gd2O3. The screened Pd−Gd2O3/C exhibits impressive ORR performance with high onset potential (0.986 VRHE), half‐wave potential (0.877 VRHE), and excellent stability. Similar ORR results are also found for Pd−Sm2O3/C, Pd−Eu2O3/C, and Pd−CeO2/C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2O3 promotes electron transfer through the Pd−O−Gd bridge, which induces the antibonding‐orbital occupancy of Pd−*OH for the optimization of *OH adsorption in the rate‐determining step of ORR. The pH‐dependent microkinetic modeling shows that Pd−Gd2O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd−Gd2O3/C exhibits superior performance in Zn‐air battery as an air cathode, implying its excellent practicability.

Importing Antibonding-Orbital Occupancy through Pd-O-Gd Bridge Promotes Electrocatalytic Oxygen Reduction.

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 O3 , Eu2 O3 , and CeO2 ) by using RE metal-organic frameworks to tune the ORR performance of the Pd sites through the Pd-REx Oy interface interaction. Taking Pd-Gd2 O3 /C as a representative, it is identified that the strong coupling between Pd and Gd2 O3 induces the formation of the Pd-O-Gd bridge, which triggers charge redistribution of Pd and Gd2 O3 . The screened Pd-Gd2 O3 /C exhibits impressive ORR performance with high onset potential (0.986 VRHE ), half-wave potential (0.877 VRHE ), and excellent stability. Similar ORR results are also found for Pd-Sm2 O3 /C, Pd-Eu2 O3 /C, and Pd-CeO2 /C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2 O3 promotes electron transfer through the Pd-O-Gd bridge, which induces the antibonding-orbital occupancy of Pd-*OH for the optimization of *OH adsorption in the rate-determining step of ORR. The pH-dependent microkinetic modeling shows that Pd-Gd2 O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd-Gd2 O3 /C exhibits superior performance in Zn-air battery as an air cathode, implying its excellent practicability.

What Is the Rate-Limiting Step of Oxygen Reduction Reaction on Fe-N-C Catalysts?

Oxygen reduction reaction (ORR) is essential to various renewable energy technologies. An important catalyst for ORR is single iron atoms embedded in nitrogen-doped graphene (Fe-N-C). However, the rate-limiting step of the ORR on Fe-N-C is unknown, significantly impeding understanding and improvement. Here, we report the activation energies of all of the steps, calculated by ab initio molecular dynamics simulations under constant electrode potential. In contrast to the common belief that a hydrogenation step limits the reaction rate, we find that the rate-limiting step is oxygen molecule replacing adsorbed water on Fe. This occurs through concerted motion of H2O desorption and O2 adsorption, without leaving the site bare. Interestingly, despite being an apparent "thermal" process that is often considered to be potential-independent, the barrier reduces with the electrode potential. This can be explained by stronger Fe-O2 binding and weaker Fe-H2O binding at a lower potential, due to O2 gaining electrons and H2O donating electrons to the catalyst. Our study offers new insights into the ORR on Fe-N-C and highlights the importance of kinetic studies in heterogeneous electrochemistry.

Effect of Zn doping on Sr3Fe2O7-δ Ruddlesden-Popper oxides as active and robust cathodes for protonic ceramic fuel cells

Perovskite oxides are promising electrodes for protonic ceramic fuel cells (PCFCs) due to their good electrochemical performance and stability. However, the lower operating temperature results in a large polarization resistance and sluggish oxygen reduction reaction (ORR) in cathodes. Herein, Ruddlesden-Popper (R–P) type perovskite Sr3Fe2-xZnxO7-δ (SFZx, x = 0, 0.1, 0.5) were successfully synthesized and the partial replacement of Fe by Zn in SFZx demonstrates a superior ORR activity. At 750 °C, the polarization resistance of SFZ05 is 0.072 Ω cm−2, which is 47% lower than that of the undoped Sr3Fe2O7-δ (SFO), and the peak power density of the single-cell with an SFZ05 cathode reaches 523.56 mW cm−2. The distribution of relaxation time (DRT) results manifest that the rate-limiting steps of ORR are charge transfer and ionic migration processes. Furthermore, SFZ05 also presented better CO2 tolerance. These results show that SFZ05 is a promising cathode candidate with high activity and stability for PCFCs.

Regulation of oxygen vacancies and electronic structures by substituting Ba2+ at A-sites of LaNi0.5Mn0.5O3 double perovskites enabling high-performance catalysts for Mg-air batteries

The air cathodes impact the electrochemical performance of primary Mg-air batteries greatly, in which the activity of catalysts plays a decisive role. Perovskites attract significant attention for their high oxygen reduction reaction (ORR) catalytic activity, unique structure, simple synthesis, and low cost. Herein, a series of La1-xBaxNi0.5Mn0.5O3 (x = 0.1, 0.2, 0.3, 0.4, 0.5) catalysts fabricated by substituting Ba2+ for La3+ at the A-sites of LaNi0.5Mn0.5O3 are reported. As a result, the catalytic performance toward ORR exhibits a volcano curve with the increase of doping amount and the highest catalytic activity was achieved at 30 % of Ba2+ content. Importantly, the experimental and computational results explain the enhancement by the large O2 adsorption capacity, the formation of oxygen vacancies, the increase in the content of Mn3+ as an adsorption active site, and the upshift of the Mn-3d band center toward the Fermi level, thereby facilitating the O2 adsorption and reducing the energy barrier of the rate determining step of ORR. The Mg-air battery with the La0.7Ba0.3Ni0.5Mn0.5O3 catalyst displays a high discharge voltage of 1.37 V and a maximum power density of 65.224 mW·cm-2. Therefore, this new ORR catalyst presents great potential in practical Mg-air batteries.

Axial Oxygen Ligands Regulating Electronic and Geometric Structure of Zn-N-C Sites to Boost Oxygen Reduction Reaction.

Zn-N-C possesses the intrinsic inertia for Fenton-like reaction and can retain robust durability in harsh circumstance, but it is often neglected in oxygen reduction reaction (ORR) because of its poor catalytic activity. Zn is of fully filled 3d10 4s2 configuration and is prone to evaporation, making it difficult to regulate the electronic and geometric structure of Zn center. Here, guided by theoretical calculations, five-fold coordinated single-atom Zn sites with four in-plane N ligands is constructed and one axial O ligand (Zn-N4 -O) by ionic liquid-assisted molten salt template method. Additional axial O not only triggers a geometry transformation from the planar structure of Zn-N4 to the non-planar structure of Zn-N4 -O, but also induces the electron transfer from Zn center to neighboring atoms and lower the d-band center of Zn atom, which weakens the adsorption strength of *OH and decreases the energy barrier of rate determining step of ORR. Consequently, the Zn-N4 -O sites exhibit improved ORR activity and excellent methanol tolerance with long-term durability. The Zn-air battery assembled by Zn-N4 -O presents a maximum power density of 182mWcm-2 and can operate continuously for over 160h. This work provides new insights into the design of Zn-based single atom catalysts through axial coordination engineering.

Boosting the Acidic Oxygen Reduction Activity of p‐Block Single‐Atomic Catalyst via p–p Orbital Coupling and Pore Engineering

Atomically dispersed main group element single‐atom catalysts (SACs) have recently attracted increasing attention in electrocatalysis. However, their performances in acidic oxygen reduction reaction (ORR) remain unsatisfactory owing to the suboptimal coordination environment, limited mass transfer, and active site exposure. Herein, a series of p‐block Sn SACs with hierarchical pore structures are prepared by a dual melting salt‐mediated soft template method. By deliberately regulating the pore structures, highly exposed Sn active sites with N/O coordination are obtained, which endow SnN3O‐50 with exceptional ORR performances, especially in acidic medium. The half‐wave potential of SnN3O‐50 is up to 0.816 V, with a loss of only 15 mV after 10 000 potential cycles. Furthermore, the peak power densities of the fuel cell and zinc–air battery assembled using SnN3O‐50 as cathodes reach 502 and 173.5 mW cm−2, respectively, demonstrating great potential for practical applications. Density functional theory (DFT) calculations reveal that the N/O coordination of Sn induces localization of 5p electrons, which leads to strong coupling with the p orbit of O2. Meanwhile, the presence of defects synergistically regulates the adsorption of reaction intermediates, thereby optimizing the free energy of the four successive ORR steps.

Strategies to Improve the Oxygen Reduction Reaction Activity on Pt-Bi Bimetallic Catalysts: A Density Functional Theory Study.

Decreasing the level of use of Pt in proton exchange membrane fuel cells is of great research interest both academically and industrially. In this work, we systematically studied the oxygen reduction reaction (ORR) following the four-electron association mechanism at various Pt-Bi surfaces with density functional theory calculations. The results showed that the introduction of Bi changes the potential-determining step of ORR. Moreover, the hydroxy adsorption free energy (GOH*) can be used as a descriptor of ORR activity, and 0.74 eV is the ideal GOH* for it to reach its maximum. Notably, we also found that the tensile strain introduced by Bi and electron transfer between Pt and Bi synergize to modulate the d-band of Pt to contract, shift downward, and break the 5d96s1 valence electron configuration of Pt, and accordingly, PtBi(100), with the lowest d-band center, gives the best ORR activity, which is even slightly higher than that of Pt(111).

Decrypting the Influence of Axial Coordination on the Electronic Microenvironment of Co-N 5 Site for Enhanced Electrocatalytic Reaction

Decrypting the Influence of Axial Coordination on the Electronic Microenvironment of Co-N ₅ Site for Enhanced Electrocatalytic Reaction

Accelerating the oxygen adsorption kinetics to regulate the oxygen reduction catalysis via Fe3C nanoparticles coupled with single Fe-N4 sites

• The single-atom Fe catalyst was synthesized by Fe 3 C|Fe-N 4 coupled sites on 1D and 2D doped-carbon structures. • The formed Fe 3 C|Fe-N 4 sites can positively regulate the electronic structure of the Fe center in the catalyst. • DFT calculations indicate that the adjacent Fe 3 C activated single Fe-N 4 sites accelerate the oxygen adsorption kinetics. • The catalyst assembled ZABs manifested a higher power density and better stability than the Pt/C-based ZABs. Manipulating the electronic structure of Fe-N 4 single-sites to accelerate the oxygen adsorption kinetics is a commendable approach to improve the oxygen reduction reaction (ORR) performance of single-atom Fe catalysts but remains a challenge. Here we propose an endogenous regulation strategy to in situ design the single-atom Fe catalyst (Fe 3 C@NCNTs) derived from 1,8-diaminonaphthalene, iron trichloride, and graphitic carbon nitride via Fe-N 4 single-sites strongly coupled with Fe 3 C nanostructures, in which the combination of 1D and 2D doped-carbon structures and the formation of Fe 3 C|Fe-N 4 coupled sites can endow the catalyst with a considerably enhanced electrocatalytic activity and remarkable cycling stability to the ORR in Zn-air batteries. Theoretical calculations further reveal that endogenous Fe 3 C nanostructures can effectively activate the atomically dispersed Fe-N 4 sites, narrowing the energy barriers of the rate-limiting steps of ORR to promote the ORR catalytic performance. This work provides an effective way to in situ tune the electronic structure of metal atoms to boost the ORR performance of single-atom catalysts for electrochemical energy systems.

Tuning oxygen vacancy of the Ba0·95La0·05FeO3−δ perovskite toward enhanced cathode activity for protonic ceramic fuel cells

Innovation of highly active cathode is of great significance to the development of protonic ceramic fuel cells (PCFCs). Herein, tailoring oxygen vacancies in Zn-doped Ba0·95La0·05FeO3−δ (BLFZ) perovskite is proved to be beneficial for promoting the formation of proton defects. Hydration ability of the triple conducting BLFZ perovskites is confirmed by electrical conductivity relaxation (ECR). The results demonstrate that BLFZ exhibits a proton surface exchange coefficient of 1.34 × 10−3 cm s−1 at 600 °C, which greatly extends active sites from the electrolyte/cathode interface to the entire electrode. Mechanism and process elementary steps of the oxygen reduction reaction (ORR) of BLFZ-BaCe0.7Zr0·1Y0.1Yb0.1O3−δ (BCZYYb) are detailedly studied. It is found that the rate-determining step of ORR is surface dissociative adsorption of oxygen on BLFZ-BCZYYb cathode. A maximum power density of 673 mW cm−2 at 700 °C is achieved and BLFZ-BCZYYb based single-cell shows no obvious degradation at 600 °C for 200 h. The good performance is ascribed to the rapid proton diffusion of BLFZ-BCZYYb composite electrode by regulating the oxygen vacancies.

Multilevel Computational Studies Reveal the Importance of Axial Ligand for Oxygen Reduction Reaction on Fe-N-C Materials.

The systematic improvement of Fe-N-C materials for fuel cell applications has proven challenging, due in part to an incomplete atomistic understanding of the oxygen reduction reaction (ORR) under electrochemical conditions. Herein, a multilevel computational approach, which combines ab initio molecular dynamics simulations and constant potential density functional theory calculations, is used to assess proton-coupled electron transfer (PCET) processes and adsorption thermodynamics of key ORR intermediates. These calculations indicate that the potential-limiting step for ORR on Fe-N-C materials is the formation of the FeIII-OOH intermediate. They also show that an active site model with a water molecule axially ligated to the iron center throughout the catalytic cycle produces results that are consistent with the experimental measurements. In particular, reliable prediction of the ORR onset potential and the Fe(III/II) redox potential associated with the conversion of FeIII-OH to FeII and desorbed H2O requires an axial H2O co-adsorbed to the iron center. The observation of a five-coordinate rather than four-coordinate active site has significant implications for the thermodynamics and mechanism of ORR. These findings highlight the importance of solvent-substrate interactions and surface charge effects for understanding the PCET reaction mechanisms and transition-metal redox couples under realistic electrochemical conditions.