Electrocatalytic Oxygen Research Articles

A ZnFeNiCoCr high-entropy alloy for efficient bifunctional oxygen electrocatalysis

A ZnFeNiCoCr high-entropy alloy for efficient bifunctional oxygen electrocatalysis

Dynamic Self-Healing of the Reconstructed Phase in Perovskite Oxides for Efficient and Stable Electrocatalytic OER.

Neither electrocatalytic activity nor structural stability is inconsequential in water electrolysis. Unfortunately, they have to be compromised in practice, especially in the anodic redox chemistry of lattice oxygen. Herein, the discovery of a La1- xCexFeO3 perovskite is presented which shows both good stability and high catalytic activity. Using advanced operando characterizations, it is identified that the self-healing evolution of the La1- xCexFeO3 perovskite plays a key role during water oxidation in the lattice oxygen-mediated mechanism (LOM) pathway. Unlike irreversible reconstruction, the formation of reconstructed active-phase α-FeOOH is reversed by re-crystallization of surface La1- xCexFeO3 upon return to noncatalytic conditions. The self-healing transformation of the α-FeOOH termination layer on the stable La1- xCexFeO3 core imparts remarkable long-term stability as well as excellent electrocatalytic performance. As a result, a composition La0.9Ce0.1FeO3@FeOOH is designed that exhibits ultralow overpotentials of 257 and 312mV to achieve 10 and 100mAcm-2, respectively. The findings provide insight into self-healing behavior toward engineering perovskite oxides for efficient and stable oxygen electrocatalysis.

Reconstructing the Coordination Environment of Fe/Co Dual-atom Sites towards Efficient Oxygen Electrocatalysis for Zn-Air Batteries.

Dual-atom catalysts with nitrogen-coordinated metal sites embedded in carbon can drive the oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc-air batteries (ZABs), and the further improvement is limited by the linear scaling relationship of intermediate binding energies in the absorbate evolution mechanism (AEM). Triggering the lattice oxygen mechanism (LOM) is promising to overcome this challenge, but has yet been verified since the lacking of bridge oxygen (O) in the rigid coordination environment of the metal centers. Here, we demonstrate that suitably tailored dual-atom catalysts of FeCo-N-C can undergo out-plane and in-plane reconstruction to form the both axial O and bridge O at the metal centers, and thus activate the LOM pathway. The tailored FeCo-N-C with shortened Fe-N bonds also favor the ORR process, therefore is a promising dual-atom oxygen catalyst. The assembled rechargeable ZABs demonstrate a peak power density of 332 mW cm-2, and exhibit no notable decline after ~ 720 h of continuous cycling.

FeN4S1 Single-Atom Sites Anchored on Three-Dimensional Porous Carbon for Highly Efficient and Durable Oxygen Electrocatalysis.

Precisely designing asymmetric active centers and exploring their electronic regulation effects to prepare efficient bifunctional single-atom catalysts (SACs) is important for boosting the practical applications of zinc-air batteries (ZABs). Herein, an effective strategy has been developed by introducing an axial S atom to the FeN4 active center, simultaneously assisted by pyrolyzing the graphene oxide (GO) sheathed zeolitic-imidazolate framework-8 (ZIF8) composite and constructing a three-dimensional (3D) porous framework with abundant FeN4S1 moieties. This structure can accelerate the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics owing to the modulated electronic redistribution and d-band center with a reduced energy barrier. The optimal S-Fe-NC/rGO showcases a lower voltage gap (ΔE) of 0.64 V between both the ORR and OER half-wave potentials at 10 mA cm-2, highlighting the excellent bifunctional activities. The assembled S-Fe-NC/rGO rechargeable liquid ZABs deliver a power density of 154.05 mW·cm-2 and a desirable durability of >900 h. More importantly, the corresponding flexible solid-state ZABs exhibit considerable foldability.

Frontispiece: Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Frontispiece: Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Frontispiz: Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Frontispiz: Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Rational Design of Diatomic Active Sites for Elucidating Oxygen Evolution Reaction Performance Trends

AbstractDiatomic catalysts, especially those with heteronuclear active sites, have recently attracted significant attention for their advantages over single‐atom catalysts in reactions with relatively high energy barrier, e.g. oxygen evolution reaction. Rational design and synthesis of heteronuclear diatomic catalysts are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report macrocyclic precursor constrained strategy to fabricate series of transition metal (MT, Ni, Co, Fe, Mn, or Cu)‐noble (MN, Ir or Ru) centers in carbon material. One notable performance trend is observed in the order of Cu−MN<Mn−MN<Fe−MN<MN<Co−MN<Ni−MN. Meanwhile, the pathway has been not altered, still following the traditional adsorption reaction mechanism. The effect of the MT atoms on the performances could possibly originate from the distinct adsorption/desorption behaviors of key intermediates (i.e. *OH, *O and/or *OOH), strongly implying that ΔG*OOH–ΔG*OH could be used as the performance descriptor. We believe that our work provides useful strategy for synthesis of diatomic active sites with sole coordination configuration and varied composition, and in‐depth insight to their catalytic mechanism, which could be used for further optimization of diatomic catalysts towards oxygen electrocatalysis.

Theoretical Investigation of Single-, Double-, and Triple- p-block Metals Anchored on g-CN Monolayer for Oxygen Electrocatalysis.

The design and development of highly active non-noble metal electrocatalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are crucial for metal-air batteries. In this work, the electrocatalytic performance of different p-block metal (PM = Sn, Sb, Pb and Bi) atoms embedded in the g-CN monolayer (PMx@g-CN, x = 1-3) for the OER and ORR was systematically investigated by density functional theory (DFT). The strong interaction between PMx atoms and g-CN substrates indicates the good stability of PMx@g-CN catalysts. Among all the designed catalysts, Bi3@g-CN is found to be a promising bifunctional electrocatalyst for both the OER and ORR with the calculated overpotential ηOER and ηORR of 0.23 and 0.25 V, respectively. With the atomic active sites of PMx increasing from x = 1 to 3, the OER and ORR catalytic activity is enhanced. The correlations between the overpotentials of the OER/ORR and Bader charge values of the anchored PMx atoms of the catalysts were established. Our findings contribute to searching for noble metal-free bifunctional electrocatalysts and shed light on the rational design of atomic active sites on electrocatalysts.

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.

Enabling High‐Rate and Long‐Cycling Zinc–Air Batteries with a ΔE = 0.56 V Bifunctional Oxygen Electrocatalyst

AbstractZn–air batteries (ZABs) are promising next‐generation energy storage devices due to their low cost, intrinsic safety, and environmental benignity. However, the sluggish kinetics of the cathodic reactions severely limits the ZAB performances in practical use, calling for high‐efficiency bifunctional oxygen reduction and evolution electrocatalysts. Herein, an ultrahigh‐active bifunctional electrocatalyst is developed with a record‐low ΔE of 0.56 V, significantly outperforming the noble‐metal‐based benchmark (Pt/C+Ir/C, ΔE = 0.77 V) and many other reported bifunctional electrocatalysts (mostly ΔE ≥ 0.60 V). The nanoscale composite of Fe‐based single‐atom sites and nanosized layered double hydroxides endows the bifunctional electrocatalyst with high conductivity and a large active surface that afford strengthened electron conduction and ion transport pathways. Furthermore, a remarkable improvement in stability is realized following the current division principle. ZABs with the bifunctional electrocatalyst deliver a high peak power density of 198 mW cm−2 and excellent cycling durability for over 6000 cycles. Moreover, ampere‐hour‐scale ZABs are constructed and cycled under 1.0 A and 1.0 Ah conditions. This work breaks the activity record for bifunctional oxygen electrocatalysis and expands the potential of ZABs for sustainable energy storage.

An open source electrochemical channel flow cell setup for kinetics studies. Application to investigations on oxygen electrocatalysis.

An open source electrochemical channel flow cell setup for kinetics studies. Application to investigations on oxygen electrocatalysis.

Evaluating nonmetal atom doping in two-dimensional VSe2 monolayers for hydrogen and oxygen electrocatalysis

Evaluating nonmetal atom doping in two-dimensional VSe2 monolayers for hydrogen and oxygen electrocatalysis

Edge-substituents and center metal optimization boosting oxygen electrocatalysis in porphyrin-based covalent organic polymers

Edge-substituents and center metal optimization boosting oxygen electrocatalysis in porphyrin-based covalent organic polymers

Prediction of perovskite oxygen vacancies for oxygen electrocatalysis at different temperatures

Efficient catalysts are imperative to accelerate the slow oxygen reaction kinetics for the development of emerging electrochemical energy systems ranging from room-temperature alkaline water electrolysis to high-temperature ceramic fuel cells. In this work, we reveal the role of cationic inductive interactions in predetermining the oxygen vacancy concentrations of 235 cobalt-based and 200 iron-based perovskite catalysts at different temperatures, and this trend can be well predicted from machine learning techniques based on the cationic lattice environment, requiring no heavy computational and experimental inputs. Our results further show that the catalytic activity of the perovskites is strongly correlated with their oxygen vacancy concentration and operating temperatures. We then provide a machine learning-guided route for developing oxygen electrocatalysts suitable for operation at different temperatures with time efficiency and good prediction accuracy.

Recent Advances in Engineering Fe-N-C Catalysts for Oxygen Electrocatalysis in Zn-Air Batteries.

Fe-N-C single-atom catalysts (SACs) have emerged as one of the most promising candidates for oxygen electrocatalysis due to their maximized atom utilization efficiency, high intrinsic activity, and strong metal-support interaction. Significant progress has been made in engineering Fe-N-C SACs for oxygen electrocatalysis in Zn-air batteries (ZABs). This review provides a comprehensive overview of the recent advancements in Fe-N-C SACs, with a special focus on effective engineering strategies, their performance in oxygen electrocatalysis, and their potential applications in ZABs. The review also discusses the key challenges and future directions in the development of Fe-N-C SACs for efficient and durable oxygen electrocatalysis in ZABs. This review aims to offer valuable insights into the current state of research in this field and to guide future efforts in the development of advanced oxygen electrocatalysts for ZABs.

Redox Activity of Co Species in the Active Sites of CoNx/CoOx Facilitates Oxygen Electrocatalysis for Zn-Air Batteries.

Developing efficient bifunctional oxygen electrocatalysts is crucial for enhancing the performance of rechargeable Zn-air batteries (ZABs). In this study, cobalt/cobalt oxides embedded in N-doped carbon nanofibers (Co/CoOx/NCNFs) were synthesized through a combination of electrospinning and annealing processes. The resulting Co/CoOx/NCNFs catalysts feature abundant CoNx and CoOx active species, leveraging the large specific surface area of nanofibers to facilitate oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The optimized Co/CoOx/NCNFs-0.1 achieved a half-wave potential (vs. RHE) of 0.82 V and required only 429 mV to reach 10 mA cm-2 in a typical three-electrode system with 0.1 M KOH using an electrochemical workstation equipped with a pine instruments rotator, outperforming the Pt/C+RuO2. The assembled ZABs exhibited high specific capacity (771 mAh gZn -1), substantial power density (981.6 mWh gZn -1), and long-term stability (>325 h). In situ Raman spectroscopy confirmed that the electrocatalytic processes involve the redox activity of Co (II and III) species derived from abundant CoNx and CoOx, elaborating the origin of the catalysts' exceptional oxygen electrocatalysis performance. This work not only presents a straightforward and effective approach for producing bifunctional oxygen electrocatalysts in ZABs but also sheds light on the catalytic mechanisms underlying ORR and OER for CoNx/CoOx-based oxygen electrocatalysts.

Strong Metal-Support Interactions in Heterogeneous Oxygen Electrocatalysis.

Molecular oxygen redox electrocatalysis involves oxygen reduction and evolution as core reactions in various energy conversion and environmental technology fields. Strong metal-support interactions (SMSIs) based nanomaterials are regarded as desirable and state-of-the-art heterogeneous electrocatalysts due to their exceptional physicochemical properties. Over the past decades, considerable advancements in theory and experiment have been achieved in related studies, especially in modulating the electronic structure and geometrical configuration of SMSIs to enable activity, selectivity, and stability. In this focuses on the concept of SMSI, explore their various manifestations and mechanisms of action, and summarizes recent advances in SMSIs for efficient energy conversion in oxygen redox electrocatalysis applications. Additionally, the correlation between the physicochemical properties of different metals and supports is systematically elucidated, and the potential mechanisms of the structure-activity relationships between SMSIs and catalytic performance are outlined through theoretical models. Finally, the obstacles confronting this burgeoning field are comprehensively concluded, targeted recommendations and coping strategies are proposed, and future research perspectives are outlined.

FeCo Bimetallic ZIF Derivatives decorated with CoFe-LDH to Promote Bifunctional Oxygen Electrocatalysis Activation.

Reasonably screening the targeted oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) constituents and constructing high-efficiency and stabilized ORR/OER bifunctional electrocatalysts are pivotal for the advancement of rechargeable zinc-air batteries (ZABs). Here, CoFe layered double hydroxide (CoFe-LDH) nanosheets are deposited on nitrogen-doped graphite-carbon polyhedra with FeCo alloy nanoparticles (FeCo/LDH-NGCP). Due to the synergic effect between FeCo-NGCP, CoFe-LDH and FeCo/LDH-NGCP, the electrocatalyst with the abundant and accessible active sites can provide good charge/mass transfer, and thus shows wonderful ORR and OER bifunctional electrocatalytic performance. In ORR tests, FeCo/LDH-NGCP catalyst displays larger half-wave potential (E1/2, 0.89 V vs. 0.85 V), higher limiting current density (JL, 5.91 mA/cm2 vs. 5.14 mA/cm2) and better stability than commercial Pt/C. As for OER, FeCo/LDH-NGCP possesses a smaller overpotential (η) of 299.6 mV at a current density of 10 mA/cm2 and more durable stability than commercial RuO2 (330.6 mV). Furthermore, in ZAB tests, the cycling stability of ZAB-FeCo/LDH-NGCP (over 470 h) outperforms the ZAB-Pt/C+RuO2 (92 h) with commercial electrocatalyst (Pt/C+RuO2). Therefore, the FeCo/LDH-NGCP catalyst offers a new perspective to construct ZABs bifunctional catalysts and their commercial application in ZABs.

Active learning accelerated exploration of single-atom local environments in multimetallic systems for oxygen electrocatalysis

Single-atom catalysts (SACs) with multiple active sites exhibit high activity for a wide range of sluggish reactions, but identifying optimal multimetallic SAC is challenging due to the vast design space. Here, we present a self-driving computational strategy that combines first-principles calculations and equivariant graph neural network (GNN) to explore over 30,000 binary metallic sites with varying combinations of 3d transition metals and different ligand environments for oxygen reduction and evolution reactions (ORR/OER). Active learning facilitates the investigation of the search space by balancing the exploration of unseen atomic structures with the exploitation of the active ones. The GNN learns the chemical environments to capture composition-structure-property relationships for ORR/OER activity and selectivity. The computational predictions of promising Co-Fe, Co-Co, and Co-Zn metal pairs are consistent with the state-of-the-art results of experimental measurements reported in the literature. This approach can be extended to a broader class of multi-element high entropic materials systems.

Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis.

Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist proton transfer in channels, few studies are dedicated to improving proton transfer at the local environments of active sites in porous materials. Herein, we report on new Co-corrole-based porous organic polymers (POPs) with improved proton transfer for electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). By tuning the pore sizes and installing proton relays at Co corrole sites, we designed and synthesized POP-2-OH with improved proton transfer both in channels and at local Co active sites. This POP shows remarkable activity for both electrocatalytic ORR with E1/2=0.91 V vs RHE and OER with η10=255 mV. Therefore, this work is significant to present a strategy to improve active site local proton transfer in porous materials and highlight the key role of such structural functionalization in boosting oxygen electrocatalysis.