Oxygen Reduction Reaction Performance Research Articles

Tuning Two-Dimensional Phthalocyanine Dual Site Metal-Organic Framework Catalysts for the Oxygen Reduction Reaction.

Metal-organic frameworks (MOFs) offer an interesting opportunity for catalysis, particularly for metal-nitrogen-carbon (M-N-C) motifs by providing an organized porous structural pattern and well-defined active sites for the oxygen reduction reaction (ORR), a key need for hydrogen fuel cells and related sustainable energy technologies. In this work, we leverage electrochemical testing with computational models to study the electronic and structural properties in the MOF systems and their relationship to ORR activity and stability based on dual transitional metal centers. The MOFs consist of two M1 metals with amine nodes coordinated to a single M2 metal with a phthalocyanine linker, where M1/M2 = Co, Ni, or Cu. Co-based metal centers, in particular Ni-Co, demonstrate the highest overall activity of all nine tested MOFs. Computationally, we identify the dominance of Co sites, relative higher importance of the M2 site, and the role of layer M1 interactions on the ORR activity. Selectivity measurements indicate that M1 sites of MOFs, particularly Co, exhibit the lowest (<4%), and Ni demonstrates the highest (>46%) two-electron selectivity, in good agreement with computational studies. Direct in situ stability characterization, measuring dissolved metal ions, and calculations, using an alkaline stability metric, confirm that Co is the most stable metal in the MOF, while Cu exhibits notable instability at the M1. Overall, this study reveals how atomistic coupling of electronic and structural properties affects the ORR performance of dual site MOF catalysts and opens new avenues for the tunable design and future development of these systems for practical electrochemical applications.

Carbon Corrosion Induced by Surface Defects Accelerates Degradation of Platinum/Graphene Catalysts in Oxygen Reduction Reaction.

Graphene supported electrocatalysts have demonstrated remarkable catalytic performance for oxygen reduction reaction (ORR). However, their durability and cycling performance are greatly limited by Oswald ripening of platinum (Pt) and graphene support corrosion. Moreover, comprehensive studies on the mechanisms of catalysts degradation under 0.6-1.6V versus RHE (Reversible Hydrogen Electrode) is still lacking. Herein, degradation mechanisms triggered by different defects on graphene supports are investigated by two cycling protocols. In the start-up/shutdown cycling (1.0-1.6V vs.RHE), carbon oxidation reaction (COR) leads to shedding or swarm-like aggregation of Pt nanoparticles (NPs). Theoretical simulation results show that the expansion of vacancy defects promotes reaction kinetics of the decisive step in COR, reducing its reaction overpotential. While under the load cycling (0.6-1.0V vs.RHE), oxygen containing defects lead to an elevated content of Pt in its oxidation state which intensifies Oswald ripening of Pt. The presence of vacancy defects can enhance the transfer of electrons from graphene to the Pt surface, reducing the d-band center of Pt and making it more difficult for the oxidation state of platinum to form in the cycling. This work will provide comprehensive understanding on Pt/Graphene catalysts degradation mechanisms.

Interlayer Polymerization to Construct a Fully Conjugated Covalent Organic Framework as a Metal-Free Oxygen Reduction Reaction Catalyst for Anion Exchange Membrane Fuel Cells.

Two-dimensional (2D) covalent organic frameworks (COFs) have a multilayer skeleton with a periodic π-conjugated molecular array, which can facilitate charge carrier transport within a COF layer. However, the lack of an effective charge carrier transmission pathway between 2D COF layers greatly limits their applications in electrocatalysis. Herein, by employing a side-chain polymerization strategy to form polythiophene along the nanochannels, a conjugated bridge is constructed between the COF layers. The as-synthesized fully conjugated COF (PTh-COF) exhibits high oxygen reduction reaction (ORR) activity with narrowed energy band gaps. Correspondingly, PTh-COF is tested as a metal-free cathode catalyst for anion exchange membrane fuel cells (AEMFCs) which showed a maximum power density of 176mWcm-2 under a current density of 533mAcm-2. The density functional theory (DFT) calculation reveals that interlayer conjugated polythiophene optimizes the electron cloud distribution, which therefore enhances the ORR performance. This work not only provides new insight into the construction of a fully conjugated covalent organic framework but also promotes the development of new metal-free ORR catalysts.

Metal–organic framework–derived trimetallic particles encapsulated by ultrathin nitrogen-doped carbon nanosheets on a network of nitrogen-doped carbon nanotubes as bifunctional catalysts for rechargeable zinc–air batteries

Economical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalysts with high activity aimed at replacing precious metal catalysts for rechargeable zinc-air batteries (ZABs) must be developed. In this study, a multiple hierarchical-structural material is developed using a facile dielectric barrier discharge (DBD) plasma surface treatment, solvothermal reaction, and high-temperature carbonization strategy. This strategy allows for the construction of nanosheets using nitrogen-doped carbon (NC) material-encapsulated ternary CoNiFe alloy nanoparticles (NPs) on a network of NC nanotubes (NCNTs), denoted as CoNiFe–NC@p–NCNTs. Precisely, the presence of abundant CoNiFe alloy NPs and the formation of M–N–C active sites created by transition metals (cobalt, nickel, and iron) coupled with NC can provide superior OER/ORR bifunctional properties. Moreover, the prepared NC layers with a multilevel pore structure contribute to a larger specific surface area, exposing numerous active sites and enhancing the uniformity of electron and mass movement. The CoNiFe0.08–NC@p–NCNTs show remarkable dual functionality for electrochemical oxygen reactions (ORR half-wave potential of 0.811 V, limiting current density of 5.73 mA cm−2 measured with a rotating disk electrode at a rotation speed of 1600 rpm, and OER overpotential of 351 mV at 10 mA cm−2), which demonstrates similar ORR performance to 20 wt% Pt/C and better OER performance than the commercial RuO2. A liquid ZAB prepared using the proposed material has excellent bifunctionality with an open-circuit voltage of 1.450 V and long-term cycling stability of 230 h@10 mA cm−2.

A Simultaneous Modulation Strategy to Construct High Dense and Accessible Co‐N4 Sites for Promoting Oxygen Reduction Reaction in Zn–Air Battery

AbstractTransition metal‐nitrogen‐carbon single‐atom catalysts (M─N─C SACs) exhibit outstanding catalytic activity for the oxygen reduction reaction (ORR). However, these catalysts still face the dual challenges of low density and low utilization of active sites in practical applications. Hence, a simultaneous modulation strategy to construct high‐density and accessible Co‐N4 sites on nitrogen‐doped porous carbon (CoH SA/NC), is reported. As expected, the optimized CoH SA/NC catalyst exhibits superior ORR activity with a half‐wave potential value of 0.874 V, outperforming that of the benchmark Pt/C catalyst. Importantly, the mass activity and turnover frequency of CoH SA/NC are 14.7 and 13.3 times higher than that of low‐density Co single atom catalyst (CoL SA/NC), respectively. Structural characterization and density functional theory (DFT) reveal that the porous structure and the high dense Co‐N4 sites synergistically improve the ORR performance, in which the high dense Co‐N4 sites induced a redistribution of the d orbital, resulting in dz2 orbital has enough electron to interact with the OOH* specie, thereby facilitating the kinetic process of ORR. Moreover, CoH SA/NC‐based Zn–Air Battery (ZAB) also showed excellent device performance, including a high‐power density (191.7 mW cm−2), high specific capacity, and outstanding stability (250 h), significantly superior to benchmark Pt/C‐based ZABs.

A facile dual isolation and protection strategy for preparation of PtFe intermetallic compound in biomass-derived carbon with high activity and durability for pH-universal bifunctional electrocatalysts

A facile dual isolation and protection strategy is developed to prepare PtFe intermetallic electrocatalyst (PtFe–N–C@bioC) on porous biomass carbon (bioC) derived from peanut shell. In preparation, meso-tetraphenylporphyrine (H2TPP) together with platinum (II)-tetraphenylporphyrin (PtTPP) are in-situ fabricated on the porous peanut shell-derived bioC matrixes and then further absorbed Fe (III) tetraphenyl porphyrin (FeTPP) molecules through π−π interactions between PtTPP/H2TPP and FeTPP to form a mixed precursor of FeTPP/PtTPP/TPP-bioC. Upon pyrolysis of FeTPP/PtTPP/TPP-bioC, PtFe bimetallic-containing N-doped carbon formed on bioC (PtFe–N–C@bioC). The resultant PtFe–N–C@bioC showed excellent oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) activity across a wide pH range. In particular, under alkaline medium, PtFe–N–C@bioC shows the ORR performance with an onset potential (Eonset) of 0.989 V, a half-wave potential (E1/2) of 0.901 V and a limiting current density (JL) of −6.214 mA cm−2. Meanwhile, PtFe–N–C@bioC delivers an enhanced mass activity (1.197 A mg−1Pt), which is 13 times larger than commercial Pt/C. For HER, PtFe–N–C@bioC shows an impressive overpotential (η10) of 17 mV at a current density of 10 mA cm−2 under acidic medium. Further, it is applied to Zn-Air batteries with a power density performance of 98.7 mW cm−2 and good durability.

Dealloyed Pt74Ni26 and Pt26Ni74 Electrodeposited Thin Film Electrocatalysts for Oxygen Reduction

Abstract Electrodeposition and microstructure of thin films close to Pt75Ni25 and Pt25Ni75 stoichiometry are described and their catalytic oxygen reduction reaction performance, dealloying, and strain evolution detailed. Multiple techniques are used to characterize the morphology, crystalline structure, and chemical homogeneity of as-deposited and dealloyed films. A fine-scale percolating network of lower-density regions is evident in the as-deposited Pt74Ni26 films while the as-deposited Pt26Ni74 films are more homogenous and compact. Electrodeposition is accompanied by development of significant in-plane tensile stress that increases at more negative applied growth potentials to reach 1.28 GPa for as-deposited Pt26Ni74. Dealloying of the near-surface regions of Pt74Ni26 is accompanied by limited expansion or opening of the low-density regions while massive dealloying of the highly stressed Pt26Ni74 results in shrinkage, extensive cracking, and formation of a bi-continuous nanoporous structure with an average pore diameter close to 5 nm. Relative to electrodeposited Pt, the alloy films exhibit enhanced area-specific oxygen reduction reaction activity (at 0.95 V vs. RHE, iR-corrected) that amounts to a factor of 3.4 for dealloyed Pt74Ni26 and 5.1 for dealloyed Pt26Ni74 while the Pt-based mass activity increased by a factor of 5.1 and 12.3, for the respective films.

Linker Mediated Electronic-State Manipulation ofConjugated Organic Polymers Enabling Highly Efficient Oxygen Reduction.

Conjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure-performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen reduction reaction (ORR). Specifically, a set of cobalt phthalocyanine conjugated polymers (CoPc-CPs) wrapped onto carbon nanotubes (denoted CNTs@CoPc-CPs) are judiciously crafted via in situ assembling square-planar cobalt tetraaminophthalocyanine (CoPc(NH2)4) with different linear aromatic dialdehyde-based organic linkers in the presence of CNTs. Intriguingly, upon varying the electronic characteristic of organic linkers from terephthalaldehyde (TA) to 2,5-thiophenedicarboxaldehyde (TDA) and then to thieno/thiophene-2,5-dicarboxaldehyde (bTDA), their corresponding CNTs@CoPc-CPs exhibit gradually improved electrocatalytic ORR performance. More importantly, theoretical calculations reveal that the charge transfer from CoPc units to electron-withdrawing linkers (i.e., TDA and bTDA) drives the delocalization of Co d-orbital electrons, thereby downshifting the Co d-band energy level. Accordingly, the active Co centers with more positive valence state exhibit optimized binding energy toward ORR-relevant intermediates and thus a balanced adsorption/desorption pathway that endows significant enhancement in electrocatalytic ORR. This work demonstrates a molecular-level engineering route for rationally designing efficient polymer catalysts and gaining insightful understanding of electrocatalytic mechanisms.

Synergistic Ni-W Dimer Sites Induced Stable Compressive Strain for Boosting the Performance of Pt as Electrocatalyst for the Oxygen Reduction Reaction.

Alloying Pt catalysts with transition metal elements is an effective pathway to enhance the performance of oxygen reduction reaction (ORR), but often accompanied with severe metal dissolution issue, resulting in poor stability of alloy catalysts. Here, instead of forming traditional alloy structure, we modify Pt surface with a novel Ni-W dimer structure by the atomic layer deposition (ALD) technique. The obtained NiW@PtC catalyst exhibits superior ORR performance both in liquid half-cell and practical fuel cell compared with initial Pt/C. It is discovered that strong synergistic Ni-W dimer structure arising from short atomic distance induced a stable compressive strain on the Pt surface, thus boosting Pt catalytic performance. This surface modification by synergistic dimer sites offers an effective strategy in tailoring Pt with excellent activity and stability, which provides a significant perspective in boosting the performance of commercial Pt catalyst modified with polymetallic atom sites.

In-situ probing polarization-induced stability of single-atom alloy electrocatalysts in metal-air battery via synchrotron-based X-ray diffraction

In this work, a novel single-atom alloy electrocatalyst (SAAE) was developed for enhanced electrocatalysis in next-generation energy technologies. The catalyst, composed of single-atom Rh and bulk Ni on FeV3O8 support, overcomes challenges related to stability and efficiency in electrochemical reactions. The work function difference between Rh and Ni, as confirmed by computational and synchrotron-based analysis, facilitates superior electric polarization and ohmic contact with FeV3O8. The FeV3O8@RhNi demonstrates outstanding performance in oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs), with high half-wave potential (0.90 V) and low overpotential (120 mV at 10 mA cm−2). In zinc-air batteries, it maintains a stable discharge–charge voltage gap, specific capacity of 810 mAh g−1, peak power density of 186 mW cm−2 at 320 mA cm−2, and cycle stabilities exceeding 859 h at 10 mA cm−2. The catalyst also proves its durability in flexible zinc–air batteries, indicating its potential for efficient electrocatalytic reactions in emerging energy technologies.

Synergistic Ni−W Dimer Sites Induced Stable Compressive Strain for Boosting the Performance of Pt as Electrocatalyst for the Oxygen Reduction Reaction

AbstractAlloying Pt catalysts with transition metal elements is an effective pathway to enhance the performance of oxygen reduction reaction (ORR), but often accompanied with severe metal dissolution issue, resulting in poor stability of alloy catalysts. Here, instead of forming traditional alloy structure, we modify Pt surface with a novel Ni−W dimer structure by the atomic layer deposition (ALD) technique. The obtained NiW@PtC catalyst exhibits superior ORR performance both in liquid half‐cell and practical fuel cell compared with initial Pt/C. It is discovered that strong synergistic Ni−W dimer structure arising from short atomic distance induced a stable compressive strain on the Pt surface, thus boosting Pt catalytic performance. This surface modification by synergistic dimer sites offers an effective strategy in tailoring Pt with excellent activity and stability, which provides a significant perspective in boosting the performance of commercial Pt catalyst modified with polymetallic atom sites.

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.

Constructing Directional Electrostatic Potential Difference via Gradient Nitrogen Doping for Efficient Oxygen Reduction Reaction.

Nitrogen doping has been recognized as an important strategy to enhance the oxygen reduction reaction (ORR) activity of carbon-encapsulated transition metal catalysts (TM@C). However, previous reports on nitrogen doping have tended to result in a random distribution of nitrogen atoms, which leads to disordered electrostatic potential differences on the surface of carbon layers, limiting further control over the materials' electronic structure. Herein, a gradient nitrogen doping strategy to prepare nitrogen-deficient graphene and nitrogen-rich carbon nanotubes encapsulated cobalt nanoparticles catalysts (Co@CNTs@NG) is proposed. The unique gradient nitrogen doping leads to a gradual increase in the electrostatic potential of the carbon layer from the nitrogen-rich region to the nitrogen-deficient region, facilitating the directed electron transfer within these layers and ultimately optimizing the charge distribution of the material. Therefore, this strategy effectively regulates the density of state and work function of the material, further optimizing the adsorption of oxygen-containing intermediates and enhancing ORR activity. Theoretical and experimental results show that under controlled gradient nitrogen doping, Co@CNTs@NG exhibits significantly ORR performance (Eonset=0.96V, E1/2=0.86V). At the same time, Co@CNTs@NG also displays excellent performance as a cathode material for Zn-air batteries, with peak power density of 132.65mAcm-2 and open-circuit voltage (OCV) of 1.51V. This work provides an effective gradient nitrogen doping strategy to optimize the ORR performance.

One-Pot Etching Pyrolysis to Defect-Rich Carbon Nanosheets to Construct Multiheteroatom-Coordinated Iron Sites for Efficient Oxygen Reduction.

Constructing multiheteroatom coordination structure in carbonaceous substrates demonstrates an effective method to accelerate the oxygen reduction reaction (ORR) of supported single-atom catalyst. Herein, the novel etching route assisted by potassium thiocyanate (KCNS) is developed to convert metal-organic framework to 2D defect-rich porous N,S-co-doped carbon nanosheets for anchoring atomically dispersed iron sites as the high-performance ORR catalysts (Fe-SACs). The well-designed KCNS-assisted etching route can generate spatial confinement template to direct the carbon nanosheet formation, etching condition to form defect-rich structure, and additional sulfur atoms to coordinate iron species. Spectral and microscopy analysis reveals that the iron element in Fe-SACs is highly isolated on carbon nanosheet and anchored by nitrogen and sulfur atoms in unsymmetrical Fe-S1N3 structure. The optimized Fe-SACs with large specific surface area could show remarkable alkaline ORR performances with a high half-wave potential of 0.920 V versus RHE and excellent durability. The rechargeable zinc-air battery assembled with Fe-SACs air electrodes delivers a large power density of 350 mW cm-2 and a stable voltage platform during charge and discharge over more than 1300 h. This work proposes a novel strategy for the preparation of single-atom catalysts with multiheteroatom coordination structure and highly exposed active sites for efficient ORR.

Highly Reversible Zn-Air Batteries Enabled by Tuned Valence Electron and Steric Hindrance on Atomic Fe-N4-C Sites.

The bifunctional oxygen electrocatalyst is the Achilles' heel of achieving robust reversible Zn-air batteries (ZABs). Herein, durable bifunctional oxygen electrocatalysis in alkaline media is realized on atomic Fe-N4-C sites reinforced by NixCo3-xO4 (NixCo3-xO4@Fe1/NC). Compared with that of pristine Fe1/NC, the stability of the oxygen evolution reaction (OER) is increased 10 times and the oxygen reduction reaction (ORR) performance is also improved. The steric hindrance alters the valence electron at the Fe-N4-C sites, resulting in a shorter Fe-N bond and enhanced stability of the Fe-N4-C sites. The corresponding solid-state ZABs exhibit an ultralong lifespan (>460 h at 5 mA cm-2) and high rate performance (from 2 to 50 mA cm-2). Furthermore, the structural evolution of NixCo3-xO4@Fe1/NC before and after the OER and ORR as well as charge-discharge cycling is explored. This work develops an efficient strategy for improving bifunctional oxygen electrocatalysis and possibly other processes.

Theoretical study of transition metal-oxygen doped carbon for oxygen reduction reaction

The transition metal doped carbon materials are currently one of the most promising electrocatalysts for the oxygen reduction reaction (ORR). In this work, the ORR properties of transition metal-oxygen doped carbon (TM-O4-C, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu) had been systematically studied by density function theory (DFT). Since the adsorption strength of OH* on TM-O4-C species was relatively strong, the effect of OH* modification was further considered. The results showed that the OH* modification can improve the ORR performance on TM-O4-C species by adjusting the d-band center of TM atoms to optimize the adsorption strength of the intermediate. Upon OH* modification, Ni-O4-OH-C species showed the most promising ORR performance with the lowest overpotential of 0.39 V. This work would shed light on the rational design of highly efficient oxygen-containing transition metal doped carbon-based materials.

Dimetallic praseodymium-cobalt carbon nanotubes as highly efficient electrocatalyst for oxygen reduction reaction

In this study, six bimetallic rare earth (RE = La, Ce, Pr, Nd, Sm, Eu) cobalt nitrogen doped carbon nanotubes (RECo-NCNTs) were synthesized with g-C3N4 derivative method. These RECo-NCNTs were characterized by SEM, BET, XPS, XRD and Raman. In addition, their catalytic performances for oxygen reduction reaction (ORR) had also been tested. The introduction of rare earths did not destroy the structure of nanotubes but apparently change their ORR performances. The PrCo-NCNTs showed the significant improvement in catalytic ability for ORR (onset potential of 0.95 V and half-wave potential of 0.79 V), which is very close to that of commercial 20 % Pt/C. Moreover, PrCo-NCNTs exhibits an excellent catalytic stability (no activity decay after 10000st cycles) and an outstanding methanol toxic tolerance. Assembled in metal–air batteries (Zn-air, Al-air and Mg-air), the PrCo-NCNTs electrode also presents high power densities and discharge voltages.

Regulation Strategies for Fe-N-C and Co-N-C Catalysts for the Oxygen Reduction Reaction.

Proton exchange membrane fuel cells (PEMFCs) and alkaline membrane fuel cells (AEMFCs) have received great attention as energy devices of the next generation. Accelerating oxygen reduction reaction (ORR) kinetics is the key to improve PEMFC and AEMFC performance. Platinum-based catalysts are the most widely used catalysts for the ORR, but their high price and low abundance limit the commercialization of fuel cells. Non-noble metal-nitrogen-carbon (M-N-C) is considered to be the most likely material class to replace Pt-based catalysts, among which Fe-N-C and Co-N-C have been widely studied due to their excellent intrinsic ORR performance and have made great progress in the past decades. With the improvement of synthesis technology and a deeper understanding of the ORR mechanism, some reported Fe-N-C and Co-N-C catalysts have shown excellent ORR activity close to that of commercial Pt/C catalysts. Inspired by the progress, regulation strategies for Fe-N-C and Co-N-C catalysts are summarized in this Review from 5 perspectives: (1) coordinated atoms, (2) environmental heteroatoms and defects, (3) dual-metal active sites, (4) metal-based particle promoters, and (5) curved carbon layers. We also make suggestions on some challenges facing Fe-N-C and Co-N-C research.

Macrocycle-based covalent-organic-polymer as efficient oxygen electrocatalysts for zinc-air flow batteries

Covalent organic polymers (COPs), as emerging porous materials with well-defined architectures and high hydrothermal stability, have attracted extensive attention in the field of electrocatalysis. Herein, we report a rational design method for preparing oxygen reduction reaction electrocatalysts with the assistance of a predesigned macrocyclic COP model molecular. With the predesigned nitrogen position and structural features in macrocyclic chain-like COP-based materials, the obtained COPMCT-Co-900 catalyst provided excellent oxygen reduction performance, where the half-wave potential (E1/2) reaches 0.85 V (vs . RHE), comparable to commercial Pt/C. We also extended the strategy to similar macrocycle COPs and Fe-based and Ni-based metal sources and studied the oxygen reduction reaction performance of corresponding catalysts, proving the universality of the method. Interestingly, we assemble COPMCT-Co-900 catalyst as air electrode catalyst of the self-made rechargeable zinc-air flow batteries, which exhibit outstanding power density (155.6 mW·cm-2) and long cycle life (90 h, 270 cycles at 10 mA·cm-2). Our studies provide a new method for the development of high-performance oxygen electrodes applied in zinc-air flow battery devices.

The electrocatalytic activity of pomelo peel-derived nitrogen-doped carbon material for oxygen reduction reaction

Exploring the non-precious metal catalysts of oxygen reduction reaction (ORR) becomes the key to promote the industrialization of new energy devices such as fuel cells and metal-air batteries because of the sluggish kinetics of ORR. Three-dimensional N-doped carbon (NC-900) material was obtained using the high-temperature pyrolysis of pomelo peel waste. The prepared NC-900 catalyst possesses an ultra-high specific surface area of 1631.3 m2·g−1, high content of 57.7 ± 0.9% pyrrolic-N, and three-dimensional porous structure. As the ORR catalyst, NC-900 has a onset potential of 0.992 V and half-wave potential of 0.859 V, comparable to 0.988 and 0.872 V of Pt/C. The typical 4-electron pathway of ORR process is occupied by the surface of NC-900. The ORR catalytic activity of NC-900 was almost unaffected by methanol. After 8 h of continuous operation, the reduction current on the surface of NC-900 was decreased only 2.7% of the initial current. Based on these outstanding ORR performances, the pomelo peel-derived NC-900 can serve as a strong competitor for the substitute of Pt/C to promote the potential industrialization of new energy devices.