Oxygen Reduction Electrocatalysts Research Articles

Ni-Doped La0.6Sr0.4CoO3 Perovskite as an Efficient Electrocatalyst for Oxygen Reduction and Evolution Reactions in Alkaline Media

The Co-based perovskite La0.6Sr0.4CoO3 has received significant attention as a potential electrocatalyst for its oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) due to its abundance, facile synthesis, and high oxygen kinetics. However, research on the catalytic performance of Ni-doped La0.6Sr0.4Co1−xNixO3 as a bifunctional cathode catalyst for Zn-air batteries (ZABs) is still scarce. In this work, lanthanum strontium cobalt-based perovskite catalysts with various Ni contents (La0.6Sr0.4Co1−xNixO3, x = 0, 0.2, 0.5, and 0.8) were synthesized using a simple combustion method. The effects of Ni doping on the morphology, structure, surface oxygen-related species, and valence states of the transition metals of the perovskite were characterized. The electrochemical behaviors of the perovskite catalysts in both ORR and OER were also assessed. The characterization results revealed that proper Ni doping can decrease particle size, increase surface oxygen vacancies, and create mixed valence states of the transition metal and, thus, lead to improvement of the electrocatalytic activity of perovskite catalysts. Among the different perovskite compositions, La0.6Sr0.4Co0.8Ni0.2O3 exhibited the best ORR/OER activity, with a higher limiting current density, smaller Tafel slope, higher half-wave potential, lower overpotential, and lower potential difference than the other compositions. When La0.6Sr0.4Co0.8Ni0.2O3 was applied as the cathodic catalyst in a primary ZAB, it delivered a peak power density of 81 mW cm−2. Additionally, in rechargeable ZABs, the La0.6Sr0.4Co0.8Ni0.2O3 catalyst exhibited a lower voltage gap (0.94 V) and higher stability during charge–discharge cycling than the commonly used catalyst Pt/C. These results indicate that Ni-doped La0.6Sr0.4Co0.8Ni0.2O3 is a promising bifunctional electrocatalyst for ZAB.

Nitrogen-doped carbon/graphitic CQDs composites with 98.8% microporosity as a highly stable electrocatalyst for oxygen reduction

Designing micropore-rich carbon materials with large specific surface area (SSA) as a carbon-based oxygen reduction reaction (ORR) electrocatalyst is still frontier but remains challenging in catalysis of zinc-air batteries. Here we propose a new strategy for synthesis of nitrogen atoms co-doped carbon sheets and carbon quantum dots (N-C@CQDs) with an SSA of 1485.3 m2 g−1 and 98.8 % micro-porosity from α-cellulose via using a complex salt (ZnCl2-NH4Cl) with low eutectic point (179 °C) as a pore regulator and K2FeO4 as a graphitization catalyst, which can serve as an active and stable carbon-based ORR electrocatalyst. The role of K2FeO4 not only promotes graphitization but also oxidizes the large-sized graphitic carbon particles into a huge amount of uniformly distributed CQDs. This catalyst has exhibited a comparable ORR activity and superior stability to the Pt/C, but a Zn-air battery assembled with the former has delivered a higher peak power density (214 mW cm−2) and a larger gravimetric energy density (ED) of (959 Wh kgZn-1), especially in which it also displays an outstanding catalytic durability with 98.7 % ED retention during a ∼110 h continuous discharge. This work provides a new pathway for design of high-performance carbon-based ORR catalysts in various energy devices.

Noncovalent composites of meso-substituted A2B2-porphyrins and carbon nanotubes for enhanced electrocatalytic oxygen reduction

Exploring highly active oxygen reduction electrocatalysts with low precious metals content is imperative but remains a considerable challenge. Herein, a series of heterobimetallic multi-walled carbon nanotubes (MWCNTs) electrocatalysts based on metal complexes are presented. These electrocatalysts feature diverse transition metals (M=Mn, Fe, Co, Ni) 5,15-bromophenyl-10, 20-methoxyphenyl porphyrin (MBMP) and tetrakis(triphenylphosphine)palladium (0) (Pd[P(Ph3)4]) anchored non-covalently on its surface. The resulting NiBMP-based MWCNTs with Pd[P(Ph3)4] (PdNiN4/MWCNTs) display outstanding electrocatalytic oxygen reduction activity (onset potential, 0.941 V; half wave potential, 0.830 V) and robust long-term durability in alkaline electrolyte. While in neutral condition, the MnBMP-based MWCNTs with Pd[P(Ph3)4] (PdMnN4/MWCNTs) are the most active heterobimetallic ORR catalyst and produce ultra-low concentration hydrogen peroxide (H2O2 yield, 1.2%–1.3%). Synergistically tuning the ORR electrocatalytic activity and electron transfer pathway is achieved by the formation of NiBMP/MnBMP-Pd[P(Ph3)4] active sites. This work indicates such metalloporphyrin-Pd[P(Ph3)4] active sites on MWCNTs have significantly positive influence on electrocatalytic ORR systems and provides facile and mild strategy for designing highly efficient ORR electrocatalysts with ultra-low loading precious metal.

PtFe Nanoalloys Supported on Fe‐Based Cubic Framework as Efficient Oxygen Reduction Electrocatalysts for Proton Exchange Membrane Fuel Cells

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

Two-dimensional phthalocyanine-based covalent organic frameworks as high-performance electrocatalysts for oxygen reduction and oxygen evolution

It is crucial to use efficient catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in energy conversion devices, aiming to mitigate energy crises. The catalytic activity of MPc-PI-COF-1 and MPc-PI-COF-2 (M = Mn, Fe, Co) towards ORR and OER is investigated systematically based on DFT methods. Different M-N4 sites can adjust the binding strength of oxygen-containing intermediates to effect catalysis activity, while the different linkers have only a minor effect. FePc-PI-COF-1 and MnPc-based COFs have low ORR overpotential (ηORR) values, even lower than Pt(111). For OER, CoPc-based COFs have comparable OER overpotential (ηOER) values to that on RuO2(110). To sum up, MnPc-based COFs are efficient ORR catalysts, and CoPc-based COFs have high OER activity. FePc-PI-COF-1 could be served as an effective bifunctional catalyst with a ηORR value of 0.38 V and ηOER value of 0.56 V. Moreover, FePc-PI-COF-1 exhibits exceptional resistance to various impurity gases, indicating its strong tolerance against poisoning. These study offer valuable insights for the rational discovery of reticular materials as highly efficient electrocatalysts.

Synergistic effect of two metal porphyrins in a polymer catalyst for oxygen electroreduction

This work considers the formation and catalytic properties of films of individual hydroxyphenyl porphyrin complexes with manganese (manganese(III) acetate 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (MnAc(4-OHPh)P)) and iron (iron(III) chloride 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (FeCl(4-OHPh)P)) and their composites. The films of individual metalloporphyrins and bimetallic composites were obtained by superoxide-assisted electrochemical deposition in dimethylsulfoxide solutions. The formation of the bimetallic (Mn + Fe) porphyrin composite was confirmed by spectral methods. An analysis of the atomic-force microscopy results showed that the composite films consisted of larger globules and were rougher than those of individual porphyrins. The electroactive surface areas of the individual porphyrin films and the composite were significantly different from each other. The mechanism and kinetics of the oxygen electroreduction reaction (ORR) on the films of individual porphyrins and bimetallic composite were evaluated using a rotating disk electrode. The kinetic current density of the Tafel slope and the position of the ORR current wave on the surface of the poly-(MnAc(4-OHPh)P + FeCl(4-OHPh)P) composite indicate smaller kinetic limitations and lower overvoltage on this material than on carbositall and films of individual porphyrins. The smaller kinetic limitations and better energy characteristics can be explained by the synergistic effect produced by the combined action of the Mn- and Fe- catalytically active centers during ORR on the composite film.

Surface-optimized carbon nanocages with tailorable atomic Fe-N4 sites to boost oxygen reduction in long stable zinc-air battery

High-efficiency and durable precious-metals-free electrocatalysts for oxygen reduction (ORR) are crucial to Zn-air battery (ZAB). Herein, a molten salt-assisted pyrolysis is reported to construct fully open carbon nanocages with highly atomically dispersed Fe-N4 sites (Fe-SA/NC) as air cathode. The chemical etching in pyrolysis can induce such highly active surface structure with abundant surface Fe anchoring sites and regulate the uncoordinated pyridinic nitrogen. The theoretical investigations reveal that engineering the adjacent uncoordinated pyridinic nitrogen can efficiently modulate the charge distribution and lower d-band center position of FeN4, thus reducing the dissociation energy of intermediate OH*. The Fe-SA/NC exhibit outstanding catalytic activity with 0.905 V (vs. RHE) half-wave potential and excellent cycling stability, surpassing commercial Pt/C and most reported M-N-C catalysts. The ZAB with the Fe-SA/NC as air cathode delivers a high power density of 240 mW cm−2, large specific capacity (815 mAh g−1) and long-term durability over 1050 h. This work highlights the rational design and fabrication of efficient M-N-C single-atom catalysts from the point of view of both morphological engineering and local coordination chemistry.

Outline of microbial fuel cells technology and their significant developments, challenges, and prospects of oxygen reduction electrocatalysts

The microbial fuel cells (MFCs) which demonstrates simultaneous production of electricity and wastewater treatment have been considered as one of the potential and greener energy production technology among the available bioelectrochemical systems. The air-cathode MFCs have gained additional benefits due to using air and avoiding any chemical substances as catholyte in the cathode chamber. The sluggish oxygen reduction reaction (ORR) kinetics at the cathode is one of the main obstacles to achieve high microbial fuel cell (MFC) performances. Platinum (Pt) is one of the most widely used efficient ORR electrocatalysts due to its high efficient and more stable in acidic media. Because of the high cost and easily poisoned nature of Pt, several attempts, such as a combination of Pt with other materials, and using non-precious metals and non-metals based electrocatalysts has been demonstrated. However, the efficient practical application of the MFC technology is not yet achieved mainly due to the slow ORR. Therefore, the review which draws attention to develop and choosing the suitable cathode materials should be urgent for the practical applications of the MFCs. In this review article, we present an overview of the present MFC technology, then some significant advancements of ORR electrocatalysts such as precious metals-based catalysts (very briefly), non-precious metals-based, non-metals and carbon-based, and biocatalysts with some significant remarks on the corresponding results for the MFC applications. Lastly, we also discussed the challenges and prospects of ORR electrocatalysts for the practical application of MFCs.

Achievement of an efficient oxygen reduction electrocatalyst based on carbon boosted with MnOx/MnCo2O4 with excellent electrocatalytic activity in neutral media

Achievement of an efficient oxygen reduction electrocatalyst based on carbon boosted with MnOx/MnCo2O4 with excellent electrocatalytic activity in neutral media

(Digital Presentation) Structure-Activity Relationship of M-N-C Electrocatalysts Synthesized Using a General Solution-Phase Coordination Approach

Metal- and nitrogen-doped carbon (M-N-C) catalysts have great potential in heterogeneous catalysis. They are used to catalyze various crucial electrochemical reactions, such as the oxygen reduction reaction (ORR), the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the CO2 reduction reaction (CO2RR).1-4 The nitrogen-coordinated metal sites (MNx) have been considered the main active sites in these M-N-C catalysts. However, the synthesis of MNx moieties often undergoes a high-temperature heat-treatment step, resulting in low site density. On the other side, the coordination environment in the MNx sites is also affected by the metal species which induced the site formation. Therefore, it is challenging to single out the role of central metal in the structure-activity relationships for these MNx sites.In this presentation, we will discuss our recent progress in the development of a solution-phase coordination synthesis approach targeting M-N-C catalysts with high active-site density and well-defined coordination environments.5, 6 A series of M-N-C catalysts are synthesized via this approach by coordinating electroactive target metal ions with the nitrogen-coordinated metal-vacancy (MVNx) sites in N-C templated by sacrificial metals. With a combined experimental and computational approach, we explore the role of sacrificial metals, including s-, p-, 3d-, 4d-, and f-block metals, in forming various MVNx sites with unique coordination configurations. The structure-activity relationship between the coordination environment and the catalytic activity for ORR, HER, OER, and CO2RR is established by comparing the MNx site structures induced by various sacrificial metals. Furthermore, we will present the activity series of metal centers in M-N-C catalysts with the same and well-defined coordination environment for ORR, HER, OER, and CO2RR. These results will guide the future development of M-N-C catalysts. Acknowledgments Financial support from the State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences is greatly appreciated. This study is financially supported by the Shanxi Province grant (Grant No. 20210302123011, 202203021212007, and 202103021224442), and Key Research and Development (R&D) Projects of Shanxi Province (202102070301018). References J. Cui, Q. Chen, X. Li and S. Zhang. Recent advances in non-precious metal electrocatalysts for oxygen reduction in acidic media and PEMFCs: an activity, stability and mechanism study. Green Chemistry, 23, 6898 (2021).H. He, H. H. Wang, J. Liu, X. Liu, W. Li and Y. Wang. Research Progress and Application of Single-Atom Catalysts: A Review. Molecules, 26, 6501 (2021).U. Martinez, S. Komini Babu, E. F. Holby, H. T. Chung, X. Yin and P. Zelenay. Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction. Advanced Materials, 31, 1806545 (2019).Y. Wang, X. Cui, L. Peng, L. Li, J. Qiao, H. Huang and J. Shi. Metal–Nitrogen–Carbon Catalysts of Specifically Coordinated Configurations toward Typical Electrochemical Redox Reactions. Advanced Materials, 33, e2100997 (2021).M. Huang, R. Ding, J. Yang, W. Shi, S. Shi, L. Chen, S. Liu and X. Yin. Formation of Nitrogen-Coordinated Metal Sites (M = Fe, Co) via Solution-Phase Coordination on Nickel- And Nitrogen-Co-Doped Carbon Templates with Metal Vacancy-Nx Sites. Journal of The Electrochemical Society, 169, 106507 (2022).M. Huang, L. Chen, R. Ding, W. Shi, Q. Qin, J. Yang, S. Liu and X. Yin. Solution-Phase Synthesis of Co-N-C Catalysts Using Alkali Metals-Induced N-C Templates with Metal Vacancy-Nx sites. ChemRxiv, doi: 10.26434/chemrxiv-2022-xnh88 (2022).

Effect of Gas-Phase Nitric Oxide Adsorption on ORR Activity of Fe-N-C Catalysts

Significant progress has been made in recent years in developing platinum group metal-free catalysts, particularly so-called Fe-N-C materials, for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells.1 However, further improvement in both activity and, especially, durability are still necessary for practical applications. One of the major factors that hinder the further enhancement of the catalysts is the lack of clear understanding of the nature of the active sites in the Fe-N-C catalysts due to the complexity of the Fe-N-C catalysts’ composition and structure. Gaseous nitric oxide was reported to be a suitable probe molecule that can bond to Fe and impede the ORR of the Fe-N-C catalysts.2,3 In this work, the effect of nitric oxide gas-phase adsorption on Fe-N-C catalyst redox feature and ORR activity for a variety of Fe-N-C catalysts from different origin will be investigated. The implication of these results on the nature of the ORR active sites of the Fe-N-C catalysts will be discussed.AcknowledgementsThis work was supported by the U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (HFTO) under the auspices of the Electrocatalysis Consortium (ElectroCat 2.0). This work was partially authored by Argonne, a U.S. Department of Energy (DOE) Office of Science laboratory operated for DOE by UChicago Argonne, LLC under contract no. DE-AC02-06CH11357.References X.X. Wang, M.T. Swihart, and G. Wu, "Achievements, challenges, and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation", Nature Catalysis, 2 (2019) 578-589.J.L. Kneebone, et al., "A Combined Probe-Molecule, Mossbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst", J. Phys. Chem. C 121 (2017) 16283-16290.P. Boldrin, D. Malko, A. Mehmood, U.I. Kramm, S. Wagner, S. Paul, N. Weidler, A. Kucernak, “Deactivation, reactivation and super-activation of Fe-N/C oxygen reduction electrocatalysts: Gas sorption, physical and electrochemical investigation using NO and O2”, Applied Catalysis B: Environmental 292 (2021) 120169.

Effects of Bifunctional Oxygen Catalyst Layer Composition on Unitized Regenerative Fuel Cell Performance

Proton exchange membrane unitized regenerative fuel cells (PEM-URFCs) can generate storable fuel (hydrogen) and oxidant (oxygen) which can then be used to produce power from the same cell. Combining electrolysis and fuel cell modes within the same cell allows PEM-URFCs to have the potential for lower mass, volume, and cost compared with discrete fuel cell and electrolyzer systems. The bifunctional oxygen catalyst layer (BOCL) catalyzes the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) at the same electrode, and there are wide potential differences and opposing mass transport phenomena involved within the BOCL when operating in electrolyzer or fuel cell mode. The BOCL composition, structure and morphology significantly affect performance and stability of PEM-URFCs. In our prior work, we showed bimetallic nanoframes provide bifunctional oxygen electrocatalysts with significantly higher activity compared with monometallic structures, evaluated using a rotating disk electrode configuration.1 We will present our investigation of the effects of the BOCL composition, structure and morphology on URFC membrane electrode assemblies (MEAs) prepared using ultrasonic spraying. Catalyst composition and loading were determined to influence URFC performance, and there are tradeoffs between fuel cell performance, electrolyzer performance, and catalyst cost. In addition to the effects of the active catalyst (either Pt for ORR or IrO2 for OER), our work supports the non-catalytically active component influences MEA performance, which is in agreement with our finding of synergistic effects of Pt and IrO2 within rotating disk electrode measurements.1 We are also evaluating the effects of porous transport layers and different operating conditions on URFC MEA performance and durability over repeated cycling. References Godínez-Salomón, F.; Albiter, L.; Mendoza-Cruz, R.; Rhodes, C.P. Bimetallic Two-dimensional Nanoframes: High Activity Acidic Bifunctional Oxygen Reduction and Evolution Electrocatalysts. ACS Appl. Energy Mater. 2020, 3, 2404-2421.

Computational Search for a Descriptor of Electrocatalysis in Transition Metal-Oxides

Currently, the most effective electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER) are comprised of noble metal oxides, which bring issues of high cost and scarcity. Discovering earth-abundant alternatives is challenging due to the costly and time-consuming experiments. High-throughput atomistic simulation of catalysts can be an efficient route for enabling the better design and discovery of new electrocatalysts. The efficient use of this approach relies on an activity descriptor that can capture the qualitative and quantitative catalytic trends. In the past, multiple descriptors based on electronic properties have been proposed either reaction-specific or system specific. Therefore, we need a descriptor, which can capture the bonding strength accurately for any sort of reaction or system.In this work, we study the trends of O*/OH* adsorption energies for a wide range of pure metal oxide polymorphs[1] namely rocksalt (MO), corundum (M2O3), rutile (MO2), pentoxide (M2O5) and MO3 in all conceivable oxidation states i.e., +2, +3, +4, +5 and +6 respectively. The main drivers of the adsorption energy are the extent of filling of the bonding and anti-bonding orbitals, along with the spin-dependent coupling strength between the metal-d and oxygen-2p atomic orbitals. This property can be easily captured with the help of crystal orbital Hamiltonian population (COHP). We have observed a strong correlation between the integrated COHP I(COHP) of the bulk system and the adsorption energy, which indicates expensive surface-level electronic calculations can be replaced by bulk-level computations. However, this correlation does not hold on two classes of systems: (i) d0 systems and (ii) systems with significant surface distortion during the reaction. We have considered a different approach to address these systems, where instead of a single bond ICOHP, we account for the summation of the ICOHP around the active site.In search of promising catalysts, we also report tetrahedral systems for 3d, 4d and 5d transition metal oxides, i.e., zinc blende, wurtzite and square planar systems. This will broaden the horizon of possible catalysts along the octahedral systems. We correlate the bulk ICOHP with the surface reactivity of these systems, which highlights the applicability of ICOHP as a universal descriptor across a series of metal oxide systems and guide the design of novel catalysts.This research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis.[1] "Unravelling Electronic Trends in O* and OH* Surface Adsorption in the MO2 Transition-Meta Oxide Series"; Benjamin M. Comer, Jiang Li, Frank Abild-Pedersen, Michal Bajdich, Kirsten Winther, 2022, (ACS J. Phys. Chem C.,)[2] “Predicting O* and OH* Surface Adsorption on Transition Metal Oxides from Bulk Structure”; Benjamin M. Comer, Neha Bothra, Jaclyn Lunger, Frank Abild-Pedersen, Michal Bajdich, Kirsten Winther, Manuscript under preparation.

CoMn2O4 nanoparticles supported on defect-rich N-doped carbon nanotubes as air electrode in rechargeable zinc-air batteries

In this study, an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions (ORR and OER) was synthetized. The catalyst comprised small-size CoMn2O4 spinel on multi-walled carbon nanotubes (CNT), interface-engineered to introduce defects and nitrogen heteroatoms, and was compared with CoMn2O4 on Vulcan carbon without surface modification. X-ray diffraction analysis confirmed the tetragonal structure with similar crystallite sizes (10–12 nm) on both carbon supports, which was validated by transmission electron microscopy (TEM). The spinel-based catalysts exhibited good activity for oxygen reactions, exhibiting a 4e − pathway for ORR on both supports, with a slightly improved in onset potentials for the supported-on N-CNT, additionally, CoMn2O4/N-CNT demonstrated superior durability, retaining 90–100% of initial current for ORR and OER, while CoMn2O4/C retained 82% and 17%. This effect on stability was corroborated by the Zinc-air battery tests, since, the CoMn2O4/N-CNT was the only catalyst that completed the 260 cycles (around of 72 h), even, the noble catalysts were only able to complete 190 cycles. Additionally, the nanocomposite demonstrated an impressive 910 mA·h/g specific capacity at 5 mA cm−2 discharge rate, surpassing CoMn2O4/C (400 mA·h/g). These findings highlight the potential of the interface-engineered nanomaterial for energy storage, offering a substantial cycling capacity boost.

Hierarchical 2D sheets of N and S co-doped Fe-based electrocatalyst for efficient oxygen reduction in advanced Zn-air battery

Currently, the scientific community is keenly interested in the design and production of efficient and durable transition metal electrocatalysts for oxygen reduction reactions (ORR). Therefore, this study reports a simple and reproducible N and S co-doped two-dimensional (2D) hierarchical porous electrocatalyst is reported. NSC the support material first was obtained by pyrolyzing trithiocyanuric acid (TTCA) and loaded on hemin to obtain the final material named Fe/NSC-800. 2D hierarchical porous structures with the large specific surface area were constructed by using TTCA as the template, S source, and additional N source. The addition of hemin not only retained the morphology of the NSC but also provided source of Fe for Fe/NSC-800. The Fe/NSC-800 possessed the limiting current density of 5.85 mA cm–2 and good ORR stability in 0.1 M KOH solution. Based on the excellent ORR performance of Fe/NSC-800, it was assembled into the primary Zn-air battery, which also exhibited satisfactory open circuit voltage (1.55 V) and energy density (880 W h kg–1). This work has contributed to the rational engineering and fabrication of high-performance ORR electrocatalysts for Zn-air battery applications.

Linkage engineering in covalent organic frameworks as metal-free oxygen reduction electrocatalysts for hydrogen peroxide production

Covalent organic frameworks (COFs) are promising platforms with tailorable structures toward metal-free electrocatalytic oxygen reduction (ORR). Here, COFs with different linkages were constructed and explored in the selective two-electron ORR (2e- ORR) for hydrogen peroxide (H2O2) production. Interestingly, imine-linked Py-TD-COF delivers a remarkable H2O2 selectivity of 80–92 %, while amine-linked Py-TD-COF-NH exhibits relatively low H2O2 selectivity of 50–61 %. Experimental and theoretical results reveal that the donor-accepter property of Py-TD-COF enables proper activation of O2, while Py-TD-COF-NH shows relatively high activation of O2 due to the electronic modulation induced by the linkage transformation. Furthermore, the potential H-bonding between the amine group and the adsorbed oxygen molecules on Py-TD-COF-NH is proved to elongate the OO bond, thus accelerating the subsequent hydrogenation and lowering the barrier for the reduction of *OOH to *O intermediates. This work highlights the importance of suitable linkages and provides a guideline for designing metal-free COF catalysts for 2e- ORR.

Bio‐inspired Design of Bidirectional Oxygen Reduction and Oxygen Evolution Reaction Molecular Electrocatalysts

AbstractThe proper utilization of renewable energy sources has emerged as a major challenge in our pursuit of a sustainable and carbon‐neutral energy landscape. Small molecule activation is a key component for proper utilization of renewable energy resources, where O2/H2O redox couple is reckoned to be a potential game changer. In this regard, electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have become the prime interest of catalyst designers. Typically, these ORR and OER electrocatalysts are developed distinctly; however, very soon, the requirement of a bidirectional ORR/OER electrocatalyst becomes obvious for practical applicability and rapid energy transduction purposes. A bidirectional catalyst is defined as a catalyst capable of driving a redox reaction in opposing directions. This review has portrayed the development of enzyme structure‐inspired design of molecular bidirectional ORR/OER catalysts. The strategic incorporation of secondary and outer coordination sphere features has significantly enhanced the performance of these catalysts, which can be monitored via the key catalytic parameters. These bifunctional OER/ORR catalysts are vital for metal‐air battery and fuel cell applications and appropriately poised to lay the foundation for an efficient, economical, and eco‐friendly pathway for sustainable energy usage with the rational assembly of energy converting and storage devices.

Fe phthalocyanine stabilized on phosphorous-doped multi-defective carbon nanoribbons as oxygen reduction electrocatalysts

Coordination polymers can be utilized as ideal precursors due to their ability to change their growth behavior and topological structure through solvent-induced effects. In this work, nanostrip-like crystalline particles, transformed from interchangeable indium-based coordination polymers (InOF-25/26), are treated to synthesize phosphorus-doped multi-defective carbon nanoribbons for efficiently anchoring iron phthalocyanine. The obtained FePc-Fe2P@25-CNR electrocatalyst exhibits a superior half-wave potential of 0.899 V and a large diffusion current density of 5.152 mA cm−2 in oxygen reduction reaction (ORR). Meanwhile, it also shows excellent stability in homemade Zn-air batteries with satisfactory charge/discharge durability over 100 cycles. In this case, the ORR performance can be improved by phosphating the carbon surface, reinforcing tight bonding with transition metal phthalocyanines, and inducing charge migration to increase the electrocatalysis kinetics, which is further validated by relevant theoretical calculation. This synthetic strategy combines structurally variable coordination polymers with metallomacrocyclic molecules, exploiting a feasible pathway for the preparation of high-performance electrochemical catalysts.

Directional manipulation of electron transfer in copper/nitrogen doped carbon by Schottky barrier for efficient anodic hydrazine oxidation and cathodic oxygen reduction

Development of bifunctional hydrazine oxidation and oxygen reduction electrocatalysts with high activity and stability is of great significance for the implementation of direct hydrazine fuel cells. Combining zero-dimensional metal nanoparticles with three-dimensional nitrogen-doped carbon nanosheets is an attractive strategy for balancing performance and cost. However, the precise construction of these composites remains a significant challenge, and thorough study of their interaction mechanisms is lacking. Herein, the CuNPs/CuSA-NPCF catalyst was constructed by anchoring copper nanoparticles on a three-dimensional nitrogen-doped porous carbon nanosheet framework through coordination of polyvinyl pyrrolidone and copper ions. The Schottky barrier of metal–semiconductor matched the Fermi level of the rectifying contact, thus enabling directional electron transfer. The resulting electron-deficient Cu nanoparticles surface exhibited Lewis acidity, which was beneficial to adsorption of hydrazine molecule. While the electron-enriched Cu–N4/carbon surface improved the adsorption of oxygen molecule, and accelerated electron supply from Cu-N4 active sites to various oxygen intermediates. The CuNPs/CuSA-NPCF Mott-Schottky catalyst exhibited excellent catalytic activity for hydrazine oxidation reaction and oxygen reduction reaction in an alkaline media. The directional manipulation of electron transfer in heterogeneous materials was an attractive universal synthesis method, providing new approach for the preparation of efficient and stable hydrazine fuel cell catalysts.

Mn-Doped Zn Metal-Organic Framework-Derived Porous N-Doped Carbon Composite as a High-Performance Nonprecious Electrocatalyst for Oxygen Reduction and Aqueous/Flexible Zinc-Air Batteries.

Developing low-cost, efficient, and stable oxygen reduction reaction (ORR) electrocatalysts is crucial for the commercialization of energy conversion devices such as metal-air batteries. In this study, we report a Mn-doped Zn metal-organic framework-derived porous N-doped carbon composite (30-ZnMn-NC) as a high-performance ORR catalyst. 30-ZnMn-NC exhibits excellent electrocatalytic activity, demonstrating a kinetic current density of 9.58 mA cm-2 (0.8 V) and a half-wave potential of 0.83 V, surpassing the benchmark Pt/C and most of the recently reported non-noble metal-based catalysts. Moreover, the assembled zinc-air battery with 30-ZnMn-NC demonstrates high peak power densities of 207 and 66.3 mW cm-2 in liquid and flexible batteries, respectively, highlighting its potential for practical applications. The excellent electrocatalytic activity of 30-ZnMn-NC is attributed to its unique porous structure, the strong electronic interaction between metal Zn/Mn and adjacent N-doped carbon, as well as the bimetallic Mn/Zn-N active sites, which synergistically promote faster reaction kinetics. This work offers a controllable design strategy for efficient electrocatalysts with porous structures and bimetallic active sites, which can significantly enhance the performance of energy conversion devices.