Oxygen Reduction Reaction Performance Research Articles

A Deep Dive into the Study of Nitrogen-Doped Carbons As Electrocatalysts for the Oxygen Reduction Reaction Via a Design of Experiments Approach

Porous nitrogen (N)-doped carbons derived from earth-abundant precursors and exhibiting tunable properties hold promise as low-cost, high-performance electrode materials for energy storage and conversion applications. As metal-free electrocatalysts for the oxygen reduction reaction (ORR) at the cathode in hydrogen fuel cells, N-doped carbons have shown selectivity and performance rivaling that of Pt/C. Alternatively, other N-doped carbons have also demonstrated low overpotentials and high selectivity for the 2-electron pathway of the ORR for the production of hydrogen peroxide. The activity and selectivity of these doped carbons are thought to result from their N-content, N-motifs, and/or porosity. However, the extent to which each of these variables impacts electrocatalytic ORR performance and whether there is an interactive effect between N-content, porous structure, etc. remains unclear. Herein, by implementing a design of experiments approach, the synthesis-structure-function relationship for N-doped carbons prepared via molten salt templating was elucidated to reveal how synthetic handles tune material properties which, in turn, determine electrocatalytic performance. Specifically, the wt% of N precursor and the synthesis temperature were found to have the most significant effect on the N-content and N-motif composition of the resulting N-doped carbons. Regarding porosity, larger surface areas and micropore volumes were realized for the carbons prepared with a larger wt% of N precursor. It was found that surface areas upwards of 300 m2/g were required to see any substantial activity (e.g. half-wave potential greater than 0.7 V vs RHE, effective electron transfer number > 3.4). Only after a threshold surface area was achieved were effects from N-content and N-motifs notable on performance and selectivity.

The Synthesis of Highly Durable Pt-Based Hollow Nanocatalysts for Oxygen Reduction Reaction

Platinum (Pt) catalysts have been considered as the most active electrocatalyst for the oxygen reduction reaction (ORR) in fuel cells. However, cost and durability of Pt catalysts are the biggest obstacles impeding their practical applications. In this talk, the combination of Pt ion-treatment and acid-treatment methods is developed to prepare Pt-based hollow nanocatalysts. Catalytic results indicated the ORR performance of our Pt-Ni nanocatalysts far exceed that of commercial Pt/C electrocatalysts, in terms of mass-specific activities it is up to a 19-fold increase than that of Pt/C and 6 times than that of Department of Energy requirement (0.44 A/mg Pt). The performance loss of Pt-Ni is negligible even after a prolonged durability test of 300,000 cycles. The in-situ spectroelectrochemical results and theoretical simulation further explain the catalytic mechanism and such excellent durability. We believe our method provides an effective strategy for the rational design of Pt-based alloy nanostructures and will help guide the future development of catalysts for their practical applications in energy conversion technologies.

Interface engineering of the dz2 electrons mobility for single atom catalytic activity and selectivity

Transition metal singlet embedded in nitrogen-doped carbon material (M-N-C) has been demonstrated as a promising electrochemical oxygen reduction reaction (ORR) catalyst; however, the unsatisfying activity and production selectivity have hampered its widespread applications in energy storage and conversion technologies. Herein, interface engineering by facilitating M-N-C catalysts (M from 3d to 4d electron-containing elements) with MXene has been utilized to regulate their ORR performance. It is found that the charge transfer occurring within the interface not only tunes the electron occupancy of the 3d/4d orbitals of the metal site, but also delocalizes the population of the dz2 states. This alternation enhances the mobility of the electrons and promotes the 4e catalytic process thermodynamically. Meanwhile, the formation of ∗HOOH, the key reaction intermediate for 2e reaction, is hindered due to the alleviation of the binding capacity, which is beneficial to improve production selectivity. This study provides foundational understanding for the ORR catalytic mechanism at the atomic level and opens up new avenues for designing high-demanded electrocatalysts.

New Insights into the ORR Catalysis on Pt Alloy Nanoparticles from an Element Specific d-Band Analysis.

Bolstered by their unique atomic structures and tailored compositions, nanoalloys exhibit extraordinary properties making them ideal materials to solve challenges in energy storage and conversion catalysis. However, a quantitative description of the structure-property relationships using an accurate descriptor-based model for nanoalloys, ranging from bimetallic to multimetallic compositions, is needed to drive efficient material design toward high-performance catalysis. In this work, we highlight the electronic property and catalytic activity relationship from an element specific d-band analysis of Pt-based alloy catalysts using X-ray absorption near-edge spectroscopy (XANES). Using a series of L10-MPt/Pt (M = Fe, Co, Ni) core/shell alloy catalysts with well-defined atomic structures, we quantified subtle differences in the Pt d-electron states and correlated the Pt d-band structure to their superior catalytic activity toward the oxygen reduction reaction (ORR). Our analysis used the upper d-band edge position as a predictive descriptor for the mass activity toward the ORR instead of the commonly used d-band center position. Together with density functional theory calculations and Nørskov d-band theory, the upper d-band edge position for the Pt states, derived from experimental measurements, elucidates new physical insights into the ORR performance of the L10-MPt/Pt core/shell catalysts. An element specific Pt d-band analysis using XANES overcomes challenges in traditional X-ray photoelectron spectroscopy-based valence d-band analysis, which cannot distinguish signals from independent elements in nanoalloys. Thus, the insights from the element specific d-band analysis presented in this work are a promising approach to determine structure-property relationships in a variety of transition metal nanoalloys and will be useful in the design of future high-performance catalysts.

Research on a Metal–Organic Framework (MOF)-Derived Carbon-Coated Metal Cathode for Strengthening Bioelectrochemical Salt Resistance and Norfloxacin Degradation

Microbial fuel cells (MFCs) can realize the conversion of chemical energy to electrical energy in high-salt wastewater, but the easily deactivated cathode seriously affects the performance of MFCs. To enhance the stability and sustainability of MFC in such circumstances, a bimetallic organic framework ZIF-8/ZIF-67 was utilized for the synthesis of a carbon cage-encapsulated metal catalysts in this study. Catalysts with different Co and Ce ratio (Co@C (without the Ce element), CoCe0.25@C, CoCe0.5@C, and CoCe1@C) were employed to modify the activated carbon cathodes of MFCs. The tests demonstrated that the MFCs with the CoCe0.5@C cathode catalyst obtained the highest maximum power density (188.93 mW/m2) and the smaller polarization curve slope, which boosted the electrochemical activity of microorganisms attached to the anode. The appropriate addition of the Ce element was conductive to the stability of the catalyst’s active center, which is beneficial for the stability of catalytic performance. Under the function of the CoCe0.5@C catalyst, the MFCs exhibited superior and stable norfloxacin (NOR) degradation efficiency. Even after three cycles, the NOR degradation rate remained at 68%, a negligible 5.6% lower than the initial stage. Furthermore, based on the analysis of microbial diversity, the abundance of electrogenic microorganisms on a bioanode is relatively high with CoCe0.5@C as the cathode catalyst. This may be because the better cathode oxygen reduction reaction (ORR) performance can strengthen the metabolic activity of anode microorganisms. The electrochemical performance and NOR degradation ability of MFC were enhanced in a high-salt environment. This paper provides an approach to address the challenge of the poor salt tolerance of cathode catalysts in MFC treatment, and presents a new perspective on resource utilization, low carbon emissions, and the sustainable treatment of high-salt wastewater.

In situ tuning of platinum 5d valence states for four-electron oxygen reduction

The oxygen reduction reaction (ORR) catalyzed by efficient and economical catalysts is critical for sustainable energy devices. Although the newly-emerging atomically dispersed platinum catalysts are highly attractive for maximizing atomic utilization, their catalytic selectivity and durability are severely limited by the inflexible valence transformation between Pt and supports. Here, we present a structure by anchoring Pt atoms onto valence-adjustable CuOx/Cu hybrid nanoparticle supports (Pt1-CuOx/Cu), in which the high-valence Cu (+2) in CuOx combined with zero-valent Cu (0) serves as a wide-range valence electron reservoir (0‒2e) to dynamically adjust the Pt 5d valence states during the ORR. In situ spectroscopic characterizations demonstrate that the dynamic evolution of the Pt 5d valence electron configurations could optimize the adsorption strength of *OOH intermediate and further accelerate the dissociation of O = O bonds for the four-electron ORR. As a result, the Pt1-CuOx/Cu catalysts deliver superior ORR performance with a significantly enhanced four-electron selectivity of over 97% and long-term durability.

Noble Metal‐Free High Entropy Perovskite Oxide with High Cationic Dispersion Enhanced Oxygen Redox Reactivity

AbstractHigh entropy perovskite oxide (HEPO) materials have received significant interest as efficient electrocatalysts owing to their chemical and structural stability, effective interaction of multiple metal active sites with the reaction intermediate species resulting in enhanced catalytic activity. The effect of high‐entropy strategy could achieve the regulation of the structural durability by tailoring the composition. Herein, we design a novel transition metal and rare‐earth metal based high entropy perovskite oxide (Co0.11Mn0.11Ni0.11Fe0.14La0.13Nd0.13Gd0.13Pr0.13)O3, showing superior catalytic activity in the oxygen reduction reaction (ORR) and also promising electrocatalyst in oxygen evolution reaction (OER). High degree of cationic dispersion in the lattice and multiple electrocatalytic active sites enhance the oxygen ion migration at the surface and facilitate electron transfer, manifesting good ORR performance. Notably, the as‐prepared high entropy material exhibits onset and half‐wave potential of 1.02 V and 0.89 V versus RHE, respectively, exceeding the performance of the benchmarked Pt/C catalyst in the ORR process with reasonable redox kinetics. Moreover, the material also presents faster kinetics with reasonably low overpotential and excellent electrochemical stability in the OER process as well. This study shows the viability of designing non‐precious high entropy materials as highly efficient oxide electrocatalyst by utilizing its broad compositional space.

Functionalization of CO2-Derived Carbon Support as a Pathway to Enhancing the Oxygen Reduction Reaction Performance of Pt Electrocatalysts

Functionalization of CO₂-Derived Carbon Support as a Pathway to Enhancing the Oxygen Reduction Reaction Performance of Pt Electrocatalysts

In situ, fast constructing interface/doping-engineered NiCo bimetal-based composites boosting electrocatalytic oxygen reduction for zinc-air battery

Investigating cost-effective, high-performance, stable and durable oxygen reduction reaction (ORR) catalysts is imperative, yet it’s still a formidable obstacle in the advancement of metal-air batteries. In this research, NiCo-bimetallic oxides in situ combined with NiCo-bimetal alloy upon the surface of carbon-based matrix (reduced graphene oxide) (NiCo/Co-NiO/rGO) were synthesized by microwave hydrothermal treatment coupled with an ultrafast Joule heating shock process. The interfacial charge transfer between the bimetal alloy and metal oxide in NiCo/Co-NiO/rGO resulted in electron redistribution at the heterointerface, where *O species migrated to the NiCo alloy surface through Mn+-O-M0 (M=Ni, Co and n=2, 3) bonds, facilitating continuous electron transport between the two phases and unveiling added active sites. Introducing abundant oxygen vacancies by Ni3+ and Co3+ facilitated charge transfer between different valence states and led to forming more active sites, thus significantly enhancing ORR performance. More importantly, solid solution strengthening within the NiCo-bimetallic alloy mitigated the oxidation and corrosion of the catalyst. Therefore, the as-synthesized NiCo/Co-NiO/rGO(5 % Co) exhibited excellent ORR performance under an alkaline medium. It achieved a half-wave potential(E1/2) of 0.85 V(vs. RHE) and maintained 89.10 % of its current density after a 12-h long-term reaction. The assembled zinc-air battery (ZAB) employing this catalyst proved remarkable specific capacity (807.04 mAh·gZn−1), power density (95.54 mW cm−2) and cycling stability (over 240 h), outperforming that of commercial Pt/C+RuO2-based ZAB device. This study presents a viable approach for fabricating low-cost dual transition metal-based catalysts, thereby boosting their electrocatalytic performance and enhancing the efficiency and longevity of metal-air batteries.

Constructing electron-enriched Co tetrahedral sites to promote oxygen electrocatalysis in rechargeable zinc-air batteries

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key performance-limiting step of rechargeable zinc-air batteries. Developing a reliable strategy to optimize the activity of Co occupied the tetrahedral site (Coth) is crucial for enhancing electrocatalytic performance and still needs further elaborate elucidation. Here, Mo dopants were used as electron donors to construct low-valence Coth sites in cobalt phosphide, resulting in downshifted d-band centers and strengthened hybridization between Co 3d and P 3p orbitals. The negative charges are easier to accumulate on three antibonding orbitals of Coth, promoting the desorption of oxygen intermediates, as evidenced using density functional theory calculations and in-situ spectroscopic investigations. The optimal catalyst delivers impressive ORR and OER performance, in terms of half-wave potential of 0.84 V for ORR and overpotential of 247 mV for OER. In general, this work opens a new opportunity to rationally regulate electronic structure of Coth sites via introducing an electron donor, as well as provides guidance for exploring electronic descriptors of tetrahedral sites.

Engineering of active site coupling to facilitate interatomic charge transfer for bifunctional oxygen electrocatalysis

Interatomic charge transfer emerges as a robust technique for enhancing catalytic efficacy in key energy reactions, specifically the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Despite its potential, advancing simultaneous improvements in reversible oxygen catalysis pose considerable challenges. Herein, we detailed an active site coupling engineering method to create a CoCu@NSC bifunctional oxygen electrode. In this configuration, OER-active Cu sites were alloyed with ORR-active Co within a N/S-doping carbon nanobox. This arrangement yielded a half-wave potential of 0.924 V for ORR, alongside an overpotential of η10 = 356 mV for OER. The fabricated CoCu@NSC cathode yielded a discharge capacity of 768 mAh/gZn, a peak power density of 295 mW/cm2, and extensive cycling durability. Work function assessments indicated that the chemical integration of Co and Cu components at the atomic level promoted interfacial charge redistribution, effectively optimizing the adsorption-desorption dynamics of intermediates at the active sites, thereby substantially enhancing the catalytic performance for both OER and ORR. Additionally, doping with N/S species enhanced the conductivity of the hollow carbon matrix, facilitating more effective mass and charge transport pathways. These insights illuminate a compelling approach for the design and synthesis of effective bifunctional oxygen electrodes that is pivotal for advanced energy storage advice.

Oxidation Evolution and Activity Origin of N-Doped Carbon in the Oxygen Reduction Reaction

N-doped carbon materials, with their applications as electrocatalysts for the oxygen reduction reaction (ORR), have been extensively studied. However, a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxidation potential of carbon, possibly leading to the oxidation of carbon materials. Consequently, the influence of the structural oxidation evolution on ORR performance and the real active sites are not clear. In this study, we discover a two-step oxidation process of N-doped carbon during the ORR. The first oxidation process is caused by the applied potential and bubbling oxygen during the ORR, leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups. This oxidation process also converts the reaction path from the four-electron (4e) ORR to the two-electron (2e) ORR. Subsequently, the enhanced 2e ORR generates oxidative H2O2, which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups, such as quinones to dicarboxyls, further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species. We also reveal the synergistic effect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*, thus leading to high efficiency and durability in electrocatalytic H2O2 production.

Engineering rich defects in nitrogen-doped porous carbon to boost oxygen reduction reaction kinetics

Metal-free carbon-based materials offer a promising alternative to Pt-based catalysts for the oxygen reduction reaction (ORR). However, challenges persist due to its sluggish kinetics and poor acid ORR performance. Here, we introduce a novel nitrogen-doped porous carbon with rich defects sites (such as pentagons, edge and vacancy defects) (PV/HPC) via a simple etching strategy. The PV/HPC demonstrates long-term stability and exceptional catalytic activity with half-wave potential of 0.9 V and average electron transfer number of 3.98 in alkaline solution while 0.78 V and 3.78 in acidic solution, indicating its efficiency and robustness as an ORR catalyst. Additionally, it achieves a higher kinetic current density of 91.9 mA cm−2 at 0.8 V, which is 1.75 times that of Pt/C (52.5 mA cm−2). Furthemore, it enables Al-air battery to attain a maximum power density of 487 mW cm−2, compared to 477 mW cm−2 for the Pt/C catalyst. Density functional theory (DFT) calculations elucidate that the introduction of multifunctional defects in nitrogen-doped porous carbon collectively reduces the reaction energy barrier of the departure of OH* and boosts the oxygen reduction reaction kinetics. This work presents a simple method to design durable and effective carbon-based ORR catalysts.

Core/shell Ni@C particle-supported N-doped carbon with hollow capsules for efficient electrocatalytic reduction of oxygen

To replace the noble metal catalysts for oxygen reduction reaction (ORR), a Ni@C-supported N-doped carbon material (Ni@C/NC) is in-situ prepared via one-step pyrolyzing the polymerizable ionic liquid of vinyl imidazole combined with Ni(NO3)2. Systemic investigations demonstrate that these nanosized Ni particles are tightly wrapped with a thin carbon layer to form the core/shell structure, meanwhile carbon capsules are synchronously yielded on the carbon matrix. As a result, both the carbon shell and the carbon capsule jointly increase the active sites of the Ni@C/NC, while the carbon shell also contributes the fast electron-transfer from Ni particle. Compared with the normal Ni-supported carbon catalyst, the Ni@C/NC shows the respectable ORR performance with the onset and half-wave potentials of 0.96 and 0.84 VRHE. After the long-term electrocatalysis (10 h), the Ni@C/NC is found to possess the great structural and electrocatalytic stabilities, which maintains 93 % of the initial current density and the well-dispersed and uniform Ni@C particles. Subsequently, a Zn-Air battery with the Ni@C/NC cathode is assembled and exhibits a peak power density of 200 mW cm−2. Therefore, the as-obtained Ni@C/NC with the high electroactivity and stability can be expected as an ideal candidate to apply in the metal-air batteries and fuel cells in the future.

Suppressing the hydrogen bonding interaction with *OOH toward efficient H2O2 electrosynthesis via remote electronic tuning of Co-N4

The non-covalent interaction that appears along with electronic tuning is often overlooked in interpreting the oxygen reduction reaction (ORR) dynamics, resulting in a limited understanding of the governing principles. Herein, through intricately engineering pedant substituents on porphyrins backbones, Co-N4 moieties featuring varied electronic configurations served as an exemplary model to elucidate the role of hydrogen bonding interaction appears along with electronic tuning in determining 2e- ORR performance. Co-TEPP with an electron-deficient Co-N4 moiety emerges as a standout performer for O2-to-H2O2 conversion. Upon covalently linking the Co-TEPP monomer on rGO to form robust organic polymer structures (Co-TEPP-COP/rGO), superior H2O2 selectivity (> 95 %), remarkable H2O2 production rate (∼18.8 mol gcat−1 h−1), and excellent performance durability are identified. Such optimized H2O2 electrosynthesis could be attributed to the suppressed hydrogen bonding interaction between *OOH and electron-deficient Co-N4 moiety, which consequently weakens *OOH binding strength to favor H2O2 electrosynthesis.

Pyridinic-N Regulated Electron Injection to Modulate *OH Adsorption at Fe-N-C Sites for an Efficient Oxygen Reduction Reaction.

To enhance the efficiency of oxygen reduction reaction (ORR) catalysts, precise control over the adsorption/desorption energy barriers of oxygen intermediates at atomically dispersed Fe-N-C sites is essential yet challenging. Addressing this, we employed a pyrolysis approach using a nitrogen-containing polymer to fabricate Fe single-atom (SA) catalysts embedded in a pyridinic-N enriched carbon matrix. This synthesis strategy yielded Fe SAs that demonstrated a superior electrochemical ORR performance, evidenced by an impressive half-wave potential of 0.941 V and a high limiting current density of 5.72 mA/cm2. Moreover, when applied in homemade Zn-air batteries, this premier catalyst exhibited exceptional specific capacity (720 mAh/gZn), peak power density (253 mW/cm2), and notable long-term stability. Theoretical insights revealed that the increased pyridinic-N content in the catalyst facilitated efficient electron transfer from N atoms to the Fe active sites, thus fine-tuning the d-band center and effectively controlling the adsorption energy barrier of *OH species. These mechanisms synergistically improve the ORR performance. Crucially, this fabrication method shows promise for adaptation to other transition metal-based SAs, including Co, Ni, and Cu, potentially establishing a versatile synthesis route for developing atomically dispersed catalyst systems in future applications.

Nitrogen and sulfur incorporated chitosan-derived carbon sphere hybrid MXene as highly efficient electrocatalyst for oxygen reduction reaction

The quest for non-precious electrocatalysts through biomass for energy applications has attracted keen interest, but optimization for fuel cells remains challenging. Herein, we have developed a nitrogen and sulfur-anchored MXene hybrid chitosan-derived carbon sphere (N,S-MXC) reporting for the first time as a novel oxygen reduction reaction (ORR) electrocatalyst. Interestingly, as the mass ratio of MXene to Chitosan varied by (1:2, 1:1, and 2:1), the microstructures of the as-prepared catalysts changed, which drastically influenced the corresponding ORR performance. Notably, when the mass ratio was maintained to be 1:2, Ti3C2 nanoparticles were dispersed on the surface of the biomass carbon core shell. They created multimodal porous morphology that helps to facilitate faster electron transfer, resulting in a high onset-potential of 0.89 V and limiting current density of −4.2 mA/cm2 as well as excellent durability with minimum half-wave potential loss of 2.3 mV after 5000 cyclic voltammetry (CV) cycles than benchmark Pt/C. In addition, the corresponding catalyst also possessed robust stability of 87.47 % and an excellent methanal poisoning tolerance effect in an alkaline medium. In a nutshell, this work paves the pathway for converting sea animal waste to develop porous carbon as supporting material for fuel cells that directly or indirectly support achieving carbon neutrality.

Anisotropic Heterobimetallic Nanomaterials with Controlled Composition for Efficient Oxygen Reduction at Ultralow Loading

AbstractHydrogen fuel cells represent a leading technology in developing green energy targeting net‐zero emissions goals by mid‐century. However, the sluggish kinetics of the oxygen reduction reaction (ORR) have hitherto demanded substantial quantities of expensive platinum (Pt) group metals. Advances in catalyst design, including the controllable fabrication of highly branched morphologies to increase the surface area‐to‐volume ratio, intermixing Pt with more affordable transition metals, and controlling composition, offer solutions that can further enhance activity and reduce expense. In this context, Pt/M (M = Fe, Ni, Co) nanopods and nanodendrites with precise composition control using more affordable starting materials are designed and crafted. The method is highly efficient, taking only 30 min and avoiding the need for high‐pressure equipment, making it highly scalable. These catalysts show superior ORR performance at an electrode loading as low as 0.0022 mgPt cm−2. One, nanodendritic Pt/Ni, achieves a mass activity of at 0.9 V versus RHE, making it 87 times more efficient in terms of Pt‐content than a commercial 10 wt% Pt/C nanoparticle standard. These findings provide new opportunities for developing next‐generation, cost‐efficient Pt‐based catalysts, by potentially advancing hydrogen fuel cell technology through performance enhancement and addressing cost challenges through catalyst design.

Engineering Synergetic Fe‐Co Atomic Pairs Anchored on Porous Carbon for Enhanced Oxygen Reduction Reaction

AbstractThe rational design of heteronuclear dual‐atom catalyst (DAC) is intricate due to the random dispersion of metal atoms under thermal treatment. Herein, a novel precursor pre‐orientation strategy is reported to construct Fe‐Co diatomic sites atomically dispersed on nitrogen doped carbon (Fe‐Co‐NC) via cubic Prussian blue analogue as metal source. Due to the specific synergy between Fe and Co centers, the obtained Fe‐Co‐NC catalyst renders outstanding oxygen reduction reaction (ORR) performance with positive half‐wave potential and good durability in wide pH range. Density functional theory further clarifies the active centers and reveals that the Fe‐Co‐NC dual atomic catalyst follows the modulation mechanism, where the intermediates tended to adsorb on Fe site, while the neighboring Co atom can assist by lowering the d‐band center of Fe site. Experimentally and theoretically emphasizes the priority of heteronuclear diatomic Fe‐Co catalysts over homonuclear Fe‐Fe‐NC and Co‐Co‐NC DAC. Moreover, the Zn‐Air battery (ZAB) and microbial fuel cell (MFC) assembled with Fe‐Co‐NC cathodes both exhibit splendid power density (382 mW cm−2 for ZAB, 2034 ± 103 mW m−2 for MFC) as well as excellent stability. This work provides a new perspective for rational construction and precise regulation for heteronuclear dual‐atom catalysts.

High performance oxygen reduction and evolution reactions by graphitization of nickel –cobalt framework system

This study presents the successful synthesis of metal-organic frameworks (MOFs) via a simple one-pot method, followed by pyrolysis at 1000 °C to be used in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A study utilizing various techniques, including field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and X-ray diffraction (XRD), investigated the properties of NiCo-MOF and its individual components before and after pyrolysis.The pristine MOFs exhibited limited electrochemical stability for both ORR and OER, while the pyrolyzed MOFs demonstrated a significant enhancement and excellent long-term stability in OER and ORR performance in alkaline media. Notably, the OER performance rivaled that of the benchmark IrO2 electrocatalyst, with similar onset potentials (1.48 V for IrO2, 1.52 V, 1.56 V, and 1.59 V for pyrolyzed NiCo-MOF, Co-MOF, and Ni-MOF, respectively). Furthermore, the pyrolyzed MOF catalysts displayed promising ORR activity in a 0.1 M KOH solution under O2 saturation, as evidenced by their onset potentials (around 0.615 V, 0.63 V, and 0.7 V vs. RHE) and favorable Tafel slopes (53, 84, and 154 mV dec⁻1, for graphitizated Ni-MOF, Co-MOF, and NiCo-MOF, respectively). These findings demonstrate the effectiveness of pyrolysis in engineering the MOF crystal structure for enhanced catalytic performance. This paves the way for further exploration of this synthesis method for the design of structurally optimized catalysts and applicable to a broad spectrum of energy technologies.