Oxygen Reduction Reaction Catalysts Research Articles

In situ Production of Hydroxyl Radicals via Three‐Electron Oxygen Reduction: Opportunities for Water Treatment

The electro‐Fenton (EF) process is an advanced oxidation technology with significant potential; however, it is limited by two steps: generation and activation of H2O2. In contrast to the production of H2O2 via the electrochemical two‐electron oxygen reduction reaction (ORR), the electrochemical three‐electron (3e‐) ORR can directly activate molecular oxygen to yield the hydroxyl radical (·OH), thus breaking through the conceptual and operational limitations of the traditional EF reaction. Therefore, the 3e‐ ORR is a vital process for efficiently producing ·OH in situ, thus charting a new path toward the development of green water‐treatment technologies. This review summarizes the characteristics and mechanisms of the 3e‐ ORR, focusing on the basic principles and latest progress in the in situ generation and efficient utilization of ·OH through the modulation of the reaction pathway, shedding light on the rational design of 3e‐ ORR catalysts, mechanistic exploration, and practical applications for water treatment. Finally, the future developments and challenges of efficient, stable, and large‐scale utilization of ·OH are discussed based on achieving optimal 3e‐ ORR regulation and the potential to combine it with other technologies.

In situ Production of Hydroxyl Radicals via Three-Electron Oxygen Reduction: Opportunities for Water Treatment.

The electro-Fenton (EF) process is an advanced oxidation technology with significant potential; however, it is limited by two steps: generation and activation of H2O2. In contrast to the production of H2O2 via the electrochemical two-electron oxygen reduction reaction (ORR), the electrochemical three-electron (3e-) ORR can directly activate molecular oxygen to yield the hydroxyl radical (·OH), thus breaking through the conceptual and operational limitations of the traditional EF reaction. Therefore, the 3e- ORR is a vital process for efficiently producing ·OH in situ, thus charting a new path toward the development of green water-treatment technologies. This review summarizes the characteristics and mechanisms of the 3e- ORR, focusing on the basic principles and latest progress in the in situ generation and efficient utilization of ·OH through the modulation of the reaction pathway, shedding light on the rational design of 3e- ORR catalysts, mechanistic exploration, and practical applications for water treatment. Finally, the future developments and challenges of efficient, stable, and large-scale utilization of ·OH are discussed based on achieving optimal 3e- ORR regulation and the potential to combine it with other technologies.

Nonpyrolytic Fe‐N‐C/Fe2O3 heterostructure with RuO2‐like OER Activity Synthesized via Polyacrylonitrile‐derived Conjugated Pyridinic‐nitrogen‐carbon Sheet

Pyrolytic single Fe atom‐nitrogen‐carbon materials (Fe‐N‐C) and their derivatives are excellent catalysts for electrochemical oxygen reduction reactions. However, they exhibit poor oxygen evolution reaction (OER) activity due to non‐optimal Fe‐O* bonding. This limitation is overcome via electronic structure modulation (i.e., tuning the heteroatom type, concentration, and location within Fe’s n ≥ 1 coordination sphere). However, the methods used are complex and energy‐intensive (i.e., 1000 to 1200°C) raising concerns about reproducibility and cost. This study introduces a method for synthesizing nonpyrolytic Fe‐N‐C/Fe2O3 composites with similar electronic structure modulation as pyrolytic Fe‐N‐C and OER activity akin to commercial RuO2. The methodology involves doping low‐melting hydrated Fe‐salts in electrospun polyacrylonitrile nanofiber to catalyze its transformation into conjugated pyridinic‐N‐rich graphite‐like sheets (i.e., N‐C) at 300°C. N‐C chelate effectively with oxygen‐vacant (Ov)‐rich Fe atoms derived from Fe2O3 NPs resulting in Fe‐N‐C/Fe2O3 heterostructures. The Fe2O3 coupling effectively tunes Fe‐N‐C’s electronic structure via Ov modulation. Consequently, the Fermi and d‐orbital energy levels are optimized leading to partial filling of the antibonding states, optimal Fe‐O* bonding, high electrochemically active surface area, and OER activity. Because Fe‐N‐C/Fe2O3 is synthesized at 300 oC using well‐established techniques, its complexity and cost are favorable compared to pyrolytic Fe‐N‐C materials.

Asymmetrically Coordinated Calcium Single Atom for High-Performance Oxygen Reduction Reaction.

S-block single atoms represent an ideal catalyst for the oxygen reduction reaction (ORR) as they can suppress the Fenton reaction. However, the symmetry of the s/p orbitals tends to generate either an excessively strong or weak interaction with intermediates. Herein, Ca single atoms coordinated with -S, -OP, and three N atoms (Ca/NPS-HC) were fabricated to modulate the adsorption of intermediates and promote the efficiency of s-block ORR catalysts. The experimental results from ORR demonstrated that the Ca/NPS-HC catalyst exhibited outstanding catalytic capability with a half-wave potential of 0.89 V, a kinetic current density of 56.6 mA cm-2 at 0.85 V, and a Tafel slope of 42 mV dec-1, outperforming commercial Pt/C. The detailed mechanistic studies revealed that the asymmetric coordination of Ca single atoms led to the symmetry-breaking of electron distribution in Ca single atoms, attenuating the s-p hybridization from the intermediate adsorption process, and thereby minimizing the energy barrier of the whole ORR.

N, S co-doped carbon nanotubes loaded with Cu nanoclusters for efficient oxygen reduction reaction.

Developing highly superior precious-metal-free electrocatalysts for oxygen reduction reaction (ORR) are challenging and great significance. In this study, it is reported that an efficient ORR catalysts with N and S co-doped carbon nanotubes anchored to copper (Cu) nanoclusters by mechanical grinding and high temperature heat treatment. The obtained Cu-S1-N-C electrocatalysts exhibited a high ORR performance with an onset potential (Eonest) of 0.989 V and a half-wave potential (E1/2) of 0.905 V (vs. RHE) in alkaline electrolyte, which was superior to that of commercial Pt/C catalyst. In contrast to N doping alone, the defect structures and active species of the catalysts were optimized by precise modulation of S-atom doping, and moreover, the introduction of S-atoms provided more thiophene-sulfur active sites. This study provides an innovative idea for designing excellent ORR catalysts.

Potential of V-Si72, V-C72, and V-Al36N36 as catalysts for oxygen reduction reaction.

The capacities of V-Si72, V-C72, and V-Al36N36 nanocages to catalyze the ORR processes have been investigated. The acceptable pathways of ORR processes on V-Si72, V-C72, and V-Al36N36 nanocages have been examined by DSD-PBEPBE-D3/aug-cc-pVDZ, PW91PW91/aug-cc-pVDZ, and COSMO model in the gas phase and water. The ΔGreaction values of reaction steps of ORR pathways on V-Si72, V-C72, and V-Al36N36 nanocages are calculated. The Eadoption and Eformation of V-Si72, V-C72, and V-Al36N36 nanocages are negative values and these nanostructures are stable materials. The H2O has the lowest Eadsorption on V-Si72, V-C72, and V-Al36N36 nanocages. The *OH formation, creation of *OH-OH*, and formation of O* are rate-determining steps of ORR mechanisms. The overpotential values of ORR processes on V-Si72, V-C72, and V-Al36N36 nanocages are 0.41, 0.37, and 0.30V, respectively. The V-Al36N36 nanocage have lower overpotential for ORR processes than V-Si72 and V-C72 nanocages by DSD-PBEPBE-D3/aug-cc-pVDZ, PW91PW91/aug-cc-pVDZ, and COSMO model in the gas phase and water. The V-Al36N36 nanocage have more negative ∆Greaction for reaction steps of ORR than V-Si72 and V-C72 nanocages. The V-Al36N36 nanocage with lower overpotential is proposed as an effective catalyst for ORR processes via studied pathways. The DSD-PBEPBE-D3/aug-cc-pVDZ method has been used to optimize and calculate the frequencies of V-Si72, V-C72, and V-Al36N36 nanocages in GAMESS software. The complexes of O, OH, OOH, and H2O with V-Si72, V-C72, and V-Al36N36 nanocages are optimized and frequencies are determined by the DSD-PBEPBE-D3/aug-cc-pVDZ method. The Gactivation and ∆Greaction of ORR pathways on V-Si72, V-C72, and V-Al36N36 nanocages are calculated by DSD-PBEPBE-D3/aug-cc-pVDZ, PW91PW91/aug-cc-pVDZ, and COSMO model in the gas phase and water.

Multi-metal ferrite as a promising catalyst for oxygen reduction reaction in microbial fuel cell.

Improving catalytic activity of cathode with noble metal-free catalysts can significantly establish microbial fuel cells (MFCs) as a sustainable and economically affordable technology. This investigation aimed to assess the viability of utilizing tri-metal ferrite (Co0.5Cu0.5 Bi0.1Fe1.9O4) as an oxygen reduction reaction (ORR) catalyst to enhance the performance of cathode in MFCs. Trimetallic ferrite was synthesized using a sol-gel auto-combustion process. Electrochemical evaluations were conducted to assess the efficacy of as-synthesized composite as an ORR catalyst, employing electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). This evaluation revealed that the impregnation of bismuth in the Co-Cu-ferrite structure improves the reduction current response and reduces the charge transfer resistance. Further experiments were conducted to test the performance of this catalyst in an MFC. The MFC with tri-metal ferrite catalyst generated a power density of 11.44 W/m3 with 21.4% coulombic efficiency (CE), which was found to be comparable with commercially available 10% Pt/C used as cathode catalyst in MFC (power density of 12.14 W/m3 and CE of 23.1%) and substantially greater than MFC having bare carbon felt cathode without any catalyst (power density of 2.49 W/m3 and CE of 7.39%). This exceptionally inexpensive ORR catalyst has adequate merit to replace commercial costlier platinum-based cathode catalysts for upscaling MFCs.

Elevating Oxygen Evolution using Iron Phthalocyanine Infused Vanillic acid Electrocatalyst.

Oxygen evolution reaction (OER) is the bottle neck step in water splitting reaction towards the realization of hydrogen based clean energy production and storage. Transition metal based N4 organics are explored extensively as oxygen electrocatalysts i.e.,(OER) and oxygen reduction reaction (ORR) catalysts because of their ease of synthesis, tuneable properties, low cost and high performance with long term stability. Here, vanillic acid functionalized iron phthalocyanine (FeVAPc) was synthesised and characterised. The novel FeVAPc exhibited good thermal stability and was coated on Ni foam for OER studies. The scanning electron microscopy images showed net-work like surface morphology and the X-ray photoelectron spectroscopy indicated the presence of Fe in +3 oxidation state. The Ni/FeVAPc demonstrated excellent electrocatalytic activity for OER with overpotential of 312 mV at 10 mA.cm-2 current density in 1.0 M KOH . The designed catalyst exhibited lesser Tafel slope value which is nearer to the benchmark catalyst, IrO2. The proposed catalyst exhibited good stability as phthalocyanines are highly stable and do not undergo decomposition even in strong acidic and basic corrosive media. Integration of FeVAPc onto Ni foam resulted in higher mass activity, lower charge transfer resistance, high active surface area leading to enhanced conductivity and activity.

Noncovalent Assembly Strategy for Efficient Synthesis of Dual‐Atom Catalysts

AbstractDiatomic catalysts (DACs), as a frontier of research on atomically dispersed catalysts, have drawn great attention, especially in electrocatalysis. However, most of the current synthetic strategies for DACs suffer from poor efficiency and high cost. In this work, a novel noncovalent assembly strategy is reported for the efficient synthesis of DACs. By the aid of two kinds of noncovalent intermolecular force, the π–π stacking and Coulomb forces, a pair of metal complex ions with opposite electrical charges is spontaneously loaded onto the carbon substrate and transformed into diatomic sites via thermal treatment. This noncovalent assembly approach shows universal feasibility for a broad spectrum of DACs (Ir–Fe, Pt–Fe, Pt–Co, and Pt–Ni). To prove the practical utility, the as‐prepared PtFe‐DAC is deployed as oxygen reduction reaction catalyst, performing excellent activity with a half‐wave potential of 0.935 V (vs RHE) and a 2.3 times higher turnover frequency than that of the single‐atomic Fe‐SAC. In situ characterization and theoretical calculation indicate that the adjacent Pt sites could endow moderate activation of oxygen molecule on Fe sites by lowering the electron pairing energy as well as the modulation of the d‐band center and spin states of Fe centers propelling the desorption of the intermediates.

Metal-free advanced energy materials for the oxygen reduction reaction in anion-exchange membrane fuel cells

The success of the next generation of anion-exchange membrane fuel cells (AEMFCs) depends on the development of active, reliable, and economical oxygen reduction reaction (ORR) catalysts. Here, we synthesize a series of ultra-low-cost metal-free ORR catalysts by doping a common pristine graphite precursor with chemically singular-type heteroatoms, namely I, S, N, or B, using single-step planetary ball milling technique. All doped-graphites show substantially enhanced ORR performance relative to the pristine (undoped) graphite. Among all the tested catalysts, N-graphite exhibited the highest ORR onset potential of 0.87 V vs. reversible hydrogen electrode. These results are supported by density functional theory calculations. The ORR catalysts also exhibit remarkable stability as evaluated through electrochemical tests. Most importantly, the AEMFCs prepared using these ultra-low-cost doped graphites deliver notable peak power densities with impressive voltage efficiencies, which further supports their efficacy in ORR catalysis and the broad implementation of this technology.

Co-doped hollow nanospheres with low Pt loading for electrocatalytic oxygen reduction and zinc-air batteries

Preparing high-performance catalysts for oxygen reduction reaction (ORR) with low Pt loading is crucial to promote the development of clean energy storage devices such as metal air batteries. Herein, Co/N-HCMs support material with isolated Co atoms and hollow flower-like structure could be prepared by a self-sacrificing template strategy. Co/N-HCMs are then used to anchor Pt to obtain PtCo/N-HCMs catalyst with low Pt loading. Thanks to its improved specific surface area, hierarchical porous structure, and reinforced metal-support interactions, the obtained PtCo/N-HCMs deliver high onset potential of 0.99 V and half-wave potential of 0.82 V, and an excellent durability. When used as air cathode catalyst, PtCo/N-HCMs-based Zinc-air battery (ZAB) exhibits a power density of up to 202 mW cm−2, which is significantly better than ZAB assembled with commercial Pt/C. This study provides an effective strategy for preparing high-performance electrocatalysts with low precious metal content for use as the cathode of metal-air batteries.

Facile and fast fabrication of CuCo alloy and N-codoped hierarchical porous carbon catalyst for efficient oxygen reduction reaction in microbial fuel cells

Designing a low-cost, high-performance oxygen reduction reaction (ORR) catalyst to replace the precious metal catalyst remains a huge challenge for microbial fuel cells (MFCs). Herein, a facile and rapid approach to fabricate highly active N-doped hierarchical porous carbon (NHPC) supported bimetal CuCo/NHPC composites with densely accessible active sites is developed by pyrolysis of Cu-doped ZIF-67 (CuCo-ZIF) precursor. In which, CuCo-ZIF precursor is synthesized through a one-pot hydrothermal method. Results showed that in addition to create additional Cu-Nx sites and increase N content, the Cu doping induces a hierarchical porous structure CuCo/NHPC composite with pores centered around 2.4, 4.2 nm and 10–60 nm, which can significantly accelerate the mass/electron transfer and improve efficient utilization of the active sites. The resulting CuCo/NHPC composite provides abundant active sites, high content of pyridinic-N and graphitic-N, which significantly boosts ORR performances. The CuCo/NHPC-T with pyrolysis temperature of 800 °C achieves remarkable ORR activity with low charge transfer resistances, high half-wave potential. The MFC assembled with CuCo/NHPC-800 (774.2 mW·m−2 and 0.713 V) significantly outperforms MFC assembled with Co-NC-800 (541.9 mW·m−2 and 0.583 V) in terms of maximum power density and open-circuit voltage. Moreover, the output voltage of MFC assembled with CuCo/NHPC-800 exhibited no significant downward trend within 30 days, which was better than that of Pt/C catalyst. This work provides a feasible time-saving route to develop promising nitrogen-enriched mesoporous carbon bimetallic ORR catalysts.

Phosphorus-Doping Enables the Superior Durability of a Palladium Electrocatalyst towards Alkaline Oxygen Reduction Reactions.

The sluggish kinetics of oxygen reduction reactions (ORRs) require considerable Pd in the cathode, hindering the widespread of alkaline fuel cells (AFCs). By alloying Pd with transition metals, the oxygen reduction reaction's catalytic properties can be substantially enhanced. Nevertheless, the utilization of Pd-transition metal alloys in fuel cells is significantly constrained by their inadequate long-term durability due to the propensity of transition metals to leach. In this study, a nonmetallic doping strategy was devised and implemented to produce a Pd catalyst doped with P that exhibited exceptional durability towards ORRs. Pd3P0.95 with an average size of 6.41 nm was synthesized by the heat-treatment phosphorization of Pd nanoparticles followed by acid etching. After P-doping, the size of the Pd nanoparticles increased from 5.37 nm to 6.41 nm, and the initial mass activity (MA) of Pd3P0.95/NC reached 0.175 A mgPd-1 at 0.9 V, slightly lower than that of Pd/C. However, after 40,000 cycles of accelerated durability testing, instead of decreasing, the MA of Pd3P0.95/NC increased by 6.3% while the MA loss of Pd/C was 38.3%. The durability was primarily ascribed to the electronic structure effect and the aggregation resistance of the Pd nanoparticles. This research also establishes a foundation for the development of Pd-based ORR catalysts and offers a direction for the future advancement of catalysts designed for practical applications in AFCs.

Heteroatom Sulfur-Modified ZIF-8 Derived Zn, N Co-Doped Carbon Nanocages as Highly Efficient ORR Catalysts for Zn-Air Batteries

Carbon-based electrocatalysts derived from zeolitic imidazolate framework-8 (ZIF-8) have garnered significant attention, owing to their structural advantages, high surface area, and tunable active sites. Herein, we report the synthesis of heteroatom sulfur (S) modified ZIF-8 derived carbon nanocages (ZnS@N/S-C) for oxygen electrocatalysis through self-assembly and two-step pyrolysis. The resultant ZnS@N/S-C exhibits catalytic activity towards oxygen reduction reaction (ORR) with high half-wave potential (0.86 V) and stability (91.4%), separately, which is comparable to or superior to Pt/C. Furthermore, the application of ZnS@N/S-C as a cathode for Zn-air batteries (ZABs) demonstrates performance metrics such as an open-circuit voltage of 1.407 V, a power density of 114.4 mW cm−2, and a specific capacity of 764.6 mAh gZn −1, etc surpassing Pt/C. The performance of ZnS@N/S-C can be attributed to the fact that the introduction of S significantly increases the specific surface area, pore volume, and defect extent of the catalyst, while optimizing the electronic structure and generating ZnS active nanocrystals. This work employs a simple sulfurization strategy to enhance the ORR activity of ZIF-8-derived Zn-based catalysts with fully filled 3d orbitals, providing guidance for the development of such materials.

Preparation and evaluation of S-rGO/ZnFe2O4/NiCoLDH nanocomposite electrocatalyst in oxygen reduction reaction

This study introduces a novel combination of sulfur-doped reduced graphene oxide (S-rGO), zinc ferrite (ZnFe2O4) and nickel cobalt layered double hydroxide (NiCoLDH) as an efficient and low-cost electrocatalyst for oxygen reduction reaction (ORR) for the first time. The hydrothermal method is used to synthesize all samples including graphene oxide (GO), S-rGO, NiCoLDH, ZnFe2O4 and S-rGO/ZnFe2O4/NiCoLDH hybrids. X-ray diffraction (XRD) analysis, field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), energy dispersive x-ray analysis (EDX), electrochemical surface area (ECSA), and fourier transform infrared spectroscopy (FTIR) analysis are used to determine the structure of synthesized electrocatalysts, physical properties, and morphology. The electrochemical measurements are carried out using cyclic voltammetry (CV), linear scanning voltammetry (LSV), chronoamperometry (ChA), and electrochemical impedance spectroscopy (EIS). The results for all samples are compared with the Pt/C commercial catalyst. According to the electrochemical results, the S-rGO/ZnFe2O4/NiCoLDH electrocatalyst has the best electrochemical performance. Moreover, the nanocomposite exhibited better electrocatalysis, a high diffusion limiting current density of −5.4 mA cm−2 and an onset potential of 0.03 V. Based on the results of this study, the LDH enhances electrical conductivity, electrocatalytic activity, active surface area, and stability of the catalyst for ORR after combining with carbon bases and ferrite.

Polyaniline 합성 시 단량체와 산화제 비율이 음이온 교환막 연료전지에 대한 산소 환원 촉매의 활성에 미치는 영향

Polyaniline 합성 시 단량체와 산화제 비율이 음이온 교환막 연료전지에 대한 산소 환원 촉매의 활성에 미치는 영향

N-P covalent bond regulation of mesoporous carbon-based catalyst for lowered oxygen reduction overpotential and enhanced zinc-air battery performance

Developing sustainable metal-free carbon-based electrocatalysts is essential for the deployment of metal-air batteries such as zinc-air batteries (ZABs), among which doping of heteroatoms has attracted tremendous interest over the past decade. However, the effect of the heteroatom covalent bonds in carbon matrix on catalysis was neglected in most studies. Here, an efficient metal-free oxygen reduction reaction (ORR) catalyst is demonstrated by the N-P bonds anchored carbon (termed N,P-C-1000). The N,P-C-1000 catalyst exhibits superior specific surface area of 1362 m2 g−1 and ORR activity with a half-wave potential of 0.83 V, close to that of 20 wt% Pt/C. Theoretical computations reveal that the p-band center for C-2p orbit in N,P-C-1000 has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. The N,P-C-1000 assembled primary ZAB can attain a large peak power density of 121.9 mW cm−2 and a steady discharge platform of ∼1.20 V throughout 120 h. Besides, when served as the cathodic catalyst in a solid-state ZAB, the battery shows flexibility, conspicuous open circuit potential (1.423 V), and high peak power density (85.8 mW cm−2). Our findings offer a strategy to tune the intrinsic structure of carbon-based catalysts for improved electrocatalytic performance and shed light on future catalysts design for energy storage technologies beyond batteries.

Entropy-Driven Ostwald Ripening Reversal Promotes the Formation of Low-Platinum Intermetallic Fuel Cell Catalysts.

Strain engineering has been widely used to optimize platinum-based oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs). PtM3 (M is base metals), a well-known high-compressive-strain intermetallic alloy, shows promise as a low platinum ORR catalyst due to high intrinsic activity. However, during the alloying of Pt with a threefold amount of M, a notable phase separation between Pt and M may occur, with M particles rapidly sintering while Pt particles grow slowly, posing a challenge in achieving a well-defined PtM3 intermetallic alloy. Here, an entropy-driven Ostwald ripening reversal phenomenon is discovered that enables the synthesis of small-sized Pt(FeCoNiCu)3 intermetallic ORR catalysts. High entropy promotes the thermodynamic driving force for the alloying Pt with M, which triggers the Ostwald ripening reversal of sintered FeCoNiCu particles and facilitates the formation of uniform Pt(FeCoNiCu)3 intermetallic catalysts. The prepared Pt(FeCoNiCu)3 catalysts exhibit a high specific activity of 3.82mAcm-2, along with a power density of ≈1.3Wcm-2 at 0.67V and 94°C with a cathode Pt loading of 0.1mgcm-2 in H2-air fuel cell.

Cu-based active sites supported on nitrogen-rich polymer derived porous carbon fibers as an oxygen reduction electrocatalyst for zinc-air batteries

The rational design of electrocatalysts with highly exposed active sites and maximized active sites utilization is challenging and urgent problem. Herein, a facile strategy is employed to fabricate Cu-based active sites anchored in nitrogen doped porous carbon nanofiber as an effective and enduring oxygen reduction reaction (ORR) electrocatalyst, which is achieved by the coordination-pyrolysis way of the pre-designed covalent organic polymer (COP) precursors with unique molecular structure. Meanwhile, COP-derived N-doped carbon nanofiber could provide porous structure and facilitate the rapid mass/electron transport, which can insure the strong fastness and high reaction activity of Cu-based active sites. The as-obtained catalyst (Cu0·4/NPC) displays excellent activity (E1/2 = 0.845 V) and stability for ORR performance. Remarkably, the Cu0·4/NPC as cathode catalyst assembled Zn-air battery achieves the peak power density of 142 mA cm−2 and a large specific capacity of 829 mA h g−1 at large current. Additionally, the Cu0·4/NPC catalyst assembled in the solid Zn-air battery achieves the peak power density of 157 mA cm−2. This work offers great opportunity to design advanced ORR catalysts with high density and maximum utilization of active sites.

Instantaneous Thermal Energy for Swift Synthesis of Single-Atom Catalysts for Unparalleled Performance in Metal-Air Batteries and Fuel Cells.

Based on experimental and computational evidence, phthalocyanine (Pc) compounds in the form of quaternary-bound metal-nitrogen (N) atoms are the most effective catalysts for oxygen reduction reaction (ORR). However, the heat treatment process used in their synthesis may compromise the ideal structure, causing the agglomeration of transition metals. To overcome this issue, a novel method is developed for synthesizing iron (Fe) single-atom catalysts with ideal structures supported by thermally exfoliated graphene oxide (GO). This is achieved through a short heat treatment of only 2.5min involving FePc and N, N-dimethylformamide in the presence of GO. According to the synthesis mechanism revealed by this study, carbon monoxide acts as a strong linker between the single Fe atoms and graphene. It facilitates the formation of a structure containing oxygen species between FeN4 and graphene, which provides high activity and stability for the ORR. These catalysts possess an enormous number of active sites and exhibit enhanced activity toward the alkaline ORR. They demonstrate excellent performance when applied to real electrochemical devices, such as zinc-air batteries and anion exchange membrane fuel cells. It is expected that the instantaneous heat treatment method developed in this study will aid in the development of high-performing single-atom catalysts.