Methanol Tolerance Research Articles

Nitrogen-doped porous carbon nanosheets derived from furfural residue as an oxygen reduction catalyst

The complex pore structure of porous carbon plays a pivotal role in determining the catalytic activity of catalysts involved in the oxygen reduction reaction (ORR), and template methods have emerged as the gold standard in the fabrication of porous carbon. This study describes the preparation of a series of carbon materials that use furfural residue and urea as carbon and nitrogen sources, respectively, in conjunction with KOH as an activating agent through a template method. The prepared catalysts have a large specific surface area and an abundance of micro/mesoporous structures, both of which facilitate ion transport and promote active site exposure. Notably, the sample with a carbon-to-nitrogen mass ratio of 1:4 (FR/C-4) exhibits an exceptionally high specific surface area (2190 m2 g−1) along with an impressive array of pore structures. Compared with commercial Pt/C, FR/C-4 demonstrates superior ORR catalytic activity with a half-wave potential (E1/2) of 0.88 V. Furthermore, FR/C-4 demonstrates remarkable stability and methanol tolerance in alkaline electrolytes, indicating its potential for a wide range of applications, such as fuel cells and metalair batteries.

Lignin-derived Fe–N–C electrocatalyst with 3D porous structure for efficient oxygen reduction reaction

Developing low-cost, high-performance oxygen reduction reaction (ORR) catalysts is crucial for the commercialization of fuel cells and zinc-air batteries. Herein, we report a lignin-derived Fe/N co-doped 3D porous carbon electrocatalyst Fe-NLC-1 as an alternative to commercial Pt/C catalysts, which was synthesized by a green and facile in situ carbonization strategy. Fe-NLC-1 exhibits higher oxygen reduction activity with a half-wave potential (E1/2) of 0.90 V vs. RHE than commercial 20 wt% Pt/C (E1/2 = 0.85 V) in the alkaline conditions, as well as excellent methanol tolerance and stability. Furthermore, the Zn-air battery loaded with Fe-NLC-1 exhibits a maximum power density of 125 mW cm−2, an open circuit voltage of 1.477 V, and stable discharge performance, which are comparable or even better than the commercial Pt/C. This study highlights the potential of biomass-derived porous carbon materials for the development of high-performance ORR electrocatalysts.

Fe3O4 encapsulated in hierarchically porous nitrogen-doped graphitic carbon layers for efficient oxygen reduction reaction: Enhanced intrinsic activity via directional interfacial charge transfer

Constructing efficient electrocatalysts for the oxygen reduction reaction (ORR) is crucial for the commercialization of metal-air batteries. Iron oxide-based catalysts exhibit promising potential for ORR. However, addressing the issue of inferior catalytic performance is essential, and a comprehensive understanding of the catalytic mechanism of iron oxide-based catalysts is also lacking. In this study, we present Fe3O4 nanoparticles encapsulated in N-doped graphitic carbon layers (NGC) hosted by hierarchically porous carbon (Fe3O4@NGC), achieved through a facile dual melt-salt template strategy. The encapsulation of Fe3O4 nanoparticles protects them from corrosion and exfoliation, endowing the catalysts with superior stability. Density functional theory (DFT) calculations discover that the electronic interaction between Fe3O4 nanoparticles and N-doped graphitic carbon layers induces directional interfacial electron transfer, which effectively modulates the surface electronic structure to improve the binding ability to O2, weaken the OO bond, and optimize the adsorption of intermediates, thus boosting the intrinsic activity. DFT unveils that the C atoms nearest to graphitic-N in NGC are active sites. Finally, the synergistic effects of Fe3O4 nanoparticles and NGC result in outstanding ORR performance and superior stability and methanol tolerance of Fe3O4@NGC, with a half-wave potential of 0.89 V, surpassing that of Pt/C by 50 mV. Fe3O4@NGC also shows better performance than Pt/C when used as the air-electrode catalyst in zinc-air battery.

Co2P/CoP embedded in N, P, S triply-doped hollow carbon towards enhanced oxygen electrocatalysis

Simultaneously dispersing phosphide crystallites and multiple heteroatoms in hollow carbon is a significant yet challenging task for achieving high-performance oxygen electrocatalysts of zinc-air batteries. Herein, a simple wrapping-pyrolysis strategy is proposed to prepare Co2P/CoP embedded in N, P, S triply-doped hollow carbon (Co2P/CoP@NPS-HC). Co2P/CoP@NPS-HC composite features hollow polyhedral structure populated with numerous catalytically active Co2P/CoP nanoparticles and N, P, S heteroatoms. This optimized catalyst exhibits excellent activity for oxygen reduction reaction, with a half-wave potential of 0.82 V vs. RHE, and impressive enhancement for oxygen evolution reaction, indicated by an overpotential of 400 mV at 10 mA cm−2. Moreover, Co2P/CoP@NPS-HC catalyst exhibits greater durability and superior methanol tolerance compared to commercial Pt/C. The excellent bifunctional electrocatalytic performance of Co2P/CoP@NPS-HC catalyst is attributed to the synergistic effect of uniformly dispersed Co2P/CoP nanoparticles and N, P, S triply-doped hollow carbon structure. The former provides abundant catalytically active sites, while the latter offers a high accessible specific surface area, as well as enhances catalytic activity and electronic conductivity due to its altered charge distribution.

Heightening polyoxometalate encapsulation efficiency for biaxial strain-induced catalytic activity boosting

Controllable assembly of polyoxometalates (POMs) in confined nanochannels is crucial to understand the host-guest structures and tailor the emerging properties for applications. Here, we report the encapsulation of polyoxometalates inside single-walled carbon nanotubes (SWNTs) for target catalytic regulation. Theoretical modeling predicts the confined polyoxomolybdates are able to induce biaxial tensile strains of SWNTs for more stable interaction with iron phthalocyanine (FePc) and tailor the charge distribution and coordination environment of targetable FeN4 sites, leading to improved catalytic activity toward oxygen reduction reaction (ORR). The polyoxomolybdates are confined in the SWNTs via redox-driven encapsulation mechanism with a POM encapsulation efficiency of about 21 %. The constructed FePc/SWNT@POM molecule catalyst exhibits a high half-wave potential of 0.90 V, excellent stability and methanol tolerance in alkaline medium. The zinc-air battery also presents prominent charge-discharge ability and long-term durability over 400 h with a peak power density of 190.8 mW cm–2.

Aminotriazine derived N-doped mesoporous carbon with a tunable nitrogen content and their improved oxygen reduction reaction performance.

The electrocatalytic activity of carbon materials is highly dependent on the controlled modulation of their composition and porosity. Herein, mesoporous N-doped carbon with different amounts of nitrogen was synthesized through a unique strategy of using a high nitrogen containing CN precursor, 3-amino 1,2,4 triazine (3-ATZ) which is generally used for the preparation of carbon nitrides, integrated with the combination of a templating method and high temperature treatment. The nitrogen content and the graphitisation of the prepared materials were finely tuned with the simple adjustment of the carbonisation temperature (800-1100 °C). The optimised sample as an electrocatalyst for oxygen reduction reaction (ORR) exhibited an onset potential of 0.87 V vs. RHE with a current density of 5.1 mA cm-2 and a high kinetic current density (Jk) of 33.1 mA cm-2 at 0.55 V vs. RHE. The characterisation results of the prepared materials indicated that pyridinic and graphitic nitrogen in the carbon framework promoted ORR activity with improved four-electron selectivity and excellent methanol tolerance and stability. DFT calculations demonstrated that the structural and planar defects in the N-doped carbon regulated the surface electronic properties of the electrocatalyst, leading to a reduction in the energy barrier for the ORR activity. This strategy has the potential to unlock a platform for designing a series of catalysts for electrochemical applications.

Candida boidinii isolates from olive curation water: a promising platform for methanol-based biomanufacturing

Methanol is a promising feedstock for biomanufacturing, but the efficiency of methanol-based bioprocesses is limited by the low rate of methanol utilization pathways and methanol toxicity. Yeast diversity is an attractive biological resource to develop efficient bioprocesses since any effort with strain improvement is more deserving if applied to innate robust strains with relevant catabolic and biosynthetic potential. The present study is in line with such rational and describes the isolation and molecular identification of seven isolates of the methylotrophic species Candida boidinii from waters derived from the traditional curation of olives, in different years, and from contaminated superficial soil near fuel stations. The yeast microbiota from those habitats was also characterized. The four C. boidinii isolates obtained from the curation of olives’ water exhibited significantly higher maximum specific growth rates (range 0.15–0.19 h−1), compared with the three isolates obtained from the fuel contaminated soils (range 0.05–0.06 h−1) when grown on methanol as the sole C-source (1% (v/v), in shake flasks, at 30°C). The isolates exhibit significant robustness towards methanol toxicity that increases as the cultivation temperature decreases from 30°C to 25°C. The better methanol-based growth performance exhibited by C. boidinii isolates from olives´ soaking waters could not be essentially attributed to higher methanol tolerance. These methanol-efficient catabolizing isolates are proposed as a promising platform to develop methanol-based bioprocesses.

Enhancement of thermostability and expression level of Rasamsonia emersonii lipase in Pichia pastoris and its application in biodiesel production in a continuous flow reactor

The acidic lipase from Rasamsonia emersonii named LIPR has great potential for biodiesel synthesis due to its strong methanol tolerance. Nonetheless, the limited thermostability of LIPR and low expression level in Escherichia coli remain major obstacles to its use in biodiesel synthesis. To enhance the thermostability, the mutant LIPR harboring mutations A126C-P238C for the formation of a new disulfide bond and amino acid substitution D214L was obtained through rational design. To our delight, the thermostability of LIPR mutant was greatly improved. Moreover, a comprehensive optimization strategy, such as employing the Mss signal peptide, co-expressing the molecular chaperone protein disulfide isomerase (PDI), knocking out the vacuolar sorting receptor gene VPS10-01, and overexpressing the dihydroxyacetone synthase gene DAS2, was adopted to obtain the combination-optimized mutant Pichia pastoris strain GS54. Furthermore, the biodiesel synthetic capability with the mutant GS54-LIPR was verified and the production yield was 52.2 % after 24 h in a shake flask. Subsequently, a continuous flow system was adopted to increase the biodiesel yield to 73.6 % within 3 h, demonstrating its efficacy in enhancing enzyme biocatalysis. The engineered GS54-LIPR mutant lipase is an efficient and reusable biocatalyst for the sustained production of biodiesel in a continuous flow reaction.

CoNi-N/P-Doped Carbon Nanotubes as Catalysts for Efficient Oxygen Reduction Reaction.

Transition metals (TMs) supported by heteroatom-doped carbon materials are considered to be the potential alternatives to the Pt/C catalyst owing to their low cost, outstanding electrocatalytic efficiency, and excellent electrochemical durability. In this paper, N/P-doped carbon nanotube (CNT) (N/P-CNT)-supported monometallic (Co, Ni) and bimetallic (CoNi) catalysts were synthesized by one-step pyrolysis using diammonium hydrogen phosphate, 2-methylimidazole and organometallic salts as precursors, and the CNT as the catalyst carrier; the effects of transition TM types and pyrolysis temperature (Tp) on the microstructure and electrochemical properties were explored. The analysis exhibited that the CoNi bimetallic catalyst was superior to both Co and Ni monometallic catalysts, and the catalysts pyrolyzed at 900 °C exhibited a better graphitization degree. The optimal CoNi-N/P-CNT-900 displayed remarkable oxygen reduction reaction electrocatalytic performance with a half-wave potential (E1/2) of 0.86 V and excellent methanol tolerance and stability. Moreover, the Zn-air battery coated with CoNi-N/P-CNT-900 demonstrated a larger open circuit voltage of 1.577 V, a larger peak power density of 212.89 mW cm-2 at 357.8 mA cm-2, as well as a higher specific capacity of 799 mA h gZn-1, superior to that of the Pt/C catalyst (1.492 V, 96.04 mW cm-2 at 216.8 mA cm-2, 735 mA h gZn-1), showing outstanding practical value. This study is expected to promote the commercialization of the electrocatalysts.

Biodiesel Production from Waste Cooking Oil Using Recombinant Escherichia coli Cells Immobilized into Fe3O4-Chitosan Magnetic Microspheres.

Developing reusable and easy-to-operate biocatalysts is of significant interest in biodiesel production. Here, magnetic whole-cell catalysts constructed through immobilizing recombinant Escherichia coli cells (containing MAS1 lipase) into Fe3O4-chitosan magnetic microspheres (termed MWCC@MAS1) were used for fatty acid methyl ester (FAME) production from waste cooking oil (WCO). During the preparation process of immobilized cells, the effects of chitosan concentration and cell concentration on their activity and activity recovery were investigated. Optimal immobilization was achieved with 3% (w/v) chitosan solution and 10 mg wet cell/mL cell suspension. Magnetic immobilization endowed the whole-cell catalysts with superparamagnetism and improved their methanol tolerance, enhancing the recyclability of the biocatalysts. Additionally, we studied the effects of catalyst loading, water content, methanol content, and reaction temperature on FAME yield, optimizing these parameters using response surface methodology and Box-Behnken design. An experimental FAME yield of 89.19% was gained under the optimized conditions (3.9 wt% catalyst loading, 22.3% (v/w) water content, 23.0% (v/w) methanol content, and 32 °C) for 48 h. MWCC@MAS1 demonstrated superior recyclability compared to its whole-cell form, maintaining about 86% of its initial productivity after 10 cycles, whereas the whole-cell form lost nearly half after just five cycles. These results suggest that MWCC@MAS1 has great potential for the industrial production of biodiesel.

Highly dispersed Co nanoparticles confined by mesopore-rich N-doped hollow carbon nanotubes for efficient oxygen reduction reaction and Zn-air battery

Oxygen reduction reaction (ORR) is an important reaction process in Zn-air batteries, and the catalyst plays a crucial role as the cathode in the system. However, the reported catalysts often exhibit poor durability and stability in the operation of air batteries. Here, we used g-C3N4 as a precursor to mix Co nanoparticles for carbonization, and synthesized a large number of carbon nanotubes (CNTs) interwoven cluster catalysts, namely Co/CNT-800. The obtained catalyst has a rolling grass like morphology, forming a highly conductive network, which helps to improve the electron transfer ability in the ORR process. At the same time, the influence of materials at different carbonization temperatures on the ORR of Zn-air batteries was studied. In alkaline media, Co/CNT-800 showed the high ORR performance, with a half-wave potential of 0.839 V (vs. RHE, Pt/C 0.845 V). After 5000 cycles, the E1/2 of the Co/CNT-800 catalyst only decreased by 9 mV, and its performance in stability tests and methanol tolerance tests was superior to Pt/C. When Co/CNT-800 catalyst is used as the air cathode for Zn-air batteries, it exhibits an excellent specific capacity of 709.2 mAh/g and a power density of 142.2 mW cm−2.This research achievement provides valuable insights for the development of high-performance Zn-air batteries and innovative guidance for the design of ORR catalysts.

Self-templated formation of ZnNC microtube with high oxygen reduction reaction overpotential for Zn-based catalyst

The synthesis of hollow morphologies without employing templates and addressing the high overpotential of the oxygen reduction reaction in Zn-N4-C-based materials poses a significant challenge. In this study, we present a straightforward yet robust approach based on a self-templated metal-organic framework (MOF-based) to synthesize ZnNC microtubes and explore the reason behind its high oxygen reduction (ORR) overpotential through density functional theory (DFT) calculation. ZnNC microtubes, benefiting from the abundant Zn-N4 active sites, hierarchical porosity, and a reasonable degree of graphitization, exhibited superior ORR activity and methanol tolerance compared to the traditional precious Pt/C catalyst. On the other hand, DFT calculation shows that Zn exhibits a d10 electronic configuration and diamagnetic nature in Zn-N4 moieties confirmed by the partial density of state (PDOS), hence the main reason behind the high ORR overpotential. This study provides a novel roadmap for further engineering efforts to achieve an ideal ORR catalyst in Zn-based materials.

Atomically dispersed Fe–N4 sites activated 3D-on-2D derived porous carbon structure toward superior oxygen reduction reaction

The oxygen reduction reaction (ORR) is a crucial step in the energy transformation devices, which requires the fabrication of a cost-effective and energy-efficient Fe single-atom catalyst (SAC) to substitute platinum. However, achieving a controllable synthesis of Fe SAC is a formidable challenge. In this study, a Fe SAC with a novel 3D-on-2D architecture was fabricated by coating 3D metal-organic frameworks (MOFs) over the surface of 2D reduced graphene oxide (rGO). In-situ combining MOF and rGO in a composite structure by adjusting their weight proportion is a key to preparing an active 3D-on-2D structured catalyst with FeN4 active sites. Thanks to the favorable conductivity of the 2D rGO-derived carbon structure and the 3D MOF structure exposing an enhanced density of FeN4 sites, FeNC@rGO-2 demonstrates exceptional ORR activity. It performs more effectively than commercial Pt/C, exhibiting excellent half-wave potentials of 0.887, 0.705, and 0.741 V in alkaline, neutral, and acidic solutions respectively. Impressively, FeNC@rGO-2 exhibits excellent stability and methanol tolerance. When FeNC@rGO-2 is assembled as cathode catalyst in Zinc-air batteries (ZAB) and microbial fuel cells (MFC), FeNC@rGO-2-ZAB reveals outstanding power density (393 mW cm−2) and good charge/discharge cycling stability. Amazingly, FeNC@rGO-2-MFC also shows superior power density (2810 ± 19 mW m−2) and efficiency of electron recovery. This study reveals that FeNC@rGO-2 has extremely high application value in energy conversion devices oriented for alkaline and neutral electrolytes.

FeNC@nitrogen doped porous carbon leaf-carbon nanotube hybrids for oxygen reduction reaction

A series of nitrogen doped porous carbon leaf-carbon nanotubes incorporated FeNx electrocatalysts (FeNC@NCL-CNT) are prepared by pyrolysis of Fe doped leaf-like Zn-zeolitic imidazolate framework (FeZn-ZIF-L) with different Fe contents. Among the catalysts, FeNC@NCL-CNT-3 exhibits the highest ORR activity in alkaline solution with onset potential (Eonset) of 0.95 V, half-wave potential (E1/2) of 0.81 V, and limiting diffusion current density of 6.14 mA cm−2. The Eonset and E1/2 of FeNC@NCL-CNT-3 are positively shifted by ca. 20 and 6 mV, respectively compared with Pt/C. The self-generated CNT caused by Fe catalysis improves the electronic conductivity and enlarges the average pore size of the catalyst from 1.77 to 8.12 nm. The highest density of pyridine-N and Fe-Nx active sites (50.7 %) and the largest electrochemically active surface area (ECSA, 1075 cm2) also contribute to its superior activity. The Tafel slope of FeNC@NCL-CNT-3 is 75.4 mV dec-1, which is close to that of Pt/C. Fe-NCL/CNT-3 shows excellent long-term stability (99.4 % retention) and superior methanol tolerance. It catalyzes ORR through 4e- path.

Fabrication of biocarbon catalyst for ORR by modulating the cellulose fraction of wheat stalk

Direct Methanol fuel cells (DMFC) have been limited in their utilization due to their slow cathodic oxygen reduction reaction (ORR) kinetics and the expensive cost of commercial Pt/C catalysts. It is critical to design an oxygen reduction process with high-efficiency catalysts. An approach for modulating the ratio of cellulose, hemicellulose, and lignin in the wheat stalk (WS)/wheat stalk binder (WS binder) precursor materials is proposed in this work. WS binder from alkalization and hydrothermal treatment was added to the WS to change the structure and shape of WS-based carbon materials by varying the ratios, which increased the ORR catalytic activity. The half-wave potential (E1/2) of the produced carbon material (15 wt% N/C (WS)) is 0.76 V, which was enhanced by 80 mV by adjusting the ratio of the WS/WS binder compared to 0 wt% N/C(WS). The E1/2 of 15 wt% Fe–N/C (WS) (0.85 V) was greater than that of commercial Pt/C (0.84 V). Besides, its catalytic oxygen reduction process was close to the 4-electron transfer pathway and had good methanol tolerance. The power density obtained with a cathode catalyst of 15 wt% Fe–N/C (WS) for DMFC was 1.39 mW cm−2 at 30 °C and 3.33 mW cm−2 at 60 °C. At different temperatures, the power densities were 1.59 and 1.54 times greater than those of commercial Pt/C catalysts, respectively.

Porous AgPd Nanomushrooms with Enhanced Methanol Tolerance for Oxygen Reduction Reaction

Porous AgPd Nanomushrooms with Enhanced Methanol Tolerance for Oxygen Reduction Reaction

Rational design of Fe, N co-doped porous carbon derived from conjugated microporous polymer as an electrocatalytic platform for oxygen reduction reaction

Porous iron–nitrogen-doped carbons (FeNC) offer a great platform for construction of cathodic oxygen reduction reaction (ORR) catalysts in fuel cells. However, challenges still remain regarding with the collapse of carbon-skeleton during pyrolysis, uneven distribution of active sites and aggregation of metal atoms. In this work, we synthesized Fe, N co-doped conjugated microporous polymer (FeN-CMP) through a facile bottom-up strategy using 1,3,5-triethynylbenzene and iron-chelated 3,8-dibromo-1,10-phenanthroline as monomers, ensuring the uniform coordination of N with Fe element in network. Then, the resulting FeN-CMP was treated by pyrolysis without structural collapse to obtain porous FeNC electrocatalyst for ORR. The most active catalyst was fabricated under 900 °C, which exhibits remarkable ORR activity in alkaline medium with half-wave potential of 0.796 V (18 mV and 105 mV positive deviation from the commercial Pt/C catalyst and post-doping catalyst), high selectivity with nearly 4e- transfer process and excellent methanol tolerance. Our study first developed porous FeNC electrocatalysts derived from Fe, N-anchoring CMPs based on pre-functionalization of monomers, which exhibits great potential as an alternative to commercial Pt/C catalyst for ORR, and provides a feasible strategy of developing multi-atoms doping catalysts for energy storage and conversion as well as heterogeneous catalysis.

Armchair ReS2 Nanoribbons: A Promising Catalyst for Hydrogen Evolution Reaction

The two-dimensional material rhenium disulphide (ReS2) is currently receiving immense attention due to its applications in electrocatalysis. This is primarily due to ReS2 possessing excellent qualities like stability in air, easy exfoliation, methanol tolerance etc. However, the two-dimensional monolayer of ReS2 is more or less catalytically inert, due to the sulfur layers covering the Re atoms. Modifications of the two-dimensional monolayer like transition metal decoration, metal cluster deposition, nanoribbon formation etc, is found to lead to enhanced activity. Here, we computationally model a particular nanostructure of two-dimensional ReS2 which is in the form of a nanoribbon, for activity directed towards hydrogen evolution reaction (HER). We study the armchair configuration nanoribbons of ReS2 and find that these have a heightened HER activity compared to the basal plane. Through free energy computations, we predict that armchair ReS2 nanoribbons can have activity comparable to platinum and platinum based catalysts, which are ideal for HER. Using the nudged elastic band method, we investigate the probable mechanism of HER, and find that the Heyrovsky reaction has zero activation barrier for armchair ReS2 nanoribbons. Our results indicate that ReS2 nanoribbon is indeed a promising material as a stable and efficient HER catalyst.

Planar Chlorination Engineering: A Strategy of Completely Breaking the Geometric Symmetry of Fe-N4 Site for Boosting Oxygen Electroreduction.

Introducing asymmetric elements and breaking the geometric symmetry of traditional metal-N4 site for boosting oxygen reduction reaction (ORR) are meaningful and challenging. Herein, the planar chlorination engineering of Fe-N4 site is first proposed for remarkably improving the ORR activity. The Fe-N4/CNCl catalyst with broken symmetry exhibits a half-wave potential (E1/2) of 0.917V versus RHE, 49 and 72mV higher than those of traditional Fe-N4/CN and commercial 20 wt% Pt/C catalysts. The Fe-N4/CNCl catalyst also has excellent stability for 25000 cycles and good methanol tolerance ability. For Zn-air battery test, the Fe-N4/CNCl catalyst has the maximum power density of 228mW cm-2 and outstanding stability during 150h charge-discharge test, as the promising substitute of Pt-based catalysts in energy storage and conversion devices. The density functional theory calculation demonstrates that the adjacent C─Cl bond effectively breaks the symmetry of Fe-N4 site, downward shifts the d-band center of Fe, facilitates the reduction and release of OH*, and remarkably lowers the energy barrier of rate-determining step. This work reveals the enormous potential of planar chlorination engineering for boosting the ORR activity of traditional metal-N4 site by thoroughly breaking their geometric symmetry.

Covalent organic frameworks derived Single-Atom cobalt catalysts for boosting oxygen reduction reaction in rechargeable Zn-Air batteries

The design and development of high-performance and long-life Pt-free catalysts for the oxygen reduction reaction (ORR) is of great important with respect to metal-air batteries and fuel cells. Herein, a new low-cost covalent organic frameworks (COFs)-derived CoNC single-atoms catalyst (SAC) is fabricated and compared with the engineered nanoparticle (NP) counterpart for ORR activity. The ORR performance of the SAC catalyst (CoSA@NC) surpasses the NP counterpart (CoNP-NC) under the same operation condition. CoSA@NC also achieves improved long-term durability and better methanol tolerance compared with the Pt/C. The zinc-air battery assembled by the CoSA@NC cathode delivers a higher power density and energy density than that of commercial Pt/C catalyst. Molecular dynamics (MD) is performed to explain the spontaneous evolution from clusters to single-atom metal configuration and density functional theory (DFT) calculations find that CoSA@NC possesses lower d-band center, resulting in weaker interaction between the surface and the O-containing intermediates. Consequently, the reductive desorption of OH*, the rate-determine step, is further accelerated.