4.7 Review

Non-Noble Metal Catalysts in Cathodic Oxygen Reduction Reaction of Proton Exchange Membrane Fuel Cells: Recent Advances

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Design of Co-NC as efficient electrocatalyst: The unique structure and active site for remarkable durability of proton exchange membrane fuel cells

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Summary: In this study, a unique Co-N-C catalyst with a developed pore structure was successfully synthesized using a melamine-encapsulated Co-ZnO-C composite. The catalyst showed superior stability and 4-electron oxygen reduction reaction (ORR) activity, due to the closed interaction between the Co-N4 moiety and organic adducts. Experimental results demonstrated that the Co-N-C catalyst exhibited remarkable durability with only 6.7% performance degradation after 100 hours, and high stability in real device operation.

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Copper-involved highly efficient oxygen reduction reaction in both alkaline and acidic media

Zehua Yang et al.

Summary: This study developed nitrogen-doped porous carbon catalysts with single Cu atoms and Cu clusters as active sites, showing excellent ORR performance in both alkaline and acidic media. It not only provides a simple strategy for fabricating efficient catalysts, but also identifies the great potential of Cu-based materials for ORR.

CHEMICAL ENGINEERING JOURNAL (2022)

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Recent progress in single-atom alloys: Synthesis, properties, and applications in environmental catalysis

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Summary: Single-atom alloys (SAAs) are novel environmental catalysts that combine the advantages of single atoms and alloys, maximizing atom utilization, reducing the use of noble metals, and enhancing catalytic performance. The synergistic, electronic and geometric effects of SAAs effectively modulate activation energy, break linear scaling relationships, and offer excellent catalytic activity and selectivity.

JOURNAL OF HAZARDOUS MATERIALS (2022)

Review Physics, Applied

Double-atom catalysts for energy-related electrocatalysis applications: a theoretical perspective

Donghai Wu et al.

Summary: Atomically dispersed metal catalysts have attracted intensive research attention due to their excellent activity, selectivity, and stability. Recently, double-atom catalyst (DAC) with a metal dimer anchored on a substrate has emerged as a research focus for energy-related electrocatalysis reactions. DACs offer more possibilities to adjust geometrical configurations and electronic structures due to the flexible dual-metal sites and the synergetic effect between the two metal atoms. This review summarizes the theoretical research on DACs for diverse energy-related electrocatalytic reactions and highlights how their outstanding attributes affect reaction pathways, catalytic activity, and product selectivity.

JOURNAL OF PHYSICS D-APPLIED PHYSICS (2022)

Article Chemistry, Physical

Atomically Dispersed Fe-Co Dual Metal Sites as Bifunctional Oxygen Electrocatalysts for Rechargeable and Flexible Zn-Air Batteries

Yuting He et al.

Summary: This study presents atomically dispersed Fe-Co dual metal sites derived from Fe and Co codoped zeolitic imidazolate frameworks, showing excellent bifunctional catalytic activity for ORR and OER in alkaline media. The FeCo-NC catalyst exhibits outstanding stability and is integrated into an air electrode for fabricating rechargeable and flexible Zn-air batteries, achieving a high power density and long-cycle stability. This work offers a method to design and synthesize atomically dispersed multi-metal site catalysts for advanced electrocatalysis.

ACS CATALYSIS (2022)

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Recent insights on iron based nanostructured electrocatalyst and current status of proton exchange membrane fuel cell for sustainable transport

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Summary: Bridging the performance gap of electrocatalysts is crucial for reducing the cost of proton exchange membrane fuel cell (PEMFC) vehicles. Platinum catalysts contribute to a significant portion of the total cost, while iron-based catalysts show promise in terms of cost-effectiveness and catalytic activity. However, there is a gap between the performance observed in laboratory tests and real operating conditions. Developing efficient iron-based catalysts is critical for commercializing PEMFC vehicles.

JOURNAL OF ENERGY CHEMISTRY (2022)

Article Chemistry, Physical

Multi-walled carbon nanotube supported manganese selenide as a highly active bifunctional OER and ORR electrocatalyst

Harish Singh et al.

Summary: In this article, a new Mn-based bifunctional electrocatalyst, MnSe, has been identified, which shows efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) activity in alkaline medium. The catalytic activity is further enhanced by using multiwalled carbon nanotubes (MWCNTs). The MnSe@MWCNT catalyst exhibits a low overpotential, exceptional methanol tolerance, and compositional stability, making it attractive for regenerative and direct methanol fuel cells.

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Article Chemistry, Physical

Nitrogen-coordinated single-atom catalysts with manganese and cobalt sites for acidic oxygen reduction

Guojie Chao et al.

Summary: This study developed an efficient catalyst based on Mn, Co, and N-co-doped carbon for acidic oxygen reduction reaction. Through analysis using electron microscopy, X-ray absorption spectroscopy, and Raman spectroscopy, it was found that the MnCo-N-C catalyst had a higher degree of graphitization, improving corrosion resistance and catalytic durability. After 50 hours of testing, the current retention of the MnCo-N-C catalyst was significantly higher (81%) compared to the Co-N-C catalyst.

JOURNAL OF MATERIALS CHEMISTRY A (2022)

Article Engineering, Environmental

Cu-N4 single atoms derived from metal-organic frameworks with trapped nitrogen-rich molecules and their use as efficient electrocatalysts for oxygen reduction reaction

Fenghong Lu et al.

Summary: To meet the demand for large-scale commercialization of proton-exchange membrane fuel cells and metal-air batteries, a novel strategy was developed to fabricate high-performance Cu-SAs/NSs. By adding nitrogen-rich molecules to promote the self-assembly of Cu/Zn bimetallic MOF, a highly porous structure and abundant Cu-N-4 active sites were formed, leading to remarkable ORR performance.

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Synthetic strategies of single-atoms catalysts and applications in electrocatalysis

Jia Li et al.

Summary: This paper reviews the research progress of single-atom electrocatalysts in multiple energy conversion reactions. It discusses the synthesis methods, control of metal sites, and electrocatalysis applications. The challenges and future directions for nonprecious-metal single-atom electrocatalysts are identified.

ELECTROCHIMICA ACTA (2022)

Article Chemistry, Physical

Molten salt-assisted carbonization and unfolding of Fe, Co-codoped ZIF-8 to engineer ultrathin graphite flakes for bifunctional oxygen electrocatalysis

Yingjie Chen et al.

Summary: In this study, a high-performance electrocatalyst with Fe, Co, and N doping was synthesized by using NaCl-assisted carbonization and unfolding method. The resulting material exhibited high specific surface area, porosity, and degree of defects, leading to excellent oxygen reduction reaction and oxygen evolution reaction properties. This synthesis method provides a feasible approach for designing high-performance electrocatalysts.

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High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Mengjie Chen et al.

Summary: A novel atomically dispersed and nitrogen coordinated carbon support was developed for high loading platinum catalysts in membrane electrode assemblies. Compared to the controls, this catalyst exhibited enhanced catalytic activity and stability for the oxygen reduction reaction, generating higher current density under heavy-duty vehicle conditions and maintaining good performance after 30,000 voltage cycles.

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Review-Single-Atom Catalysts as Promising Candidates for Single-Atom Catalysts as Promising Candidates for Electrochemical Applications

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Summary: This review article focuses on the recent applications of single-atom catalysts (SACs) in electrocatalysis, including CO2 reduction, oxygen evolution, hydrogen evolution, oxygen reduction, and electrochemical detection. By precise scientific design and controllable construction of SACs, cost-effective and environmentally friendly catalysts can be obtained.

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Theoretically Revealed and Experimentally Demonstrated Synergistic Electronic Interaction of CoFe Dual-Metal Sites on N-doped Carbon for Boosting Both Oxygen Reduction and Evolution Reactions

Xuyan Zhou et al.

Summary: Heteronuclear double-atom catalysts modify the charge density of active metal sites and enhance catalytic activities. CoFe-N-C exhibits exceptional ORR and OER electro-catalytic activities in alkaline media.

NANO LETTERS (2022)

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Exploring Durable Single-Atom Catalysts for Proton Exchange Membrane Fuel Cells

Xin Wan et al.

Summary: This review explores the structure-stability relationship of Fe-N-C catalysts, providing valuable guidance for improved stability. Recent achievements include the discovery of several site-specific degradation mechanisms and identification of intrinsically stable active sites, and the discussion of Fe-free single-atom catalysts as an alternative solution.

ACS ENERGY LETTERS (2022)

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Atomically dispersed metal-nitrogen-carbon electrocatalysts for oxygen reduction reaction: from synthesis strategies to activity engineering

Dan Wang et al.

Summary: Atomically dispersed catalysts have great potential in energy and catalysis fields due to their high atom utilization efficiency, tunable electronic structures, and favorable catalytic performance. This article summarizes the effective synthesis strategies for achieving well-defined active dispersion and discusses activity engineering approaches for atomically dispersed metal nitrogen-carbon catalysts, with the aim of clarifying structure-property correlations.

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Cobalt phosphide nanoparticles encapsulated in manganese, nitrogen co-doped porous carbon nanosheets with rich nanoholes for high-efficiency oxygen reduction reaction

Qi-Dong Ruan et al.

Summary: This study presents a cost-effective and high-performance oxygen reduction electrocatalyst for renewable energy devices, which surpasses commercial Pt/C catalysts.

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A Novel Control Algorithm of the Air Supply Subsystem: Based on Dynamic Modeling of Proton Exchange Membrane Fuel Cell

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The strain induced synergistic catalysis of FeN4 and MnN3 dual-site catalysts for oxygen reduction in proton-/anion- exchange membrane fuel cells

Shiqing Huang et al.

Summary: A new Fe-Mn-N-C dual-atom catalyst has been synthesized in this study, which improves the activity of oxygen reduction reaction by tailoring its electronic structure, and exhibits excellent performance in proton/anion-exchange membrane fuel cells.

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Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Tatyana Reshetenko et al.

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APPLIED CATALYSIS B-ENVIRONMENTAL (2022)

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PGM-Free Oxygen-Reduction Catalyst Development for Proton-Exchange Membrane Fuel Cells: Challenges, Solutions, and Promises

Yanghua He et al.

Summary: In this Account, recent advances in synthesizing efficient PGM-free catalysts for proton-exchange membrane fuel cells (PEMFCs) were highlighted, with an emphasis on effective strategies to improve activity and stability. The formation mechanism of MN4 active sites and their correlation to catalytic properties were discussed, providing guidance for rational catalyst design. The trade-off between activity and stability was identified as a key challenge in developing efficient catalysts for PEMFCs.

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Fe, Cu-codoped metal-nitrogen-carbon catalysts with high selectivity and stability for the oxygen reduction reaction

Yuemin Wang et al.

Summary: FeCu-based M-N-C catalysts exhibit higher selectivity and stability in the ORR, with lower peroxide yields compared to Fe-N-C. Additionally, FeCu-based M-N-C catalysts show only a 15 mV attenuation in their half-wave potentials after accelerated degradation tests.

CHINESE CHEMICAL LETTERS (2021)

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Jing Wang et al.

Summary: A newly explored zinc-based single-atom catalyst with a unique N-2-Zn-B-2 configuration demonstrates impressive ORR activity and remarkable long-term stability, achieved through manipulating the s-band by constructing a B,N co-coordinated Zn-B/N-C catalyst.

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A highly efficient Fenton-like catalyst based on isolated diatomic Fe-Co anchored on N-doped porous carbon

Jingren Yang et al.

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CHEMICAL ENGINEERING JOURNAL (2021)

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Cu-assisted induced atomic-level bivalent Fe confined on N-doped carbon concave dodecahedrons for acid oxygen reduction electrocatalysis

Yan Luo et al.

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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (2021)

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Electrochemical Oxygen Reduction to Hydrogen Peroxide via a Two-Electron Transfer Pathway on Carbon-Based Single-Atom Catalysts

Kai Sun et al.

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MOF Structure Engineering to Synthesize Co-N-C Catalyst with Richer Accessible Active Sites for Enhanced Oxygen Reduction

Jiaojiao Gao et al.

Summary: A new metal-organic framework (MOF) structure-engineering strategy was developed to synthesize accordion-like MOF with higher loading amount and better spatial isolation of Co using acetate (OAc) assistance. The resulting Co-N-C catalyst exhibited higher density of active sites and remarkable ORR activity in alkaline electrolytes, along with outstanding durability and tolerance to methanol in both alkaline and acidic media.
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Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics

Masaru Kato et al.

Summary: A Cu-, Fe-, and N-doped carbon nanotubes ORR electrocatalyst, (Cu,Fe)-N-CNT, was synthesized in this study, which showed a selective 4e(-) reduction efficiency of O-2 to H2O2 of about 99%, demonstrating higher catalytic activity and selectivity compared to other non-PGM catalysts. The research findings suggest that heterometallic cooperation has a significant impact on the ORR kinetics.

ACS CATALYSIS (2021)

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Atomic Zn Sites on N and S Codoped Biomass-Derived Graphene for a High-Efficiency Oxygen Reduction Reaction in both Acidic and Alkaline Electrolytes

Rong Jiang et al.

Summary: A novel catalyst, A-Zn@NSG, has been developed for oxygen reduction reaction with superior catalytic performance surpassing reported Zn-N-C-based catalysts and comparable to state-of-the-art non-precious-metal-based ORR catalysts. Experimental and computational results reveal the Zn-N-4 active site nature of the A-Zn@NSG catalyst, where the surrounding S atoms can donate electrons to atomic Zn centers, enhancing the binding of adsorbed O species and promoting the cleavage of the O-O bond of the adsorbed OOH species, resulting in heightened ORR activity.

ACS APPLIED ENERGY MATERIALS (2021)

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Novel Mn-/Co-Nx Moieties Captured in N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Activity and Stability in Acidic and Alkaline Media

Syed Shoaib Ahmad Shah et al.

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ACS APPLIED MATERIALS & INTERFACES (2021)

Review Chemistry, Multidisciplinary

Recent Advances in Electrocatalysts for Proton Exchange Membrane Fuel Cells and Alkaline Membrane Fuel Cells

Fei Xiao et al.

Summary: The article summarizes the current development status of PEMFCs and AMFCs, including electrocatalyst design, catalyst layer optimization, and cell performance. It discusses and compares the activity, stability, and fuel cell performance of different types of electrocatalysts for the oxygen reduction and hydrogen oxidation reactions, while also exploring research directions for further development.

ADVANCED MATERIALS (2021)

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First demonstration of phosphate enhanced atomically dispersed bimetallic FeCu catalysts as Pt-free cathodes for high temperature phosphoric acid doped polybenzimidazole fuel cells

Yi Cheng et al.

Summary: The study developed atomically dispersed bimetallic FeCu coordinated with nitrogen-doped carbon nanotubes (FeCu/N-CNTs) as Pt-free oxygen reduction reaction (ORR) electrocatalysts, which showed similar performance to Pt/C but with better stability and enhanced activity in the presence of phosphate. DFT calculations revealed that the phosphate promotion effect was due to stronger binding of phosphate on Cu sites, leading to lower activation energy barrier for O-2 cleavage. FeCu/N-CNTs were also found to have better ORR activity compared to Fe single atom catalysts coordinated with nitrogen-doped carbon nanotubes, Fe/N-CNTs. The results demonstrate the potential of FeCu/N-CNTs as true Pt-free, highly active and durable cathodes in high temperature polymer electrolyte fuel cells based on PA/PBI.

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Fei Xiao et al.

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NANO LETTERS (2021)

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Regulating Fe-spin state by atomically dispersed Mn-N in Fe-N-C catalysts with high oxygen reduction activity

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Summary: This article discusses the importance of cathode electrocatalyst support materials in proton exchange membrane fuel cells (PEMFC) and highlights various new carbon-based materials introduced for this purpose. It also outlines strategies to improve the performance of electrocatalysts and their impact on the oxygen reduction reaction (ORR).

ACTA METALLURGICA SINICA-ENGLISH LETTERS (2021)

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Zhe Chen et al.

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APPLIED CATALYSIS B-ENVIRONMENTAL (2021)

Article Chemistry, Physical

Co/N-doped carbon nanotubes-grafted porous carbon sheets architecture as efficient electrocatalyst for oxygen reduction reaction

Deying Leng et al.

Summary: This study introduces a low-cost and effective method to produce Co/N-CNT/PCS catalysts, which exhibit excellent ORR electrocatalytic activity, long-term stability, and potential as a major contender in the field of PEMFCs.

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Dual-Metal Hetero-Single-Atoms with Different Coordination for Efficient Synergistic Catalysis

Xin Zhao et al.

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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The role of supported dual-atom on graphitic carbon nitride for selective and efficient CO2 electrochemical reduction

Shuang Zhu et al.

Summary: The role of dual-metal atoms on graphite carbon nitride for selective and efficient CO2 electrochemical reduction was studied, and RuCu@g-CN and RuFe@g-CN were found to be the most promising electrocatalysts for CO2RR.

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Miriam M. Tellez-Cruz et al.

Summary: The study of electrochemical catalyst conversion of renewable electricity and carbon oxides into chemical fuels is crucial for mitigating the global energy crisis. Research efforts are currently focused on developing high-performance membranes and nanomaterials with high catalytic activity to improve fuel cell performance and reduce the use of expensive platinum group metals.

POLYMERS (2021)

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Recent advances in the design of a high performance metal-nitrogen-carbon catalyst for the oxygen reduction reaction

Cheng-Wei Ye et al.

Summary: Developing efficient cathode oxygen reduction reaction (ORR) catalysts is crucial for the widespread application of fuel cells. Recent studies have made significant progress in designing high-performance M-N-C catalysts through strategies like increasing active site density, improving intrinsic activity, facilitating mass transfer, and avoiding linear scaling relationship.

JOURNAL OF MATERIALS CHEMISTRY A (2021)

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Recent advances in non-precious metal electrocatalysts for oxygen reduction in acidic media and PEMFCs: an activity, stability and mechanism study

Jiayao Cui et al.

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Summary: Research shows that atomically dispersed metal-nitrogen-carbon catalysts have significant potential in improving the oxygen reduction reaction and membrane electrode assembly performance of proton exchange membrane fuel cells, indicating promising avenues for addressing current bottlenecks in hydrogen energy conversion.

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Polymer electrolyte membrane fuel cell and hydrogen station networks for automobiles: Status, technology, and perspectives

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Atomic Fe-Zn dual-metal sites for high-efficiency pH-universal oxygen reduction catalysis

Jie Xu et al.

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NANO RESEARCH (2021)

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Applications of Atomically Dispersed Oxygen Reduction Catalysts in Fuel Cells and Zinc-Air Batteries

Qiaoqiao Zhang et al.

Summary: Due to energy crisis and environmental concerns, single-atom catalysts (SACs) have attracted attention for oxygen reduction reactions (ORR) in fuel cells and Zn-air batteries. The research focuses on transition-metal-based electrocatalysts and explores synthesis, characterization, ORR mechanisms, and performance evaluations in different types of electrochemical devices. Challenges and future directions for SACs in fuel cells and Zn-air batteries are also discussed.

ENERGY & ENVIRONMENTAL MATERIALS (2021)

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Yuli Ma et al.

Summary: Theoretical calculations show that single-metal-atom doped 2D WO2 can serve as an excellent catalytic material for OER/ORR, with small overpotentials comparable to IrO2 or Pt-based catalysts.

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