Oxygen Reduction Research Articles

Mass Transportation Facilitated Porous Fe/Co Dual‐Site Catalytic Cathodes for Ultrahigh‐Power‐Density Al–Air Fuel Cells

AbstractThe development of oxygen‐dependent fuel cells is frequently hindered by the high cost of cathode materials and the sluggish kinetics of the oxygen reduction reaction (ORR). It is thus crucial to explore low‐cost and high‐activity catalysts with accelerated mass transport. Here, a high‐throughput screening method is developed by integrating an explicit solvation model with machine learning potential‐based molecular dynamics simulations, which enables the efficient evaluation of a vast array of diverse diatomic combinations and ultimately identifying Fe–Co dual‐atomic sites as the optimal ORR electrocatalysts. The superior electrocatalytic performance of the diatomic Fe/Co sites loaded on 3D‐interconnected ordered macroporous carbon (FeCo‐3DMNC) is experimentally verified, achieving high ORR activity with half‐wave potentials of 0.806 V in acidic and 0.905 V in alkaline environments. Additionally, innovative hybrid acid/alkali aluminum–air fuel cells (hA/A‐AAFCs) incorporating FeCo‐3DMNC as the cathode catalyst demonstrate a notably high open‐circuit voltage of 2.72 V and a record‐breaking power density of 827 mW cm−2, significantly outperforming conventional alkaline aluminum–air fuel cells. This work marks a significant advancement by combining cutting‐edge computational screening with rigorous experimental validation to develop promising electrocatalysts, potentially paving the way for the advanced energy storage and conversion technologies.

Boosting the Performance and Durability of Fe-N-C Fuel Cell Catalysts via Integrating Mo2C Clusters.

Carbon-supported nitrogen-coordinated iron single-atom (Fe-N-C) catalysts have been regarded among the most promising platinum-group-metal-free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Nevertheless, their limited intrinsic activity and unsatisfactory stability have hindered their practical applications. Here, it is reported that the integration of Mo2C clusters effectively enhances the ORR activity and stability of Fe-N-C catalysts. The composite catalyst of Fe single atoms and Mo2C clusters co-embedded on nitrogen-doped carbon (FeSA/Mo2C-NC) exhibits an excellent ORR activity with a half-wave potential of 0.82V in acidic media and a high peak power density of 0.5W cm-2 in an H2-air PEMFC. Moreover, improved stability is achieved with nearly no decay under H2-air conditions for 80h at 0.4V. Experiments with theoretical calculations elucidate that the etching effect of the phosphomolybdic acid precursor optimizes the pore size distribution of the composite catalyst, thereby exposing more active sites. The Mo2C clusters modulate the electronic configuration of the Fe-N4 sites, optimizing adsorption energy for ORR intermediates and strengthening the Fe-N bond to mitigate demetalation. This work provides valuable insights into the construction of single-atom/nanoaggregate hybrid catalysts for efficient energy-related applications.

Hybrid Nanoalloy‐Cluster‐Single Atom Sites Based Aerophilic Carbon Fiber Membranes as Binder‐Free Cathodes for Ultra‐Long‐Life Zn‐air Batteries

AbstractHigh‐efficient and durable electrocatalysts for oxygen reduction and oxygen evolution reaction (ORR/OER) are desirable to Zn‐air batteries (ZABs). However, most of catalysts in powder form with sole active sites remain challenging in achieving the satisfactory bifunctional catalysis and suffer from peeling off during the long‐term operation. Herein, hybrid CoFe active sites are constructed containing nanoalloys (≈10 nm), clusters (< 2 nm), and single atoms on aerophilic carbon fiber membranes as binder‐free air cathodes for ultra‐long‐life ZABs. In particular, the high air‐permeability of membranes (0.2 s) can prevent the active sites from blocking by O2 bubbles and promote the mass transfer. The theoretical and experimental results confirm that the hydrophilic CoFe2O4/CoFeOOH sites reconstructed on the surface of CoFe nanoalloys are mainly responsible for OER. While for single atoms and clusters on nitrogen (N)‐doped carbon matrix, they play a synergetic role in optimizing the adsorption energy to enhance ORR activity. Thus, the as‐prepared catalysts exhibit an ultra‐low ORR/OER potential gap (0.64 V). When further assembled as freestanding air‐electrodes, it exhibits an outstanding cycling lifespan of 1200 and 155 h in liquid‐ and quasi‐solid‐state ZABs respectively, which are fivefold and twofold higher than those of powder‐based cathodes (240/67 h).

CoFe2O4 with the In-Situ Formed Oxygen Vacancies and Co Particles as an Efficient Bifunctional Catalyst for Rechargeable Zinc-Air Batteries.

Rechargeable zinc-air batteries (RZABs) are considered as one of the most promising clean energy device due to their abundant resources, low cost and environmental friendliness. However, their energy efficiency and cycle life are far from satisfactory due to the poor activity and stability of bi-functional electrocatalyst in air cathode. In this work, an efficient bi-functional catalyst (rGO-CoFe2O4/Co) was derived from its precursor (rGO-CoFe2O4) through a simple annealing process. Electrochemical measurements prove that rGO-CoFe2O4/Co with the in-situ formed Co nano particles and rich oxygen vacancies appears excellent oxygen reduction reaction and oxygen evolution reaction catalytic activity compared to its counterpart. Its half-wave potential is 0.81 V (vs RHE) and the OER overpotential is only 310 mV (vs RHE). In addition, rechargeable zinc-air batteries assembled with rGO-CoFe2O4/Co show the highest peak power density (128.9 mW cm-2) and cycling stability compared to rGO-CoFe2O4 and commercial Pt/C-RuO2 catalysts. This work provides a simple strategy for the design of advanced bifunctional catalysts.

N/S Codoped Porous Carbon Spheres by Extended Stöber Method for Highly Efficient Oxygen Reduction Reaction and Loaded with Pt for Methanol Oxidation Reaction

N/S Codoped Porous Carbon Spheres by Extended Stöber Method for Highly Efficient Oxygen Reduction Reaction and Loaded with Pt for Methanol Oxidation Reaction

Exploring the Potential of Bimetallic PtPd/C Cathode Catalysts to Enhance the Performance of PEM Fuel Cells.

Bimetallic platinum-containing catalysts are deemed promising for electrolyzers and proton-exchange membrane fuel cells (PEMFCs). A significant number of laboratory studies and commercial offers are related to PtNi/C and PtCo/C electrocatalysts. The behavior of PtPd/C catalysts has been studied much less, although palladium itself is the metal closest to platinum in its properties. Using a series of characterization methods, this paper presents a comparative study of structural characteristics of the commercial PtPd/C catalysts containing 38% wt. of precious metals and the well-known HiSpec4000 Pt/C catalyst. The electrochemical behavior of the catalysts was studied both in a three-electrode electrochemical cell and in the membrane electrode assemblies (MEAs) of hydrogen-air PEMFCs. Both PtPd/C samples demonstrated higher values of the electrochemically active surface area, as well as greater specific and mass activity in the oxygen reduction reaction in comparison with conventional Pt/C, while not being inferior to the latter in durability. The MEA based on the best of the PtPd/C catalysts also exhibited higher performance in single tests and long-term durability testing. The results of this study conducted indicate the prospects of using bimetallic PtPd/C materials for cathode catalysts in PEMFCs.

Molecular Unravelling of the Structural Effect of Quinone Redox Mediators on Oxygen Reduction Reaction in Aprotic Lithium-Oxygen Batteries.

Redox mediators (RMs) provide tantalizing solutions to unlock the energy capabilities of aprotic lithium-oxygen (Li-O2) batteries by driving solution-mediated Li2O2 growth. However, the structural effect of RMs on the catalytic efficiency of the oxygen reduction reaction remains incompletely understood. Herein, we present the interplay between the structure of RMs and their discharge capabilities by a comparative study of model quinone (Q)-based RMs. Specifically, at low current densities, incorporating electron-withdrawing groups onto the Q ring can positively move the discharge potential and deliver larger discharge capacity by extending the lifespan of the LiQO2 intermediate and allowing for Li2O2 growth into deeper electrolyte regions. Conversely, at high current densities, the absence of electron-withdrawing groups facilitates homogeneous reaction kinetics from LiQ to regenerate Q (i.e., decreased lifespan of LiQO2), mitigating electrode potential polarization and preserving catalytic activity of Q for higher discharge capacity. The work establishes structure-property relationships that guide the rational design of RMs toward next-generation Li-O2 batteries.

A review of ordered PtCo3 catalyst with higher oxygen reduction reaction activity in proton exchange membrane fuel cells

This review is devoted to the potential advantages of ordered alloy catalysts in proton exchange membrane fuel cells (PEMFCs), specifically focusing on the development of the low Pt content, high activity, and durability ordered PtCo3 catalyst. Due to the sluggish oxygen reduction reaction (ORR) kinetics and poor durability, the overall performance of the fuel cell is affected, and its application and promotion are limited. To address this issue, researchers have explored various synthetic strategies, such as element doping, morphology adjusting, structure controlling, ordering and support/metal interaction enhancement. This article extensively discussed the Pt related ORR catalysts and follows an in-depth analysis of ordered PtCo3. The introduction briefly discusses the direction of development of fuel cell catalysts and frontier progress, including theoretical mechanism, practical preparation, and Pt-containing electrode structures, etc. The subsequent chapter focuses on the Pt-Co catalyst, the evolution process of Pt alloy to Pt-Co alloy and the improvement scheme are introduced. The next chapter describes the properties of PtCo3. Although the ordered PtCo3 catalyst has a wide range of applicability due to low cost and high activity catalyst. However, besides the common agglomeration and sintering problems of Pt-Co alloy, its commercial application still faces unique problems of oversized crystal size, phase segregation, ordering transformation and transition metal dissolution. Therefore, in Chapter 4, this overview provides some possible improvement methods for three specific functions: crystal refinement, enhancing the effect of support and active substances, and anti-dissolution.

Celebrating Ten Years of Covalent Organic Frameworks for Solar Energy Conversion: Past, Present and Future

AbstractAccelerated anthropogenic emission of greenhouse gases due to increasing energy demands has created a negative impact on our planet. Therefore, the replacement of fossil by renewable energy resources has become of paramount interest, both societally and scientifically. It is within this setting that organic photocatalysts have emerged as a new generation of earth‐abundant catalysts for the conversion of solar radiation into chemical energy. In 2014, the first example of a covalent organic framework (COF) photocatalyst for the hydrogen evolution reaction was reported by our group, which has not only marked the beginning of COF photocatalysis for solar fuel production but also helped to accelerate research into “soft photocatalysis” based on porous polymers in general. In the last decade, significant progress has been made toward developing COFs as robust, molecularly precise platforms emulating artificial photosynthesis. This mini‐review commemorates the 10th anniversary of COF photocatalysis and gives a brief historical overview of the milestones in the field since its inception in 2014. We review milestones in the development of COFs for solar fuel production and related photocatalytic transformations, including hydrogen evolution, oxygen evolution, overall water splitting, CO2 reduction, N2 fixation, oxygen reduction, and alcohol oxidation. We discuss lessons learned for the design of structure‐property‐function relationships in COF photocatalysts, and future perspectives and challenges for the field of “soft photocatalysis” are given.

Celebrating Ten Years of Covalent Organic Frameworks for Solar Energy Conversion: Past, Present and Future.

Accelerated anthropogenic emission of greenhouse gases due to increasing energy demands has created a negative impact on our planet. Therefore, the replacement of fossil by renewable energy resources has become of paramount interest, both societally and scientifically. It is within this setting that organic photocatalysts have emerged as a new generation of earth-abundant catalysts for the conversion of solar radiation into chemical energy. In 2014, the first example of a covalent organic framework (COF) photocatalyst for the hydrogen evolution reaction was reported by our group, which has not only marked the beginning of COF photocatalysis for solar fuel production but also helped to accelerate research into "soft photocatalysis" based on porous polymers in general. In the last decade, significant progress has been made toward developing COFs as robust, molecularly precise platforms emulating artificial photosynthesis. This mini-review commemorates the 10th anniversary of COF photocatalysis and gives a brief historical overview of the milestones in the field since its inception in 2014. We review milestones in the development of COFs for solar fuel production and related photocatalytic transformations, including hydrogen evolution, oxygen evolution, overall water splitting, CO2 reduction, N2 fixation, oxygen reduction, and alcohol oxidation. We discuss lessons learned for the design of structure-property-function relationships in COF photocatalysts, and future perspectives and challenges for the field of "soft photocatalysis" are given.

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.

Adsorbate Resonance Induces Water-Metal Bonds in Electrochemical Interfaces.

This study delves into the intricate interactions between surface-near species, OH and H2O, on electrodes in electrochemical interfaces. These species are an inevitable part of many electrocatalytic energy conversion reactions such as the oxygen reduction reaction. In our modeling, we utilize high statistics on a dataset of complex solid solutions with high atomic variability to show the emergence of H2O-metal covalent bonds under specific conditions. Based on density functional theory (DFT) calculations ofadsorption energies onmany thousands of different surface compositions, we provide a quantifiable physical understanding of this induced water covalency, which is rooted in simple quantum mechanics. Directional hydrogen bonding between surface-near H2O and OH, enables surface bonding electrons to delocalize mediatedby near-symmetrical adsorbate resonance structures. The different adsorbate resonance structures differ by surface coordination explaining the induced H2O-metal bonding.

Adsorbate Resonance Induces Water‐Metal Bonds in Electrochemical Interfaces

This study delves into the intricate interactions between surface‐near species, OH and H2O, on electrodes in electrochemical interfaces. These species are an inevitable part of many electrocatalytic energy conversion reactions such as the oxygen reduction reaction. In our modeling, we utilize high statistics on a dataset of complex solid solutions with high atomic variability to show the emergence of H2O‐metal covalent bonds under specific conditions. Based on density functional theory (DFT) calculations of adsorption energies on many thousands of different surface compositions, we provide a quantifiable physical understanding of this induced water covalency, which is rooted in simple quantum mechanics. Directional hydrogen bonding between surface‐near H2O and OH, enables surface bonding electrons to delocalize mediated by near‐symmetrical adsorbate resonance structures. The different adsorbate resonance structures differ by surface coordination explaining the induced H2O‐metal bonding.

Metal‐Organic Framework Materials as Bifunctional Electrocatalyst for Rechargeable Zn‐Air Batteries

AbstractRechargeable Zn‐air batteries offer the advantages of environmental friendliness, safety, low prices and high energy density, and are highly valued. However, the major challenge faced by rechargeable Zn‐air batteries nowadays is the low energy efficiency due to the slow reaction kinetics of electrocatalyst at the air cathode. Bifunctional catalysts are key to the development of Zn‐air batteries by improving their overall performance and long‐term cycling stability. Metal‐organic framework (MOF) materials have shown great benefits as oxygen electrocatalysts in promoting oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). This paper reviews the recent advances of three kinds of MOF materials as bifunctional catalysts for rechargeable Zn‐air batteries. Additionally, this paper also discusses the synthetic design strategy of MOF composite derivatives, and concludes by suggesting the application of MOF materials in the field of rechargeable Zn‐air batteries.

High-entropy design of Ruddlesden-Popper structured LNO for enhanced performance in proton solid oxide fuel cells

Protionic Ceramic Fuel Cells (PCFCs) are devices that efficiently convert chemical energy to electrical energy at low temperatures. Significant research efforts have been directed towards the development of cathodes with enhanced catalytic activity. In this work, a high-entropy approach was employed at the A site of La2NiO4+δ (LNO) with a Ruddlesden-Popper (R-P) structure, resulting in the synthesis of the LaPr0.2Sm0.2Ba0.2Sr0.2Ca0.2NiO4+δ (HE-LPSBSCN) cathode. A comprehensive series of tests demonstrated that this high-entropy strategy improved the oxygen reduction reaction (ORR) activity, hydration behavior, well operational stability, and electronic conductivity of LNO. The HE-LPSBSCN cathode demonstrated record-breaking performance, achieving a maximum power density of 2004 mW cm−2 at 700 °C. This finding provides novel insights for the rational design and optimization of highly catalytically active cathodes for PCFCs.

Recycling of spent heat pack towards Fe-Fe3O4@NC catalyst for ORR in direct methanol fuel cells and Al-air batteries

The effective repurposing of waste materials is crucial for sustainable development. The widespread use of disposable iron-based chemical warmers (IBCW) generates substantial solid waste annually. In this study, IBCWs were repurposed as raw materials to synthesize different electrocatalyst composites comprising metallic and oxide forms of iron embedded in nitrogen-doped carbon (NC). The composites were evaluated as oxygen reduction reaction (ORR) catalysts. The optimized Fe-Fe3O4@NC demonstrated enhanced ORR kinetics, with an onset potential of 0.92 V and a half-wave potential of 0.86 V vs. RHE. As an air cathode for direct methanol fuel cell (DMFC), Fe-Fe3O4@NC achieved a power density of 33.3 mW cm−2 at 88 mA cm−2, demonstrating its practical applicability. Additionally, a quasi solid-state aluminium-air battery (SAAB) was assembled using this catalyst as the air cathode with a PVA-KOH gel electrolyte and the separator. The quasi SAAB exhibited an open circuit voltage (OCV) of 1.46 V, a power density of 40 mW cm-2, and good rate capability compared to Pt/C. The combined effect of metallic and oxide iron with nitrogen doping enhances the overall catalytic activity. This study demonstrates that IBCWs can be effectively transformed into valuable catalysts for renewable energy applications, enabling clean and sustainable utilization of waste materials.

Advances in Liquid-Phase Synthesis: Monitoring of Kinetics for Platinum Nanoparticles Formation, and Pt/C Electrocatalysts with Monodispersive Nanoparticles for Oxygen Reduction

The growing demand for hydrogen–air fuel cells with a proton-exchange membrane has increased interest in the development of scalable technologies for the synthesis of Pt/C catalysts that will allow us to fine-tune the microstructure of such materials. We have developed a new in situ technique for controlling the kinetics of the transformation of a platinum precursor into its nanoparticles and deposited Pt/C catalysts, which might be applicable during the liquid-phase synthesis in concentrated solutions and carbon suspensions. The technique is based on the analysis of changes in the redox potential and the reaction medium coloring during the synthesis. The application of the developed technique under conditions of scaled production has made it possible to obtain Pt/C catalysts with 20% and 40% platinum loading, containing ultra-small metal nanoparticles with a narrow size distribution. The electrochemically active surface area of platinum and the mass activity of synthesized catalysts in the oxygen electroreduction reaction have proved to be significantly higher than those of commonly used commercial analogs. At the same time, despite the small size of nanoparticles, the catalysts’ degradation rate turned out to be the same as that of commercial analogs.

Fuel Cell Catalyst Layers with Platinum Nanoparticles Synthesized by Sputtering onto Liquid Substrates.

Platinum (Pt) nanoparticles are widely used as catalysts in proton exchange membrane fuel cells. In recent decades, sputter deposition onto liquid substrates has emerged as a potential alternative for nanoparticle synthesis, offering a synthesis process free of contaminant oxygen, capping agents, and chemical precursors. Here, we present a method for the synthesis of supported nanoparticles based on magnetron sputtering onto liquid poly(ethylene glycol) (PEG) combined with a heat-treatment step for attachment of nanoparticles to a carbon support. Transmission electron microscopy imaging reveals Pt nanoparticle growth during the heat-treatment process, facilitated by the carbon support and the reducing properties of PEG. Following the heat treatment, a bimodal size distribution of Pt nanoparticles is observed, with sizes of 2.5 ± 0.8 and 6.7 ± 1.8 nm, compared to 1.8 ± 0.4 nm after sputtering. Synthesized Pt nanoparticles display excellent specific and mass activities for the oxygen reduction reaction, with 1.75 mA/cm2 Pt and 0.27 A/mgPt respectively, measured at 0.9 V vs the reversible hydrogen electrode. The specific activities reported herein outperform literature values of commercial Pt/C catalysts with similar loading and are on par with values of bulk Pt and mass-selected nanoparticles of comparable size. Also, the mass activities agree well with the literature values. The results provide new insights into the growth processes of SoL-synthesized carbon-supported Pt catalyst nanoparticles, and most crucially, the high performance of the synthesized catalyst layers, along with the possibility of nanoparticle growth through a straightforward heat-treatment step at relatively low temperatures, offer a scalable new approach for producing fuel cell catalysts with more efficient material utilization and new material combinations.

Optimizing Activity and Stability in AgCl‐CuO Electrocatalysts: Insights from Different Morphologies for Enhanced ORR Performance

Highly enduring and methanol‐tolerant electrocatalysts are pertinent to revolutionizing direct methanol fuel cell (DMFC) technologies. Transition metal‐based electrocatalysts are anticipated to rank among the remarkable electrocatalysts for boosting the sluggish Oxygen Reduction Reaction (ORR) kinetics. Herein, we report a facile approach to optimize the activity and stability of the AgCl‐CuO systems. The tailored Nano Particle‐Nano Rod (NP‐NR) and Nano Leaf (NL) like morphologies deliver remarkable bifunctional catalytic performance for oxygen reduction and hydrogen evolution reactions, sustained activity, and comparatively better stability for ORR. A meager shift of only 0.014 V and 0.024 V in the half‐wave potential is observed in the NP‐NR and NL structures, respectively, for the ORR even after 2500 cycles. Furthermore, both the AgCl‐CuO composite exhibits an excellent tolerance to methanol.

Electrodeposited Manganese Dioxides and Their Composites as Electrocatalysts for Energy Conversion Reactions.

Enhancing the efficiencies of electrochemical reactions for converting renewable energy into clean chemical fuels as well as generating clean energy is critical to achieving carbon neutrality. However, this enhancement can be achieved using materials that are not constrained by resource limitations and those that can be converted into devices in a scalable manner, preferably for industrial applications. This review explores the applications of electrochemically deposited manganese dioxides (MnO2) and their composites as electrochemical catalysts for oxygen evolution (OER) and hydrogen evolution reactions for converting renewable energy into chemical fuels. It also explores their applications as electrochemical catalysts for oxygen reduction reaction (ORR) and bifunctional OER/ORR for the efficient operation of fuel cells and metal-air batteries, respectively. Manganese is the second most abundant transition metal in the Earth's crust, and electrodeposition represents a binder-free and scalable technique for fabricating devices (electrodes). To propose an improved catalyst design, the studies on the electrodeposition mechanism of MnO2as well as the fabrication techniques for MnO2-based nanocomposites accumulated in the development of electrodes for supercapacitors are also included in this review.