Cathodic Oxygen Reduction Reaction Research Articles

Cobalt/nitrogen doped hollow carbon sphere-bamboo like carbon nanotube for highly efficient oxygen reduction reaction

The exploration of non-Pt catalysts with high electrocatalytic activity and durability is especially important for cathodic oxygen reduction reaction (ORR) in fuel cell. Here, cobalt and nitrogen doped hollow carbon sphere-bamboo like carbon nanotube (Co/NHCS-BCNT) is prepared by using SiO2 sphere as sacrificial template. Co nanoparticles are confined in the cavity and top end of the in-situ formed BCNT, which can not only avoid the agglomeration of Co nanoparticles but also inhibit corrosion in caustic electrolyte. The synergistic effect between NHCS and well-dispersed Co particles makes Co/NHCS-BCNT have superior catalytic activity toward ORR. The electrochemical surface area (ECSA) of Co/NHCS-BCNT is 222 cm2, which is higher than those of NHCS (164 cm2) and HCS (135 cm2). The onset potential and half-wave potential of Co/NHCS-BCNT are 0.941 V and 0.814 V, respectively, which are close to commercial Pt/C (0.949 V, 0.807 V). The Tafel slope of Co/NHCS-BCNT (63.8 mV dec-1) is lower than that of Pt/C (71.7 mV dec-1). In addition, Co/NHCS-BCNT shows excellent durability and fuel selectivity.

Resonant structure substrate anchors Pt to form ordered alloys for efficient oxygen reduction reaction

Platinum-based ordered alloys have excellent catalytic performance for the cathodic oxygen reduction reaction (ORR) in fuel cells. However, these alloys exhibit a lower degree of ordering and larger crystal grains after heat treatment. Herein, a series of cyanamide group molecules (cyanamide, dicyandiamide, melamine) was employed as substrates to modify Pt-based alloys by promoting the binding between metal ions, leading to the preparation of ∼ 4 nm PtM (M = Co, Fe, Ni) ordered alloys after heat treatment. Among them, the PtCo ordered alloy prepared using hydrolyzed cyanamide with a unique resonance structure exhibits a high degree of order (93.1 %), and its mass activity of 0.915 A mgPt-1 at 0.9 V is superior to that of Pt/C. The theoretically calculated adsorption energies of these alloys demonstrate that the resonance structure of the cyanamide substrate is beneficial for alloy formation, thereby facilitating ordered alloy synthesis.

Single-atom Fe catalysts with pyrrolic-type FeN4 sites for efficient oxygen reduction reaction: Identifying the roles of different N species

Developing electrocatalysts with efficient cathode oxygen reduction reaction (ORR), for example, iron-based single-atom catalysts (Fe-SACs), has been deemed necessary to accelerate the commercialisation process of zinc (Zn)–air batteries. Nevertheless, determining how various nitrogen species and active metal centres coordinate on an atomic scale remains unclear and inadequately explained. Herein, we demonstrate a soft-template-aided technique using Fe-containing molecules (e.g. iron phthalocyanine [FePc], Fe-1,10-phenanthroline [Fe-Phen] and Fe-glucose) to enhance the performance of Fe-SACs in terms of ORR. In this technique, FePc molecules can be converted into atomically dispersed pyrrolic-type iron–nitrogen (FeN4) sites during a pyrolytic process. The resultant catalyst exhibits excellent ORR activity (half-wave potential = 0.90 V) in alkaline medium and standing battery performance when used in Zn–air batteries (peak power density = 197.3 mW cm−2 and specific capacity = 796.2 mAh g−1). As per the findings from control experiments and characterisation studies, electron transfer between the support and the active Fe centre amplifies the ORR performance. Theoretical calculations substantiate that Fe sites coordinated with pyrrolic N atoms govern the electronic configuration of the catalysis, reducing the free energy absorption of reaction intermediates and thus increasing its intrinsic ORR capability. Herein, we aim to offer a fresh perspective on the relation between coordination environments and catalytic activity in ORR catalysts.

Nickel adsorbed algae biochar based oxygen reduction reaction catalyst

Lately, the bio electrochemical systems are emerging as an efficient wastewater treatment and energy conversion technology. However, their scaling-up is considerably restrained by slow-rate of cathodic oxygen reduction reaction (ORR) or otherwise by the high cost associated with the available efficient ORR catalysts. In this investigation, a cost-effective and eco-friendly approach for synthesizing Ni based ORR catalyst utilizing biosorption property of microalgae is accomplished. The synthesised Ni adsorbed algal biochar (NAB) served as an efficient cathode catalyst for enhancing ORR in a microbial carbon-capture cell (MCC). On increasing the initial concentration of Ni2+ in the aqueous medium from 100 mgL−1 to 500 mgL−1, the biosorption capacity was found to increase from 3 mgg−1 to 32 mgg−1 of algae cell. The MCC operated with NAB based cathode catalyst loading of 2 mgcm-2 exhibited 3.5 times higher power density (4.69 Wm−3) as compared to the one with commercial activated carbon. A significant organic matter removal (82 %) in the anodic chamber with simultaneous algal biomass productivity in the cathodic chamber was attained by MCC with cathode loaded with 2 mgcm−2 of NAB. Hence, this easily synthesised low-cost catalyst, out of waste stream, proved its ability to improve the performance of MCC.

Preparation and performance of the non-platinum catalyst for oxygen reduction reaction in fuel cells

The oxygen reduction reaction (ORR) of the fuel cells is a core of energy conversion, whereas its kinetics is slow due to the limitation of the activation energy barrier, which dramatically limits the commercial development of fuel cells. At present, the main electrocatalyst for the cathode oxygen reduction reaction of fuel cells is the platinum (Pt)-based catalyst. Still, as a precious metal, Pt has a high price, low reserves, and poor stability. These shortcomings seriously affect the mass production and commercialization of fuel cells. Therefore, there is an urgent need for the development of fuel cells to study a low price, sufficient production, high stability, and pollution-free non-Pt catalyst. The main research content of this paper is to use biomass sycamore ball as a carbon source, mixed with ferric chloride (III) hexahydrate and melamine, and prepare the carbon, nitrogen, and iron co-doped ORR catalyst by high-temperature calcination under a nitrogen atmosphere. The physical characterization and electrochemical testing of the obtained samples were conducted at room temperature. The results showed that the pretreatment of sycamore ball powder to iron ratio of 1:3 had the best catalytic performance.

Study on Influence Factors of H2O2 Generation Efficiency on Both Cathode and Anode in a Diaphragm-Free Bath.

Electrosynthesis of H2O2 via both pathways of anodic two-electron water oxidation reaction (2e-WOR) and cathodic two-electron oxygen reduction reaction (2e-ORR) in a diaphragm-free bath can not only improve the generation rate and Faraday efficiency (FE), but also simplify the structure of the electrolysis bath and reduce the energy consumption. The factors that may affect the efficiency of H2O2 generation in coupled electrolytic systems have been systematically investigated. A piece of fluorine-doped tin oxide (FTO) electrode was used as the anode, and in this study, its catalytic performance for 2e-WOR in Na2CO3/NaHCO3 and NaOH solutions was compared. Based on kinetic views, the generation rate of H2O2 via 2e-WOR, the self-decomposition, and the oxidative decomposition rate of the generated H2O2 during electrolysis in carbonate electrolytes were investigated. Furthermore, by choosing polyethylene oxide-modified carbon nanotubes (PEO-CNTs) as the catalyst for 2e-ORR and using its loaded electrode as the cathode, the coupled electrolytic systems for H2O2 generation were set up in a diaphragm bath and in a diaphragm-free bath. It was found that the generated H2O2 in the electrolyte diffuses and causes oxidative decomposition on the anode, which is the main influent factor on the accumulated concentration in H2O2 in a diaphragm-free bath.

Synthesis of NbC@C(Nx) nanoparticles using DC arc discharge plasma for highly efficient oxygen reduction reaction

Development of the low-cost, high-efficiency, and durable non-precious metal electrocatalysts for cathodic oxygen reduction reaction (ORR) is of vital importance for fuel cells and metal-air batteries. Herein, the carbon-coated NbC nanoparticles (NbC@C NPs) were prepared using DC arc discharge plasma under a methane atmosphere. Then, the nitrogen-doping was conducted by heat treatment, resulting in nitrogen-doped carbon-coated NbC nanoparticles (NbC@C(Nx) NPs). Benefiting from the merit of unique core-shell structure and best synergy between the nitrogen-doped carbon shell and the NbC core, the obtained highest nitrogen-doped NbC@C(N1.36) NPs showed an onset potential (Eonset) of 0.89 V (vs. RHE) and a half-wave potential (E1/2) of 0.79 V, which are comparable to those of commercial Pt/C (20 wt%) (Eonset = 0.90 V, E1/2 = 0.80 V), and its diffusion-limited current density (JL) of 5.99 mA·cm−2 is even higher than that of commercial Pt/C (5.43 mA·cm−2). Moreover, it exhibited a remarkable long-term durability and impressive methanol resistance than Pt/C catalyst. In addition, the real-time optical emission spectrum (OES) analysis of arc plasma shows that the electron temperature (Te) is 7562.9 K in local thermal equilibrium (LTE) plasma. Therefore, the use of the DC arc discharge plasma method opens a fast and simple way to develop cost-effective and highly efficient non-precious metal catalysts for ORR.

Universal Sublimation Strategy to Stabilize Single-Metal Sites on Flexible Single-Wall Carbon-Nanotube Films with Strain-Enhanced Activities for Zinc-Air Batteries and Water Splitting.

Single-metal-site catalysts have recently aroused extensive research in electrochemical energy fields such as zinc-air batteries and water splitting, but their preparation is still a huge challenge, especially in flexible catalyst films. Herein, we propose a sublimation strategy in which metal phthalocyanine molecules with defined isolated metal-N4 sites are gasified by sublimation and then deposited on flexible single-wall carbon nanotube (SWCNT) films by means of π-π coupling interactions. Specifically, iron phthalocyanine anchored on the SWCNT film prepared was directly used to boost the cathodic oxygen reduction reaction of the zinc-air battery, showing a high peak power density of 247 mW cm-2. Nickel phthalocyanine and cobalt phthalocyanine were, respectively, stabilized on SWCNT films as the anodic and cathodic electrocatalysts for water splitting, showing a low potential of 1.655 V at 10 mA cm-2. In situ Raman spectra and theoretical studies demonstrate that highly efficient activities originate from strain-induced metal phthalocyanine on SWCNTs. This work provides a universal preparation method for single-metal-site catalysts and innovative insights for electrocatalytic mechanisms.

Impact of Heat Treatment on the Oxygen Reduction Reaction Performance of PtCo/C(N) Electrocatalyst in PEM Fuel Cell

AbstractThe synthesis of efficient and stable Pt alloy catalysts is a major challenge for the commercialization of PEMFC. Herein, we report a PtCo/C(N) electrocatalyst prepared by Na2CO3‐assisted urea liquid‐phase deposition strategy as an efficient cathodic oxygen reduction reaction electrocatalyst, and test its activity and stability in a rotating disc electrode and a single‐cell. The membrane electrode prepared with PtCo/C(N)‐800 °C catalyst has an output voltage of 0.652 V at 2 A/cm2 and a maximum power density of 1.501 W/cm2, which are 36 mV and 81 W/cm2 higher than those of commercial Pt/C catalyst, respectively. In addition, the mass activity and half‐wave potential of PtCo/C(N)‐800 °C are 2.44 times and 50 mV higher than those of commercial Pt/C, respectively. After 5000 voltammetric cycles, its mass activity and half‐wave potential only lose 35 A/gPt and 9 mV, respectively. XPS results show that the binding energy of Pt 4f is positively shifted relative to Pt/C‐TKK, and the d‐band center of Pt decreases, leading to weak chemical interaction between the oxygen‐containing intermediate and the surface of the electrocatalyst, which is conducive to the improvement of the ORR activity and stability of the catalyst.

Tailoring Ba0.5Sr0.5FeO3-δ cobalt-free perovskites with zinc as triple-conducting cathodes for protonic ceramic fuel cells

Developing triple-conducting cathode is an available way to enhancing the electrochemical performance of protonic ceramic fuel cells (PCFCs). Here we report a systematical investigation on the performance of cobalt-free perovskites Ba0.5Sr0.5Fe1-xZnxO3-δ (x = 0, 0.1, and 0.2; BSF, BSFZ0.1, and BSFZ0.2) as triple-conducting cathodes for PCFCs. Zn doping improves the hydration capacity, oxygen vacancy concentration, surface exchange coefficient, and bulk diffusion coefficient of BSFZx (x = 0.1 and 0.2) as compared to the bare BSF. Theory calculations show that Zn doping benefits the oxygen vacancy formation, which is conducive to the promotion of cathodic oxygen reduction reaction (ORR). Among materials investigated, the BSFZ0.2 perovskite possesses an abundance of oxygen vacancies, strong hydration capacity and exceptional triple conductivity (H+/O2−/e−), and thus showing the lowest polarization resistance (Rp) of 0.328 Ω cm2 at 700 °C under wet air. At 700 °C, the cell reaches a maximum power density of 497 mW cm−2 in H2 using BSFZ0.2-30 wt% BaZr0.4Ce0.4Y0.15Zn0.05O3-δ (BZCYZ) composite cathode based on 25-μm-thick BZCYZ electrolyte, and there is no obvious deterioration in performance after operation for 100 h. The rate-limiting steps of ORR on BSFZ0.2-BZCYZ composite cathode are determined to be the surface oxygen incorporated into lattice reaction processes. These findings demonstrate that the proposed BSFZ0.2 holds great potential as a cobalt-free triple-conducting cathode for PCFCs.

Ta/Nb doping motivating cubic phase stability and CO2 tolerance of Sr2Co1.6Fe0.4O6-δ double perovskite for high-performing SOFC cathode

Developing cathodes that are both phase-stable and tolerant to carbon dioxide (CO2) is a crucial and challenging task for solid-oxide fuel cells (SOFCs) operating at reduced temperatures. The activity of oxygen reduction reaction (ORR) in SOFC cathodes is typically influenced by factors such as geometric features and oxygen vacancies. In this study, new and robust cathodes for SOFCs, Sr2Co1.5Fe0.4Ta0.1O5+δ (SCFT) and Sr2Co1.5Fe0.4Nb0.1O5+δ (SCFN) are developed by doping a small amount of niobium (Nb) and tantalum (Ta) into Sr2Co1.6Fe0.4O5+δ (SCF) using a simple solid-state reaction technique. The effects of Nb/Ta doping on the crystal structure, oxygen vacancies, electrical conductivity, and electrochemical properties of SCFT and SCFN are investigated. The results reveal that these materials possess a fully cubic structure in the Fm-3m space group, with improved oxygen vacancy and electrical conductivity. They also exhibit good chemical compatibility with electrolytes at 1100 °C for 8 h and remain thermally stable when exposed to air and CO2 at 700 °C, without any additional phase formation. The area-specific resistance (ASR) of the SCFT cathode is found to be only 0.06 Ω cm2, whereas the SCFN cathode has an ASR of 0.10 Ω cm2. The superior performance of SCFT can be attributed to the higher oxygen vacancy, which enhances oxygen surface exchange kinetics and diffusivity compared to SCFN. When tested in a single cell using humidified H2 as the fuel and ambient air as the oxidant, the SCFT cathode achieves a power density of 656 mW cm−2 at 700 °C, while the SCFN cathode reaches 559 mW cm−2, indicating the potential of SCFT as a promising cathode material for SOFCs. The excellent performance of these materials can be attributed to their mixed electronic-ionic conduction properties, unique structural features, and high observed oxygen vacancy, which contribute to their remarkable electronic conductivity and significant ionic mobility.

Recent progress in the characterization and application of exo-electrogenic microorganisms.

Exo-electrogenic microorganisms are characterized by their special metabolic capability of transferring metabolic electrons out of their cell, into insoluble external electron acceptors such as iron or manganese oxides and electrodes, or vice versa take up electron from electrodes. Their conventional application is primarily limited to microbial fuel cells for electrical power generation and microbial electrolysis cells for the production of value-added products such as biohydrogen, biomethane and hydrogen peroxide. The utility of exo-electrogenic organisms has expanded into many other applications in recent times. Such examples include microbial desalination cells, microbial electro-synthesis cells producing value-added chemicals such as bio-butanol and their applications in other carbon sequestration technologies. Additionally, electrochemically-active organisms are now beginning to be employed in biosensor applications for environmental monitoring. Additionally, the utility of biocathodes in bio-electrochemical systems is also a novel application in catalyzing the cathodic oxygen reduction reaction to enhance their electrochemical performance. Advances have also been made in the expansion and use of other organisms such as the usage of photosynthetic microorganisms for the fabrication of self-sustained bio-electrochemical systems. This review attempts to provide a comprehensive picture of the state-of the art of exo-electrogenic organisms and their novel utility in bioelectrochemical systems.

New perspective crosslinking electrochemistry and other research fields: beyond electrochemical reactors.

Over the years, electrochemical reactors have evolved significantly, with modern reactors now able to achieve a high current density and power output in compact sizes. This leap in performance has not only greatly accelerated the rate of electrochemical reactions but also had a broader impact on the environment. Traditional research perspectives, focused primarily on the internal working systems of reactors, possibly overlook the potential of electrochemical systems in regulating their surrounding environment. A novel research perspective considering the interaction between electrochemical processes and their environmental context as a unified subject of study has gradually emerged alongside the dramatic development of electrochemical techniques. This viewpoint introduces a paradigm shift: electrochemical reactors are not isolated entities but rather are integral parts that interact with their surroundings. Correspondingly, this calls for an innovative research methodology that goes beyond studying the electrochemical processes in isolation. Rather, it integrates the design of the electrochemical system with its specific application environment, ensuring seamless integration for optimal performance under various practical conditions. Therefore, performance metrics should include not only the basic parameters of the electrochemical reactions but also the adaptability of the electrochemical system in real-world scenarios beyond the laboratory. By focusing on environmental integration and application-driven design, the applications of electrochemical technology can be more effectively leveraged. This perspective is exemplified by an electrochemical system based on coupled cathodic oxygen reduction and anodic oxygen evolution reactions. By adopting this new research paradigm, the applications of this electrochemical system can be extended to fields like medical treatment, food science, and microbial fermentation, with an emphasis on tailored designs for these specific application fields. This comprehensive and systematic new research approach aims to fully explore the potential applications of electrochemical technology and foster interdisciplinary collaboration in the electrochemical field.

Porous carbonaceous materials simultaneously dispersing N, Fe and Co as bifunctional catalysts for the ORR and OER: electrochemical performance in a prototype of a Zn-air battery.

Infiltration of the mesoporous structure of SBA-15 silica as a hard template with phenanthroline complexes of Fe3+ and Co2+ allowed the simultaneous dispersion of nitrogen, iron and cobalt species on the surface of the obtained carbonaceous CMK-3 silica replica, with potential as bifunctional heterogeneous catalysts for the cathodic oxygen reduction and evolution reactions (ORR and OER). The textural properties and mesopore structure depended on the composition of the material. The carbonaceous FeCoNCMK-3 (1/1), obtained with an Fe/Co molar ratio of 1/1, exhibited an ordered cylindrical mesoporous structure with a high mesopore volume, a rather homogeneous composition in terms of total and surface concentrations of iron and cobalt, and a balanced presence of pyridinic-, pyrrolic- and graphitic-N species. FeCoNCMK-3 (1/1) could improve the ORR kinetics by adsorption and reduction of O2 through the 4-electron mechanism with a current density of -17.37 mA cm-2, Eonset of 1.13 V vs. RHE and E1/2 of 0.75 V when compared to metal-free, monometallic or bimetallic electrocatalysts with a higher amount of cobalt than that of iron. In addition, FeCoNCMK-3 (1/1) exhibited activity for the OER, presenting lower values of Eonset (1.52 V), Ej10 (1.78 V) and the Tafel slope (76.3 mV dec-1) with respect to other catalysts. When evaluated as a cathode in a prototype of a Zn-air battery, FeCoNCMK-3 (1/1) exhibited a high open circuit voltage of 1.41 V, a peak power density of 66.84 mW cm-2, a large specific capacity of 818.88 mA h gZn-1, and cycling for 20 h but with deactivation upon cycling.

Component-controlled synthesis of PdxSny nanocrystals on carbon nanotubes as advanced electrocatalysts for oxygen reduction reaction.

Pd-based bimetallic or multimetallic nanocrystals are considered to be potential electrocatalysts for cathodic oxygen reduction reaction (ORR) in fuel cells. Although much advance has been made, the synthesis of component-controlled Pd-Sn alloy nanocrystals or corresponding nanohybrids is still challenging, and the electrocatalytic ORR properties are not fully explored. Herein, component-controlled synthesis of PdxSny nanocrystals (including Pd3Sn, Pd2Sn, Pd3Sn2, and PdSn) has been realized, which are in situ grown or deposited on pre-treated multi-walled carbon nanotubes (CNTs) to form well-coupled nanohybrids (NHs) by a facile one-pot non-hydrolytic system thermolysis method. In alkaline media, all the resultant PdxSny/CNTs NHs are effective at catalyzing ORR. Among them, the Pd3Sn/CNTs NHs exhibit the best catalytic activity with the half-wave potential of 0.85 V (vs. RHE), good cyclic stability, and excellent methanol-tolerant capability due to the suited Pd-Sn alloy component and its strong interaction or efficient electronic coupling with CNTs. This work is conducive to the advancement of Pd-based nanoalloy catalysts by combining component engineering and a hybridization strategy and promoting their application in clean energy devices.

Illuminating Oxygen Reduction Reaction Kinetics in High Temperature Polymer Electrolyte Membrane Fuel Cells Using EIS

Owing to their notable power efficiency and zero greenhouse emissions, High Temperature Polymer Electrolyte Membrane Fuel Cells (HTPEMFCs) hold immense promise as a prospective candidate for generating clean energy. However, their commercialization is still impeded by the cathodic Oxygen Reduction Reaction (ORR) kinetics, which after almost half a century not only remain elusive, but constitute the most energy-intensive process, requiring large amounts of the expensive Pt catalyst to mitigate.In this work we provide solid experimental evidence, that the simple three elementary step Dissociative Adsorption Pathway (DAP) with two intermediate species (Oad and OHad), can accurately capture both the steady state (IV) and the Electrochemical Impedance Spectra (EIS) as well.Detailed EIS and IV experimental data were recorded at 180 °C under differential conditions, using a single serpentine HTPEMFC with a 4 cm2 active area. The fuel cell operated at the activation regime, where ORR potential losses dominate but mass transport limitations are negligible. The experimental data were successfully fitted with the derived analytic IV and EIS microkinetic model.The use of the DAP in accordance with the Transitions State Theory (TST), allowed the extraction and analysis of ORR kinetics and energetics. The deconvoluted EIS outlined the important role of the intrinsic kinetic inertia , i.e. the outcome of the competitive nature of the elementary reaction steps on the adsorbed intermediate species. Kinetic inertia not only dominated EIS and the polarization resistance, but demonstrated that the commonly used Butler Volmer and apparent Tafel slope kinetic approach is incapable of describing the multistep ORR kinetics. With the help of the Degree of Rate Control (DRC) analysis, we successfully identified the O2(g) dissociative adsorption as the rate limiting step.Finally, from an energetics perspective, by employing the TST kinetics formulation, we were able to calculate the free Gibbs’ transition states activation (kinetics) and reaction steps’ energies (thermodynamics). These results clarified that, the high ORR overpotential losses stem from the combined strength of both kinetically and thermodynamically imposed barriers, which originate from the high bonding strength of Oad on the Pt surface and the rather high activation energy of the O2(g) adsorption step.

Boosting Oxygen Reduction Reaction with Fe-Based Single-Atom Catalysts: The Role of Cluster Interactions

Fuel cells (FCs) have emerged as a promising alternative for efficient electricity production in the future [1]. However, their widespread commercialization is hindered by their prohibitive cost due to the large amount of platinum used in these electrochemical systems [2]. Platinum is used to accelerate the unfavorable kinetics of the cathodic oxygen reduction reaction (ORR) [3]. To achieve large-scale and cost-effective development of FCs, it is essential to find high-performance platinum-free catalysts. Two solutions are mainly reported in the literature: the development of non-precious metal-based carbon catalysts and metal-free carbon catalysts. However, the work reported on these two types of carbon catalysts is sometimes contradictory regarding the actual nature of the active sites and the mechanisms of reduction of oxygen molecules on the catalyst [4].Pyrolyzed metal-nitrogen-carbon (M-N-C) catalysts for the ORR, especially single-atom catalysts (SACs), have been widely studied because they exhibit excellent electrocatalytic performance, thanks to the high content of metal atoms anchored on a carbon support [5]. Recent research has indicated that the combination of single-atom active sites with metal nanoclusters can further improve the catalytic activity, but the underlying mechanism remains unclear [6]. Therefore, it is necessary to develop model catalysts based on both single-atoms and nanoclusters to better understand their catalytic activity.In this work, we prepared nitrogen-doped and iron-doped carbon catalysts (called Fe-NC below) with precise control of the type of iron in the material. First, the functionalization of an activated carbon was performed by carbonizing it under air in the presence of urea. Then, the sample was placed in an autoclave for hydrothermal treatment in the presence of FeCl3.6H2O to allow the incorporation of iron, and thermal post-treatment was applied to synthesize model catalysts (Fig. 1a). The precursor ratio and final pyrolysis temperature were adjusted and optimized to produce either iron-based single atoms (SA) (here referred to as FeSA-NC) or atomic clusters (AC) associated with single atoms (here referred to as FeSA+AC-NC). The results show that the iron-based catalysts exhibit outstanding catalytic activity (Fig. 1b) and durability (Fig. 1c) in alkaline medium for the ORR, even better than commercial Pt (20 wt.%)/C in the case of FeSA+AC-NC. The analysis provided insight into the development of highly efficient multifunctional electrocatalysts, where the presence of iron nanoclusters was found to be a crucial determinant of the catalytic activity for the ORR.[1] M.K. Debe, Electrocatalyst approaches and challenges for automotive fuel cells, Nature. 486 (2012) 43–51. https://doi.org/10.1038/nature11115.[2] C. Sealy, The problem with platinum, Mater. Today. 11 (2008) 65–68. https://doi.org/10.1016/S1369-7021(08)70254-2.[3] M. Borghei, J. Lehtonen, L. Liu, O.J. Rojas, Advanced Biomass-Derived Electrocatalysts for the Oxygen Reduction Reaction, Adv. Mater. 30 (2018) 1703691. https://doi.org/10.1002/adma.201703691.[4] A. Dessalle, J. Quílez-Bermejo, V. Fierro, F. Xu, A. Celzard, Recent progress in the development of efficient biomass-based ORR electrocatalysts, Carbon. 203 (2023) 237–260. https://doi.org/10.1016/j.carbon.2022.11.073.[5] K. Liu, J. Fu, Y. Lin, T. Luo, G. Ni, H. Li, et al., Insights into the activity of single-atom Fe-N-C catalysts for oxygen reduction reaction, Nat. Commun. 13 (2022) 2075. https://doi.org/10.1038/s41467-022-29797-1.[6] X. Wan, Q. Liu, J. Liu, S. Liu, X. Liu, L. Zheng, et al., Iron atom–cluster interactions increase activity and improve durability in Fe–N–C fuel cells, Nat. Commun. 13 (2022) 2963. https://doi.org/10.1038/s41467-022-30702-z. Figure 1

Strong Coupling Effects between Single Metal Site-Rich Carbon and PtCo Intermetallic Catalysts for Heavy-Duty Meas

Developing active and durable low-platinum group metal (PGM) oxygen reduction reaction (ORR) catalysts for proton-exchange membrane fuel cells (PEMFCs) remains a critical challenge for heavy-duty vehicle (HDV) applications. This work comprehensively studies synergistic catalysts, composed of Pt-based nanoparticles and supports with atomically dispersed M-N-C sites (MnSA-NC), using a suite of experimental techniques and DFT calculations. DFT calculations predicted that the presence of Mn-N4 sites could induce a strong coupling effect between Pt and support, which can strongly bind with Pt to immobilize the Pt clusters and weaken the adsorption of oxygen on the Pt surface to enhance intrinsic activity. In addition to the favorable MnN4 dopants, the MnSA-NC support is optimal support with sufficient surface areas, porosities, and adequate graphitization degree. Subsequently, well-dispersed Pt and ordered L12-Pt3Co nanoparticles with an average diameter of 2.1 nm and 3.3 nm were deposited on the MnSA-N-C support, which was comprehensively studied as the ORR cathode catalyst for PEMFCs, presenting remarkable performance and durability. In particular, the Pt@MnSA-NC catalyst achieved a mass activity (MA) of 0.70 A mgPt −1 at 0.9 V iR -free and maintained 86 % of its initial performance after a 30,000-cycle accelerated stress test (AST). The L12-Pt3Co@MnSA-NC catalyst achieved much higher performance, with MA of 0.91 A mgPt −1 and current density of 1.63 A cm−2 at 0.7 V in an H2-air fuel cell at 150 kPaabs with 0.10 mgPt cm−2 on the cathode. Furthermore, under HDV operating conditions (250 kPaabs and 0.20 mgPt cm-2), the L12-Pt3Co@MnSA-NC catalyst delivered an impressive current density of 1.80 A cm−2 at 0.7 V, with only 13 % performance loss after the 30,000 cycles AST, showing great potential to meet the DOE target set for HDVs.

Polymer of Intrinsic Microporosity as Binders for both Acidic and Alkaline Oxygen Reduction Electrocatalysis

AbstractIn this work, a new polymeric binder (polymer of intrinsic microporosity, PIM‐1) has been investigated and discussed to prepare and characterize composite materials for the cathodic oxygen reduction reaction. The new binder is a polymer of intrinsic microporosity, a family of organic compounds with molecularly rigid (glassy) structure, good mechanical and chemical stability. Their influence on the electrocatalytic behaviour of a commercial electrocatalyst during the oxygen reduction reaction in acidic and alkaline media has been investigated, discussed and compared to the behaviour of common cationic and anionic polymer binders, using rotating disk electrode (RDE) techniques. Polymers of intrinsic microporosity perform similarly well, and sometimes better (due to rigidity and gas permeation) when compared to commercial binders. Thus, herein, we showed that PIMs do represent a very promising and versatile alternative as binders in electrocatalysis.

Simultaneously Geometrical and Electronic Modulation of L10-PtZn by Trace Ge Boosts High-performance Oxygen Reduction Reaction.

Developing a highly active, durable, and low-platinum-based electrocatalyst for the cathodic oxygen reduction reaction (ORR) is for breaking the bottleneck of large-scale applications of proton exchange membrane fuel cells (PEMFCs). Herein, ultrafine PtZn intermetallic nanoparticles with low Pt-loading and trace germanium (Ge) involvement confined in the nitrogen-doped porous carbon (Ge-L10-PtZn@N-C) are reported. The Ge-L10-PtZn@N-C exhibit superior ORR activity with a mass activity of 3.04 A mg-1 Pt and specific activity of 4.69mA cm-2, ≈12.2- and 10.2-times improvement compared to the commercial Pt/C (20%) at 0.90V in 0.1m KOH. The cathodic catalyst Ge-L10-PtZn@N-C assembled in the PEMFC shows encouraging peak power densities of 316.5 (at 0.86V) and 417.2mW cm-2 (at 0.91V) in alkaline and acidic fuel-cell, respectively. The combination of experiment and density functional theory calculations (DFT) results robustly reveal that the participation of trace Ge can not only trigger a "growth site locking effect" to effectively inhibit nanoparticle growth, bring miniature nanoparticles, enhance dispersion uniformity, and achieve the exposure of the more electrochemical active site, but also effectively modulates the electronic structure, hence optimizing the adsorption/desorption of the oxygen intermediates.