Materials For Oxygen Reduction Reaction Research Articles

Deep Eutectic Solvent and Molten Salt-Assisted Construction of Wheat Straw-Derived N/O Co-Doped Porous Carbon for Flexible Zinc-Air Batteries.

As a common biomass resource, wheat straw is gradually being derived as carbon materials for oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Herein, the wheat straw-derived carbon was prepared by ball milling and pyrolysis using deep eutectic solvent (DES) as the medium, which avoided the cumbersome procedures. The hydrogen bond of DES was utilized to reconstructed into a hydrogen bond network structure between DES and lignin/cellulose/hemicellulose of wheat straw. The hydrogen bond network structure was converted into N/O co-doped porous carbon (N/O-WSPC) with abundant N/O co-doped sites after high-temperature pyrolysis. Meanwhile, KHCO3 was employed to further generate hierarchical pore structures and increase the specific surface area of the N/O-WSPC. The N/O co-doped sites provided intrinsic ORR activity, while the porous structure facilitates the mass transfer effect. Therefore, the N/O-WSPC exhibited a half-wave potential of 0.87 V (vs. RHE) and a limiting current density of 5.98 mA cm-2 for ORR. The N/O-WSPC-based flexible ZAB displayed an energy density of 652.23 Wh kg-1 and a charging-discharging cycle duration for over 19 h. The DES-assisted strategy facilitates the sustainable and efficient application of wheat straw-derived carbon materials in energy storage and conversion devices.

Tracking the Early-life of PtNi/C Shape-Controlled Catalysts upon their Integration in PEMFC

Abstract The integration of promising bimetallic electrocatalytic active materials for oxygen reduction reaction (ORR) into practical and functional proton-exchange membrane fuel cell (PEMFC) electrodes remains largely impeded by the poor performances that these exhibit at high current loads. The early life of PtNi/C catalysts presenting either structurally faceted/ordered or defective/disordered surface morphology is compared to that of both spherical PtNi/C and Pt/C catalysts. Different single-cell operating conditions were studied. At low current density, in the kinetically limited region, a good agreement between liquid electrolyte and single-cell configuration is reported and the kinetic benefit of PtNi/C catalysts compared to Pt/C is (at least partially) maintained. However, PtNi/C catalysts show severe limitations in the O2 mass transport limited region. Morphological and compositional changes were monitored at each stage showing that Ni atoms are leached at every step from ink formulation to the first PEMFC test. We show that Ni is already redistributed in the membrane in the fresh membrane electrode assembly (MEA) state. Ni2+ cationic contamination of the ionomer/membrane contributes to the disappointing results obtained in MEA configuration. In addition, for shaped-controlled PtNi/C, the surface faceting loss combined with restructuring via coalescence and crystallite growth further compromise their transfer in technological devices.

Axial Coordination Engineering on Fe-N-C Materials for Oxygen Reduction: Insights from Theory.

Axial coordination engineering has emerged as an effective strategy to regulate the catalytic performance of metal-N-C materials for oxygen reduction reaction (ORR). However, the ORR mechanism and activity changes of their active centers modified by axial ligands are still unclear. Here, a comprehensive investigation of the ORR on a series of FeN4-L moieties (L stands for an axial ligand) is performed using advanced density functional theory (DFT) calculations. The axial ligand has a substantial effect on the electronic structure and catalytic activity of the FeN4 center. Specially, FeN4-C6H5 is screened as a promising active moiety with superior ORR activity, as further revealed by constant-potential calculations and kinetic analysis. The enhanced activity is attributed to the weakened *OH adsorption caused by the altered electronic structure. Moreover, microkinetic modeling shows that at pH=1, FeN4-C6H5 possesses an impressive theoretical half-wave potential of ~1.01 V, superior to the pristine Fe-N-C catalysts (~0.88 V) calculated at the same level. These findings advance the understanding of the ORR mechanism of FeN4-L and provide guidance for optimizing the ORR performance of single-metal-atom catalysts.

Redox-mediated synthesis of Cu2O/CuO/Mn3O4/C quaternary nanocomposites as an efficient electrode material for oxygen reduction reaction and supercapacitor application

Earth-abundant transition metal oxides (TMOs) hold significant promise as electroactive materials in various electrochemical energy conversion and storage applications, offering economic and environmental advantages over their less abundant counterparts. In this work, a simple and cost-effective redox-mediated reaction strategy under hydrothermal conditions has been adopted to synthesize the quaternary nanocomposites Cu2O/CuO/Mn3O4/C with variable amounts of carbon. The synthesized nanocomposites have been characterized using various analysis techniques, including powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Brunauer–Emmett–Teller (BET). The synthesized COM5 nanocomposite (Cu2O/CuO/Mn3O4/C-50), when used as an electrocatalyst for the oxygen reduction reaction (ORR), demonstrates a good limiting current density (JL), half-wave potential (E1/2), and onset potential (Eonset) of −5.50 mA/cm2, 0.75 V, and 0.95 V, respectively, as per the polarization curve. The COM5 nanocomposite exhibits a four-electron transfer mechanism, calculated using the Koutecky-Levich (K-L) equation. In an O2-saturated 0.1M KOH solution, the COM5 nanocomposite has shown a superior relative current durability of 84.46% over 14,000 s compared to the commercially available 10 wt% Pt/C, indicating its potential application in the ORR. However, for supercapacitor applications, the COM3 nanocomposite (Cu2O/CuO/Mn3O4/C-20) as active electrode material in galvanic charge-discharge (GCD) study shows superior performance (201 F/g at 1 A/g) compared to the COM2 nanocomposite (117 F/g at 1 A/g) in neutral aqueous electrolyte, possibly due to the lower charge transfer resistance (Rct) of 24.04 Ω compared to COM2 (34.63 Ω). In two-electrode studies, the COM3 nanocomposite exhibits a good energy density of 24.19 Wh/kg at 1 A/g and a 4.7 kW/kg power density at 5 A/g. Additionally, the COM3 nanocomposite shows excellent long-term durability (74% capacitance retention) at the current density of 5 A/g for 8000 cycles. The electrochemical findings indicate that the COM3 nanocomposite stands out as a superior electrode material for supercapacitors, while the COM5 nanocomposite proves to be an effective electrocatalyst for the oxygen reduction reaction.

Concurrent Amorphization and Nanocatalyst Formation in Cu-Substituted Perovskite Oxide Surface: Effects on Oxygen Reduction Reaction at Elevated Temperatures.

The activity and durability of chemical/electrochemical catalysts are significantly influenced by their surface environments, highlighting the importance of thoroughly examining the catalyst surface. Here, Cu-substituted La0.6Sr0.4Co0.2Fe0.8O3-δ is selected, a state-of-the-art material for oxygen reduction reaction (ORR), to explore the real-time evolution of surface morphology and chemistry under a reducing atmosphere at elevated temperatures. Remarkably, in a pioneering observation, it is discovered that the perovskite surface starts to amorphize at an unusually low temperature of approximately 100 °C and multicomponent metal nanocatalysts additionally form on the amorphous surface as the temperature raises to 400 °C. Moreover, this investigation into the stability of the resulting amorphous layer under oxidizing conditions reveals that the amorphous structure can withstand a high-temperature oxidizing atmosphere (≥650 °C) only when it has undergone sufficient reduction for an extended period. Therefore, the coexistence of the active nanocatalysts and defective amorphous surface leads to a nearly 100% enhancement in the electrode resistance for the ORR over 200 h without significant degradation. These observations provide a new catalytic design strategy for using redox-dynamic perovskite oxide host materials.

N, S, P tri-doped porous graphene electrocatalyst with excellent oxygen reduction activity for zinc-air battery

The heteroatom-doped graphene has attracted a lot of research due to its excellent physical, chemical and electrochemical properties considered to be the most promising electrocatalytic material for oxygen reduction reaction (ORR). Multi-doping can exert the synergistic effect between different doped heteroatoms and effectively improve the catalytic activity of doped graphene catalysts. N, P, S tri-doped graphene catalysts were prepared by simple and convenient hydrothermal and high-temperature treatment. The experimental results show that different phosphorus sources have a significant impact on the structure and performance of the prepared catalyst materials. The NSP-Gr-1 catalyst shows the high onset potential (1.035 V), half-wave potential (0.79 V) and limiting current density (−5.33 mA cm−2) for ORR. The power density of the zinc-air battery assembled with the NSP-Gr-1 catalyst achieves 163.1 mW cm−2 at 186.7 mA cm−2, which is much higher than the maximum power density of 140.0 mW cm−2 at 190 mA cm−2 for commercial Pt/C. The discharge stability under different current densities is outstanding.

Mechanistic pathways and kinetic studies of oxygen reduction reaction (ORR) at Covalent Triazine Frameworks (CTFs)

Herein, four different metal-free nitrogen containing Covalent Triazine Frameworks (CTFs) based on their applied monomers (DCP, DCBP, mDCB and pDCB) are synthesized via a classical ionothermal synthesis route (ZnCl2, 400/600 °C). These materials are fully characterized and their electrochemical activities for ORR are tested and compared to each other including Carbon Super P and Pt black as standards in 0.1 M KOH. While DCP provides similar catalytic activity to Carbon Super P showing mostly a 2eˉ process (n=2.95) with high H2O2 formation of 52.6 %, the other three CTFs (DCBP, mDCB and pDCB) possess higher ORR activities, surprisingly even much higher limiting current densities than Pt black, proving that O2 is mainly reduced via direct 4eˉ pathway since n values are in the range of 3.52 to 3.62 and the detected H2O2 values are in the range of 19–23.9 %. Among the studied CTFs, mDCB reaches a limiting current density of −5.61 mA cm-2 (1.21 mA cm-2 larger than that for Pt black, −4.40 mA cm-2) with 0.11 V larger onset potential compared to Pt black. The significant electrochemical performances of the CTF materials in ORR via a 4eˉ process are correlated to the high specific surface areas (up to 2500 m2 g-1), large pore volumes (up to 2.05 cm3 g-1) and the largest total N-graphitic/quaternary contents as well as micro-mesoporous structure properties.

The electrocatalytic activity of pomelo peel-derived nitrogen-doped carbon material for oxygen reduction reaction

Exploring the non-precious metal catalysts of oxygen reduction reaction (ORR) becomes the key to promote the industrialization of new energy devices such as fuel cells and metal-air batteries because of the sluggish kinetics of ORR. Three-dimensional N-doped carbon (NC-900) material was obtained using the high-temperature pyrolysis of pomelo peel waste. The prepared NC-900 catalyst possesses an ultra-high specific surface area of 1631.3 m2·g−1, high content of 57.7 ± 0.9% pyrrolic-N, and three-dimensional porous structure. As the ORR catalyst, NC-900 has a onset potential of 0.992 V and half-wave potential of 0.859 V, comparable to 0.988 and 0.872 V of Pt/C. The typical 4-electron pathway of ORR process is occupied by the surface of NC-900. The ORR catalytic activity of NC-900 was almost unaffected by methanol. After 8 h of continuous operation, the reduction current on the surface of NC-900 was decreased only 2.7% of the initial current. Based on these outstanding ORR performances, the pomelo peel-derived NC-900 can serve as a strong competitor for the substitute of Pt/C to promote the potential industrialization of new energy devices.

Pyridinic and Pyrrolic-N induced carbon nanotubes support bimetallic oxide nanoparticles as high-performance electrocatalysts for oxygen reduction reaction

In-expensive MnO2-based nanostructure has been considered the ideal electrode material for oxygen reduction reaction (ORR) in fuel cell technology. Regardless of their highly active ORR performance, the fuel cross-over capacity and stability of MnO2-based catalysts are still far from satisfying. Herein, we report the highly active SnO2 nanoparticles (NPs) integrated on N-induced carbon nanotube (SnO2@NC) are combined with MnO2 nanoparticles through the electrodeposition to form effective nanostructured in which the MnO2 NPs and SnO2@NC in situ grown on a glassy carbon electrode (MnO2/SnO2@NC) with well-controlled reaction parameters, that exhibits superior ORR activity for the first time. We assessed the marginal role of pyridinic-N and pyrrolic-N in the electrocatalytic ORR activity, synthesis of MnO2/SnO2 bimetallic oxide electrocatalysts, and distribution behavior of NPs. Bimetallic MnO2/SnO2@NC electrode has unique synergistic interactions between MnO2/SnO2 NPs and NC support, which increases electro-active sites, and fast charge transfers towards ORR as compared to other as-prepared electrodes on account of the rational design of the electrode-electrolyte interface plays a significant role in expediting the ORR kinetics. Additionally, the surface nanostructure features, crystalline structure, as well as electronic chemical states of the MnO2/SnO2 NPs embedded in N-induced CNTs, were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Furthermore, bimetallic MnO2/SnO2@NC nanostructure leads an outstanding ORR performance in the 0.1 M KOH electrolyte, delivering a halfwave potential (-0.878 V) and remarkable limiting current density (-4.14 mA cm−2) and much better tolerance to the ethanol cross-over effect with high stability. Thus, the present strategy opens a new path to the design of a pyridinic-N and pyrrolic-N-oriented bimetallic oxide nanostructure as a high-active electrocatalyst for ORR application.

Sonochemically synthesized structures of manganese oxide (MO): A cathode material for oxygen reduction reaction in fuel cell applications

Tailored nanostructures of manganese oxide (MO) were synthesized using a single-step sonochemical method with various morphology-directing agents. The tailored nanostructures of MO were utilized as the cathode material to catalyze the oxygen reduction reaction (ORR) occurring within fuel cells. The obtained MO with various structures were characterized via X-ray diffraction (XRD) analysis, and morphological characterizations were carried out via field emission scanning electron microscopy (FESEM). Raman studies were done to assess the various modes of Raman for MO nanostructures. All the nanostructures of MO were used to modify the surface of the glassy carbon electrode (GCE) to enhance its efficacy in catalyzing the ORR. Amongst five different nanostructures and the conventionally used Pt/C catalyst, MO@NH3OH has shown excellent performance with a higher current density of −0.854 mA/cm2 and a shifted overpotential of −0.44 V. Methanol solution with a higher concentration of 0.5 M was used for the tolerance study and it was observed that MO@NH3OH had shown adequate tolerance and remained unsusceptible to methanol passed towards the cathode side. The stability of the nanostructures was assessed over ∼3000 s using chronoamperometry (CA) and it was found that nanostructures exhibited an impressive 97 % retention of current, which is comparable to the Pt/C electrocatalyst. Therefore, the nanostructure of MO with nanowire morphology could be regarded as a promising Pt-free electrocatalyst obtained via a facile one-step process offering remarkable selectivity and stability while maintaining cost-effectiveness.

Importing Antibonding-Orbital Occupancy through Pd-O-Gd Bridge Promotes Electrocatalytic Oxygen Reduction.

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 O3 , Eu2 O3 , and CeO2 ) by using RE metal-organic frameworks to tune the ORR performance of the Pd sites through the Pd-REx Oy interface interaction. Taking Pd-Gd2 O3 /C as a representative, it is identified that the strong coupling between Pd and Gd2 O3 induces the formation of the Pd-O-Gd bridge, which triggers charge redistribution of Pd and Gd2 O3 . The screened Pd-Gd2 O3 /C exhibits impressive ORR performance with high onset potential (0.986 VRHE ), half-wave potential (0.877 VRHE ), and excellent stability. Similar ORR results are also found for Pd-Sm2 O3 /C, Pd-Eu2 O3 /C, and Pd-CeO2 /C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2 O3 promotes electron transfer through the Pd-O-Gd bridge, which induces the antibonding-orbital occupancy of Pd-*OH for the optimization of *OH adsorption in the rate-determining step of ORR. The pH-dependent microkinetic modeling shows that Pd-Gd2 O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd-Gd2 O3 /C exhibits superior performance in Zn-air battery as an air cathode, implying its excellent practicability.

Importing Antibonding‐Orbital Occupancy through Pd−O−Gd Bridge Promotes Electrocatalytic Oxygen Reduction

AbstractThe active‐site density, intrinsic activity, and durability of Pd−based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon‐based rare‐earth (RE) oxides (Gd2O3, Sm2O3, Eu2O3, and CeO2) by using RE metal–organic frameworks to tune the ORR performance of the Pd sites through the Pd−RExOy interface interaction. Taking Pd−Gd2O3/C as a representative, it is identified that the strong coupling between Pd and Gd2O3 induces the formation of the Pd−O−Gd bridge, which triggers charge redistribution of Pd and Gd2O3. The screened Pd−Gd2O3/C exhibits impressive ORR performance with high onset potential (0.986 VRHE), half‐wave potential (0.877 VRHE), and excellent stability. Similar ORR results are also found for Pd−Sm2O3/C, Pd−Eu2O3/C, and Pd−CeO2/C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2O3 promotes electron transfer through the Pd−O−Gd bridge, which induces the antibonding‐orbital occupancy of Pd−*OH for the optimization of *OH adsorption in the rate‐determining step of ORR. The pH‐dependent microkinetic modeling shows that Pd−Gd2O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd−Gd2O3/C exhibits superior performance in Zn‐air battery as an air cathode, implying its excellent practicability.

Unlocking efficiency in oxygen reduction reaction: Synergistic edge dopants of nitrogen and boron in carbon nano onions

Oxygen reduction reaction (ORR) is a crucial process for energy conversion and storage devices. Despite platinum (Pt) being the state-of-the-art material for ORR, the limited performance of Pt-based catalyst, Pt scarcity, and vulnerability of global supply chains for critical minerals, have made it imperative to develop alternative electrocatalysts that either contain no precious metals at all or require only a very low loading of these valuable resources. In this study, we demonstrate that the incorporation of co-dopants, nitrogen (N) and boron (B), with a dissimilar electronegativity is a promising approach to develop metal-free electrocatalysts for ORR. We discovered that the interaction between N and B plays a vital role in both (i) incorporating the dopants in high-curvature carbon nano-onions (CNOs) and (ii) promoting ORR performance. Tuning the annealing temperature was crucial to achieve a desirable N-B chemical configuration and synergistic effects of N and B on ORR catalysis. Our investigation revealed that N,B-doped CNOs prepared at 700 °C exhibit the best ORR performance in 0.1 M KOH with a dominant 4-electron pathway and excellent durability. Based on X-ray photoelectron spectroscopy (XPS), Raman analysis, and high-resolution scanning transmission electron microscopy (HR-STEM), we conclude that abundant N and B sites, especially N-C-B (isolated) sites, at the edges in conjunction with high surface activity of CNOs are responsible for such outstanding performances. This study provide insights into the design of metal-free catalysts for efficient ORR catalysis, and the importance of alternative electrocatalysts in the current global supply chain disrutipn scenario.

Recent Progress on Carbon‐Based Electrocatalysts for Oxygen Reduction Reaction: Insights on the Type of Synthesis Protocols, Performances and Outlook Mechanisms

AbstractDue to their low cost, accessibility of resources, and improved stability and durability, carbon‐based nanomaterials have attracted significant attention as cathode materials for oxygen reduction reactions. These materials also exhibit intrinsic physical and electrochemical features. However, their potential for use in fuel cells is constrained by low ORR activity and slow kinetics. Carbon nanomaterials can be functionalized and doped with heteroatoms to change their morphologies and generate a large number of oxygen reduction active sites to lessen the problems. Doping the carbon lattice with heteroatoms like N, S, and P and functionalizing the carbon structure with −OCH3, −F, −COO−, −O− are two of these modifications that can change specific properties of the carbon nanomaterials like expanding interlayer distance, producing a large number of active sites, and enhancing oxygen reduction activity. When compared to pristine carbon‐based nanomaterials, these doped and functionalized carbon nanomaterials, including their composites, exhibit accelerated rate performance, outstanding stability, and higher methanol tolerance. This article summarizes the most recent developments in heteroatom‐doped and functionalized carbon‐based nanomaterials, covering different synthesis approaches, characterization methods, electrochemical performance, and oxygen reduction reaction mechanisms. As cathode materials for fuel cell technologies, the significance of heteroatom co‐doping and transition metal heteroatom co‐doping is also underlined.

A CoFe2 Alloy‐Functionalized Few‐Layer Graphene Sheet Nanocomposite as an Electrocatalyst of the Oxygen Reduction Reaction

AbstractSearching for a high‐efficiency, recycled and cheap catalytic material for oxygen reduction reaction (ORR) is urgently needed in fuel cells. In this study, we successfully fabricated a nanocomposite consisting of CoFe2 alloy functionalized few‐layer graphene sheets (CoFe2/FLGs) by employing ferric nitrate, cobalt nitrate, and glucose as precursors. Various measurements conducted in this research confirm that the nanosized CoFe2 alloy particles are evenly dispersed within the FLGs and possess significant magnetism. Electrochemical measurements reveal that the CoFe2/FLGs exhibit a high positive onset potential (0.901 V), follow a four‐electron pathway, display a low Tafel slope (77.21 mV/dec), possess a low charge‐transfer resistance (∼72 Ω), and exhibit strong methanol tolerance. Consequently, the resulting CoFe2/FLGs nanocomposite demonstrates excellent electrocatalytic performance and recyclability for the ORR, positioning it as a promising catalyst for fuel cells.

Waste Tire Derived Carbon Support for Non-Platinum-Group Metal Catalyst Materials for Oxygen Reduction Reaction in Alkaline Medium

Extensive use of non-renewable energy sources and excessive accumulation of hard-to-recycle waste, such as end-of-life tires, are among the most significant environmental problems today. For a more sustainable future, it is essential to find alternative solutions to energy and special waste management. For example, waste tires can be used to synthesize high-tech porous carbon materials, which can be used as a carbon support in fuel cell catalysts. [1] While fuel cells offer a promising alternative to some fossil fuel-based technologies, low temperature fuel cell catalysts rely on expensive platinum. Non-platinum-group metal (NPGM) catalysts, such as iron and nitrogen co-doped carbon materials are good contenders to platinum-based catalysts for the oxygen reduction reaction. Synthesizing porous carbon materials for more economically viable NPGM fuel cell catalysts could provide one way to use waste tires more sustainably and lower the cost of efficient fuel cell catalysts.For this work, a carbon material was synthesized by pyrolyzing tire granules (Imdex A/S) at 1000 °C for three hours in Ar [2]. Based on this carbon material, several iron and nitrogen co-doped catalyst materials were synthesized using Fe(NO3)3 as the iron source, dicyandiamide or guanidine as the nitrogen source, and ZnCl2 as a pore modifier. All synthesized materials were acid washed overnight to remove redundant elements such as Zn from the pore modifier and various impurities originating from the tire granules (mainly Si, S, Ca, and Zn). Finally, the materials pyrolyzed for a second time. The pyrolysis temperature, choice of nitrogen compound, and precursor ratios were varied for the syntheses described in this work.The NPGM catalyst materials were characterized by various physical and electrochemical methods to describe the relationship between the catalyst structure and the activity of the oxygen reduction reaction. SEM and SEM-EDX were used to evaluate the morphology and composition of the catalyst materials. N2 sorption data suggested that the specific surface area ranged from 77 to 194 m2 g-1 for all materials. Electrochemical characterization was performed in 0.1M KOH solution using the rotating disk electrode method. The highest onset potential (Eon = 920 mV vs RHE) was reached by a material using guanidine as the nitrogen source pyrolyzed at 900 °C, which is comparable to other recently described NPGM materials [3], including waste-tire derived NPGM catalysts [4]. Acknowledgements: This work was supported by the following projects: PRG676 “ Development of express analysis methods for micro-mesoporous materials for Estonian peat derived carbon supercapacitors” (1.01.2020- 31.12.2024)"Advanced materials and high-technology devices for sustainable energetics, sensorics and nanoelectronics” (TK141) (1.01.2016−1.03.2023) References [1] J. S. Gnanaraj et al., Sustainability 10(8), 2840 (2018)[2] J. Laanemäe, R. Jäger, P. Teppor, O. Volobujeva, and Enn Lust, ECS Transactions, 108, p. 39 (2022)[3] R. Gutru et al., International Journal of Hydrogen Energy, 47 (2022)[4] M. Muhyuddin et al., Electrochemica Acta, 433, 141254 (2022)

Waste Tire Derived Carbon Support for Non-Platinum-Group Metal Catalyst Materials for Oxygen Reduction Reaction in Alkaline Medium

A porous carbon material was synthesized using waste tire granules via pyrolysis. Six non-platinum-group metal catalyst materials were synthesized based on this carbon material, Fe(NO3)3 · 9H2O, and either dicyandiamide or guanidine carbonate as the nitrogen source. Synthesis parameters such as pyrolysis temperature, precursor mass ratios, and acid washing time were varied for each material. All catalysts were characterized physically using HR-SEM, SEM-EDX, and N2 sorption analyses as well as electrochemically using the rotating disk electrode method in 0.1 M KOH. The materials were rich in nanofibers, and exhibited moderate porosity and specific surface area (S BET = 77-194 m2 g-1). By modifying the synthesis parameters of the materials, the electrochemical properties were successfully improved, achieving E onset = 0.92 V vs RHE and E 1/2 = 0.82 V vs RHE (Fe-guan III 900). The number of transferred electrons in the ORR was n = 4 for the more active materials.

N-doping carbon-coated Cu@C(N) nanocapsules synthesized by arc plasma toward high-performance ORR electrocatalyst

The development of efficient and cost-effective methods for the synthesis of non-precious metal as the catalytic material for oxygen reduction reaction (ORR) is addressing a key barrier to fuel cell deployment in a wide range of applications. In this study, core-shell carbon-coated copper nanoparticles (Cu@C) were prepared using arc discharge plasma under argon and hydrogen atmospheres. And nitrogen doping was achieved during the subsequent heat treatment using dicyandiamide as the nitrogen source. The results showed that the catalysts had better ORR catalytic activity, better stability and better methanol tolerance than Pt/C, and the ORR reaction process was nearly four-electron pathway. The successful doping of nitrogen increased the reaction sites. And the addition of copper core improved the conductivity of the catalytic material. Meanwhile, the N-C shell layer protected the Cu nanoparticles from dissolving in aqueous solutions or being chemically oxidized, facilitating the electronic interaction of the core Cu nanoparticles with the N-C shell layer. This study provides an insight into the preparation of high-efficiency non-precious metal-based ORR electrocatalysts by DC arc plasma, a beneficial method.

In Situ Structure of a Mo-Doped Pt-Ni Catalyst during Electrochemical Oxygen Reduction Resolved from Machine Learning-Based Grand Canonical Global Optimization.

Pt-Ni alloy is by far the most active cathode material for oxygen reduction reaction (ORR) in the proton-exchange membrane fuel cell, and the addition of a tiny amount of a third-metal Mo can significantly improve the catalyst durability and activity. Here, by developing machine learning-based grand canonical global optimization, we are able to resolve the in situ structures of this important three-element alloy system under ORR conditions and identify their correlations with the enhanced ORR performance. We disclose the bulk phase diagram of Pt-Ni-Mo alloys and determine the surface structures under the ORR reaction conditions by exploring millions of likely structure candidates. The pristine Pt-Ni-Mo alloy surfaces are shown to undergo significant structure reconstruction under ORR reaction conditions, where a surface-adsorbed MoO4 monomer or Mo2O x dimers cover the Pt-skin surface above 0.9 V vs RHE and protect the surface from Ni leaching. The physical origins are revealed by analyzing the electronic structure of O atoms in MoO4 and on the Pt surface. In viewing the role of high-valence transition metal oxide clusters, we propose a set of quantitative measures for designing better catalysts and predict that six elements in the periodic table, namely, Mo, Tc, Os, Ta, Re, and W, can be good candidates for alloying with PtNi to improve the ORR catalytic performance. We demonstrate that machine learning-based grand canonical global optimization is a powerful and generic tool to reveal the catalyst dynamics behavior in contact with a complex reaction environment.

Multicore-shell structure CuxCoy-Fe alloy nitrogen doped mesoporous hollow carbon nanotubes composites for oxygen reduction reaction

Carbon-based materials with transition metal modifications are the dominant materials for oxygen reduction reaction (ORR), but the synthesis in a simple and efficient way is still a great challenge. Herein, multicore-shell structure CuxCoy-Fe alloy nitrogen doped mesoporous hollow carbon nanotubes (N-MHCNT/CuxCoy-Fe@C) were designed and synthesized by a facile and environment-friendly method. In the process of pyrolysis, polypyrrole serving as the substrate to form N-doped hollow carbon nanotubes and the polydopamine (PDA) acts as the carbon and nitrogen source to form a shell structure. Additionally, the cubic CuxCoy-Fe MOFs synthesized at room temperature collapses to form multiple alloy cores. Notably, the mesoporous structure of N-MHCNT/CuxCoy-Fe@C enhances the mass transfer process, while the carbon shell protects the metal active sites. Moreover, mesoporous hollow carbon, rich M-Nx (M=Cu, Co, Fe) active sites, the synergistic effects between N-MHCNTs, CuxCoy-Fe alloys and multiple core-shell structures allowed N-MHCNT/Cu2Co1-Fe@C exhibited high activity and long-term durability in ORR. Besides, the RRDE tests confirms the reaction kinetics of N-MHCNT/Cu2Co1-Fe@C as a mainly 4-electron reaction with an electron transfer number of 3.78 (Pt/C is 3.86) and a low hydrogen peroxide yield of 16%. This work provides a new strategy for the development of non-precious metal ORR catalysts by rational structural design and metal ratio adjustment.