Oxygen Reduction Electrocatalysts Research Articles

Manganese and Nitrogen Doped Biomass-Based Activated Carbons As Electrocatalysts for Oxygen Reduction and Water Splitting

In this study, an efficient manganese (Mn) and nitrogen (N) co-doped carbon materials were prepared using the three raw materials, namely alder charcoal (Mn-N-CAC), hydrothermally carbonised birch wood (Mn-N-CW), and black liquor (Mn-N-CBL). At first, biomass-based activated carbon materials were synthesized. Mn and N were co-doped in one step using the reaction mixture containing Mn2+ ions source, activated carbon material, and dicyandiamide (DCDA) in dimethylformamide (DMF). DMF was evaporated and the mixture was treated for 60 min at a temperature of 800 ºC. The specific surface area, morphology, structure, and composition of Mn-N-C were determined using BET, TEM, XPS, Raman, XRD, and ICP-OES. Activity of resulted Mn-N-C materials was evaluated for oxygen reduction (ORR) as well as for hydrogen and oxygen evolution (HER and OER) using linear-sweep voltammetry (LSV) with a rotating disk electrode (RDE) in alkaline media.It was found that all Mn-N-C materials had a high specific surface area in the range of approximately of 1800 to 2200 m2 g-1 but the Mn-N-CBL presented a higher contribution of the mesopores in comaparison to Mn-N-CAC and Mn-N-CW which are similar. All synthesized Mn-N-C materials exhibit excellent electrocatalytic activity for ORR with the onset and half-wave potentials of approximately 0.88‒0.90 and 0.80‒0.84 V, respectively, showing the 4e‒ electrons transfer path in 0.1 M KOH solution. The Mn-N-C materials also show enhanced activity for HER and OER in alkaline media. Acknowledgment The “Sustainably Produced Carbon Nanomaterials for Energy Applications (SuNaMa)” benefits from a 988000 € grant from Iceland, Liechtenstein, and Norway through the EEA Grants. The aim of the project is to develop innovative, high-performance, highly conductive, electrocatalytically active, durable, cost-effective, and high surface area nanocarbon materials. Project contract with the Research Council of Lithuania (LMTLT) No. is S-BMT-21-12 (LT08-2-LMT-K-01-055).

Operando x-Ray Absorption Spectroscopy Investigation of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction

Oxygen reduction reaction (ORR) plays a key role in the development of fuel cell technology, and great efforts have been made to reduce the amount of platinum, required to speed up this sluggish reaction, or, even more desirable, to use efficient electrocatalysts based on earth-abundant metals. To date, numerous single-atom catalysts in the form of metal-doped carbon-nitrogen materials (MNC) have proved to be a promising alternative to ORR Pt-based materials. [1-3]In this study we employed advanced spectroscopic techniques, namely Mössbauer spectroscopy and operando X-ray absorption (XAS) spectroscopy, to understand the structural and electronic factors underlying an increase in the catalytic turn over frequency (TOF) of bimetallic FeSnNC and FeCoNC catalysts, relative to the parent FeNC materials. In particular, 57Fe Mössbauer spectroscopy identified a larger ratio of D1/D2 species in both bimetallic catalysts, supporting a larger ratio of Fe(III)-Nx/Fe(II)-Nx sites. The combination of extended X-ray absorption fine structure (EXAFS) modeling, and the analysis of operando X-ray absorption near-edge spectroscopy (XANES) spectra revealed a disordered carbon structure around FeNx active sites, and variations in the iron oxidation state that can be linked to the enhanced intrinsic catalytic reactivity (TOF). This talk is therefore intended to draw attention to the potential of the XAS technique, especially when applied to in-situ/operando studies in the field of electrocatalysis. References F. Luo, A. Roy, L. Silvioli, D.A. Cullen, A. Zitolo, M.T. Sougrati, I.C. Oguz, T. Mineva, D. Teschner, S. Wagner, J. Wen, F. Dionigi, U.I. Kramm, J. Rossmeisl, F. Jaouen and P. Strasser. P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nature Materials 2020, 19, 1215-1223A. Zitolo, N. Ranjbar, T. Mineva, J. Li, Q. Jia, S. Stamatin, G.F. Harrington, S.M. Lyth, P. Krtil, S. Mukerjee, E. Fonda, F. Jaouen. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications 2017, 8(1), 957A. Zitolo, V. Goellner, V. Armel, M. T. Sougrati, T. Mineva, L. Stievano, E. Fonda, F. Jaouen. Identification of catalytic sites for oxygen reduction in iron and nitrogen doped graphene materials. Nature Materials 2015, 14, 937-942

From Synthesis to Application: Ni3 Fe N As Oxygen Reduction Electrocatalyst in Anion Exchange Membrane Fuel Cells

Catalysis has played a crucial role in advancing and commercializing energy conversion technologies. It is essential to identify abundant, active, and stable materials to enable the reliable and cost-efficient use of catalysts in renewable technologies such as fuel cells (FCs) and electrolyzers. Suitable candidates, like nonprecious metals, can be found in the transition metals' first row, where materials like bimetallics, metal oxides, and metal nitrides can be obtained. Recently, these materials have shown high activity toward the Oxygen Reduction Reaction (ORR) and the Oxygen Evolution Reaction (OER) in an alkaline medium, which can be related to good performance in FCs and electrolyzers. However, most of the studies do not go further than half-cell reactions. In this study, we explored the synthesis of a metal nitride, Ni3FeN, and its application as a cathode material in hydrogen fuel Anion Exchange Membrane Fuel Cells (AEMFC). A one-step ammonolysis synthesis was done to obtain Ni3FeN supported on carbon. Various metal loadings were synthesized with nanoparticles sizes of 7 ± 2 nm and 10 ± 4 nm for 40% and 60%, respectively, revealed with Transmission Electron Microscopy (TEM). High-resolution Scanning Transmission Electron Microscopy (STEM) images and Energy Dispersive X-ray (EDX) mapping analysis revealed a metal nitride core and a metal oxide shell of ca. 3 nm. The bulk electronic structure was further evaluated using X-ray Absorption Spectroscopy (XAS), where the EXAFS modeling suggests a bulk nitride electronic structure. Consequently, cyclic voltammetry (CV) was used to investigate the electrochemical properties and ORR performance of the Ni3FeN catalyst in 1 M KOH. The catalyst exhibited a stable electrochemical structure with a slight decrease in E1/2 of 10 mV (from 0.85 V to 0.84 V) during a 100 K ORR accelerated durability test (ADT). In addition, Levich and Rotating Ring Disk Electrode (RRDE) analyses showed that the number of electrons transferred during the ORR was consistent with a 4-electron pathway. Furthermore, the Ni3FeN catalyst was tested as the cathode in an AEMFC, obtaining a power density output of 400 mW/cm2, highlighting its potential for alkaline medium fuel cell applications.

Highly Durable Electrocatalyst with Low-Loading Pt-Co Dispersed over Graphene Nanofiber for Oxygen Reduction Reaction Under PEMFC Condition

Proton exchange membrane fuel cell (PEMFC) has been demonstrated as a highly efficient energy conversion technology. The sluggish oxygen reduction reaction (ORR) at the fuel cell cathode requires 3 to 5 times more catalysts than the hydrogen oxidation reaction at the anode (1). Currently, platinum is still the catalyst material of choice. However, the heavy use of scarce Pt in the electrodes represents a major cost barrier to the commercialization of PEMFCs. Tremendous efforts have been dedicated to reduce or remove Pt usage through the development of Pt-transition metal catalysts, as highlighted recently by dealloyed PtNi (2), Mo-doped PtNi(3), and ordered PtCo (4); or through the development of transition metals-nitrogen-carbon based PGM-free catalysts (5, 6).In the fuel cell, catalysts should be highly dispersed over the electrode surface to be easily accessible by the reactants, especially at the high fuel cell current density where a large influx of O2 must be converted. For the Pt alloy catalyst of large crystallites, there won’t be enough crystallites available to spread over the electrode surface to encounter the incoming O2 if the total loading of platinum has to be maintained ultralow. Furthermore, unprotected Pt nano-alloys may lose their nanostructure and crystallinity from the dissolution and agglomeration during the ORR process. The PGM-free catalysts, on the other hand, have high catalytic site density with uniform distribution when prepared by homogenous precursors such as metal-organic framework or porous organic polymer, rendering them highly efficient in interacting with O2 flux. Their key drawback, however, is the poor stability operated under PEMFC condition.In this presentation, we will describe a method of preparing highly active yet stable electrocatalysts containing ultralow Pt content using polymer fiber containing cobalt zeolitic imidazolate framework as precursor. The new catalyst contains Pt-Co nanoparticels situated over the PGM-free catalystically active support (7,8). The ORR activities of the new catalyst was first tested in O2 saturated acidic electrolyte by rotating ring disk electrode (RRDE) before fabricated into the membrane electrode assembly (MEA) and evaluated under fuel cell operating condition. The synergistic catalysis between PtCo NPs and the PGM-free active substrate led to an unprecedented oRR performance in both RRDE and fuel cell. For example, the fuel cell test demonstrated a mess activity of 2.43 A/mgPt for the new catalysts and > 80% retention of the initial mass activity after 60000 continuous voltage cycles from 0.6 – 1.0 V.The characterizations of the fresh and the post-electrochemical test samples were investigated by x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), x-ray absorption near-edge structure (XANES), extended x-ray absorption fine structure (EXAFS), transmission electron microscopy (TEM), Raman spectroscopy and BET surface analysis. We also performed DFT calculation on the ORR thermodynamic barriers over both Pt-Co NPs and PGM-free site as the descriptors for reaction pathway. The results reveal that the synergistic interaction between Pt-Co and PGM active substrate contribute significantly to both activity and durability enhancements.Acknowledgments:This work was supported by Argonne National Laboratory through Maria Goeppert Mayer Fellowship, US; Overseas Outstanding Youth Fund project, shanghai Jiao Tong university, Shanghai, China, State Key Laboratory of Metal Matrix Composites, shanghai Jiao Tong university, Shanghai, China. The works performed at Argonne National Laboratory’s Center for Nanoscale Materials and Advanced Photo Source, and Hydrogen research center, shanghai Jiao Tong university.Reference: H. A. Gasteiger, N. M. Markovic, Just a Dream-or Future Reality? Science 324, 48-49 (2009).B. Han et al., Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells. Energy & Environmental Science 8, 258-266 (2015).X. Huang et al., High-performance transition metal–doped Pt3Ni octahedra for oxygen reduction reaction. Science 348, 1230-1234 (2015).D. Wang et al., Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat Mater 12, 81-87 (2013).L. Chong et al., Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells. ChemElectroChem 3, 1541-1545 (2016).J. Shui, C. Chen, L. Grabstanowicz, D. Zhao, D. J. Liu, Highly efficient nonprecious metal catalyst prepared with metal-organic framework in a continuous carbon nanofibrous network. Proc Natl Acad Sci U S A 112, 10629-10634 (2015).L. Chong et al., Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks. Science, (2018).L. Chong et al., Highly durable fuel cell electrocatalyst with low-loading Pt-Co nanoparticles dispersed over single-atom Pt-Co-N-graphene nanofiber. Chem Catalysis 3, 100541.

Elucidating Oxygen Reduction Mechanisms on Organic Mixed Ionic-Electronic Conducting Polymers

Atmospheric oxygen is an attractive oxidant for the generation of electricity from chemical fuels and for the electrochemical production of hydrogen peroxide. Although not universal, it is generally assumed that an electrocatalyst is needed to reduce oxygen. Recently, a variety of organic mixed ionic-electronic conducting polymers (OMIECs) have been reported to exhibit catalytic behavior for both the 4-electron/4-proton and the 2-electron/2-proton oxygen reduction reaction (ORR).This work sets out to identify the oxygen reduction mechanism of OMIECs through a multi-faceted experimental and theoretical approach. We primarily focus our efforts on p(NDI-T2 P75)—a random copolymer comprised of naphthalene diimide (NDI) and bithiophene (T2) units with 75% polar sidechains—and then expand the understanding built on this system to a range of other OMIECs. Using rotating ring disk electrochemistry, we find that the investigated OMIECs exhibit a high selectivity towards the 2-electron ORR product. Using operando UV-Vis and Raman spectroscopy measurements, we identify changes in OMIEC performance when in the presence of O2. To gain further insights about the catalytic reaction path, we construct and test a microkinetic model. Through this model, we show that the performance of the tested OMIECs can be rationalized through an EC’D reaction mechanism. Our results suggest that these materials do not operate as electrocatalysts for the initial reduction of oxygen to superoxide but do function as catalysts for the disproportionation of superoxide.

Microwave-Assisted Synthesis of Nitrogen-Doped Carbon Catalysts for Oxygen Reduction Reaction with Tunable Selectivity

The oxygen reduction reaction (ORR) is the core reaction in electrocatalysis systems such as fuel cells, metal-air batteries and hydrogen peroxide (H2O2) electro-generation. The ORR reaction mechanism has two possible pathways, namely, two-electron (2e−) or four-electron (4e−) processes that enable a reduction of oxygen into H2O2 or water (H2O), respectively. Both paths are useful where the former can provide on-site direct production of H2O2 and the latter is desired in fuel cells and batteries since it enables higher energy efficiency. Optimal ORR electrocatalyst should exhibit high activity, selectivity, stability, and low cost. Carbon materials modified with heteroatoms (e.g. nitrogen (N)) are considered potential alternatives for costly noble metal catalysts including Pt for ORR in fuel cells, and Au for the ORR to H2O2 (1,2). The typical synthesis procedure for the porous nitrogen-doped carbons (N–C) is based on the single or multiple pyrolysis steps of nitrogen-rich carbon precursor. The reactions required a pyrolysis step at the temperature range of 500-1200 °C and timing of one to tens of hours. Such processes showed a highly negative environmental impact due to high energy consumption. The production of 1 ton of activated carbon from lignocellulosic biomass feedstock requires 669.83 kWh (equivalent to an emission of 62.78 tons of CO2) (3). The synthesis of the N–C by microwave (MW) irradiation can reduce energy usage and ensure a more environmentally sustainable and economically viable approach. This procedure necessitates non-transparent materials to electromagnetic waves that can convert MW energy into heat and simultaneously enable the carbonization of the starting material.This work investigated the electrocatalytic activity towards ORR for N–C–MW catalysts derived from polyaniline (PANI) prepared in a one-step MW carbonization approach. PANI was selected due to two reasons: (i) N–C made by thermal pyrolysis of PANI showed improved electrocatalytic activity toward ORR where both the 4e− and the 2e− electron transfer pathways are feasible depending on the nature of active sides (4), (ii) PANI displayed good MW adsorption properties (5). The work aimed to identify the influence of the MW reaction condition on the resulting structure of the N–C–MW and the direction of the ORR. The N–C–MW samples were prepared under MW power of 450 and 800 W and time of 70, 140 and 210 s. The ORR activity of N–C–MW samples was investigated by cyclic voltammetry in the alkaline media (O2-saturated 0.1 M KOH). The experiment was performed in a three-electrode configuration composed of a rotating ring (Pt)–disk (glassy carbon) electrode (RRDE), a graphite rod as the counter electrode and a reversible hydrogen electrode (RHE) as the reference electrode. An influence of catalyst loading on disk electrode (0.05, 0.1 and 0.2 mg/cm2) was analyzed. All investigated MW reaction conditions resulted in the formation of porous disordered carbon structures with nitrogen and oxygen functionalities confirmed by X-ray photon-electron spectroscopy. The shorter time (70 s) and lower power (450 W) of MW treatment resulted in the formation of structures with a low carbonization rate and simultaneously a relatively poor catalytic activity for ORR (an onset potential of ∼0.65 V vs RHE). The samples carbonized under moderate (power of 450 W and 800 W, time of 140 s) and severe (power of 450 W, time of 210 s) reaction conditions showed higher selectivity to H2O2 or water H2O, respectively. The selectivity of 80 % to H2O2 was achieved for the N–C–MW-800W-140s sample at the potential of 0.6 V vs RHE at the catalyst loading of 0.05 mg/cm2. The results showcase the potential of MW carbonization in producing ORR electrocatalysts with diverse functionalization, leading to modified reaction selectivity that can be utilized in various electrocatalytic applications. Acknowledgments The research leading to these results was supported by the Johannes Amos Comenius Programme, European Structural and Investment Funds, project 'CHEMFELLS V‘ (No. CZ.02.01.01/00/22_010/0003004). References Yang, S. et al., Toward the decentralized electrochemical production of H2O2: A focus on the catalysis. ACS Catalysis, 2018.Bouleau, L. et al., Best practices for ORR performance evaluation of metal-free porous carbon electrocatalysts. Carbon, 2022.Wang, YX. et al., Quantifying environmental and economic impacts of highly porous activated carbon from lignocellulosic biomass for high-performance supercapacitors. Energies, 2022.Silva, R. et al., Efficient metal-free electrocatalysts for oxygen reduction: Polyaniline-derived N- and O-doped mesoporous carbons. Journal of the American Chemical Society, 2013.Oyharçabal, M. et al., Influence of the morphology of polyaniline on the microwave absorption properties of epoxy polyaniline composites. Composites Science and Technology, 2013. Figure 1

Nickel Oxide-Aerogel Electrocatalysts for Oxygen Evolution Reaction in Alkaline Media: Experimental Approaches and Modeling-Assisted Strategies for Improving Performance and Durability

Anion exchange membrane water electrolyzers (AEMWEs) represent an attractive technology for producing “green” hydrogen that enables operation on pure water using platinum group metal (PGM)-free electrocatalysts at both anode and cathode. Also, AEMWEs do not require the use of highly concentrated and corrosive alkaline electrolytes and PGM-based catalysts, which are the major drawbacks of the incumbent low-temperature liquid-alkaline and proton exchange membrane electrolyzers, respectively.1,2 In this context, the development of PGM-free electrocatalysts for oxygen evolution reaction (OER) in alkaline media has attracted considerable research interest. Among different types of transition metal-based oxides, Ni oxides doped with Fe have shown the highest OER activity in alkaline media.3,4 Recently, we have developed at Los Alamos National Laboratory (LANL) a series of Ni oxide-based aerogel materials that, primarily in combination with Fe in different proportions, have shown respectable OER performance in the electrochemical cell and at the AEMWE anode operating on either neat deionized water or with a supporting electrolyte, 0.1 M KOH or K2CO3.5 For application at the AEMWE anode, the catalyst integration into the electrode catalyst layer, i.e., combining the catalyst with anion exchange ionomer (AEI) and binding agents, is crucial to prevent catalyst layer delamination and to create a good catalyst/electrolyte interface, which in turn enables high OH- conductivity within the catalyst layer.6 This latter aspect is especially important for achieving high AEMWE performance in pure water operation. In this work, we investigate the impact of combining our Ni-Fe oxide aerogel catalysts with different AEIs (various backbone chemistries, OH- functional groups) and different binding agents (e.g., Nafion ionomer) on the AEMWE performance. We will show that full activation of the catalyst by phase transformation from the original Ni oxide-like structure to the active layered (oxy)hydroxide is essential for achieving high OER activity, and it can be influenced by the catalyst layer composition. By advanced characterization techniques such as high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy, and Mössbauer spectroscopy, we will shed light onto the phase transformation process that results in superior OER activity of these materials in alkaline media.Following our prior machine learning studies aimed at optimizing for the synthesis of oxygen reduction electrocatalysts,7,8 we will also show how to improve the synthesis of Ni oxide aerogel-based OER catalysts to maximize activity and stability. This work is further supported by density functional theory (DFT) modeling studies to better understand reaction mechanisms, active sites, and ultimately what role transition metal dopants (Fe and Co) play in modifying OER activity. Studies of in situ dissolution of these dopants using DFT-generated, phase-constrained Pourbaix diagrams9 will guide synthesis through understanding this likely materials degradation pathway. References H. A. Miller et al., Sustain. Energy Fuels, 4, 2114–2133 (2020).C. Santoro et al., ChemSusChem, 202200027 (2022).S. Fu et al., Nano Energy, 44, 319–326 (2018)D. Xu et al., ACS Catal., 9, 7–15 (2019).P. Zelenay and D. Myers, "ElectroCat (Electrocatalysis Consortium);” U.S. Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Program, 2022 Annual Merit Review and Peer Evaluation Meeting, June 6-8, 2022. https://www.hydrogen.energy.gov/pdfs/review22/fc160_myers_zelenay_2022_o.pdfL. Osmieri et al., J. Power Sources, 556, 232484 (2023).M. R. Karim et al., ACS Appl. Energy Mater., 3, 9083–9088 (2020).W. J. M. Kort-Kamp et al., J. Power Sources, 559 (2023).E. F. Holby, G. Wang, and P. Zelenay, ACS Catal., 10, 14527–14539 (2020).

Nanostructured Fe-N-C Electrocatalysts with CeO2 Additives for PEM Fuel Cells

The development of cost-effective electrocatalysts for polymer electrolyte membrane fuel cells (PEM fuel cells) is essential for the widespread use of this technology. The high cost and limited availability of Pt-group metals (PGMs) used as catalyst materials are the main barriers to the widespread commercialization and development of PEM fuel cells. [1] Therefore, the use of high surface area and effective catalysts without Pt have gained great importance in PEM fuel cells. This study introduces high surface area electrocatalysts that are free of platinum group metals (non-PGM) consisting of iron-nitrogen-carbon (Fe-N-C). Here, the uniform distribution of Fe was achieved using graphene oxide (GO) nanoparticles to enhance the catalyst's performance for oxygen reduction reaction (ORR). [2] Furthermore, the addition of a small amount of cerium oxide (CeO2) nanoparticles to the catalyst layer helps to prevent the degradation of the catalyst and ionomer by preventing H2O2 formation as well as increasing the ORR activity due to high oxygen storage capacity. [3] Initially, GO is synthesized by improved Hummer’s method. The GO nanoparticles are obtained through a process involving ball-milling and acid treatment. These nanoparticles are then thermally reduced and nitrogen-doped to form nitrogen-doped reduced graphene oxide nanoparticles. Fe-N-C complexes are synthesized by reacting these nanoparticles with FeCl2 precursor, which are then hydrothermally treated to introduce CeO2 additives. The resulting catalysts are analyzed using various techniques (FT-IR, XPS, SEM, TEM, EDX) and display excellent electrochemical performance. The ORR activity of the Fe-N-C catalysts was investigated and compared with the electrocatalysts prepared with larger graphene oxide particles. A similar comparison is also made with and without CeO2 additives. The authors gratefully acknowledge the financial support of The Scientific and Technological Research Council of Turkey (TÜBİTAK) (Grant Number: 122M429) References [1] He, C., Desai, S., Brown, G., & Bolleplli, S. (2005). PEM fuel cell catalysts: Cost, performance, and durability. The electrochemical society Interface, 14(3), 41.[2] Weiss, J., Zhang, H., & Zelenay, P. (2020). Recent progress in the durability of Fe-NC oxygen reduction electrocatalysts for polymer electrolyte fuel cells. Journal of Electroanalytical Chemistry, 875, 114696.[3] Taşdemir, A., Iskandarani, B., Yürüm, A., Gürsel, S. A., & Kaplan, B. Y. (2021). CeO2 nanorod decorated NrGO additives for boosting PEMFC performance. International Journal of Hydrogen Energy, 46(63), 32250-32260.

Mechanisms of Stabilization and Degradation of Transition Metal Oxygen Electroreduction Catalysts with in-Situ Electrochemical Flow Cell ICP-MS

Proton exchange membrane hydrogen fuel cell (PEMFC) deployment is presently limited by the high material cost of oxygen reduction reaction (ORR) electrocatalysts at the cathode. Developing low-cost, earth-abundant alternatives for use in acidic environments presents a material stability challenge, especially for long-term device operation. Platinum (Pt)-based materials are used in typical commercial PEMFC cathode formulations due to their simultaneous high performance and long-term stability despite the prohibitively high material cost. Developing lower-cost, longer-life catalyst materials based on earth abundant transition metals can accelerate the adoption of PEMFC technology. The impact of potential, current density, and local microenvironment has been shown to cause degradation of non-Pt materials but standard ex situ measurements can only probe surface restructuring and cumulative dissolution after operation. Material-specific degradation mechanisms that are strong functions of the operating conditions cannot be ascertained without in situ quantification of material degradation under PEMFC-relevant conditions. Information about the degradation pathways of these non-precious catalysts can assist with material design for devices; however, most efforts towards developing an in-situ understanding of PEMFC cathode catalyst degradation under operating conditions are generally limited to Pt-based materials. Extensive in situ characterization has revealed Pt-specific mechanistic information about corrosion pathways as well as conditions that exacerbate Pt alloy leaching. It has been hypothesized that the Pt degradation processes are related to oxide formation under potential cycling. With this critical in-situ information, Pt conditioning protocols have been developed to enhance material lifetime; however, investigations on non-precious materials are less common. Insights into non-precious catalyst degradation in PEMFC operating conditions are not as well-established but could be essential in enabling low-cost materials for commercial use. There is a need for more insights into a vast array of materials which necessitates the development of faster, preferably benchtop techniques for degradation analysis.In this work, we use an in situ electrochemical flow cell assembly and coupled it with an inductively coupled plasma-mass spectrometer (ICP-MS) to quantify the loss of material in real time for several non-Pt materials under reaction conditions. The flow cell is fed by a peristaltic pump at 2.5 mL/min of gas-saturated acidic electrolyte for optimal mass transport. The cell has a three-electrode configuration with a compression-mounted metal foil working electrode, silver/silver chloride reference electrode, and Pt counter electrode downstream of other components. We evaluate a variety of transition metals across the spectrum of ORR activity: palladium, silver, nickel, copper, manganese, and cobalt. Each metal is tested under oxygen and nitrogen saturation in five electrolytes of identical pH: perchloric acid, sulfuric acid, nitric acid, hydrochloric acid, and hydrobromic acid. This setup allows for nearly real time measurement of ORR kinetics and in situ element-specific dissolution rates as a function of time. With careful design of experimental conditions and controlled variables, we are able to suggest mechanisms of degradation with specific reference to conditions under which material loss occurred such as high/low potential, oxygen-saturated/nitrogen-saturated electrolyte, or faradaic/non-faradaic current. We find some metals are stable under nitrogen-saturated electrolyte but corrode more under oxygen-saturated electrolyte only while ORR active. Furthermore, other metals are stable in nitrogen saturated electrolyte at all tested electrochemical conditions but unstable under oxygen saturated electrolyte but only outside the ORR range, implying that cathodic faradaic processes might be stabilizing the surface at low potentials. This stabilization where a thermodynamically unstable material (based on its Pourbaix diagram) exhibits greater immunity while performing ORR in certain electrolytes could inform the development stability mechanisms that direct the design of next generation, non-precious PEMFC cathode catalyst materials. With combined in situ catalyst stability analysis in five pH 1 electrolytes, we can recommend specific conditions for optimizing activity and stability based on the potential range of operation and the electrolyte composition/saturation. We can also distill mechanistic insights from these experiments by creating models that validate causes of catalyst degradation. These models are built using “graphical causal modeling”, which is a mathematical field that goes beyond correlative predictions by venturing into causal inference. We hope to expand this framework into other electrocatalytic reactions of interest. The in-situ ICP-MS electrochemical flow cell setup exhibits promise for accelerating materials stability analysis for enabling next generation Pt-free ORR electrocatalysts through practical experiments and direct comparability to established electrochemical techniques.

The Influence of Silica Dioxide in the Electrocatalytic Performances of rGO/Fe<sub>3</sub>O<sub>4</sub> as Oxygen Reduction Electrocatalyst

In this study, synthesis of reduced graphene oxide-iron oxide-silica dioxide (rGO/Fe3O4/SiO2) was done through a facile chemical process. Physical characterization was carried out as such Fourier transform infrared spectroscopy (FTIR) which confirmed the presence of silica peak in the spectrum of rGO/Fe3O4/SiO2, while RAMAN displayed the vibrational bands of carbon materials studied. Results of SEM-EDX and TEM confirmed the unification of SiO2 on rGO/Fe3O4 nanocomposite with difference in morphologic structure. X-ray diffraction (XRD) analysis exhibited that addition of SiO2 increased the crystalline size of the nanocomposite. Nitrogen adsorption isotherm analysis describes the nanocomposites fall in the mesopore region. The nanocomposite was then drop-casted on the surface of glassy carbon electrode (GCE) for fabrication of the electrode which denoted as rGO/Fe3O4/SiO2/GCE. Electrochemical characterization of modified electrode was studied using electron impedance spectroscopy (EIS), which showed the minimal resistance charge transfer. Oxygen reduction reaction analysis shows that electrocatalytic reduction of oxygen was excellent with four-electron transfer when calculated using Randles-Sevcik equation. All the analysis was compared to the nanocomposites without the addition of silica oxide (rGO/Fe3O4). This work proves that addition of nanoparticle in a compound as a matrix improves the oxygen reduction potential of rGO/Fe3O4/SiO2/GCE composite.

Preparation of a high-yield Fe–N4 site-containing hierarchical porous carbon eletrocatalyst for effective oxygen reduction and zinc-air battery: The effect of dual protection-exposure mechanism

Iron-based catalysts are considered highly promising as non-noble metal catalysts for oxygen electroreduction. However, the optimization of iron-based catalysts is limited by the well-designed carbon support and high-efficiency catalytic sites. Furthermore, achieving high production yield on an industrial scale while maintaining high performance would also be highly encouraged. Therefore, a dual-protection-exposure mechanism was employed for a hierarchical porous carbon (HPC) embedded with Fe–N4 sites (Fe–N4/HPC) catalysts, which were prepared through the ionothermal carbonization of Fe/ZnTBrPP@MgCl2 [5, 10, 15, 20-tetrakis (4′-bromophenyl) porphyrinato iron (FeTBrPP) mixed with ZnTBrPP on MgCl2·6H2O template]. Apart from self-protection-exposure of the Fe/ZnTBrPP itself, the hydrated salt template provided a secondary protection and exposure simultaneously. As a result, the Fe–N4/HPC retains more Fe–N4 sites and a larger BET surface, resulting in excellent ORR activity and durability in alkaline (0.922 V vs. RHE). Interestingly, under the conditions of using hydrated magnesium salt as a soft template, the yield rate of the Fe–N4/HPC significantly higher than the product without hydrated salt. Furthermore, the utilization of Fe–N4/HPC as the cathode in a zinc-air battery demonstrated remarkable performance, achieving an high peak power density (94 mW cm−2) and good stability.

Recent advances in Fe-N-C- and Co-N-C-based materials as bifunctional electrocatalysts for oxygen reduction and oxygen evolution

Recent advances in Fe-N-C- and Co-N-C-based materials as bifunctional electrocatalysts for oxygen reduction and oxygen evolution

The Recent Progress of Oxygen Reduction Electrocatalysts Used at Fuel Cell Level.

Proton exchange membrane fuel cells (PEMFCs) are gaining significant interest as an attractive substitute for traditional fuel cells, with higher energy density, lower environmental pollution, and better operation efficiency. However, the cathode reaction, i.e., the oxygen reduction reaction (ORR), is widely proved to be inefficient, and therefore an obstacle to the widespread development of PEMFCs. The requirement for affordable highly-efficient ORR catalysts is extremely urgent to be met, especially at fuel cell level. Unfortunately, most previous reports focus on the ORR performance at rotating disk electrodes (RDE) level instead of membrane electrode assembly (MEA) level, making it harder to evaluate ORR catalysts operating under real vehicle conditions. Obviously, it is extremely necessary to develop an in-depth understanding of the structure-activity relationship of highly-efficient ORR catalysts applied at MEA level. In this work, an overview of the latest advances in ORR catalysts is provided with an emphasis on their performance at MEA level, hoping to cover the novel and systemic insights for innovative and efficient ORR catalyst design and applications in PEMFCs.

Volatile guest molecule mediated strategy to convert covalent organic framework into nitrogen, sulfur-doped carbon as metal-free oxygen reduction electrocatalysts

Covalent organic framework (COF) derived metal-free carbon materials have emerged as promising electrocatalysts for the oxygen reduction reaction (ORR). Herein, a volatile guest molecule mediated-pyrolysis strategy was explored on a designed thiophene-rich and imine-linked COF. Through the modulation of guest mediators (iodine and sulfur), the properties of the as-obtained carbon materials can be well regulated. The optimized nitrogen and sulfur dual-doped carbon electrocatalyst demonstrates remarkable ORR activity with a half-wave potential of 0.87 V and impressive durability, with only an 8% current loss over 21 h. The corresponding assembled zinc-air battery has a comparable power density (60 mW cm−2) to that of the commercial Pt/C. It is proposed that the coexistence of the guest mediators iodine and sulfur in the channels of COFs could prevent the loss of N species. The enhanced N content and N/S ratio are assumed to be responsible for the ORR performance. This study puts forward a novel strategy to prepare COF-derived carbon materials mediated by volatile guest molecules, which may provide new insights into the development of metal-free ORR catalysts.

Single transition metal atom supported on NiOOH as highly efficient electrocatalyst for oxygen reduction and oxygen evolution reaction: A DFT study

Developing non-noble metal bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts with high activity and abundance is urgently needed. In this regard, the structures of 3d, 4d, and 5d transition metal (except Tc, Cd, and Hg) supported on NiOOH are constructed and studied by density functional theory calculations. Two sites on NiOOH support the single transition metal located at the top of the Ni or O atom in the substrate, namely TM−Ni@NiOOH or TM−O@NiOOH. According to the analysis of stability, 15 kinds of catalysts are not considered in the subsequent catalytic performance study due to poor stability and structural deformation. The calculated binding energy of the reaction species values on TM−Ni@NiOOH and TM−O@NiOOH indicate that Co−Ni@NiOOH, Ni−Ni@NiOOH, Fe−O@NiOOH, Co−O@NiOOH, and Ni−O@NiOOH exhibit appropriate binding strength of the reaction species. The Gibbs free energy analysis manifests that Ni−O@NiOOH is expected to be the promising bifunctional catalyst because it possesses low ORR/OER overpotentials with 0.45/0.55 V values. The potential determining step of the bifunctional catalyst Ni−O@NiOOH for ORR is the step of *OH reduction, while for OER is *O formation. At last, the calculated results of the deformation charge density and Mulliken charge manifest that the relatively strong interaction between reaction species and catalyst surface is due to their strong electron transfer. This work provides a perspective on TM atom supported on layered double hydroxides design for the ORR and OER processes.

Recycling the Spent LiNi1- x - yMnxCoyO2 Cathodes for High-Performance Electrocatalysts toward Both the Oxygen Catalytic and Methanol Oxidation Reactions.

The traditional recycling methods of the spent lithium ion batteries (LIBs) involve the intricate and cumbersome steps. This work proposes a facile method of acid leaching followed by the sulfurization treatment to achieve the high Li leaching efficiency, and obtain high-performance multi-function electrocatalysts for oxygen reduction (ORR), oxygen evolution (OER), and methanol oxidation reactions (MOR) from the spent LIB ternary cathodes. By this method, the Li leaching efficiency from the spent LIB ternary cathode can reach 98.3%, and the transition metal sulfide heterostructures (LNMCO-H-450S) consisting MnS, NiS2, and NiCo2S4 phases can be obtained. LNMCO-H-450S shows the superior bifunctional oxygen catalytic activities with ORR half-wave potential of 0.763V and OER potential at 10mA cm-2 of 1.561V, surpassing most of the state-of-the-art electrocatalysts. LNMCO-H-450S also demonstrates the superior MOR catalytic activity with the potential at 100mA cm-2 being 1.37V. Using LNMCO-H-450S as the oxygen catalyst, this work can construct the aqueous and solid-state zinc-air batteries with high power density of 309 and 257mW cm-2, respectively. This work provides a promising strategy for the efficient recovery of Li, and reutilization of Ni, Co, and Mn from the spent LIB ternary cathodes.

Stability of Carbon Supported Silver Electrocatalysts for Alkaline Oxygen Reduction and Evolution Reactions.

Ag-based electrocatalysts are promising candidates to catalyze the sluggish oxygen reduction reaction (ORR) in anion exchange membrane fuel cells (AEMFC) and oxygen evolution reaction (OER) in unitized regenerative fuel cells. However, to be competitive with existing technologies, the AEMFC with Ag electrocatalyst must demonstrate superior performance and long-term durability. The latter implies that the catalyst must be stable, withstanding harsh oxidizing conditions. Moreover, since Ag is typically supported by carbon, the strict stability requirements extend to the whole Ag/C catalyst. In this work, Ag supported on Vulcan carbon (Ag/VC) and mesoporous carbon (Ag/MC) materials is synthesized, and their electrochemical stability is studied using a family of complementary techniques. We first employ an online scanning flow cell combined with inductively coupled plasma mass spectrometry (SFC-ICP-MS) to estimate the kinetic dissolution stability window of Ag. Strong correlations between voltammetric features and the dissolution processes are discovered. Very high silver dissolution during the OER renders this material impractical for regenerative fuel cell applications. To address Ag stability during AEMFC load cycles, accelerated stress tests (ASTs) in O2-saturated solutions are carried out in rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) setups. Besides tracking the ORR performance evolution, an ex situ long-term Ag dissolution study is performed. Moreover, morphological changes in the catalyst/support are tracked by identical-location transmission electron microscopy (RDE-IL-TEM). Voltammetry analysis before and after AST reveals a smaller change in ORR activity for Ag/MC, confirming its higher stability. RRDE results reveal a higher increase in the H2O2 yield for Ag/VC after the ASTs. The RDE-IL-TEM measurements demonstrate different degradation processes that can explain the changes in the long term performance. The results in this work point out that the stability of carbon-supported Ag catalysts depends strongly on the morphology of the Ag nanoparticles, which, in turn, can be tuned depending on the chosen carbon support and synthesis method.

Single-step Synthesis of Highly Porous Nitrogen-doped Carbon by Solid–gas Mechanochemical Treatment as an Oxygen Reduction Electrocatalyst

Single-step Synthesis of Highly Porous Nitrogen-doped Carbon by Solid–gas Mechanochemical Treatment as an Oxygen Reduction Electrocatalyst

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2 O2.

The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e- ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e- ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H2 O2 production. The work here gives not only new understandings on the 2e- ORR catalysis, but also the robust catalyst which can be directly used in industry.

Self-Sacrificial Templated Nanoarchitectonics of Nitrogen-Doped Carbon Derived from Viologen-Based Covalent Triazine Polymer: An Oxygen Reduction Electrocatalyst in Zinc–Air Batteries

Self-Sacrificial Templated Nanoarchitectonics of Nitrogen-Doped Carbon Derived from Viologen-Based Covalent Triazine Polymer: An Oxygen Reduction Electrocatalyst in Zinc–Air Batteries