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      Chemical Structure of Fe–Ni Nanoparticles for Efficient Oxygen Evolution Reaction Electrocatalysis

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          Abstract

          Bimetallic iron–nickel-based nanocatalysts are perhaps the most active for the oxygen evolution reaction (OER) in alkaline electrolytes. Recent developments in literature have suggested that the ratio of iron and nickel in Fe–Ni thin films plays an essential role in the performance and stability of the catalysts. In this work, the metallic ratio of iron to nickel was tested in alloy bimetallic nanoparticles. Similar to thin films, nanoparticles with iron–nickel atomic compositions where the atomic iron percentage is ≤50% outperformed nanoparticles with iron–nickel ratios of >50%. Nanoparticles of Fe 20Ni 80, Fe 50Ni 50, and Fe 80Ni 20 compositions were evaluated and demonstrated to have overpotentials of 313, 327,, and 364 mV, respectively, at a current density of 10 mA/cm 2. While the Fe 20Ni 80 composition might be considered to have the best OER performance at low current densities, Fe 50Ni 50 was found to have the best current density performance at higher current densities, making this composition particularly relevant for electrolysis conditions. However, when stability was evaluated through chronoamperometry and chronopotentiometry, the Fe 80Ni 20 composition resulted in the lowest degradation rates of 2.9 μA/h and 17.2 μV/h, respectively. These results suggest that nanoparticles with higher iron and lower nickel content, such as the Fe 80Ni 20 composition, should be still taken into consideration while optimizing these bimetallic OER catalysts for overall electrocatalytic performance. Characterization by electron microscopy, diffraction, and X-ray spectroscopy provides detailed chemical and structural information on as-synthesized nanoparticle materials.

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          Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation.

          Fe plays a critical, but not yet understood, role in enhancing the activity of the Ni-based oxygen evolution reaction (OER) electrocatalysts. We report electrochemical, in situ electrical, photoelectron spectroscopy, and X-ray diffraction measurements on Ni(1-x)Fe(x)(OH)2/Ni(1-x)Fe(x)OOH thin films to investigate the changes in electronic properties, OER activity, and structure as a result of Fe inclusion. We developed a simple method for purification of KOH electrolyte that uses precipitated bulk Ni(OH)2 to absorb Fe impurities. Cyclic voltammetry on rigorously Fe-free Ni(OH)2/NiOOH reveals new Ni redox features and no significant OER current until >400 mV overpotential, different from previous reports which were likely affected by Fe impurities. We show through controlled crystallization that β-NiOOH is less active for OER than the disordered γ-NiOOH starting material and that previous reports of increased activity for β-NiOOH are due to incorporation of Fe-impurities during the crystallization process. Through-film in situ conductivity measurements show a >30-fold increase in film conductivity with Fe addition, but this change in conductivity is not sufficient to explain the observed changes in activity. Measurements of activity as a function of film thickness on Au and glassy carbon substrates are consistent with the hypothesis that Fe exerts a partial-charge-transfer activation effect on Ni, similar to that observed for noble-metal electrode surfaces. These results have significant implications for the design and study of Ni(1-x)Fe(x)OOH OER electrocatalysts, which are the fastest measured OER catalysts under basic conditions.
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            Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion

            Microkinetic analyses of aqueous electrochemistry involving gaseous H2 or O2, i.e., hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are revisited. The Tafel slopes used to evaluate the rate determining steps generally assume extreme coverage of the adsorbed species (θ ≈ 0 or ≈1), although, in practice, the slopes are coverage-dependent. We conducted detailed kinetic analyses describing the coverage-dependent Tafel slopes for the aforementioned reactions. Our careful analyses provide a general benchmark for experimentally observed Tafel slopes that can be assigned to specific rate determining steps. The Tafel analysis is a powerful tool for discussing the rate determining steps involved in electrocatalysis, but our study also demonstrated that overly simplified assumptions led to an inaccurate description of the surface electrocatalysis. Additionally, in many studies, Tafel analyses have been performed in conjunction with the Butler-Volmer equation, where its applicability regarding only electron transfer kinetics is often overlooked. Based on the derived kinetic description of the HER/HOR as an example, the limitation of Butler-Volmer expression in electrocatalysis is also discussed in this report.
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              Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis

              The rational design of non-precious transition metal perovskite oxide catalysts holds exceptional promise for understanding and mastering the kinetics of oxygen electrocatalysis instrumental to artificial photosynthesis, solar fuels, fuel cells, electrolyzers, and metal–air batteries. In this Review, we discuss the state-of-the-art understanding of non-precious transition metal oxides that catalyze the oxygen reduction and evolution reactions. Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to making use of photosynthesis, advancing solar fuels, fuel cells, electrolyzers, and metal–air batteries. We first present key insights, assumptions and limitations of well-known activity descriptors and reaction mechanisms in the past four decades. The turnover frequency of crystalline oxides as promising catalysts is also put into perspective with amorphous oxides and photosystem II. Particular attention is paid to electronic structure parameters that can potentially govern the adsorbate binding strength and thus provide simple rationales and design principles to predict new catalyst chemistries with enhanced activity. We share new perspective synthesizing mechanism and electronic descriptors developed from both molecular orbital and solid state band structure principles. We conclude with an outlook on the opportunities in future research within this rapidly developing field.
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                Author and article information

                Journal
                ACS Omega
                ACS Omega
                ao
                acsodf
                ACS Omega
                American Chemical Society
                2470-1343
                11 October 2019
                22 October 2019
                : 4
                : 17
                : 17209-17222
                Affiliations
                [1] Ralph E. Martin Department of Chemical Engineering, Institute for Nanoscience and Engineering, and §Department of Chemistry and Biochemistry, University of Arkansas , Fayetteville, Arkansas 72701, United States
                []Advanced Photon Source, Argonne National Lab , Argonne, Illinois 60439, United States
                Author notes
                Article
                10.1021/acsomega.9b01692
                6811848
                a1608f96-8288-4835-96c7-b7dcfaf8fb08
                Copyright © 2019 American Chemical Society

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                : 09 June 2019
                : 03 October 2019
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