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      In situ formation of Ni 3Se 4 nanorod arrays as versatile electrocatalysts for electrochemical oxidation reactions in hybrid water electrolysis

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          Abstract

          Ni 3Se 4 nanorod arrays are versatile and efficient electrocatalysts for different electrochemical oxidation reactions in hybrid water electrolysis.

          Abstract

          Water splitting is limited by the sluggish kinetics of anodic oxygen evolution, thus extensive studies have focused on developing highly efficient electrocatalysts for water oxidation. Nevertheless, replacing sluggish water oxidation with smart anodic reactions would greatly lower the overall cost of energy and the electrode by using earth-abundant electrocatalysts. Herein, a Ni 3Se 4 nanorod array is prepared by an in situ hydrothermal selenization method and demonstrates excellent activity for anodic reactions. Assisted by this versatile Ni 3Se 4 nanorod array, only 240 mV overpotential is required to drive 10 mA cm −2 of oxygen evolution current steadily. By substituting oxygen evolution with urea and hydrazine oxidation, the anodic potential can be reduced from 1.47 V to 1.38 V and even further to 0.32 V to afford 10 mA cm −2 anodic current density. Substituting anodic reactions coupled with the non-precious electrocatalyst demonstrated in the hybrid water electrolysis in this study has promising potential for future energy conversion, environmental treatment and valuable chemical upgrading.

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          Most cited references43

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          Combining theory and experiment in electrocatalysis: Insights into materials design

          Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. This review discusses design strategies for state-of-the-art heterogeneous electrocatalysts and associated materials for several different electrochemical transformations involving water, hydrogen, and oxygen, using theory as a means to rationalize catalyst performance. By examining the common principles that govern catalysis for different electrochemical reactions, we describe a systematic framework that clarifies trends in catalyzing these reactions, serving as a guide to new catalyst development while highlighting key gaps that need to be addressed. We conclude by extending this framework to emerging clean energy reactions such as hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, where the development of improved catalysts could allow for the sustainable production of a broad range of fuels and chemicals.
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            A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles.

            The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.
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              Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

              Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.
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                Author and article information

                Contributors
                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                2018
                2018
                : 6
                : 32
                : 15653-15658
                Affiliations
                [1 ]Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education)
                [2 ]Key Laboratory of Material Chemistry and Service Failure
                [3 ]School of Chemistry and Chemical Engineering
                [4 ]Wuhan National Laboratory for Optoelectronics
                [5 ]Huazhong University of Science and Technology
                [6 ]School of Materials Science and Engineering
                [7 ]University of Shanghai for Science and Technology
                [8 ]Shanghai 200093
                [9 ]P. R. China
                Article
                10.1039/C8TA06361C
                a7c065cf-75d2-4219-a97b-e8bb4e46a6b5
                © 2018

                http://rsc.li/journals-terms-of-use

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