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      Approaches for measuring the surface areas of metal oxide electrocatalysts for determining their intrinsic electrocatalytic activity

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          Abstract

          A summary and analysis of approaches for measuring the surface areas of metal oxide electrocatalysts for evaluating their intrinsic electrocatalytic activity.

          Abstract

          Great attention has been recently drawn to metal oxide electrocatalysts for electrocatalysis-based energy storage and conversion devices. To find the optimal electrocatalyst, a prerequisite is an activity metric that reasonably evaluates the intrinsic electrocatalytic activity of a particular catalyst. The intrinsic activity is commonly defined as the specific activity which is the current per unit catalyst surface area. Thus, the precise assessment of intrinsic activity highly depends on the reliable measurement of catalyst surface area, which calls for the knowledge of experimental approaches for determining the surface areas of metal oxide electrocatalysts. This tutorial review aims to summarize and analyze the approaches for measuring the surface areas of metal oxide electrocatalysts for evaluating and comparing their intrinsic electrocatalytic activities. We start by comparing the popular metrics for activity estimation and highlighting the importance of surface-area-normalized activity ( i.e. specific activity) for intrinsic chemistry analysis. Second, we provide some general guidelines for experimentally measuring the electrochemically active surface area (ECSA). Third, we review the methods for the surface area measurement of metal oxide electrocatalysts. The detailed procedure for each method is explicitly described to provide a step-by-step manual that guides researchers to perform the measurement; the rationales and uncertainties for each method are discussed to help readers justify the reliable assessment of surface area. Next, we give our recommendations on selecting a rational experimental approach for the surface area measurement of a particular metal oxide electrocatalyst. Lastly, we discuss the future challenges of ECSA measurement and present an exemplary novel ECSA technique.

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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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            What Are Batteries, Fuel Cells, and Supercapacitors?

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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
                CSRVBR
                Chemical Society Reviews
                Chem. Soc. Rev.
                Royal Society of Chemistry (RSC)
                0306-0012
                1460-4744
                May 7 2019
                2019
                : 48
                : 9
                : 2518-2534
                Affiliations
                [1 ]School of Materials Science and Engineering
                [2 ]Nanyang Technological University
                [3 ]Singapore
                [4 ]Institute of Chemistry
                [5 ]The Hebrew University of Jerusalem
                [6 ]Jerusalem 9190401
                [7 ]Israel
                [8 ]Singapore-HUJ Alliance for Research and Enterprise (SHARE)
                [9 ]Key Lab of Organic Optoelectronics and Molecular Engineering
                [10 ]Department of Chemistry
                [11 ]Tsinghua University
                [12 ]Beijing
                [13 ]China
                [14 ]School of Chemical Engineering
                [15 ]The University of Adelaide
                [16 ]Adelaide
                [17 ]Australia
                [18 ]Nanomaterials for Energy and Energy-Water Nexus (NEW)
                Article
                10.1039/C8CS00848E
                30976760
                55e7eafb-8f07-4a7b-88b6-6dbdbe8a7611
                © 2019

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

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