The Oxygen Evolution Reaction: Mechanistic Concepts and Catalyst Design

Doyle, Richard L.; Lyons, Michael E. G.

doi:10.1007/978-3-319-29641-8_2

Cited by 112 publications

(137 citation statements)

References 184 publications

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“…Ni based materials have raised substantial interest in the electrochemical community as alkaline OER electrocatalysts. [4,15,[18][19][20][21][22][23] They are stable under alkaline OER conditions, relatively inexpensive, earth abundant and the performance of plain nickel is better than other nonprecious metals. Enhancing its performance by the use of porous catalyst carriers and/or different chemical forms of nickel oxyhydroxide has been a line of recent research.…”

Section: Introductionmentioning

confidence: 99%

Accelerated Durability Test for High‐Surface‐Area Oxyhydroxide Nickel Supported on Raney Nickel as Catalyst for the Alkaline Oxygen Evolution Reaction

et al. 2019

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We demonstrate a fit‐for‐purpose accelerated durability test (ADT) of a high‐surface‐area catalyst for the alkaline oxygen evolution reaction (OER). Using an automatized electrochemical setup enabled us to run a complex ADT protocol including online detection of the effective solution resistance as well as linear voltammetry, cyclic voltammetry, cyclic galvanograms, and electrochemical impedance spectroscopy (EIS) for 55 h in total. Using this protocol, we tested the service life stability of a nickel oxyhydroxide (NiOx) catalyst based on Raney Ni. The catalyst was prepared by growing nickel oxyhydroxide on high‐surface‐area Raney Ni and subsequent formation of the active phase. The successful synthesis of the active NiOx phase is supported by cyclic voltammetry and Raman spectroscopy. The as prepared and activated Raney NiOx exhibits an overpotential for the OER of 304 mV at 10 mA cm−2 with a Tafel slope of 53 mV dec−1 and roughness factors as high as 4515 determined by EIS during OER. By concentrating for the ADT protocol on current densities relevant for coupling water electrolysis to photovoltaics, it is demonstrated that Raney NiOx is a promising anode material candidate as it is earth abundant and its active phase exhibits high OER activity as well as stability.

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Section: Introductionmentioning

confidence: 99%

Accelerated Durability Test for High‐Surface‐Area Oxyhydroxide Nickel Supported on Raney Nickel as Catalyst for the Alkaline Oxygen Evolution Reaction

et al. 2019

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“…A Tafel slope of 120 mV dec −1 in OER catalysis implies that the first electron transfer is the rate-limiting step. 43 is not typically associated with a specific rate-limiting step but is not 51 While a specific rate-determining step on the Co 3 O 4 electrodes cannot be suggested, the marked difference in Tafel behavior between SS-Co and Co 3 O 4 electrodes suggests that there may be differences in OER mechanism, for example different rate limiting steps, between the two catalyst preparations. It is also important to note that mass transport through the mesoporous ITO electrode could affect the observed Tafel behavior.…”

Section: Resultsmentioning

confidence: 90%

Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt

Swierk

Tilley

2017

J. Electrochem. Soc.

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Cobalt oxides are an earth abundant material that exhibits high electrocatalytic activity for the oxygen evolution reaction (OER) across a wide pH range. Recent studies suggest that OER catalysis can proceed through an active site comprised of one or two cobalt atoms but that multiple adjacent cobalt centers are preferred to stabilize high valent cobalt oxo-intermediates by delocalization. Utilizing molecular precursors to prepare single, isolated cobalt atoms (SS-Co) and small clusters of Co 3 O 4 we find that OER proceeds more efficiently on Co 3 O 4 . Using electrochemical impedance spectroscopy (EIS), these results were rationalized at an atomic level. The EIS results support a hypothesis that charge transfer related to the formation of reaction intermediates proceeds more easily on Co 3 O 4 than on SS-Co, which is attributed to the difficulty in forming Co(IV) = O and unlikely nucleophilic attack by water to form Co(II) Conversion of solar energy into a useful chemical fuel for later use represents a major scientific goal in the evolution toward a society fully powered by renewable energy.-1 Several potential fuel targets exist including hydrogen from proton reduction; methane, methanol and higher order carbon species from carbon dioxide reduction; and ammonia via nitrogen reduction. To achieve meaningful rates of fuel production, any of these potential reduction reactions must be coupled to an oxidative reaction that generates both electrons and protons. The most sensible candidate to provide these electrons and protons is water, which can be decomposed via the oxygen evolution reaction (OER):In all proposed systems, the OER occurs at the anode and is coupled to the reductive reaction occurring at the cathode. Ideally, the potential needed to drive the OER and its partner reaction is generated via a photovoltaic process. In a photoelectrochemical cell with the catalysts directly coupled to the light absorber, the efficiency of the catalyst, in particular the OER catalyst is paramount. A key figure of merit for a catalyst used in a photoelectrochemical cell is the amount of overpotential required to achieve a desired current density (typically ∼10 mA cm −2 ). 2 In addition, because photoelectrochemical cells operate at lower current densities than electrolyzers, a larger amount of catalyst is needed and so cost becomes a key consideration. Finding OER catalysts that are both active and cost effective is a major challenge. Iridium and ruthenium OER catalysts are highly active across a wide pH range but are costly.3-9 By contrast, some lower cost non-noble metals also show activity for OER. Fe x Ni 1-x OOH catalysts exhibit low overpotentials for OER (∼300 mV for 10 mA cm −2 ) in base.10-13 Natural photosynthesis utilizes a manganese oxo cluster 14 and manganese oxides show some facility for OER, albeit at large overpotentials. [15][16][17][18] Some copper complexes also demonstrate electrocatalytic OER behavior at high pH. 19,20 As an alternative to noble metal catalysts, cobalt oxides are a promising potent...

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“…However, one should also note that the Cu foams can be damaged if the scanning speed is too slow. To compare with, commercial RuO 2 shows an overpotential of 400 mV at 50 mA cm −2 and Tafel slope of 111 mV dec −1 , also much larger than these of Cu/Cu oxides/Co(OH) 2 -8 h. According to the reaction pathway proposed by Krasil'shchikov (Doyle and Lyons, 2016), the Cu/Cu oxides/Co(OH) 2 -8 h have a Tafel slope of 58 mV dec −1 , indicating that the second electron transfer process, i.e., MO − → MO + e − , maybe the rate-determining step (RDS) of OER generation. To further understand the catalytic performance, electrochemical impedance spectroscopy was carried out (Figure 5c) and the fitted results of Nyquist plot are shown in Table S2, where Cu/Cu oxides/Co(OH) 2 -8 h has the smallest semicircle radius, indicating faster catalytic kinetics.…”

Section: Resultsmentioning

confidence: 93%

Co(OH)2 Nanosheets Supported on Laser Ablated Cu Foam: An Efficient Oxygen Evolution Reaction Electrocatalyst

Zhou

Yin

et al. 2020

Front. Chem.

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Highly efficient and low-cost non-noble metal based electrocatalysts for oxygen evolution reaction (OER) have attracted more and more attention in recent years. However, the current research has been focused on the construction of novel OER electrocatalysts themselves, little attention has been paid to the modification of the substrates. In this work, a different strategy is proposed via laser ablation to fabricate the Cu foams with rich micro/nano-structures as OER substrates. Later, the precipitation conversion method was utilized to grow cobalt hydroxide on the laser fabricated Cu foams. The as-produced Cu/Cu oxides/Co(OH) 2 electrocatalysts exhibit high OER activity in 1 M KOH, requiring an overpotential of only 259 mV at a current density of 50 mA cm −2 with excellent mild-term durability. The improved catalytic performance of the prepared samples can be attributed to the increased surface area, rich active sites, and the superhydrophilicity of the laser produced micro/nano-structures.

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The Oxygen Evolution Reaction: Mechanistic Concepts and Catalyst Design

Cited by 112 publications

References 184 publications

Accelerated Durability Test for High‐Surface‐Area Oxyhydroxide Nickel Supported on Raney Nickel as Catalyst for the Alkaline Oxygen Evolution Reaction

Accelerated Durability Test for High‐Surface‐Area Oxyhydroxide Nickel Supported on Raney Nickel as Catalyst for the Alkaline Oxygen Evolution Reaction

Electrocatalytic Water Oxidation by Single Site and Small Nuclearity Clusters of Cobalt

Co(OH)2 Nanosheets Supported on Laser Ablated Cu Foam: An Efficient Oxygen Evolution Reaction Electrocatalyst

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