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Journal ArticleDOI

Amorphous Cobalt–Iron Hydroxide Nanosheet Electrocatalyst for Efficient Electrochemical and Photo-Electrochemical Oxygen Evolution

01 Apr 2017-Advanced Functional Materials (John Wiley & Sons, Ltd)-Vol. 27, Iss: 14, pp 1603904
TL;DR: In this article, amorphous cobalt-iron hydroxide (CoFeH) nanosheets are synthesized by facile electrodeposition as an efficient catalyst for both electrochemical and PEC water oxidation.
Abstract: Finding efficient electrocatalysts for oxygen evolution reaction (OER) that can be effectively integrated with semiconductors is significantly challenging for solar-driven photo-electrochemical (PEC) water splitting. Herein, amorphous cobalt–iron hydroxide (CoFeH) nanosheets are synthesized by facile electrodeposition as an efficient catalyst for both electrochemical and PEC water oxidation. As a result of the high electrochemically active surface area and the amorphous nature, the optimized amorphous CoFeH nanosheets exhibit superior OER catalytic activity in alkaline environment with a small overpotential (280 mV) to achieve significant oxygen evolution (j = 10 mA cm−2) and a low Tafel slope (28 mV dec−1). Furthermore, CoFeH nanosheets are simply integrated with BiVO4 semiconductor to construct CoFeH/BiVO4 photoanodes that exhibit a significantly enhanced photocurrent density of 2.48 mA cm−2 (at 1.23 V vs reversible hydrogen electrode (RHE)) and a much lower onset potential of 0.23 V (vs RHE) for PEC-OER. Careful electrochemical and optical studies reveal that the improved OER kinetics and high-quality interface at the CoFeH/BiVO4 junction, as well as the excellent optical transparency of CoFeH nanosheets, contribute to the high PEC performance. This study establishes amorphous CoFeH nanosheets as a highly competitive candidate for electrochemical and PEC water oxidation and provides general guidelines for designing efficient PEC systems.
Citations
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Journal ArticleDOI
TL;DR: The excellent OER activity of sAu/NiFe LDH is ascribe to the charge redistribution of active Fe as well as its surrounding atoms causing by the neighboring sAU on NiFe oxyhydroxide stabilized by interfacial CO32- and H2O interfacing with LDH.
Abstract: A fundamental understanding of the origin of oxygen evolution reaction (OER) activity of transition-metal-based electrocatalysts, especially for single precious metal atoms supported on layered double hydroxides (LDHs), is highly required for the design of efficient electrocatalysts toward further energy conversion technologies. Here, we aim toward single-atom Au supported on NiFe LDH (sAu/NiFe LDH) to clarify the activity origin of LDHs system and a 6-fold OER activity enhancement by 0.4 wt % sAu decoration. Combining with theoretical calculations, the active behavior of NiFe LDH results from the in situ generated NiFe oxyhydroxide from LDH during the OER process. With the presence of sAu, sAu/NiFe LDH possesses an overpotential of 0.21 V in contrast to the calculated result (0.18 V). We ascribe the excellent OER activity of sAu/NiFe LDH to the charge redistribution of active Fe as well as its surrounding atoms causing by the neighboring sAu on NiFe oxyhydroxide stabilized by interfacial CO32– and H2O in...

724 citations

Journal ArticleDOI
Yanyong Wang1, Dafeng Yan1, Samir El Hankari1, Yuqin Zou1, Shuangyin Wang1 
TL;DR: Recent progress onLDHs and their derivatives as advanced electrocatalysts for water splitting is summarized, current strategies for their designing are proposed, and significant challenges and perspectives of LDHs are discussed.
Abstract: Layered double hydroxide (LDH)-based materials have attracted widespread attention in various applications due to their unique layered structure with high specific surface area and unique electron distribution, resulting in a good electrocatalytic performance. Moreover, the existence of multiple metal cations invests a flexible tunability in the host layers; the unique intercalation characteristics lead to flexible ion exchange and exfoliation. Thus, their electrocatalytic performance can be tuned by regulating the morphology, composition, intercalation ion, and exfoliation. However, the poor conductivity limits their electrocatalytic performance, which therefore has motivated researchers to combine them with conductive materials to improve their electrocatalytic performance. Another factor hampering their electrocatalytic activity is their large lateral size and the bulk thickness of LDHs. Introducing defects and tuning electronic structure in LDH-based materials are considered to be effective strategies to increase the number of active sites and enhance their intrinsic activity. Given the unique advantages of LDH-based materials, their derivatives have been also used as advanced electrocatalysts for water splitting. Here, recent progress on LDHs and their derivatives as advanced electrocatalysts for water splitting is summarized, current strategies for their designing are proposed, and significant challenges and perspectives of LDHs are discussed.

459 citations

Journal ArticleDOI
Ying Li1, Fumin Li1, Xin-Ying Meng1, Shu-Ni Li1, Jinghui Zeng1, Yu Chen1 
TL;DR: In this paper, an etch-free one-step approach to directly synthesize the ultrathin Co3O4 nanomeshes (Co-UNMs) by employing a CoCl2/K3Co(CN)6 cyanogel as the reaction precursor was presented.
Abstract: Ultrathin transition-metal-based nanomeshes can perfectly combine the advantages of two-dimensional (2D) ultrathin nanosheets and porous nanostructures, which have wide applications in energy storage and conversion. In this work, we present an etch-free one-step approach to directly synthesize the ultrathin Co3O4 nanomeshes (Co-UNMs) by employing a CoCl2/K3Co(CN)6 cyanogel as the reaction precursor. The 2D planar structural unit and solid properties of the cyanogel result in the preferential assembly of generated crystal nuclei at the solid–liquid interface (i.e., cyanogel–solution interface) in the 2D direction, which plays a key role in the formation of nanomeshes. The as-prepared Co-UNMs with 1.5 nm thickness and abundant pores have high surface area and numerous defect atoms, resulting in enhanced activity for the oxygen evolution reaction (OER) in alkaline media, such as a low overpotential of 307 mV at 10 mA cm–2, a small Tafel slope of 76 mV dec–1, and attractive durability in 1 M KOH electrolyte.

395 citations

References
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Journal ArticleDOI
TL;DR: The biggest challenge is whether or not the goals need to be met to fully utilize solar energy for the global energy demand can be met in a costeffective way on the terawatt scale.
Abstract: Energy harvested directly from sunlight offers a desirable approach toward fulfilling, with minimal environmental impact, the need for clean energy. Solar energy is a decentralized and inexhaustible natural resource, with the magnitude of the available solar power striking the earth’s surface at any one instant equal to 130 million 500 MW power plants.1 However, several important goals need to be met to fully utilize solar energy for the global energy demand. First, the means for solar energy conversion, storage, and distribution should be environmentally benign, i.e. protecting ecosystems instead of steadily weakening them. The next important goal is to provide a stable, constant energy flux. Due to the daily and seasonal variability in renewable energy sources such as sunlight, energy harvested from the sun needs to be efficiently converted into chemical fuel that can be stored, transported, and used upon demand. The biggest challenge is whether or not these goals can be met in a costeffective way on the terawatt scale.2

8,037 citations

Journal ArticleDOI
TL;DR: In this paper, the authors report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts for water oxidation.
Abstract: 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 ...

4,808 citations

Journal ArticleDOI
TL;DR: The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward a series of key clean energy conversion reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties.
Abstract: A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

3,918 citations

Journal ArticleDOI
09 Dec 2011-Science
TL;DR: 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 eg symmetry of surface transition metal cations in an oxide.
Abstract: 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.

3,876 citations

Journal ArticleDOI
22 Aug 2008-Science
TL;DR: A catalyst that forms upon the oxidative polarization of an inert indium tin oxide electrode in phosphate-buffered water containing cobalt (II) ions is reported that not only forms in situ from earth-abundant materials but also operates in neutral water under ambient conditions.
Abstract: The utilization of solar energy on a large scale requires its storage. In natural photosynthesis, energy from sunlight is used to rearrange the bonds of water to oxygen and hydrogen equivalents. The realization of artificial systems that perform "water splitting" requires catalysts that produce oxygen from water without the need for excessive driving potentials. Here we report such a catalyst that forms upon the oxidative polarization of an inert indium tin oxide electrode in phosphate-buffered water containing cobalt (II) ions. A variety of analytical techniques indicates the presence of phosphate in an approximate 1:2 ratio with cobalt in this material. The pH dependence of the catalytic activity also implicates the hydrogen phosphate ion as the proton acceptor in the oxygen-producing reaction. This catalyst not only forms in situ from earth-abundant materials but also operates in neutral water under ambient conditions.

3,695 citations