Immobilization of a molecular cobalt electrocatalyst by hydrophobic interaction with a hematite photoanode for highly stable oxygen evolution

Joya, Khurram Saleem; Morlanés, Natalia; Maloney, Edward J.; Rodionov, Valentin O.; Takanabe, Kazuhiro

doi:10.1039/c5cc05681k

Cited by 46 publications

(36 citation statements)

References 43 publications

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“…[1][2] Thus, the light-driven water transformation into cheap energy carriers is possible through cost effective electrocatalytic and photoelectrochemical (PEC) systems. [3][4] Electrochemical and photoelectrochemical water splitting systems to make hydrogen and oxygen with high efficiency and at a moderate overpotential are vital and energetically very challenging. Besides having an efficient light harvesting and charge separation scheme for a PEC based device, development of robust and active water oxidation catalysts (WOCs) is a principle bottleneck in this pursuit.…”

Section: Introductionmentioning

confidence: 99%

Efficient electrochemical water oxidation in neutral and near-neutral systems with a nanoscale silver-oxide catalyst

et al. 2016

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Section: Introductionmentioning

confidence: 99%

Efficient electrochemical water oxidation in neutral and near-neutral systems with a nanoscale silver-oxide catalyst

et al. 2016

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confidence: 99%

“…1,2 In this quest, catalytic water oxidation is regarded as a primary process, and many inorganic materials and transition metal-oxides are considered good candidates for this conversion. 2,3 Metal-oxide catalysts can be electrodeposited on conducting substrates from carbonate, phosphate, or borate electrolytes in the presence of metal ions. 4−6 To eliminate the possibility for interaction of metal ions with the cathodic sites during electrolysis, membranes or separators are usually employed that make the system more complex and introduce resistance and diffusion limitations in the electrochemical process.…”

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confidence: 99%

Controlled Surface-Assembly of Nanoscale Leaf-Type Cu-Oxide Electrocatalyst for High Activity Water Oxidation

Joya

Groot

2016

ACS Catal.

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ABSTRACT:The controlled surface deposition of a robust and highperformance nanostructured copper-oxide (CuO x -NLs) electrocatalyst for water oxidation is presented. The material exhibits a characteristic leaf-type morphology and self-assembles on a copper substrate by straightforward constant-current anodization. The oxygen onset occurs at about 1.55 V versus RHE (η = 320 mV), which is 400−500 mV less than for amorphous Cu-oxide films. A Tafel slope of 44 mV dec −1 is obtained, which is the lowest observed relative to other copper-based materials. Long-term catalytic performance and stability tests of the electrocatalytic CuO x -NLs sample show a stable current density of >17 mA cm −2 for oxygen evolution, which was sustained for many hours.KEYWORDS: electrocatalyst, water oxidation, copper-oxide, nanoscale leaves, oxygen evolution T here are continuous efforts to develop a strategy to produce renewable and cleaner energy carriers from abundant solar radiation and water.1,2 In this quest, catalytic water oxidation is regarded as a primary process, and many inorganic materials and transition metal-oxides are considered good candidates for this conversion.2,3 Metal-oxide catalysts can be electrodeposited on conducting substrates from carbonate, phosphate, or borate electrolytes in the presence of metal ions. 4−6 To eliminate the possibility for interaction of metal ions with the cathodic sites during electrolysis, membranes or separators are usually employed that make the system more complex and introduce resistance and diffusion limitations in the electrochemical process.7 New preparation methods are required that are easily implemented, and catalytic materials are desired to perform in metal ion free systems for sustained electrochemical operation. 8,9 In addition, control over the catalyst morphology and surface structure is important to induce a high surface area and phase purity, facilitating both charge transfer and mass transport during catalysis reaction. 9,10Stable and efficient metal-oxide derived electrocatalysts can develop in a carbonate/bicarbonate system under mild conditions. 5,11 HCO 3 − /CO 3 2− is suggested to facilitate proton management and prevent the degradation of these catalytic materials under anodic conditions. 12−14 We observed that anodization of a copper electrode via repetitive potentialsweeps or at constant-potential in a carbonate buffer induces the formation of very small copper-oxide particulate materials (CuO x -NPs) having oxygen onset at ∼1.59 V versus RHE (η ≥ 360 mV). In addition, we found that nanoscale leaf-shaped Cuoxide (CuO x -NLs) surface structures ( Figure S1) are formed during controlled anodization of a chemically etched copper substrate at a constant current density of 4.0 mA cm −2 in a carbonate system. The CuO x -NLs exhibit a remarkably low overpotential for water oxidation (η = 320 mV) relative to other Cu-based electrocatalysts 13−15 and many inorganic materials. 16,17 Scanning electron microscopy (SEM) imaging shows a leaves-type copper-oxide matrix (Figur...

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“…In a follow up experiment, a hydrophobic perfluorinated Co‐phthalocyanine (CoFPc) catalyst ( 43 , Figure 12) was bound on a Fe 2 O 3 surface by a simple drop‐casting method. The resulting assembly exhibited an impressive PEC durability for OER without a photocurrent decrease even after 1 h of irradiation 61. In a comparison with Fe 2 O 3 , the resulting hybrid photoanode showed a ≈200 mV cathodic shift in onset potential, and a current density of 1.0 mA cm −2 at 1.23 V versus RHE, even outperforming Co‐Pi/Fe 2 O 3 by 200%.…”

Section: Benchmarks Of Hybrid System Assemblies For Photoelectrochemimentioning

confidence: 97%

Hybrid Photoelectrochemical Water Splitting Systems: From Interface Design to System Assembly

Niu

Wang

et al. 2019

Advanced Energy Materials

164

113

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Photoelectrochemical (PEC) water splitting has attracted increasing attention due to its potential to mitigate energy and environmental issues. Hybrid PEC systems containing semiconductor photosensitizers and molecular catalysts are reported to be highly active and stable for water splitting with great potential for facilitating clean fuels production. In this review, following a showcasing of the fundamental details of hybrid PEC systems for water splitting, semiconductor/molecular catalyst interface designs are highlighted, with a focus on interfacial physicochemical interactions and binding, and interfacial energetics and dynamics for efficient charge transfer. Recent advances in hybrid system assemblies for PEC water splitting are also briefly introduced. Finally, future challenges and directions in the field of hybrid PEC water splitting for solar energy conversion are reviewed. The current review provides state‐of‐the‐art strategies for optimized interface design for creating highly active and stable PEC water splitting assemblies.

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Immobilization of a molecular cobalt electrocatalyst by hydrophobic interaction with a hematite photoanode for highly stable oxygen evolution

Abstract: A highly stable performance was achieved during photoelectrochemical oxygen evolution using a molecular cobalt catalyst utilizing its hydrophobic nature.

Cited by 46 publications

References 43 publications

Efficient electrochemical water oxidation in neutral and near-neutral systems with a nanoscale silver-oxide catalyst

Efficient electrochemical water oxidation in neutral and near-neutral systems with a nanoscale silver-oxide catalyst

Controlled Surface-Assembly of Nanoscale Leaf-Type Cu-Oxide Electrocatalyst for High Activity Water Oxidation

Hybrid Photoelectrochemical Water Splitting Systems: From Interface Design to System Assembly

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