Quentin Daniel

Nickel–vanadium monolayer double hydroxide for efficient electrochemical water oxidation

Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel–vanadium-layered double hydroxide that shows a current density of 27 mA cm−2 (57 mA cm−2 after ohmic-drop correction) at an overpotential of 350 mV for water oxidation. Such performance is comparable to those of the best-performing nickel–iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel–vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting.

Organic Dye-Sensitized Tandem Photoelectrochemical Cell for Light Driven Total Water Splitting

Light driven water splitting was achieved by a tandem dye-sensitized photoelectrochemical cell with two photoactive electrodes. The photoanode is constituted by an organic dye L0 as photosensitizer and a molecular complex Ru1 as water oxidation catalyst on meso-porous TiO2, while the photocathode is constructed with an organic dye P1 as photoabsorber and a molecular complex Co1 as hydrogen generation catalyst on nanostructured NiO. By combining the photocathode and the photoanode, this tandem DS-PEC cell can split water by visible light under neutral pH conditions without applying any bias.

Hollow Iron-Vanadium Composite Spheres: A Highly Efficient Iron-Based Water Oxidation Electrocatalyst without the Need for Nickel or Cobalt

Noble-metal-free bimetal-based electrocatalysts have shown high efficiency for water oxidation. Ni and/or Co in these electrocatalysts are essential to provide a conductive, high-surface area and a chemically stable host. However, the necessity of Ni or Co limits the scope of low-cost electrocatalysts. Herein, we report a hierarchical hollow FeV composite, which is Ni- and Co-free and highly efficient for electrocatalytic water oxidation with low overpotential 390 mV (10 mA cm-2 catalytic current density), low Tafel slope of 36.7 mV dec-1 , and a considerable durability. This work provides a novel and efficient catalyst, and greatly expands the scope of low-cost Fe-based electrocatalysts for water splitting without need of Ni or Co.

Immobilization of a Molecular Ruthenium Catalyst on Hematite Nanorod Arrays for Water Oxidation with Stable Photocurrent

Photoelectrochemical (PEC) cells for light-driven water splitting are prepared using hematite nanorod arrays on conductive glass as the photoanode. These devices improve the photocurrent of the hematite-based photoanode for water splitting, owing to fewer surface traps and decreased electron recombination resulting from the one-dimensional structure. By employing a molecular ruthenium co-catalyst, which contains a strong 2,6-pyridine-dicarboxylic acid anchoring group at the hematite photoanode, the photocurrent of the PEC cell is enhanced with high stability for over 10 000 s in a 1 m KOH solution. This approach can pave a route for combining one-dimensional nanomaterials and molecular catalysts to split water with high efficiency and stability.

Bis(1,1-bis(2-pyridyl)ethane)copper(I/II) as an efficient redox couple for liquid dye-sensitized solar cells

A new redox couple, [Cu(bpye)2]+/2+, has been synthesized, and applied in dye-sensitized solar cells (DSSCs). Overall efficiencies of 9.0% at 1 sun and 9.9% at 0.5 sun were obtained, which are considerably higher than those obtained for cells containing the reference redox couple, [Co(bpy)3]2+/3+. These results represent a record for copper-based complex redox systems in liquid DSSCs. Fast dye regeneration, sluggish recombination loss processes, faster electron self-exchange reactions and suitable redox potentials are the main reasons for the observed increase in efficiency. In particular, the main disadvantage of cobalt complex-based redox couples, charge-transport problems, appears to be resolved by a change to copper complex redox couples. The results make copper complex-based redox couples very promising for further development of highly efficient DSSCs.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm−2. The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.Splitting water into high-energy fuel represents a renewable way to generate energy, yet the sluggish oxidation kinetics drives up technological costs. Here, the authors prepare tri-metallic core-shell electrodes using nickel, iron, and copper metals to accelerate electricity-driven water splitting.

Molecular engineering for efficient and selective iron porphyrin catalysts for electrochemical reduction of CO2 to CO

Iron porphyrins Fe-pE, Fe-mE, and Fe-oE were synthesized and their electrochemical behavior for CO2 reduction to CO has been investigated. The controlled potential electrolysis of Fe-mE gave exclusive 65% Faradaic efficiency (FE) whereas Fe-oE achieved quasi-quantitative 98% FE (2% H2) for CO production.

Gas-templating of hierarchically structured Ni–Co–P for efficient electrocatalytic hydrogen evolution

One of the grand challenges for developing scalable and sustainable hydrogen producing systems is the lack of efficient and robust earth-abundant element based catalysts for the hydrogen evolution reaction (HER). Herein, a hierarchically structured Ni–Co–P film was fabricated via a gas templating electro-deposition method. This film exhibits remarkably high catalytic performance for the HER in 1 M KOH with respective current densities of −10 and −500 mA cm−2 at the overpotentials of −30 and −185 mV with a Tafel slope of 41 mV dec−1. A controlled potential electrolysis experiment demonstrates that the as-prepared Ni–Co–P film is an efficient and robust catalyst with a faradaic efficiency close to 100%. Systematic characterization suggests that the unique hierarchical structure and the mutual participation of nano-sized Ni/Co based components are responsible for the high HER catalytic activity.

Electrocatalytic Water Oxidation Promoted by 3 D Nanoarchitectured Turbostratic δ-MnOx on Carbon Nanotubes

The development of manganese-based water oxidation electrocatalysts is desirable for the production of solar fuels, as manganese is earth-abundant, inexpensive, non-toxic, and has been employed by the Photosystem II in nature for a billion years. Herein, we directly constructed a 3 D nanoarchitectured turbostratic δ-MnOx on carbon nanotube-modified nickel foam (MnOx /CNT/NF) by electrodeposition and a subsequent annealing process. The MnOx /CNT/NF electrode gives a benchmark catalytic current density (10 mA cm-2 ) at an overpotential (η) of 270 mV under alkaline conditions. A steady current density of 19 mA cm-2 is obtained during electrolysis at 1.53 V for 1.0 h. To the best of our knowledge, this work represents the most efficient manganese-oxide-based water oxidation electrode and demonstrates that manganese oxides, as a structural and functional model of oxygen-evolving complex (OEC) in Photosystem II, can also become comparable to those of most Ni- and Co-based catalysts.

Identifying MnVII-oxo Species during Electrochemical Water Oxidation by Manganese Oxide

Summary Identifying surface active intermediate species is essential to reveal the catalytic mechanism of water oxidation by metal-oxides-based catalysts and to develop more efficient catalysts for oxygen-oxygen bond formation. Here we report, through electrochemical methods and ex situ infrared spectroscopy, the identification of a MnVII = O intermediate during catalytic water oxidation by a c-disordered δ-MnOx with an onset-potential-dependent reduction peak at 0.93 V and an infrared peak at 912 cm−1. This intermediate is proved to be highly reactive and much more oxidative than permanganate ion. Therefore, we propose a new catalytic mechanism for water oxidation catalyzed by Mn oxides, with involvement of the MnVII = O intermediate in a resting state and the MnIV−O−MnVII = O as a real active species for oxygen-oxygen bond formation.