Enhancing Electrochemical Efficiency of Hydroxyl Radical Formation on Diamond Electrodes by Functionalization with Hydrophobic Monolayers.

Electrochemical formation of high-energy species such as hydroxyl radicals in aqueous media is inefficient because oxidation of H2O to form O2 is a more thermodynamically favorable reaction. Boron-doped diamond (BDD) is widely used as an electrode material for generating •OH radicals because it has a very large kinetic overpotential for O2 production, thus increasing electrochemical efficiency for •OH production. Yet, the underlying mechanisms of O2 and •OH production at diamond electrodes are not well understood. We demonstrate that boron-doped diamond surfaces functionalized with hydrophobic, polyfluorinated molecular ligands (PF-BDD) have significantly higher electrochemical efficiency for •OH production compared with hydrogen-terminated (H-BDD), oxidized (O-BDD), or poly(ethylene ether)-functionalized (E-BDD) boron-doped diamond samples. Our measurements show that •OH production is nearly independent of surface functionalization and pH (pH = 7.4 vs 9.2), indicating that •OH is produced by oxidation of H2O in an outer-sphere electron-transfer process. In contrast, the total electrochemical current, which primarily produces O2, differs strongly between samples with different surface functionalizations, indicating an inner-sphere electron-transfer process. X-ray photoelectron spectroscopy measurements show that although both H-BDD and PF-BDD electrodes are oxidized over time, PF-BDD showed longer stability (≈24 h of use) than H-BDD. This work demonstrates that increasing surface hydrophobicity using perfluorinated ligands selectively inhibits inner-sphere oxidation to O2 and therefore provides a pathway to increased efficiency for formation of •OH via an outer-sphere process. The use of hydrophobic electrodes may be a general approach to increasing selectivity toward outer-sphere electron-transfer processes in aqueous media.

Proton-Induced Trap States, Injection and Recombination Dynamics in Water-Splitting Dye-Sensitized Photoelectrochemical Cells.

Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) utilize a sensitized metal oxide and a water oxidation catalyst in order to generate hydrogen and oxygen from water. Although the Faradaic efficiency of water splitting is close to unity, the recombination of photogenerated electrons with oxidized dye molecules causes the quantum efficiency of these devices to be low. It is therefore important to understand recombination mechanisms in order to develop strategies to minimize them. In this paper, we discuss the role of proton intercalation in the formation of recombination centers. Proton intercalation forms nonmobile surface trap states that persist on time scales that are orders of magnitude longer than the electron lifetime in TiO2. As a result of electron trapping, recombination with surface-bound oxidized dye molecules occurs. We report a method for effectively removing the surface trap states by mildly heating the electrodes under vacuum, which appears to primarily improve the injection kinetics without affecting bulk trapping dynamics, further stressing the importance of proton control in WS-DSPECs.

Understanding the Effect of Monomeric Iridium(III/IV) Aquo Complexes on the Photoelectrochemistry of IrO(x)·nH2O-Catalyzed Water-Splitting Systems.

Soluble, monomeric Ir(III/IV) complexes strongly affect the photoelectrochemical performance of IrO(x)·nH2O-catalyzed photoanodes for the oxygen evolution reaction (OER). The synthesis of IrO(x)·nH2O colloids by alkaline hydrolysis of Ir(III) or Ir(IV) salts proceeds through monomeric intermediates that were characterized using electrochemical and spectroscopic methods and modeled in TDDFT calculations. In air-saturated solutions, the monomers exist in a mixture of Ir(III) and Ir(IV) oxidation states, where the most likely formulations at pH 13 are [Ir(OH)5(H2O)](2-) and [Ir(OH)6](2-), respectively. These monomeric anions strongly adsorb onto IrO(x)·nH2O colloids but can be removed by precipitation of the colloids with isopropanol. The monomeric anions strongly adsorb onto TiO2, and they promote the adsorption of ligand-free IrO(x)·nH2O colloids onto mesoporous titania photoanodes. However, the reversible adsorption/desorption of electroactive monomers effectively short-circuits the photoanode redox cycle and thus dramatically degrades the photoelectrochemical performance of the cell. The growth of a dense TiO2 barrier layer prevents access of soluble monomeric anions to the interface between the oxide semiconductor and the electrode back contact (a fluorinated tin oxide transparent conductor) and leads to improved photoanode performance. Purified IrO(x)·nH2O colloids, which contain no adsorbed monomer, give improved performance at the same electrodes. These results explain earlier observations that IrO(x)·nH2O catalysts can dramatically degrade the performance of metal oxide photoanodes for the OER reaction.

Effects of electron trapping and protonation on the efficiency of water-splitting dye-sensitized solar cells.

Water-splitting dye-sensitized photoelectrochemical (WS-DSPECs) cells employ molecular sensitizers to absorb light and transport holes across the TiO2 surface to colloidal or molecular water oxidation catalysts. As hole diffusion occurs along the surface, electrons are transported through the mesoporous TiO2 film. In this paper we report the effects of electron trapping and protonation in the TiO2 film on the dynamics of electron and hole transport in WS-DSPECs. When the sensitizer bis(2,2'-bipyridine)(4,4'-diphosphonato-2,2'-bipyridine)ruthenium(II) is adsorbed from aqueous acid instead of from ethanol, there is more rapid hole transfer between photo-oxidized sensitizer molecules that are adsorbed from strong acid. However, the photocurrent and open-circuit photovoltage are dramatically lower with sensitizers adsorbed from acid because intercalated protons charge-compensate electron traps in the TiO2 film. Kinetic modeling of the photocurrent shows that electron trapping is responsible for the rapid electrode polarization that is observed in all WS-DSPECs. Electrochemical impedance spectroscopy suggests that proton intercalation also plays an important role in the slow degradation of WS-DSPECs, which generate protons at the anode as water is oxidized to oxygen.