Chong-Yong Lee

Wiring of Photosystem II to Hydrogenase for Photoelectrochemical Water Splitting

In natural photosynthesis, light is used for the production of chemical energy carriers to fuel biological activity. The re-engineering of natural photosynthetic pathways can provide inspiration for sustainable fuel production and insights for understanding the process itself. Here, we employ a semiartificial approach to study photobiological water splitting via a pathway unavailable to nature: the direct coupling of the water oxidation enzyme, photosystem II, to the H2 evolving enzyme, hydrogenase. Essential to this approach is the integration of the isolated enzymes into the artificial circuit of a photoelectrochemical cell. We therefore developed a tailor-made hierarchically structured indium-tin oxide electrode that gives rise to the excellent integration of both photosystem II and hydrogenase for performing the anodic and cathodic half-reactions, respectively. When connected together with the aid of an applied bias, the semiartificial cell demonstrated quantitative electron flow from photosystem II to the hydrogenase with the production of H2 and O2 being in the expected two-to-one ratio and a light-to-hydrogen conversion efficiency of 5.4% under low-intensity red-light irradiation. We thereby demonstrate efficient light-driven water splitting using a pathway inaccessible to biology and report on a widely applicable in vitro platform for the controlled coupling of enzymatic redox processes to meaningfully study photocatalytic reactions.

Graphene-supported [{Ru4O4(OH)2(H2O)4}-(gamma-SiW10O36)2]10- for highly efficient electrocatalytic

The electrochemistry of the Ru-containing polyoxometalate (POM) water oxidation molecular catalyst, Rb8K2[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10− (Rb8K2-1), has been studied by cyclic and rotating disk electrode voltammetric methods in aqueous media under acidic and neutral pH conditions using bare glassy carbon (GC) and graphene modified GC electrodes. High concentrations of supporting electrolyte are needed in neutral pH conditions to overcome the electrical double layer effect associated with the highly negatively charged 1. Complex 1 can be confined within the highly porous wet graphene film to form a stable modified electrode, which shows excellent catalytic activity and high stability toward the water oxidation reaction under neutral pH conditions, particularly in the presence of 1.0 M Ca(NO3)2. The catalytic activity of the graphene supported 1electrode is nearly two orders of magnitude higher than that reported with a polymer coated multiwalled carbon nanotube supported 1electrode when both are employed at a moderate overpotential of 0.35 V.

Anodic Nanotubular/porous Hematite Photoanode for Solar Water Splitting: Substantial Effect of Iron Substrate Purity

Anodization of iron substrates is one of the most simple and effective ways to fabricate nanotubular (and porous) structures that could be directly used as a photoanode for solar water splitting. Up to now, all studies in this field focused on achieving a better geometry of the hematite nanostructures for a higher efficiency. The present study, however, highlights that the purity of the iron substrate used for any anodic-hematite-formation approach is extremely important in view of the water-splitting performance. Herein, anodic self-organized oxide morphologies (nanotubular and nanoporous) are grown on different iron substrates under a range of anodization conditions, including elevated temperatures and anodization supported by ultrasonication. Substrate purity has not only a significant effect on oxide-layer growth rate and tube morphology, but also gives rise to a ninefold increase in the photoelectrochemical water-splitting performance (0.250 vs. 0.028 mA cm−2 at 1.40 V vs. reversible hydrogen electrode under AM 1.5 100 mW cm−2 illumination) for 99.99 % versus 99.5 % purity iron substrates of similar oxide geometry. Elemental analysis and model alloys show that particularly manganese impurities have a strong detrimental effect on the water-splitting performance.

Solar water splitting: preserving the beneficial small feature size in porous α-Fe2O3 photoelectrodes during annealing

We prepared mesoporous α-Fe2O3/FTO electrodes by a simple anodic precipitation and annealing method. The classic problem is that when annealed in air at >500 °C, the individual particle size increases from ≈20 nm to 40–60 nm. This grain growth is highly detrimental for the water splitting efficiency. In the present work we show that grain coarsening can efficiently be prevented by a two-step annealing method in Ar, leading to photocurrent densities for such electrodes (obtained in 1 M KOH solution) of up to 2.6 mA cm−2 at 1.6 V vs. RHE under AM 1.5 100 mW cm−2 illumination, which is significantly higher than 1.5 mA cm−2 for conventionally annealed samples.

Enhancing the Water Splitting Efficiency of Sn‐Doped Hematite Nanoflakes by Flame Annealing

The effect of flame annealing on the water-splitting properties of Sn decorated hematite (α-Fe2O3) nanoflakes has been investigated. It is shown that flame annealing can yield a considerable enhancement in the maximum photocurrent under AM 1.5 (100 mW cm(-2)) conditions compared to classic furnace annealing treatments. Optimizing the annealing time (10 s at 1000 °C) leads to a photocurrent of 1.1 mA cm(-2) at 1.23 V (vs. RHE) with a maximum value 1.6 mA cm(-2) at 1.6 V (vs. RHE) in 1 M KOH. The improvement in photocurrent can be attributed to the fast direct heating that maintains the nanoscale morphology, leads to optimized Sn decoration, and minimizes detrimental substrate effects.

Photoelectrochemical H2 Evolution with a Hydrogenase Immobilized on a TiO2‐Protected Silicon Electrode

Abstract The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron‐transfer processes at highly active and well‐defined catalytic sites on a light‐harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO2‐coated p‐Si photocathode for the photo‐reduction of protons to H2. The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO2 layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p‐Si|TiO2|hydrogenase photocathode displays visible‐light driven production of H2 at an energy‐storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p‐type semiconductor photocathode through the engineering of the enzyme–materials interface.

Evaluation of levels of defect sites present in highly ordered pyrolytic graphite electrodes using capacitive and faradaic current components derived simultaneously from large-amplitude Fourier transformed ac voltammetric experiments.

The level of edge plane defect sites present in highly ordered pyrolytic graphite (HOPG) electrodes has been evaluated via analysis of dc, ac fundamental, and higher-order ac harmonics available from a single large-amplitude Fourier transformed (FT) ac voltammetric experiment. Deliberate introduction of a low level of edge plane defect was achieved by polishing, with a higher level being introduced via electrochemical pretreatment. Kinetics regimes associated with fast electron transfer on the edge plane defect sites and slow electron transfer on the basal plane surface are resolved under ac conditions when using the surface-sensitive [Fe(CN)(6)](3-/4-) redox probe. However, because of their insensitivity to slow electron transfer, higher-order ac faradaic harmonics almost exclusively detect only the much faster processes that emanate from edge plane defect sites. Thus, detection of fourth- and higher-order ac Faradaic harmonic components that are devoid of background capacitive current is possible at freshly cleaved HOPG in the region near the reversible potential for the [Fe(CN)(6)](3-/4-) process. Under these circumstances, dc cyclic voltammograms exhibit only reduction and oxidation peaks separated by more than 1 V. The fundamental ac harmonic provides detailed information on the capacitive current, which increases with the level of edge plane defect sites. Apparent charge transfer rate constants also can be derived from peak-to-peak separations obtained from the dc aperiodic component. Estimates of the percentage of edge plane defect sites based on ac higher harmonics, capacitance, and dc aperiodic component that are available from a single experiment have been compared. The edge plane defect levels deduced from capacitance (fundamental harmonic ac component) and higher harmonic Faradaic currents are considered to be more reliable than estimations based on apparent rate constants derived from the dc aperiodic component or conventional dc cyclic voltammogram.

Revelation of Multiple Underlying RuO2 Redox Processes Associated with Pseudocapacitance and Electrocatalysis

Advances in basic knowledge relevant to the pseudocapacitive and electrocatalytic properties of RuO(2) materials require a detailed understanding of the redox chemistry that occurs at the electrode interface. Although several redox processes have been identified via dc cyclic voltammograms derived from surface-confined RuO(2) materials, mechanistic details remain limited because the faradaic signals of interest are heavily masked by the background current. Here, it is shown that the underlying electron transfer reactions associated with the VI to II oxidation states of surface-confined RuO(2) materials in acidic medium are far more accessible in the background current free fourth and higher harmonic components available via large-amplitude Fourier transformed ac voltammetry. Enhanced resolution and sensitivity to both electron transfer and protonation processes and discrimination against solvent and background capacitance are achieved so that the Ru(V) to Ru(VI) process can be studied for the first time. Thus, kinetic and thermodynamic information relevant to each ruthenium redox level is readily deduced. The relative rate of electron transfer and the impact of protonation associated with Ru(VI) to Ru(II) redox processes are found to depend on the nature of the RuO(2) materials (extent of crystallinity and hydration) and concentration of sulfuric acid electrolyte. In the electrocatalytic oxidation of glucose in alkaline medium, access to the underlying electron transfer processes allows ready detection of the redox couple associated with the catalysis. Thus, application of an advanced ac electroanalytical technique is shown to provide the methodology for enhancing our understanding of the charge transfer processes of RuO(2), relevant to pseudocapacitance and electrocatalysis.

A comparison of the higher order harmonic components derived from large-amplitude Fourier transformed ac voltammetry of myoglobin and heme in DDAB films at a pyrolytic graphite electrode.

A debate as to whether heme remains bound or is released in myoglobin molecules incorporated into a didodecyldimethylammonium bromide (DDAB) film adhered to a pyrolytic graphite electrode has prompted a comparison of their electrochemistry by the highly sensitive large-amplitude Fourier transformed ac voltammetric method. The accessibility of third, fourth, and higher harmonic components that are devoid of background current and the enhanced resolution relative to that available in dc voltammetry have allowed a detailed comparison of the Fe(III)/Fe(II) and Fe(II)/Fe(I) redox processes of myoglobin and heme molecules to be undertaken as a function of buffer composition and pH and in the presence and absence of NaBr in the buffer and/or film. Under most conditions examined, only very subtle differences, in the Fe(III)/Fe(II) process were found, implying this process cannot be used to indicate the intactness or otherwise of myoglobin in myoglobin-DDAB films. In contrast, higher order ac harmonics obtained from myoglobin-DDAB and heme-DDAB films reveal pH dependent differences with respect to the Fe(II)/Fe(I) couple. Analysis of the ac harmonics, and with the hypothesis that the Fe(II)/Fe(I) process reflects the myoglobin state, suggests that the majority of the iron heme is released from myoglobin-DDAB (pH 5.0, no NaBr) films in contact with pH 5.0 (0.1 M sodium acetate) buffer solution devoid of or containing NaBr. However, myoglobin films prepared with pH 5.0 buffer containing NaBr shows significant difference in the higher harmonic shapes and midpoint potentials in the Fe(II)/Fe(I) process relative to the case when heme molecules are used, although as noted in other studies, a significant fraction of the Mb is rendered electroinactive in the presence of NaBr. The voltammetric responses of myoglobin and heme-DDAB (pH 5.0) films in contact with pH 7.0 (0.1 M) phosphate buffer solution also exhibit significant differences in the Fe(II)/Fe(I) redox couple in the higher harmonics in contrast to a report [de Groot, M.T.; Merkx, M.; Koper, M. T. M. J. Am. Chem. Soc. 2005, 127, 16224] that claimed identical midpoint potentials apply to both films under conditions of dc cyclic voltammetry. The FT-ac voltammetric data therefore suggest that a substantial fraction of myoglobin in myoglobin-DDAB (pH 5.0) films in contact with pH 7.0 phosphate buffer solution remains intact. No evidence of a catalytic effect that enhanced the released of heme from myoglobin was found at the pyrolytic graphite electrode surface. In summary, higher harmonic ac voltammetric data indicate that the Fe(II)/Fe(I) process but not the Fe(III)/Fe(II) reflects the state of myoglobin in DDAB films. On this basis, films prepared at pH 5.0 should include NaBr, or else films should be prepared at neutral pH to achieve films with myoglobin remains in its intact near native state when a myoglobin-DDAB film is confined to a graphite electrode surface. Otherwise, the release of heme in myoglobin molecules incorporated into a DDAB film is likely to be a dominant reaction pathway.

Mediator Enhanced Water Oxidation Using Rb4[RuII(bpy)3]5[{RuIII4O4(OH)2(H2O)4}(γ-SiW10O36)2] Film Modified Electrodes

The water insoluble complex Rb4[Ru(II)(bpy)3]5[{Ru(III)4O4(OH)2(H2O)4}(γ-SiW10O36)2], ([Ru(II)bpy]5[Ru(III)4POM]), was synthesized from Rb8K2[{Ru(IV)4O4(OH)2(H2O)4}(γ-SiW10O36)2] and used for electrocatalytic water oxidation under both thin- and thick-film electrode conditions. Results demonstrate that the [Ru(II)bpy]5[Ru(III)4POM] modified electrode enables efficient water oxidation to be achieved at neutral pH using thin-film conditions, with [Ru(bpy)3](3+)([Ru(III)bpy]) acting as the electron transfer mediator and [Ru(V)4POM] as the species releasing O2. The rotating ring disc electrode (RRDE) method was used to quantitatively determine the turnover frequency (TOF) of the catalyst, and a value of 0.35 s(-1) was obtained at a low overpotential of 0.49 V (1.10 V vs Ag/AgCl) at pH 7.0. The postulated mechanism for the mediator enhanced catalytic water process in a pH 7 buffer containing 0.1 M LiClO4 as an additional electrolyte includes the following reactions (ion transfer for maintaining charge neutrality is omitted for simplicity): [Ru(II)bpy]5[Ru(III)4POM] → [Ru(III)bpy]5[Ru(V)4POM] + 13 e(-) and [Ru(III)bpy]5[Ru(V)4POM] + 2H2O → [Ru(III)bpy]5[Ru(IV)4POM] + O2 + 4H(+). The voltammetry of related water insoluble [Ru(II)bpy]2[S2M18O62] (M = W and Mo) and [Fe(II)Phen]x[Ru(III)4POM] materials has also been studied, and the lack of electrocatalytic water oxidation in these cases supports the hypothesis that [Ru(III)bpy] is the electron transfer mediator and [Ru(V)4POM] is the species responsible for oxygen evolution.