Dye-sensitized Photoelectrode Research Articles

Highly Efficient Photoelectrochemical Alkene Epoxidation on a Dye-Sensitized Photoanode.

In photoelectrochemical (PEC) cells, selective oxidation of organic substrates coupled with hydrogen evolution represents a promising approach for value-added chemical production and solar energy conversion. In this study, we report on PEC epoxidation of alkenes at a ruthenium dye-sensitized photoanode in a CH3CN/H2O mixed solvent with LiBr as a mediator and water as the oxygen source. The dye-sensitized photoanode was found to exhibit significant advantages in the simultaneous improvement of charge separation and suppression of charge recombination. First, LiBr as a redox mediator plays a critical role in charge separation, leading to an excellent excited electron injection efficiency of 95% and a high dye regeneration efficiency of 87%. Second, the predominant charge recombination pathway on the dye-sensitized photoanode is efficiently blocked by the reaction between alkene and the in situ generated bromine oxidant. As a result, the current system achieved a remarkable photocurrent density of over 4 mA cm-2 with a record-high incident photo-to-current efficiency (IPCE) of 51% and extraordinary selectivity of up to 99% for the epoxidation of a wide range of alkenes. Meanwhile, nearly 100% Faradaic efficiency for hydrogen evolution was obtained. The performance shown here exceeds that obtained by metal oxide-based semiconductor photoanodes under comparable conditions, demonstrating the great potential of dye-sensitized photoelectrodes for organic synthesis owing to their diversity and tunability.

Embedding biocatalysts in a redox polymer enhances the performance of dye-sensitized photocathodes in bias-free photoelectrochemical water splitting

Dye-sensitized photoelectrodes consisting of photosensitizers and molecular catalysts with tunable structures and adjustable energy levels are attractive for low-cost and eco-friendly solar-assisted synthesis of energy rich products. Despite these advantages, dye-sensitized NiO photocathodes suffer from severe electron-hole recombination and facile molecule detachment, limiting photocurrent and stability in photoelectrochemical water-splitting devices. In this work, we develop an efficient and robust biohybrid dye-sensitized NiO photocathode, in which the intermolecular charge transfer is enhanced by a redox polymer. Owing to efficient assisted electron transfer from the dye to the catalyst, the biohybrid NiO photocathode showed a satisfactory photocurrent of 141±17 μA·cm−2 at neutral pH at 0 V versus reversible hydrogen electrode and a stable continuous output within 5 h. This photocathode is capable of driving overall water splitting in combination with a bismuth vanadate photoanode, showing distinguished solar-to-hydrogen efficiency among all reported water-splitting devices based on dye-sensitized photocathodes. These findings demonstrate the opportunity of building green biohybrid systems for artificial synthesis of solar fuels.

Effects of increasing ligand conjugation in Cu(I) photosensitizers on NiO semiconductor surfaces.

Dye-sensitized photoelectrodes may be used as heterogeneous components for fuel-forming reactions in photoelectrochemical cells. There has been increasing interest in developing Earth-abundant cheaper photosensitizers based on first-row transition metals. We describe here the synthesis, characterization, and study of the ground and excited state properties of three Cu(I) complexes bearing ligands with varying electron-accepting capacities and conjugation that may act as photosensitizers for wide bandgap semiconductors. Femtosecond transient absorption studies indicate that the nature of the final excited state is dictated by the extent of conjugation in the electron-accepting ligand, where shorter conjugation leads to the formation of a singly reduced ligand and longer conjugation leads to the formation of a ligand-centered final excited state. These complexes were surface anchored onto nanostructured NiO on conductive fluorine-doped tin oxide glass to fabricate photocathodes. It was found that even though the ligands with increasing conjugation have an effect on the formation of the final excited state in solution, all complexes exhibit similar photocurrents upon white light illumination, suggesting that charge transfer to NiO happens in advance of the formation of the final excited state.

(Invited) Dye-Sensitized Molecular Photoelectrodes for CO2 Reduction Using Water as a Reductant

Photocatalytic CO2 reduction using visible light and water as a reductant has been one of the important targets for solving global warming problem and shortage of energy and carbon resources. In this presentation, I talk about two projects, i.e., (1) supramolecular photocatalysts with both functions as photosensitizer and catalysts and (2) photocatalytic CO2 reduction coupled to water oxidation.(1) Highly efficient supramolecular photocatalysts for CO2 reduction1-3 Since CO2 is the most oxidized state of carbon, one-electron reduction of CO2 is an extraordinarily high endergonic reaction. From the viewpoints of low-energy light application, the multi-electron reduction of CO2 via chemical reactions promises to be a more valuable process. This is a main reason why both a photosensitizer and a catalyst are required to promote efficient photocatalytic CO2 reduction. We have developed so-called supramolecular photocatalyts that have both the photosensitizer and the catalyst units. This bonding in the supramolecular photocatalysts can accelerate electron transfer between the two units, which improves the performance of the photocatalytic system, especially on the surface of photofunctional solid materials as described below.(2) Molecular photoelectrodes for photocatalytic CO2 reduction with water as a reductant 1,4 The molecular photocatalytic systems have a weakness, i.e., weak oxidation power in the excited state. For practical application, water should be used as an electron donor. For overcoming this problem, we have developed a hybrid system consisting of the supramolecular photocatalyst and semiconductor electrodes. The hybrid photoelectrochemical cell consisting of this hybrid photocathode and n-type semiconductor photoanode induced visible-light-driven CO2 reduction with water as a reductant to generate CO and O2. References “Photocatalytic Systems for CO2 Reduction: Metal-Complex Photocatalysts and Their Hybrids with Photofunctional Solid Materials” Kumagai, H.; Tamaki, Y.; Ishitani, O., Acc. Chem. Res. 2022, 55, 978-990.“Mechanistic study of photocatalytic CO2 reduction using a Ru(II)-Re(I) supramolecular photocatalyst” Kamogawa, K.; Shimoda, Y.; Miyata, K.; Onda, K.; Yamazaki, Y.; Tamaki, Y.; Ishitani, O., Chem. Sci. 2021, 12, 9682-9693.“Supramolecular Photocatalysts for the Reduction of CO2” Tamaki, Y.; Ishitani, O., ACS Cat. 2017, 7, 3394-3409.“Supramolecular photocatalysts fixed on the inside of the polypyrrole layer in dye sensitized molecular photocathodes: application to photocatalytic CO2 reduction coupled with water oxidation. Kuttassery, F.; Kumagai, H.; Kamata, R.; Ebato, Y.; Higashi, M.; Suzuki, H.; Abe, R.; Ishitani, O., Chem. Sci. 2021, 12, 13216-13232. Figure 1

Studying Molecular Rearrangement of P1 Dye at a Passivating Alumina Surface Using Vibrational Sum-Frequency Generation Spectroscopy: Effect of Atomic-Level Roughness.

The effect of roughness and thickness of alumina layers, mimicking the passivation layer commonly used in dye-sensitized photoelectrodes, on the molecular adsorption of P1 dye, 4-(bi(4-(2,2-dicyano-vinyl)-thiophene-2-yl]-phenyl]-aminobenzoic acid) has been studied using surface-sensitive vibrational sum frequency generation(VSFG) spectroscopy. The VSFG spectra reveal the formation of poorly ordered dye layers on relatively rough surfaces where XPS measures a higher dye loading. Furthermore, these poorly ordered dye molecules are responsible for the generation of trapped electronic states as probed by successive photoluminescence (PL) measurements. Surface sensitive VSFG spectroscopy in combination with XPS and PL measurements provide complementary spectral information on ordering of the adsorbed dyes, their density on the surface and electronic states of the adsorbed monolayer which are prerequisite for improving our understanding of molecularly functionalized photoelectrodes and their further development.

Charge Recombination Deceleration by Lateral Transfer of Electrons in Dye-Sensitized NiO Photocathode.

Control of charge separation and recombination is critical for dye-sensitized solar cells and photoelectrochemical cells, and for p-type cells, the latter process limits their photovoltaic performance. We speculated that the lateral electron hopping between dyes on a p-type semiconductor surface can effectively separate electrons and holes in space and retard recombination. Thus, device designs where lateral electron hopping is promoted can lead to enhanced cell performance. Herein, we present an indirect proof by involving a second dye to monitor the effect of electron hopping after hole injection into the semiconductor. In mesoporous NiO films sensitized with peryleneimide (PMI) or naphthalene diimide (NDI) dyes, dye excitation led to ultrafast hole injection into NiO from either excited PMI* (τ < 200 fs) or NDI* (τ = 1.2 ps). In cosensitized films, surface electron transfer from PMI- to NDI was rapid (τ = 24 ps). Interestingly, the subsequent charge recombination (ps-μs) with NiO holes was much slower when NDI- was generated by electron transfer from PMI- than when NDI was excited directly. We therefore indicate that the charge recombination is slowed down after the charge hopping from the original PMI sites to the NDI sites. The experimental results supported our hypothesis and revealed important information on the charge carrier kinetics for the dye-sensitized NiO photoelectrode system.

Photoelectrochemical C-H Activation Through a Quinacridone Dye Enabling Proton-Coupled Electron Transfer.

Dye-sensitized photoanodes for C-H activation in organic substrates are assembled by vacuum sublimation of a commercially available quinacridone (QNC) dye in the form of nanosized rods onto fluorine-doped tin oxide (FTO), TiO2 , and SnO2 slides. The photoanodes display extended absorption in the visible range (450-600 nm) and ultrafast photoinduced electron injection (<1 ps, as revealed by transient absorption spectroscopy) of the QNC dye into the semiconductor. The proton-coupled electron-transfer reactivity of QNC is exploited for generating a nitrogen-based radical as its oxidized form, which is competent in C-H bond activation. The key reactivity parameter is the bond-dissociation free energy (BDFE) associated with the N⋅/N-H couple in QNC of 80.5±2.3 kcal mol-1 , which enables hydrogen atom abstraction from allylic or benzylic C-H moieties. A photoelectrochemical response is indeed observed for organic substrates characterized by C-H bonds with BDFE below the 80.5 kcal mol-1 threshold, such as γ-terpinene, xanthene, or dihydroanthracene. This work provides a rational, mechanistically oriented route to the design of dye-sensitized photoelectrodes for selective organic transformations.

Hydrogen Environmental Benefits Depend on the Way of Production: An Overview of the Main Processes Production and Challenges by 2050

Dye-Sensitized Solar Cells In article number 2100093 by Anish Babu Athanas and Swarnalatha KalaiyarHerein, a new coumarin-based ruthenium(II) dye with tunable photophysical and redox properties is designed and synthesized. The dyesensitized TiO2 photoelectrodes are tested as photocurrent generators for both water-splitting reactions and dye-sensitized solar cells. The photoelectrochemical devices furnish a water-splitting efficiency of 4.98% and power conversion efficiency of 4.16%.

Effects of PbS-NPs doping on the photovoltaic performance of natural dye-sensitized TiO2 photoelectrodes

In this work, we report the synthesis of TiO2 photoelectrodes sensitized with different natural organic dyes extracted (using methanol) from spinach, raspberry and passion fruit for their application in Dye-Sensitized Solar Cells (DSSC). The effects of Lead Sulfide (PbS) NanoParticles (NPs) doping on the sensitized TiO2 photoelectrodes photovoltaic performance were mainly studied. Good absorption in the visible range (400–700 [nm]) was observed for natural dyes extracted from spinach and raspberry, observing characteristic peaks associated with chlorophylls, β-carotenes and phycoerythrin pigments. On the other hand, natural dye synthesized from passion fruit showed a poor absorption in this range concerning the previous mentioned sources. Cells using spinach and raspberry based dyes generally showed good Fill Factors (FF) higher than 55%, observing depreciable or negative influence of the PbS doping. Open-Circuit voltages (Voc), Short-Circuit current densities (Jsc) and Power Conversion Efficiencies (PCE) in the range of 0.35–0.55 [V], 0.01–0.12 [mA/cm2] and 0.002–0.03 [%] were respectively estimated.

Structure and Energetics of Dye-Sensitized NiO Interfaces in Water from Ab Initio MD and Large-Scale GW Calculations

The energy-level alignment across solvated molecule/semiconductor interfaces is a crucial property for the correct functioning of dye-sensitized photoelectrodes, where, following the absorption of solar light, a cascade of interfacial hole/electron transfer processes has to efficiently take place. In light of the difficulty of performing X-ray photoelectron spectroscopy measurements at the molecule/solvent/metal-oxide interface, being able to accurately predict the level alignment by first-principles calculations on realistic structural models would represent an important step toward the optimization of the device. In this respect, dye/NiO surfaces, employed in p-type dye-sensitized solar cells, are undoubtedly challenging for ab initio methods and, also for this reason, much less investigated than the n-type dye/TiO2 counterpart. Here, we consider the C343-sensitized NiO surface in water and combine ab initio molecular dynamics (AIMD) simulations with GW (G0W0) calculations, performed along the MD trajectory to reliably describe the structure and energetics of the interface when explicit solvation and finite temperature effects are accounted for. We show that the differential perturbative correction on the NiO and molecule states obtained at the GW level is mandatory to recover the correct (physical) interfacial energetics, allowing hole transfer from the semiconductor valence band to the highest occupied molecular orbital (HOMO) of the dye. Moreover, the calculated average driving force quantitatively agrees with the experimental estimate.

(Invited) A Systems View of Solar Energy Conversion Efficiency in Dye-Sensitized Photoanodes

Dye-sensitized photoelectrodes are highly complex structures, involving large internal surface areas hosting tightly coupled interfacial and electrolyte chemistry. How the electrode architecture and the chemical reactions in them are connected to measured photovoltages and photocurrents for the simplest case of the dye-sensitized solar cell is examined using full-system multiscale reaction-diffusion simulations. These calculations provide a fully spatially resolved time history of the system, spanning nm-microns and ns-sec. In this talk, a basic but physically realistic computational framework will be introduced, and several aspects of system behaviors revealed by the simulations will be described. The influence of molecular diffusion on photocurrents, within the photoelectrode and across the system, will be described. Whether electron-electrolyte recombination within the photoanode is responsible for losses that limit efficiency is also examined. Recombination reactions are found to be significant, but are not performance-limiting because the reactions drive shifts in the electrolyte chemistry to support efficient dye cycling, and compensate for losses. This phenomenon can compensate for efficiency limitations due to diffusion between the photoanode and the cathode. The implications of these findings for strategies to improve the efficiency of this class of systems are discussed.

Dye Anchoring on CuCrO2 Surfaces for p-Type Dye-Sensitized Solar Cell Applications: An Ab Initio Study

The possibility of stably anchoring dye molecules on the exposed surface of a p-type semiconductor is crucial to have efficient dye-sensitized photoelectrodes. Here, we theoretically characterize the adsorption mechanism of carboxylic and phosphonic anchoring groups onto the (012) surface of stoichiometric and reduced CuCrO2 delafossite. Density functional theory is employed to accurately predict the preferred adsorption modes and their energies, both in the gas phase and solution (water and acetonitrile). On the stoichiometric (012) surface, we found a strong selectivity toward molecular monodentate binding modes at the highly active Cr-sites, stabilized by strong hydrogen bonds with the surface oxygens, for both anchoring groups; deprotonated bidentate bridging anchoring is only identified when the proton transferred to the surface is kept far away from the molecule during the structural relaxation process. On the other hand, the bidentate anchoring becomes the preferred adsorption mode when Cu+ vacancies are considered at the topmost layer of the surface slab. The identification of stable bidentate bridging anchoring modes on the CuCrO2 surface might have important implications for the device stability as well as for the efficiency of the interfacial hole injection and suggest it as an alternative material to NiO for p-type dye-sensitized solar cells.

Organic Semiconductors as Photoanodes for Solar-driven Photoelectrochemical Fuel Production.

The direct conversion of solar energy into chemical fuels, such as hydrogen, via photoelectrochemical (PEC) water splitting requires the efficient oxidation of water at a photoanode. While transition metal oxides have shown a significant success as photoanodes, their intrinsic limitations make them the bottleneck of PEC water splitting. Recently, initial research reports suggest that organic semiconductors (OSCs) could be possible alternative photoanode materials in both dye-sensitized and thin film photoelectrode configurations. Herein we review the progress to date, with a focus on the major issues faced by OSCs: stability and low photocurrent density in aqueous photoelectrochemical conditions. An outlook to the future of OSCs in photoelectrochemistry is also given.

Singlet Fission and Electron Injection from the Triplet Excited State in Diphenylisobenzofuran–Semiconductor Assemblies: Effects of Solvent Polarity and Driving Force

Singlet fission has emerged as a promising way to overcome the Shockley-Queisser limit in solar energy conversion devices, and a few studies have claimed proof-of-principle results using dye-sensitized photoelectrodes. However, a detailed understanding of what factors govern the fate of the excited state on mesoporous surfaces is still lacking. Here, we have studied how the excitation progresses into singlet fission, electron injection, or formation of molecular charge separated states in diphenylisobenzofuran derivatives with flexible carbon linkers attached to nanocrystalline mesoporous ZrO2, TiO2, and SnO2 thin films. We show that singlet fission occurs for the molecule attached to ZrO2 films when the assembly is immersed in nonpolar solvents, and that singlet fission is hampered by the formation of a molecular charge separated state in more polar solvents. On TiO2 surfaces, direct electron injection from the singlet excited state outcompetes the singlet fission. Instead, triplet formation occurs via charge recombination from the conduction band of TiO2 in nonpolar solvents. When the molecule is attached to SnO2 films, singlet fission partly outcompetes electron injection from the singlet excited state and the two processes occur in parallel. Subsequent to singlet fission on SnO2, triplet injection into the conduction band of SnO2 is observed. The results presented here provide a detailed picture of the singlet fission dynamics in molecules attached to mesoporous semiconductor surfaces, demonstrating that both the semiconductor substrate as well as the environment around the molecules have a large impact, which can be useful in the design of future devices.

Biohybrid electrodes for photoelectrochemical solar energy conversion

Photoelectrochemical (PEC) properties have been investigated in natural basil dye-sensitized hybrid photoelectrodes for solar energy conversion. Basil dye was used as a photosensitizer. A layer of basil dye was drop cast on the sputtered ZnO film and dried at various temperatures. The effect of heat treatment on the growth of the dye layer was studied in this work. The results suggest that heat treatment plays an important role in the performance of PECs. Biohybrid photoelectrodes were demonstrated for PEC and photoswitching applications. The hybrid structure showed an increase in device efficiency until 50 °C, which further decreases with increasing temperature. The energy conversion efficiency is 0.021% to 0.11%. The present studies will play an important role in designing and developing better performance PEC devices to generate clean electricity and solar fuels.

A Robust, Precious-Metal-Free Dye-Sensitized Photoanode for Water Oxidation: A Nanosecond-Long Excited-State Lifetime through a Prussian Blue Analogue.

Herein, we establish a simple synthetic strategy affording a heterogeneous, precious metal-free, dye-sensitized photoelectrode for water oxidation, which incorporates a Prussian blue (PB) structure for the sensitization of TiO2 and water oxidation catalysis. Our approach involves the use of a Fe(CN)5 bridging group not only as a cyanide precursor for the formation of a PB-type structure but also as an electron shuttle between an organic chromophore and the catalytic center. The resulting hetero-functional PB-modified TiO2 electrode demonstrates a low-cost and easy-to-construct photoanode, which exhibits favorable electron transfers with a remarkable excited state lifetime on the order of nanoseconds and an extended light absorption capacity of up to 500 nm. Our approach paves the way for a new family of precious metal-free robust dye-sensitized photoelectrodes for water oxidation, in which a variety of common organic chromophores can be employed in conjunction with CoFe PB structures.

Stable Molecular Photocathode for Solar-Driven CO2 Reduction in Aqueous Solutions

The performance of dye-sensitized photoelectrodes for artificial photosynthesis is typically limited by instability in aqueous solutions. We describe here a new molecular-based photocathode that integrates functional chromophore–catalyst assemblies for long-term solar-driven CO2 reduction in stabilized polymeric film structures. The assemblies include a silane surface-anchoring bridge, a ruthenium polypyridyl chromophore, and a rhenium-based molecular catalyst. They were prepared on nanocrystalline oxide films by silanization of the oxide and two-step electropolymerization of vinyl-derivatized precursors. The integrated photocathode was stable toward CO2 reduction for over 10 h with a Faradaic efficiency of ∼65%. The long-term stability arises from the silane surface-anchoring groups and the carbon–carbon bonds formed by electropolymerization between the three components. Transient absorption measurements on a nano-to-microsecond time scale show that the assemblies undergo rapid hole injection into the ox...

Dye sensitized photoelectrolysis cells.

To advance the progress of photoelectrolysis, various promising devices integrated with p- and n-type photocatalysts and dye sensitized photoelectrodes have been systematically studied. This review discusses, from theory to practice, an integration strategy for state-of-the-art dye sensitized solar cells (DSSCs) with potential p- and n-type photo-electrocatalysts or directly with dye sensitized photoanodes and cathodes for hydrogen and oxygen production through water splitting. Thorough insight into the theoretical approach which systematically drives the photoelectrolysis reaction directly or in a coupled mode, with diverse configurations of DSSCs and other photovoltaic (PV) cells, is crucial to understand the underlying fundamental concepts and elucidate trends in such reactions, and will serve as a guide to design new electrocatalysts and their integration with new PV devices, while simultaneously underlining major gaps that are required to address the challenges. Likewise, challenges, opportunities and frontiers in tandem and hybrid perovskite electrolysis processes are also discoursed in the present tutorial review. We illustrate our analysis by encompassing these integrated systems to photo-electrolysis, artificial photosynthesis such as CO2 conversion into value-added chemical reduction-products, where advancements in new catalysts and solution-processed inexpensive PV devices can certainly enrich the overall performance of the renewable production of solar fuels, including solar driven carbonaceous fuels.

Fabrication of anthocyanin-sensitized nanocrystalline titanium dioxide solar cells using supercritical carbon dioxide

This study describes an inexpensive, facile process for fabricating dye-sensitized solar cell (DSSC) using nanocrystalline titanium dioxide as the photoelectrode. The results of this work showed that the low surface tension characteristics of supercritical carbon dioxide could save dyeing time when used as a medium to dye nanocrystalline titanium dioxide photoelectrodes with anthocyanin. Metallographic microscopy observations of the dyed photoelectrodes revealed that the supercritical dyeing process produced a deeper color in the TiO2 photoelectrode than did dip dyeing. The absorption spectrum of the product showed that the supercritical dyeing time can be shortened to 1/10 that of the traditional dip process under total absorption equivalent. In addition, the I–V characteristics of the dyed photoelectrode exhibited a critical surplus of current and voltage, which was another indication of the superiority of the supercritical dyeing process. The supercritical dye-sensitized photoelectrodes showed improved values of Isc (1.2mA) and Voc (290mV).

All-vanadium photoelectrochemical storage cells using dye sensitized geometry-enhanced TiO2 nanobelts

Photoelectrochemical (PEC) devices, which use solar energy to drive charge transfer, have been considered as a low cost and effective approach to harvest energy from the sun. Dye sensitization designs are promising alternative to traditional semiconductor-based cells, as they can absorb a wide spectrum of light and provide free energy for PEC reactions. However, an intricate balance exists between a number of series charge-transfer processes related to the dye sensitizer, redox species, and photoelectrode. Here, we study a dye-sensitized photoelectrode using nanostructured anatase TiO2 nanobelts (TNBs) in the newly developed all-vanadium PEC storage cell (all-V PESC) to understand the performance dominating factor as well as to enhance photoexcitation and charge transfer, thus the solar energy storage efficiency. Preliminary results show enhanced photocurrent and reduced charge transfer resistance under AM1.5 illumination upon dye sensitization. Under visible light, however, large specific surface area of the photoelectrode seems to dominate the PEC performance.