Assessing the Charge Carrier Dynamics at Hybrid Interfaces of Organic Photoanodes for Solar Fuels.

Organic semiconductors (OSCs) have emerged as promising active layers for photoanodes to drive photoelectrochemical (PEC) oxidation reactions. Interfacing an OSC with an inorganic electron transport layer (ETL) is key to enabling both high performance and stability. While spectroelectrochemical techniques have been established for the evaluation of inorganic interfaces, allowing rational optimization toward higher performances, a similar level of understanding for hybrid organic-inorganic interfaces remains elusive. To close this knowledge gap, we first perform a systematic parameter study (ETL thickness, potential dependency, and light intensity) on a state-of-the-art organic photoanode to establish factors determining the photoelectrochemical impedance spectroscopy (PEIS) response. Coupled with in situ UV-Vis characterizations, key charge transfer processes are clearly assigned to the PEIS features.

Composition-tunable transition metal dichalcogenide nanosheets via a scalable, solution-processable method.

The alloying of two-dimensional (2D) transition metal dichalcogenides (TMDs) is an established route to produce robust semiconductors with continuously tunable optoelectronic properties. However, typically reported methods for fabricating alloyed 2D TMD nanosheets are not suitable for the inexpensive, scalable production of large-area (m2) devices. Herein we describe a general method to afford large quantities of compositionally-tunable 2D TMD nanosheets using commercially available powders and liquid-phase exfoliation. Beginning with Mo(1-x)WxS2 nanosheets, we demonstrate tunable optoelectronic properties as a function of composition. We extend this method to produce Mo0.5W0.5Se2 MoSSe, WSSe, and quaternary Mo0.5W0.5SSe nanosheets. High-resolution scanning transmission electron microscopy (STEM) imaging confirms the atomic arrangement of the nanosheets, while an array of spectroscopic techniques is used to characterize the chemical and optoelectronic properties. This transversal method represents an important step towards upscaling tailored TMD nanosheets with a broad range of tunable optoelectronic properties for large-area devices.

Enabling Direct Photoelectrochemical H2 Production using Alternative Oxidation Reactions on WO3.

The efficient and inexpensive conversion of solar energy into chemical bonds, such as in H2 via the photoelectrochemical splitting of H2O, is a promising route to produce green industrial feedstocks and renewable fuels, which is a key goal of the NCCR Catalysis. However, the oxidation product of the water splitting reaction, O2, has little economic or industrial value. Thus, upgrading key chemical species using alternative oxidation reactions is an emerging trend. WO3 has been identified as a unique photoanode material for this purpose since it performs poorly in the oxygen evolution reaction in H2O. Herein we highlight a collaboration in the NCCR Catalysis that has gained insights at the atomic level of the WO3 surface with ab initio computational methods that help to explain its unique catalytic activity. These computational efforts give new context to experimental results employing WO3 photoanodes for the direct photoelectrochemical oxidation of biomass-derived 5-(hydroxymethyl) furfural. While yield for the desired product, 2,5-furandicarboxylic acid is low, insights into the reaction rate constants using kinetic modelling and an electrochemical technique called derivative voltammetry, give indications on how to improve the system.

Efficient Cu2O Photocathodes for Aqueous Photoelectrochemical CO2 Reduction to Formate and Syngas.

Photoelectrochemical carbon dioxide reduction (PEC-CO2R) represents a promising approach for producing renewable fuels and chemicals using solar energy. However, attaining even modest solar-to-fuel (STF) conversion efficiency often necessitates the use of costly semiconductors and noble-metal catalysts. Herein, we present a Cu2O/Ga2O3/TiO2 photocathode modified with Sn/SnOx catalysts through a simple photoelectrodeposition method. It achieves a remarkable half-cell STF efficiency of ∼0.31% for the CO2R in aqueous KHCO3 electrolyte, under AM 1.5 G illumination. The system enables efficient production of syngas (FE: ∼62%, CO/H2 ≈ 1:2) and formate (FE: ∼38%) with a consistent selectivity over a wide potential range, from +0.34 to -0.16 V vs the reversible hydrogen electrode. We ascribe the observed performance to the favorable optoelectronic characteristics of our Cu2O heterostructure and the efficient Sn/SnOx catalysts incorporated in the PEC-CO2R reactions. Through comprehensive experimental investigations, we elucidate the indispensable role of Cu2O buried p-n junctions in generating a high photovoltage (∼1 V) and enabling efficient bulk charge separation (up to ∼70% efficiency). Meanwhile, we discover that the deposited Sn/SnOx catalysts have critical dual effects on the overall performance of the PEC devices, serving as active CO2R catalysts as well as the semiconductor front contact. It could facilitate interfacial electron transfer between the catalysts and the semiconductor device for CO2R by establishing a barrier-free ohmic contact.

Edge-Sharing Octahedrally Coordinated NiFe Dual Active Sites on ZnFe2 O4 for Photoelectrochemical Water Oxidation.

The structural properties of octahedral sites (BOh ) in spinel oxides (AB2 O4 ) play vital roles in the electrochemical performance of oxygen-related reactions. However, the precise manipulation of AB2 O4 remains challenging due to the complexity of their crystal structure. Here, a simple and versatile molten-salt-mediated strategy is reported to introduce Ni2+ in Boh sites intentionally on the surface of zinc ferrite (ZnFe2 O4 , ZFO) to promote the active sites for photoelectrochemical (PEC) water splitting. The as-created photoanode (ZFO-MSNi) shows a remarkable cathodic shift of ≈ 450 mV (turn-on voltage of ≈ 0.6 VRHE ) as well as three times the 1-sun photocurrent density at 1.23 VRHE for PEC water oxidation in comparison with bare ZFO. A comprehensive structural characterization clearly reveals the local structure of the introduced Ni2+ in ZFO-MSNi. Fewer surface trapping states are observed while the precisely introduced Ni2+ and associated neighboring Fe(3-σ)+ (0<σ<1) sites unite in an edge-sharing octahedral configuration to function as NiFe dual active sites for PEC water oxidation. Moreover, open circuit potential measurements and rapid-scan voltammetry investigation give further insight into the enhanced PEC performance. Overall, this work displays a versatile strategy to regulate the surface active sites of photoelectrodes for increasing performance in PEC solar energy conversion systems.

Photogenerated charge transfer in Dion-Jacobson type layered perovskite based on naphthalene diimide.

Incorporating organic semiconducting spacer cations into layered lead halide perovskite structures provides a powerful approach to mitigate the typical strong dielectric and quantum confinement effects by inducing charge-transfer between the organic and inorganic layers. Herein we report the synthesis and characterization of thin films of novel DJ-phase organic-inorganic layered perovskite semiconductors using a naphthalene diimide (NDI) based divalent spacer cation, which is shown to accept photogenerated electrons from the inorganic layer. With alkyl chain lengths of 6 carbons, an NDI-based thin film exhibited electron mobility (based on space charge-limited current for quasi-layered 〈n〉 = 5 material) was found to be as high as 0.03 cm2 V-1 s-1 with no observable trap-filling region suggesting trap passivation by the NDI spacer cation.

Understanding and Mitigating the Degradation of Perovskite Solar Cells Based on a Nickel Oxide Hole Transport Material during Damp Heat Testing.

The development of stable materials, processable on a large area, is a prerequisite for perovskite industrialization. Beyond the perovskite absorber itself, this should also guide the development of all other layers in the solar cell. In this regard, the use of NiOx as a hole transport material (HTM) offers several advantages, as it can be deposited with high throughput on large areas and on flat or textured surfaces via sputtering, a well-established industrial method. However, NiOx may trigger the degradation of perovskite solar cells (PSCs) when exposed to environmental stressors. Already after 100 h of damp heat stressing, a strong fill factor (FF) loss appears in conjunction with a characteristic S-shaped J-V curve. By performing a wide range of analysis on cells and materials, completed by device simulation, the cause of the degradation is pinpointed and mitigation strategies are proposed. When NiOx is heated in an air-tight environment, its free charge carrier density drops, resulting in a band misalignment at the NiOx/perovskite interface and in the formation of a barrier impeding hole extraction. Adding an organic layer between the NiOx and the perovskite enables higher performances but not long-term thermal stability, for which reducing the NiOx thickness is necessary.

Photoelectrochemical CO2 Reduction at a Direct CuInGaS2/Electrolyte Junction.

Photoelectrochemical (PEC) CO2 reduction has received considerable attention given the inherent sustainability and simplicity of directly converting solar energy into carbon-based chemical fuels. However, complex photocathode architectures with protecting layers and cocatalysts are typically needed for selective and stable operation. We report herein that bare CuIn0.3Ga0.7S2 photocathodes can drive the PEC CO2 reduction with a benchmarking 1 Sun photocurrent density of over 2 mA/cm2 (at -2 V vs Fc+/Fc) and a product selectivity of up to 87% for CO (CO/all products) production while also displaying long-term stability for syngas production (over 44 h). Importantly, spectroelectrochemical analysis using PEC impedance spectroscopy (PEIS) and intensity-modulated photocurrent spectroscopy (IMPS) complements PEC data to reveal that tailoring the proton donor ability of the electrolyte is crucial for enhancing the performance, selectivity, and durability of the photocathode. When a moderate amount of protons is present, the density of photogenerated charges accumulated at the interface drops significantly, suggesting a faster charge transfer process. However, with a high concentration of proton donors, the H2 evolution reaction is preferred.

Transparent Porous Conductive Substrates for Gas-Phase Photoelectrochemical Hydrogen Production.

Gas diffusion electrodes are essential components of common fuel and electrolysis cells but are typically made from graphitic carbon or metallic materials, which do not allow light transmittance and thus limit the development of gas-phase based photoelectrochemical devices. Herein, the simple and scalable preparation of F-doped SnO2 (FTO) coated SiO2 interconnected fiber felt substrates is reported. Using 2-5 µm diameter fibers at a loading of 4 mg cm-2 , the resulting substrates have porosity of 90%, roughness factor of 15.8, and Young's Modulus of 0.2 GPa. A 100 nm conformal coating of FTO via atmospheric chemical vapor deposition gives sheet resistivity of 20 ± 3 Ω sq-1 and loss of incident light of 41% at illumination wavelength of 550 nm. The coating of various semiconductors on the substrates is established including Fe2 O3 (chemical bath deposition), CuSCN and Cu2 O (electrodeposition), and conjugated polymers (dip coating), and liquid-phase photoelectrochemical performance commensurate with flat FTO substrates is confirmed. Finally, gas phase H2 production is demonstrated with a polymer semiconductor photocathode membrane assembly at 1-Sun photocurrent density on the order of 1 mA cm-2 and Faradaic efficiency of 40%.

Light-Responsive Oligothiophenes Incorporating Photochromic Torsional Switches.

We present a quaterthiophene and sexithiophene that can reversibly change their effective π-conjugation length through photoexcitation. The reported compounds make use of light-responsive molecular actuators consisting of an azobenzene attached to a bithiophene unit by both direct and linker-assisted bonding. Upon exposure to 350 nm light, the azobenzene undergoes trans-to-cis isomerization, thus mechanically inducing the oligothiophene to assume a planar conformation (extended π-conjugation). Exposure to 254 nm wavelength promotes azobenzene cis-to-trans isomerization, forcing the thiophenic backbones to twist out of planarity (confined π-conjugation). Twisted conformations are also reached by cis-to-trans thermal relaxation at a rate that increases proportionally with the conjugation length of the oligothiophene moiety. The molecular conformations of quaterthiophene and sexithiophene were characterized by using steady-state UV-vis spectroscopy, X-ray crystallography and quantum-chemical modeling. Finally, we tested the proposed light-responsive oligothiophenes in field-effect transistors to probe the photo-induced tuning of their electronic properties.

Covalent Organic Framework Nanoplates Enable Solution-Processed Crystalline Nanofilms for Photoelectrochemical Hydrogen Evolution.

As covalent organic frameworks (COFs) are coming of age, the lack of effective approaches to achieve crystalline and centimeter-scale-homogeneous COF films remains a significant bottleneck toward advancing the application of COFs in optoelectronic devices. Here, we present the synthesis of colloidal COF nanoplates, with lateral sizes of ∼200 nm and average heights of 35 nm, and their utilization as photocathodes for solar hydrogen evolution. The resulting COF nanoplate colloid exhibits a unimodal particle-size distribution and an exceptional colloidal stability without showing agglomeration after storage for 10 months and enables smooth, homogeneous, and thickness-tunable COF nanofilms via spin coating. Photoelectrodes comprising COF nanofilms were fabricated for photoelectrochemical (PEC) solar-to-hydrogen conversion. By rationally designing multicomponent photoelectrode architectures including a polymer donor/COF heterojunction and a hole-transport layer, charge recombination in COFs is mitigated, resulting in a significantly increased photocurrent density and an extremely positive onset potential for PEC hydrogen evolution (over +1 V against the reversible hydrogen electrode), among the best of classical semiconductor-based photocathodes. This work thus paves the way toward fabricating solution-processed large-scale COF nanofilms and heterojunction architectures and their use in solar-energy-conversion devices.

High Performance Semiconducting Nanosheets via a Scalable Powder-Based Electrochemical Exfoliation Technique.

The liquid-phase exfoliation of semiconducting transition metal dichalcogenide (TMD) powders into 2D nanosheets represents a promising route toward the scalable production of ultrathin high-performance optoelectronic devices. However, the harsh conditions required negatively affect the semiconducting properties, leading to poor device performance. Herein we demonstrate a gentle exfoliation method employing standard bulk MoS2 powder (pressed into pellets) together with the electrochemical intercalation of a quaternary alkyl ammonium. The resulting nanosheets are produced in high yield (32%) and consist primarily of mono-, bi-, triatomic layers with large lateral dimensions (>1 µm), while retaining the semiconducting polymorph. Exceptional optoelectronic performance of nanosheet thin-films is observed, such as enhanced photoluminescence, charge carrier mobility (up to 0.2 cm2 V-1 s-1 in a multisheet device), and photon-to-current efficiency while maintaining high transparency (>80%). Specifically, as a photoanode for iodide oxidation, an internal quantum efficiency up to 90% (at +0.3 V vs Pt) is achieved (compared to only 12% for MoS2 nanosheets produced via ultrasonication). Further using a combination of fluorescence microscopy and high-resolution scanning transmission electron microscopy (STEM), we show that our gently exfoliated nanosheets possess a defect density (2.33 × 1013 cm-2) comparable to monolayer MoS2 prepared by vacuum-based techniques and at least three times less than ultrasonicated MoS2 nanoflakes. Finally, we expand this method toward other TMDs (WS2, WSe2) to demonstrate its versatility toward high-performance and fully scalable van der Waals heterojunction devices.

Bulk Heterojunction Organic Semiconductor Photoanodes: Tuning Energy Levels to Optimize Electron Injection.

The use of a bulk heterojunction of organic semiconductors to drive photoelectrochemical water splitting is an emerging trend; however, the optimum energy levels of the donor and acceptor have not been established for photoanode operation with respect to electrolyte pH. Herein, we prepare a set of donor polymers and non-fullerene acceptors with varying energy levels to probe the effect of photogenerated electron injection into a SnO2-based substrate under sacrificial photo-oxidation conditions. Photocurrent density (for sacrificial oxidation) up to 4.1 mA cm-2 was observed at 1.23 V vs reversible hydrogen electrode in optimized photoanodes. Moreover, we establish that a lower-lying donor polymer leads to improved performance due to both improved exciton separation and better charge collection. Similarly, lower-lying acceptors also give photoanodes with higher photocurrent density but with a later photocurrent onset potential and a narrower range of pH for good operation due to the Nernstian behavior of the SnO2, which leads to a smaller driving force for electron injection at high pH.

Identifying Reactive Sites and Surface Traps in Chalcopyrite Photocathodes.

Gathering information on the atomic nature of reactive sites and trap states is key to fine tuning catalysis and suppressing deleterious surface voltage losses in photoelectrochemical technologies. Here, spectroelectrochemical and computational methods were combined to investigate a model photocathode from the promising chalcopyrite family: CuIn0.3 Ga0.7 S2 . We found that voltage losses are linked to traps induced by surface Ga and In vacancies, whereas operando Raman spectroscopy revealed that catalysis occurred at Ga, In, and S sites. This study allows establishing a bridge between the chalcopyrite's performance and its surface's chemistry, where avoiding formation of Ga and In vacancies is crucial for achieving high activity.

Benzodithiophene-Based Spacers for Layered and Quasi-Layered Lead Halide Perovskite Solar Cells.

Incorporating extended pi-conjugated organic cations in layered lead halide perovskites is a recent trend promising to merge the fields of organic semiconductors and lead halide perovskites. Herein, we integrate benzodithiophene (BDT) into Ruddlesden-Popper (RP) layered and quasi-layered lead iodide thin films (with methylammonium, MA) of the form (BDT)2 MAn-1 Pbn I3n+1 . The importance of tuning the ligand chemical structure is shown as an alkyl chain length of at least six carbon atoms is required to form a photoactive RP (n=1) phase. With N=20 or 100, as prepared in the precursor solution following the formula (BDT)2 MAN-1 PbN I3N+1 , the performance and stability of devices surpassed those with phenylethylammonium (PEA). For N=100, the BDT cation gave a power conversion efficiency of up to 14.7 % vs. 13.7 % with PEA. Transient photocurrent, UV photoelectron spectroscopy, and Fourier transform infrared spectroscopy point to improved charge transport in the device active layer and additional electronic states close to the valence band, suggesting the formation of a Lewis adduct between the BDT and surface iodide vacancies.

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.

A Direct Z-Scheme for the Photocatalytic Hydrogen Production from a Water Ethanol Mixture on CoTiO3/TiO2 Heterostructures.

Photocatalytic H2 evolution from ethanol dehydrogenation is a convenient strategy to store solar energy in a highly valuable fuel with potential zero net CO2 balance. Herein, we report on the synthesis of CoTiO3/TiO2 composite catalysts with controlled amounts of highly distributed CoTiO3 nanodomains for photocatalytic ethanol dehydrogenation. We demonstrate these materials to provide outstanding hydrogen evolution rates under UV and visible illumination. The origin of this enhanced activity is extensively analyzed. In contrast to previous assumptions, UV-vis absorption spectra and ultraviolet photoelectron spectroscopy (UPS) prove CoTiO3/TiO2 heterostructures to have a type II band alignment, with the conduction band minimum of CoTiO3 below the H2/H+ energy level. Additional steady-state photoluminescence (PL) spectra, time-resolved PL spectra (TRPLS), and electrochemical characterization prove such heterostructures to result in enlarged lifetimes of the photogenerated charge carriers. These experimental evidence point toward a direct Z-scheme as the mechanism enabling the high photocatalytic activity of CoTiO3/TiO2 composites toward ethanol dehydrogenation. In addition, we probe small changes of temperature to strongly modify the photocatalytic activity of the materials tested, which could be used to further promote performance in a solar thermophotocatalytic reactor.

Crown Ether Modulation Enables over 23% Efficient Formamidinium-Based Perovskite Solar Cells.

The use of molecular modulators to reduce the defect density at the surface and grain boundaries of perovskite materials has been demonstrated to be an effective approach to enhance the photovoltaic performance and device stability of perovskite solar cells. Herein, we employ crown ethers to modulate perovskite films, affording passivation of undercoordinated surface defects. This interaction has been elucidated by solid-state nuclear magnetic resonance and density functional theory calculations. The crown ether hosts induce the formation of host-guest complexes on the surface of the perovskite films, which reduces the concentration of surface electronic defects and suppresses nonradiative recombination by 40%, while minimizing moisture permeation. As a result, we achieved substantially improved photovoltaic performance with power conversion efficiencies exceeding 23%, accompanied by enhanced stability under ambient and operational conditions. This work opens a new avenue to improve the performance and stability of perovskite-based optoelectronic devices through supramolecular chemistry.

Passivation Mechanism Exploiting Surface Dipoles Affords High-Performance Perovskite Solar Cells.

The employment of 2D perovskites is a promising approach to tackling the stability and voltage issues inherent in perovskite solar cells. It remains unclear, however, whether other perovskites with different dimensionalities have the same effect on efficiency and stability. Here, we report the use of quasi-3D azetidinium lead iodide (AzPbI3) as a secondary layer on top of the primary 3D perovskite film that results in significant improvements in the photovoltaic parameters. Remarkably, the utilization of AzPbI3 leads to a new passivation mechanism due to the presence of surface dipoles resulting in a power conversion efficiency (PCE) of 22.4%. The open-circuit voltage obtained is as high as 1.18 V, which is among the highest reported to date for single junction perovskite solar cells, corresponding to a voltage deficit of 0.37 V for a band gap of 1.55 eV.

Generalized Synthesis to Produce Transparent Thin Films of Ternary Metal Oxide Photoelectrodes.

Developing facile approaches to prepare non-light-scattering ternary oxide thin film photoelectrodes is an important goal for solar water splitting tandem cells. Herein, a novel synthesis route is reported that employs ethylenediaminetetraacetic acid (EDTA) to enable compatible water solubility of diverse metal cations, which affords transparent films by solution processing. By using BiVO4 as a model material, a remarkable improvement in transparency is demonstrated, quantified by the direct transmittance at 600 nm of >80 % versus the <10 % observed with state-of-the-art electrodeposited thin films while maintaining reasonable solar-driven oxidation photocurrents (1.75 mA cm-2 in the presence of a sulfite hole scavenger). Furthermore, it is demonstrated that the synthesis technique can be applied in a general fashion towards the synthesis of diverse n- and p-type metal oxide materials, such as ZnFe2 O4 and CuFeO2 .