Photoelectrochemical Water Splitting Cells Research Articles

“There is plenty of energy at the bottom”: A spectral conversion approach for upconversion-powered water-splitting PEC cell

An avant-garde step towards the use of the long infrared tail of the incident solar radiation with untapped and crucial applications in photocatalysis and energy harvesting schemes is presented: “there is plenty of energy at the bottom”. In detail, a pure photonic approach to enhance titanium dioxide (TiO2) photocatalytic activity is proposed, by using rare-earth doped luminescent glassy materials, capable of performing NIR-to-UV-VIS spectral conversion (up-conversion). Therefore we report infrared-driven boosting of green hydrogen production in a photo-electrochemical water-splitting cell using TiO2 electrodes, revisiting the original design of Fujishima and Honda fifty years later. This proof-of-concept comprises infrared-induced hydrogen and oxygen evolution via water-splitting and determines univocally the role of a solely photonic effect to split water. Thus, the conversion of the incident NIR radiation, before its interaction with the photocatalyst, emerges as a significant contribution to the state-of-the-art for an effective harvest of the near-infrared portions of sunlight.

Operation of Amorphous TiO2-Protected Photocathodes Described with the Maxwell Equivalent Circuit.

The use of amorphous TiO2 (a-TiO2), deposited by atomic layer deposition, is a common strategy to protect semiconductors from degradation when used in water-splitting photoelectrochemical (PEC) cells. Electrochemical impedance spectroscopy (EIS) is a suitable technique to study these PEC cells because it is capable of deconvoluting multiple processes occurring during operation, therefore providing information about mechanisms leading to the overall device performance. When biased under hydrogen evolution conditions, EIS shows that two simultaneous processes occur in a-TiO2-protected photocathodes, which introduces an ambiguity in choosing the correct equivalent circuit to describe the operating device. In this report, a model p-Si|a-TiO2|Pt photocathode system is used to show that the Maxwell circuit best describes the operating mechanism, as opposed to the more commonly used Voight and nested circuits. This indicates that, under hydrogen evolution conditions, both faradaic and nonfaradaic processes are occurring. Whereas the faradaic process corresponds to the hydrogen evolution reaction itself, the nonfaradaic process is traced to the p-Si|a-TiO2 interface.

Synthesis, characterization and application of quinoxaline-based organic dyes as anodic sensitizers in photoelectrochemical cells

Three new D-A-π-A organic dyes (1a-c) containing a 2,3-diphenylquinoxaline core as the main chromophore were designed to act as sensitizers for the TiO2-based photoanode of dye-sensitized photoelectrochemical cells (DS-PEC) for water splitting. The dyes structures featured a cyanoacrylic acid group as the terminal acceptor/anchoring moiety and three different donor groups of moderate strength, namely mono- and dialkoxy-substituted benzenes, which were introduced to modulate the energies of the respective HOMO levels and enable the electron transfer from a Ru-based molecular water oxidation catalyst (WOC). Dyes 1a-c were synthesized following a C–H activation strategy and fully characterized. In addition, the previously known catalyst Ru(bda)(PyP)2 (bda = 2,2′-bipyridine-6,6′-dicarboxylate; PyP = pyridin-4-methyl phosphonic acid) was also prepared by modification of a reported procedure. The dynamics of charge transfer processes involving the dyes adsorbed on nanocrystalline TiO2 films were investigated by means of transient absorption spectroscopy. Photo-electrochemical experiments carried out on photoanodes functionalized with 1a-c and Ru(bda)(PyP)2 in 0.1 M aq. Na2SO4 electrolyte showed the production of photocurrents up to ca. 0.15 mA cm−2 at + 0.5 V vs. NHE, and highlighted how modifications of the TiO2 staining procedure can lead to significant differences in cell performances.

Unbiased Photoelectrochemical H2O2 Coupled to H2 Production via Dual Sb2S3‐Based Photoelectrodes with Ultralow Onset Potential

AbstractThe productions of hydrogen peroxide (H2O2) and hydrogen (H2) in a photoelectrochemical (PEC) water splitting cell suffer from an onset potential that limits solar conversion efficiencies. Moreover, the formation of H2O2 through two‐electron PEC water oxidation reaction competes with four‐electron oxidation evolution reaction. Herein, we developed the surface selenium doped antimony trisulfide photoelectrode with the integrated ruthenium cocatalyst (Ru/Sb2(S,Se)3) to achieve the low onset potential and high Faraday efficiency (FE) for selective H2O2 production. The photoanode exhibits an outstanding average FE of 85 % in the potential range of 0.4–1.6 VRHE and the H2O2 yield of 1.01 μmol cm−2 min−1 at 1.6 VRHE, especially at low potentials of 0.1–0.55 VRHE with 80.4 % FE. Impressively, an unassisted PEC system that employs light and electrolyte was constructed to simultaneously produce H2O2 and H2 production on both the Ru/Sb2(S,Se)3 photoanode and the Pt/TiO2/Sb2S3 photocathode. The integrated system enables the average PEC H2O2 production rate of 0.637 μmol cm−2 min−1 without applying any addition bias. To our knowledge, this is the first demonstration that Sb2S3‐based photoelectrodes exhibit H2O2/H2 two‐side production with a strict key factor of the system, which represents its powerful platform to achieve high efficiency and productivity and the feasibility to facilitate value‐added products in neutral conditions.

Unbiased Photoelectrochemical H2O2 Coupled to H2 Production via Dual Sb2S3-Based Photoelectrodes with Ultralow Onset Potential.

The productions of hydrogen peroxide (H2O2) and hydrogen (H2) in a photoelectrochemical (PEC) water splitting cell suffer from an onset potential that limits solar conversion efficiencies. Moreover, the formation of H2O2 through two-electron PEC water oxidation reaction competes with four-electron oxidation evolution reaction. Herein, we developed the surface selenium doped antimony trisulfide photoelectrode with the integrated ruthenium cocatalyst (Ru/Sb2(S,Se)3) to achieve the low onset potential and high Faraday efficiency (FE) for selective H2O2 production. The photoanode exhibits an outstanding average FE of 85 % in the potential range of 0.4-1.6 VRHE and the H2O2 yield of 1.01 μmol cm-2 min-1 at 1.6 VRHE, especially at low potentials of 0.1-0.55 VRHE with 80.4 % FE. Impressively, an unassisted PEC system that employs light and electrolyte was constructed to simultaneously produce H2O2 and H2 production on both the Ru/Sb2(S,Se)3 photoanode and the Pt/TiO2/Sb2S3 photocathode. The integrated system enables the average PEC H2O2 production rate of 0.637 μmol cm-2 min-1 without applying any addition bias. To our knowledge, this is the first demonstration that Sb2S3-based photoelectrodes exhibit H2O2/H2 two-side production with a strict key factor of the system, which represents its powerful platform to achieve high efficiency and productivity and the feasibility to facilitate value-added products in neutral conditions.

Plasmon-enhanced sub-Debye-length nanogap photoelectrochemical cells for field-assisted electrolyte-free water splitting

This work studies pure water splitting (i.e., no additional electrolyte) using plasmonic sub-Debye-length nanogap photoelectrochemical cells (NPECs). With 60 nm Au gratings covered by 4 nm amorphous TiO2 under 638 nm normal incident illumination, we demonstrate up to 66 × higher photocurrent at 1.5 V than that of Au-gratings-only NPECs. In addition, we are able to efficiently drive pure water splitting at voltages as low as 1.3 V, which is very close to the theoretical thermodynamic potential threshold of 1.23 V. Our electromagnetic finite difference time domain (FDTD) simulation results (Lumerical Inc.) show a 240 × increase in the electric field intensity near the TiO2 layer compared to the incident electric field. We attribute our observations to 1) Hot spots generated by surface plasmonic resonance (SPR) on Au gratings, which greatly increase the number of electron-hole pairs; 2) The 60 nm gap distance between electrodes, which is smaller than the Debye length of pure water (∼220 nm) resulting in a much higher electric field by eliminating the shield effect and by coupling two half-reactions of water splitting together; and 3) The 4 nm amorphous TiO2, which improves hot carriers separation. Our NPEC is a promising device for efficient hydrogen production enabling the utilization of visible light.

Laser-Printed Photoanode: Femtosecond Laser-Induced Crystalline Phase Transformation of WO3 Nanorods for Space-Efficient and Flexible Thin-Film Solar Water-Splitting Cells.

Despite its potential for clean hydrogen harvesting, photoelectrochemical (PEC) water-splitting cells face challenges in commercialization, particularly related its harvesting performance and productivity at an industrial scale. Herein, a facile fabrication method of flexible thin-film photoanode for PEC water-splitting to overcome these limitations, based on laser processing technologies, is proposed. Laser-induced graphene, a carbon structure produced through direct laser writing carbonization (DLWC), plays a dual role: a flexible and stable current collector and a substrate for the hydrothermal synthesis of tungsten trioxide (WO3) nanorods (NRs). To facilitate water-splitting, a femtosecond-pulsed laser (fs laser) is focused on the WO3 NRs, converting their crystalline phase from pristine orthorhombic to monoclinic structure without thermal damage. With NiFe layered double hydroxide (LDH) catalyst, the flexible thin-film photoanode exhibits good PEC performance (1.46mAcm-2 at 1.23 VRHE) and retains ≈90% of its performance after 3000 bending cycles. With its excellent mechanical properties, the flexible photoanode can be operated in various shapes with different curvatures, enabling space-efficient PEC water-splitting by loading larger photoanode within a given space. This study is expected to contribute to the advancement of large-scale solar water-splitting cells, introducing a new approach to enhance H2/O2 production and expand its application range.

Non-innocent partners: bias distribution between photoanodes and cathodes in photoelectrochemical overall water-splitting cells.

Non-innocent partners: bias distribution between photoanodes and cathodes in photoelectrochemical overall water-splitting cells.

Bias distribution and regulation in photoelectrochemical overall water-splitting cells.

The water oxidation half-reaction at anodes is always considered the rate-limiting step of overall water splitting (OWS), but the actual bias distribution between photoanodes and cathodes of photoelectrochemical (PEC) OWS cells has not been investigated systematically. In this work, we find that, for PEC cells consisting of photoanodes (nickel-modified n-Si [Ni/n-Si] and α-Fe2O3) with low photovoltage (Vph < 1V), a large portion of applied bias is exerted on the Pt cathode for satisfying the hydrogen evolution thermodynamics, showing a thermodynamics-controlled characteristic. In contrast, for photoanodes (TiO2 and BiVO4) with Vph > 1V, the bias required for cathode activation can be significantly reduced, exhibiting a kinetics-controlled characteristic. Further investigations show that the bias distribution can be regulated by tuning the electrolyte pH and using alternative half-reaction couplings. Accordingly, a volcano plot is presented for the rational design of the overall reactions and unbiased PEC cells. Motivated by this, an unbiased PEC cell consisting of a simple Ni/n-Si photoanode and Pt cathode is assembled, delivering a photocurrent density of 5.3±0.2mA cm-2.

Nonstoichiometric In–S group yielding efficient carrier transfer pathway in In2S3 photoanode for solar water oxidation

AbstractThe construction of high‐efficiency photoanodes is essential for developing outstanding photoelectrochemical (PEC) water splitting cells. Furthermore, insufficient carrier transport capabilities and sluggish surface water oxidation kinetics limit its application. Using a solvothermal annealing strategy, we prepared a nonstoichiometric In–S (NS) group on the surface of an In2S3 photoanode in situ and unexpectedly formed a type II transfer path of carrier, thereby reducing the interfacial recombination and promoting the bulk separation. First‐principles calculations and comprehensive characterizations demonstrated NS group as an excellent oxygen evolution cocatalyst (OEC) that effectively facilitated carrier transport, lowered the surface overpotential, increased the surface active site, and accelerated the surface oxygen evolution reaction kinetics by precisely altering the rate‐determining steps of * to *OH and *O to *OOH. These synergistic effects remarkably enhanced the PEC performance, with a high photocurrent density of 5.02 mA cm−2 at 1.23 V versus reversible hydrogen electrode and a negative shift in the onset potential by 310 mV. This work provides a new strategy for the in situ preparation of high‐efficiency OECs and provides ideas for constructing excellent carrier transfer and transport channels.

Comparing Charge Dynamics in Organo-Inorganic Halide Perovskite: Solid-State versus Solid-Liquid Junctions

In this study, we explore the dynamics of a perovskite-electrolyte photoelectrochemical cell, pivotal for advancing electrolyte-gated field effect transistors, water-splitting photoelectrochemical and photocatalytic cells, supercapacitors, and CO2 capture and reduction technologies. The instability of hybrid perovskite materials in aqueous electrolytes presents a significant challenge, yet recent breakthroughs have been achieved in stabilizing organo-inorganic halide perovskite films. This stabilization is facilitated by employing liquid electrolytes, specifically those formed by dissolving tetrabutylammoniumperchlorate in dichloromethane. A critical aspect of this research is the comparative analysis of charge and ion kinetics at the perovskite/liquid electrolyte interface versus the perovskite/solid charge transport layer interface. Employing Intensity Modulated Photocurrent Spectroscopy (IMPS), Open-Circuit Voltage Decay (OCVD), and Capacitance-Frequency (C-F) methods, the study scrutinizes charge dynamics in both perovskite/electrolyte and perovskite/solid interfaces. Furthermore, the investigation extends to contrasting the properties of solid–liquid and solid-state junctions, focusing on mobile ions, electric field impacts, and electron-hole transport. The research also examines variations in recombination resistance and ionic double layer charging in perovskite-based devices, aiming to elucidate the operational mechanisms and kinetic complexities at the hybrid perovskite/electrolyte interface.

Proton exchange membrane photoelectrochemical cell for water splitting under vapor feeding

This review provides an overview of recent advancements in vapor-fed photoelectrochemical (PEC) systems specifically designed for utilizing water vapor as a hydrogen resource. The PEC system under water vapor feeding utilizes a proton exchange membrane as a solid polymer electrolyte. Additionally, it utilizes gas-diffusion photoelectrodes composed of a fibrous conductive substrate with macroporous structures. Herein, the porous photoelectrodes are composed of n-type oxides for oxygen evolution reactions and used with a Pt electrocatalyst cathode for hydrogen evolution reactions. The topics covered include the conceptual framework of vapor-fed PEC hydrogen production, strategic design of gas-phase PEC reaction interfaces, and development of porous photoanodes such as titanium dioxide (TiO2), strontium titanate (SrTiO3), tungsten trioxide (WO3), and bismuth vanadate (BiVO4). A significant enhancement in the PEC efficiency was achieved through the application of a thin proton-conducting ionomer film on these porous photoelectrodes for surface functionalization. The rational design of proton exchange membrane-based PEC cells will play a pivotal role in realizing renewable-energy-driven hydrogen production from atmospheric humidity in the air.

High-throughput parallel testing of ten photoelectrochemical cells for water splitting: case study on the effects of temperature in hematite photoanodes.

High-throughput testing of photoelectrochemical cells and materials under well-defined operating conditions can accelerate the discovery of new semiconducting materials, the characterization of the phenomena occurring at the semiconductor-electrolyte interface, or the understanding of the coupled multi-physics transport phenomena of a complete working cell. However, there have been few high-throughput systems capable of dealing with complete cells and applying variations in real-life operating conditions, like temperature or irradiance. Understanding the effects of the variations of these real-life operating conditions on the performance of photoelectrode materials requires reliable and reproducible measurements. In this work, we report on a setup that simultaneously tests ten individual, identical photoelectrochemical cells whilst controlling temperature. The effects of temperature from 26 to 65 °C were studied in tin-doped hematite photoanodes for water splitting - as a reference case - through cyclic voltammetry and electrochemical impedance spectroscopy. The increase of surface-state-mediated charge recombination with temperature mainly penalized the energy conversion efficiency due to the reduction of the photovoltage produced. For parallel measurements in the ten individual cells, standard deviations from 20 to 60 mV for the onset potentials and less than 0.2 mA cm-2 for saturation current densities quantified the reproducibility of the results.

Dye-sensitized photoelectrochemical cells constructed using metal-free perylene diimide-based oxygen production polymers and calixarene dyes

Calixarene dyes and perylene diimide-based oxygen production polymers are attached to TiO2 thin films to create, for the first time, a dye-sensitized photoelectrochemical cell for pure light-driven water splitting.

Supramolecular interaction of a molecular catalyst with a polymeric carbon nitride photoanode enhances photoelectrochemical activity and stability at neutral pH.

Polymeric carbon nitride (CN) emerged as an alternative, metal-free photoanode material for water-splitting photoelectrochemical cells (PECs). However, the performance of CN photoanodes is limited due to the slow charge separation and water oxidation kinetics due to poor interaction with water oxidation catalysts (WOCs). Moreover, operation under benign, neutral pH conditions is rarely reported. Here, we design a porous CN photoanode connected to a highly active molecular Ru-based WOC, which also acts as an additional photo-absorber. We show that the strong interaction between the π-system of the heptazine units within the CN with the CH groups of the WOC's equatorial ligand enables a strong connection between them and an efficient electronic communication path. The optimized photoanode exhibits a photocurrent density of 180 ± 10 μA cm-2 at 1.23 V vs. the reversible hydrogen electrode (RHE) with 89% faradaic efficiency for oxygen evolution with turnover numbers (TONs) in the range of 3300 and a turnover frequency (TOF) of 0.4 s-1, low onset potential, extended incident photon to current conversion, and good stability up to 5 h. This study may lead to the integration of molecular catalysts and polymeric organic absorbers using supramolecular interactions.

Operando spectroscopic characterization of formamidinium lead iodide perovskite quantum dots for tracking electrochemical reactions

Multidimensional ABX3 hybrid perovskites three-dimensionally confined dot-shaped structure demonstrate versatile potential to photoelectrochemical cells for water splitting, hydrogen generation, solar cells, and light-emitting diodes. To apply perovskite quantum dots (PQDs) to solar-driven chemistry and optoelectronic devices, understanding the photoinduced charge carrier dynamics of PQDs under electrochemical conditions or applied bias are important. In this study, the detailed transformation mechanism of formamidinium lead iodide perovskite quantum dots under electrochemical conditions was studied by tracking the products of the reaction through cyclic voltammetry, X-ray photoemission spectroscopy, in-situ UV–visible spectroelectrochemistry, etc. Through comprehensive characterizations, the mechanism of irreversible oxidative transformation of perovskite quantum dots was presented. This study provides deeper insight into the electrochemical behavior of PQDs for successful solar-driven chemistry and optoelectronic device applications.

Enhancing solar energy conversion with nickel/iron oxyhydroxide-modified hematite photoanodes: The role of Fe species in alkaline electrolyte

Hematite photoanodes have shown potential for use in practical applications of photoelectrochemical (PEC) water splitting cells due to their abundance and stability, yet their efficiency needs to be improved. To optimize photoanode performance, co-catalysts such as amorphous nickel/iron oxyhydroxide layers are often deposited on the surface of hematite to enhance activity by catalyzing oxygen evolution. Recent studies have shown that the role of oxyhydroxide layers in changing PEC activity can vary depending on factors such as film morphology, co-catalyst layer thickness, and electrolyte composition. In this study, we investigate the effect of NiOOH and (Ni,Fe)OOH layers on the PEC activity of electrodeposited nanostructured hematite films. Our analysis of charge transfer and recombination rate constants determined from chronoamperometry and electrochemical impedance data suggests that the coatings' role is purely passivating, which is crucial for discontinuous electrodeposited films. Importantly, we show that the passivating properties of these coatings are enhanced by the presence of ppm concentrations of Fe in the electrolyte. We believe that our findings will be useful for further development of hematite photoanodes.

Impact of Varying the Photoanode/Catalyst Interfacial Composition on Solar Water Oxidation: The Case of BiVO4(010)/FeOOH Photoanodes.

Photoanodes used in a water-splitting photoelectrochemical cell are almost always paired with an oxygen evolution catalyst (OEC) to efficiently utilize photon-generated holes for water oxidation because the surfaces of photoanodes are typically not catalytic for the water oxidation reaction. Suppressing electron-hole recombination at the photoanode/OEC interface is critical for the OEC to maximally utilize the holes reaching the interface for water oxidation. In order to explicitly demonstrate and investigate how the detailed features of the photoanode/OEC interface affect interfacial charge transfer and photocurrent generation for water oxidation, we prepared two BiVO4(010)/FeOOH photoanodes with different Bi:V ratios at the outermost layer of the BiVO4 interface (close to stoichiometric vs Bi-rich) while keeping all other factors in the bulk BiVO4 and FeOOH layers identical. The resulting two photoanodes show striking differences in the photocurrent onset potential and photocurrent density for water oxidation. The ambient pressure X-ray photoelectron spectroscopy results show that these two BiVO4(010)/FeOOH photoanodes show drastically different Fe2+:Fe3+ ratios in FeOOH both in the dark and under illumination with water, demonstrating the immense impact of the interfacial composition and structure on interfacial charge transfer. Using computational studies, we reveal the effect of the surface Bi:V ratio on the hydration of the BiVO4 surface and bonding with the FeOOH layer, which in turn affect the band alignments between BiVO4 and FeOOH. These results explain the atomic origin of the experimentally observed differences in electron and hole transfer and solar water oxidation performance of the two photoanodes having different interfacial compositions.

Transferable Highly (001) Oriented Sb2Se3 Nanorod Films on Flexible Substrates for Innovative Optoelectronic Devices

AbstractThin films of antimony chalcogenides, Sb2X3 (X = S, Se, or SxSe1−x), comprised of (001) oriented nanorods are highly desirable for optoelectronic applications owing to their light trapping capacity and highly efficient charge transport along the optimally aligned quasi‐1D (Sb4X6)n ribbons. Here, highly (001) oriented Sb2Se3 nanorod (Sb2Se3NR) layers are obtained via a novel template growth method, and transfer these layers to functional substrates via a polymer‐assisted technique. Transferable layers overcome the current challenges associated with achieving oriented growth directly on the desired substrate. Using a combination of a low‐temperature processable SnO2 nanoparticle transport layer and encapsulation/etching techniques photodetector devices are fabricated with excellent electrical contact. The optimized transferred devices show broad range photoresponse with signal‐to‐noise ratios up to 105 and responsivities reaching 0.96 mA W−1. Importantly, access to low‐temperature processing enables the fabrication of flexible devices. Based on this platform, a proof‐of‐concept self‐powered flexible heart rate monitor is fabricated. The achievement of transferable Sb2Se3NR layers introduced in this work is expected to be readily applicable to generate new (001) Sb2Se3 device architectures that may otherwise not be achievable via direct deposition, with application in photoelectrochemical water splitting, battery electrodes, and solar cells.

Interplay between Collective and Localized Effects of Point Defects on Photoelectrochemical Performance of TiO2 Photoanodes for Oxygen Evolution

AbstractAmong the various photoanode materials investigated for photoelectrochemical water splitting cells, TiO2 stands out due to its abundance, stability, and favorable valence band edge for water oxidation. In this study, the importance of introducing and combining oxygen and titanium vacancy point defects in anatase TiO2 photoanodes to improve their performance is unveiled, achieving a photocurrent density of 0.73 (±0.015) mA cm−2 at +1.23 VRHE under 100 mW cm−2 of simulated sunlight or 26.4 mA cm−2 at +1.23 VRHE under 100 mW cm−2 of 365 nm light. The characterization by X‐ray photoelectron spectroscopy, surface photovoltage, and electron paramagnetic resonance demonstrates that these oxygen and titanium vacancies can have both collective and localized positive effects on the material, leading to a narrowing of the bandgap, an increase in donor density, and an increase in hydroxyl groups on the surface of TiO2. These result in enhanced light absorption, conductivity, and photovoltage, as well as a more negative flat‐band potential and increase in hole flux to the semiconductor–electrolyte interface. These findings provide valuable insights into the role of point defects in modulating the properties of TiO2 and have important implications for the development of high‐performance TiO2‐based devices.