Unraveling Electron Dynamics in p-type Indium Phosphide (100): A Time-Resolved Two-Photon Photoemission Study.

Renewable ("green") hydrogen production through direct photoelectrochemical (PEC) water splitting is a potential key contributor to the sustainable energy mix of the future. We investigate the potential of indium phosphide (InP) as a reference material among III-V semiconductors for PEC and photovoltaic (PV) applications. The p(2 × 2)/c(4 × 2)-reconstructed phosphorus-terminated p-doped InP(100) (P-rich p-InP) surface is the focus of our investigation. We employ time-resolved two-photon photoemission (tr-2PPE) spectroscopy to study electronic states near the band gap with an emphasis on normally unoccupied conduction band states that are inaccessible through conventional single-photon emission methods. The study shows the complexity of the p-InP electronic band structure and reveals the presence of at least nine distinct states between the valence band edge and vacuum energy, including a valence band state, a surface defect state pinning the Fermi level, six unoccupied surface resonances within the conduction band, as well as a cluster of states about 1.6 eV above the CBM, identified as a bulk-to-surface transition. Furthermore, we determined the decay constants of five of the conduction band states, enabling us to track electron relaxation through the bulk and surface conduction bands. This comprehensive understanding of the electron dynamics in p-InP(100) lays the foundation for further exploration and surface engineering to enhance the properties and applications of p-InP-based III-V-compounds for, e.g., efficient and cost-effective PEC hydrogen production and highly efficient PV cells.

Technological Pathways to Produce Compressed and Highly Pure Hydrogen from Solar Power.

Hydrogen (H2 ) produced from renewables will have a growing impact on the global energy dynamics towards sustainable and carbon-neutral standards. The share of green H2 is still too low to meet the net-zero target, while the demand for high-quality hydrogen continues to rise. These factors amplify the need for economically viable H2 generation technologies. The present article aims at evaluating the existing technologies for high-quality H2 production based on solar energy. Technologies such as water electrolysis, photoelectrochemical and solar thermochemical water splitting, liquid metal reactors and plasma conversion utilize solar power directly or indirectly (as carbon-neutral electrons) and are reviewed from the perspective of their current development level, technical limitations and future potential.

Influence of Excess Charge on Water Adsorption on the BiVO4(010) Surface.

We present a combined computational and experimental study of the adsorption of water on the Mo-doped BiVO4(010) surface, revealing how excess electrons influence the dissociation of water and lead to hydroxyl-induced alterations of the surface electronic structure. By comparing ambient pressure resonant photoemission spectroscopy (AP-ResPES) measurements with the results of first-principles calculations, we show that the dissociation of water on the stoichiometric Mo-doped BiVO4(010) surface stabilizes the formation of a small electron polaron on the VO4 tetrahedral site and leads to an enhanced concentration of localized electronic charge at the surface. Our calculations demonstrate that the dissociated water accounts for the enhanced V4+ signal observed in ambient pressure X-ray photoelectron spectroscopy and the enhanced signal of a small electron polaron inter-band state observed in AP-ResPES measurements. For ternary oxide surfaces, which may contain oxygen vacancies in addition to other electron-donating dopants, our study reveals the importance of defects in altering the surface reactivity toward water and the concomitant water-induced modifications to the electronic structure.

Quantification of the Activator and Sensitizer Ion Distributions in NaYF4 :Yb3+ , Er3+ Upconverting Nanoparticles Via Depth-Profiling with Tender X-Ray Photoemission.

The spatial distribution and concentration of lanthanide activator and sensitizer dopant ions are of key importance for the luminescence color and efficiency of upconverting nanoparticles (UCNPs). Quantifying dopant ion distributions and intermixing, and correlating them with synthesis methods require suitable analytical techniques. Here, X-ray photoelectron spectroscopy depth-profiling with tender X-rays (2000-6000 eV), providing probe depths ideally matched to UCNP sizes, is used to measure the depth-dependent concentration ratios of Er3+ to Yb3+ , [Er3+ ]/[Yb3+ ], in three types of UCNPs prepared using different reagents and synthesis methods. This is combined with data simulations and inductively coupled plasma-optical emission spectroscopy (ICP-OES) measurements of the lanthanide ion concentrations to construct models of the UCNPs' dopant ion distributions. The UCNP sizes and architectures are chosen to demonstrate the potential of this approach. Core-only UCNPs synthesized with XCl3 ·6H2 O precursors (ß-phase) exhibit a homogeneous distribution of lanthanide ions, but a slightly surface-enhanced [Er3+ ]/[Yb3+ ] is observed for UCNPs prepared with trifluroacetate precursors (α-phase). Examination of Yb-core@Er-shell UCNPs reveals a co-doped, intermixed region between the single-doped core and shell. The impact of these different dopant ion distributions on the UCNP's optical properties is discussed to highlight their importance for UCNP functionality and the design of efficient UCNPs.

Extraction of mobile charge carrier photogeneration yield spectrum of ultrathin-film metal oxide photoanodes for solar water splitting.

Light absorption in strongly correlated electron materials can excite electrons and holes into a variety of different states. Some of these excitations yield mobile charge carriers, whereas others result in localized states that cannot contribute to photocurrent. The photogeneration yield spectrum, ξ(λ), represents the wavelength-dependent ratio between the contributing absorption that ultimately generates mobile charge carriers and the overall absorption. Despite being a vital material property, it is not trivial to characterize. Here, we present an empirical method to extract ξ(λ) through optical and external quantum efficiency measurements of ultrathin films. We applied this method to haematite photoanodes for water photo-oxidation, and observed that it is self-consistent for different illumination conditions and applied potentials. We found agreement between the extracted ξ(λ) spectrum and the photoconductivity spectrum measured by time-resolved microwave conductivity. These measurements revealed that mobile charge carrier generation increases with increasing energy across haematite's absorption spectrum. Low-energy non-contributing absorption fundamentally limits the photoconversion efficiency of haematite photoanodes and provides an upper limit to the achievable photocurrent that is substantially lower than that predicted based solely on absorption above the bandgap. We extended our analysis to TiO2 and BiVO4 photoanodes, demonstrating the broader utility of the method for determining ξ(λ).

Protonated Imine-Linked Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution.

Covalent organic frameworks (COFs) have emerged as an important class of organic semiconductors and photocatalysts for the hydrogen evolution reaction (HER)from water. To optimize their photocatalytic activity, typically the organic moieties constituting the frameworks are considered and the most suitable combinations of them are searched for. However, the effect of the covalent linkage between these moieties on the photocatalytic performance has rarely been studied. Herein, we demonstrate that donor-acceptor (D-A) type imine-linked COFs can produce hydrogen with a rate as high as 20.7 mmol g-1 h-1 under visible light irradiation, upon protonation of their imine linkages. A significant red-shift in light absorbance, largely improved charge separation efficiency, and an increase in hydrophilicity triggered by protonation of the Schiff-base moieties in the imine-linked COFs, are responsible for the improved photocatalytic performance.

Analysis of the interfacial characteristics of BiVO4/metal oxide heterostructures and its implication on their junction properties.

The formation of heterostructures has proven to be a viable way to achieve high photoelectrochemical water splitting efficiencies with BiVO4 based photoanodes. Especially, cobalt and nickel based oxides are suitable low cost contact materials. However, the exact role of these contact materials is not yet completely understood because of the difficulty to individually quantify the effects of surface passivation, charge carrier separation and catalysis on the efficiency of a heterostructure. In this study, we used photoelectron spectroscopy in combination with in situ thin film deposition to obtain direct information on the interface structure between polycrystalline BiVO4 and NiO, CoOx and Sn-doped In2O3 (ITO). Strong upwards band bending was observed for the BiVO4/NiO and BiVO4/CoOx interfaces without observing chemical changes in BiVO4, while limited band bending and reduction of Bi and V was observed while forming the BiVO4/ITO interface. Thus, the tunability of the Fermi level position within BiVO4 seems to be limited to a certain range. The feasibility of high upwards band bending through junctions with high work function (WF) compounds demonstrate that nickel oxide and cobalt oxide are able to enhance the charge carrier separation in BiVO4. Similar studies could help to identify whether new photoelectrode materials and their heterostructures would be suitable for photoelectrochemical water splitting.

Gradient Self-Doped CuBi2O4 with Highly Improved Charge Separation Efficiency.

A new strategy of using forward gradient self-doping to improve the charge separation efficiency in metal oxide photoelectrodes is proposed. Gradient self-doped CuBi2O4 photocathodes are prepared with forward and reverse gradients in copper vacancies using a two-step, diffusion-assisted spray pyrolysis process. Decreasing the Cu/Bi ratio of the CuBi2O4 photocathodes introduces Cu vacancies that increase the carrier (hole) concentration and lowers the Fermi level, as evidenced by a shift in the flat band toward more positive potentials. Thus, a gradient in Cu vacancies leads to an internal electric field within CuBi2O4, which can facilitate charge separation. Compared to homogeneous CuBi2O4 photocathodes, CuBi2O4 photocathodes with a forward gradient show highly improved charge separation efficiency and enhanced photoelectrochemical performance for reduction reactions, while CuBi2O4 photocathodes with a reverse gradient show significantly reduced charge separation efficiency and photoelectrochemical performance. The CuBi2O4 photocathodes with a forward gradient produce record AM 1.5 photocurrent densities for CuBi2O4 up to -2.5 mA/cm2 at 0.6 V vs RHE with H2O2 as an electron scavenger, and they show a charge separation efficiency of 34% for 550 nm light. The gradient self-doping accomplishes this without the introduction of external dopants, and therefore the tetragonal crystal structure and carrier mobility of CuBi2O4 are maintained. Lastly, forward gradient self-doped CuBi2O4 photocathodes are protected with a CdS/TiO2 heterojunction and coated with Pt as an electrocatalyst. These photocathodes demonstrate photocurrent densities on the order of -1.0 mA/cm2 at 0.0 V vs RHE and evolve hydrogen with a faradaic efficiency of ∼91%.

Plasmonic enhancement of the optical absorption and catalytic efficiency of BiVO4 photoanodes decorated with Ag@SiO2 core-shell nanoparticles.

Recent progress in the development of bismuth vanadate (BiVO4) photoanodes has firmly established it as a promising material for solar water splitting applications. Performance limitations due to intrinsically poor catalytic activity and slow electron transport have been successfully addressed through the application of water oxidation co-catalysts and novel doping strategies. The next bottleneck to tackle is the modest optical absorption in BiVO4, particularly close to its absorption edge of 2.4 eV. Here, we explore the modification of the BiVO4 surface with Ag@SiO2 core-shell plasmonic nanoparticles. A photocurrent enhancement by a factor of ~2.5 is found under 1 sun illumination (AM1.5). We show that this enhancement consists of two contributions: optical absorption and catalysis. The optical absorption enhancement is induced by the excitation of localized surface plasmon resonances in the Ag nanoparticles, and agrees well with our full-field electromagnetic simulations. Far-field effects (scattering) are found to be dominant, with a smaller contribution from near-field plasmonic enhancement. In addition, a significant catalytic enhancement is observed, which is tentatively attributed to the electrocatalytic activity of the Ag@SiO2 nanoparticles.

Optimization of amorphous silicon double junction solar cells for an efficient photoelectrochemical water splitting device based on a bismuth vanadate photoanode.

A photoelectrochemical water splitting device (PEC-WSD) was designed and fabricated based on cobalt-phosphate-catalysed and tungsten-gradient-doped bismuth vanadate (W:BiVO4) as the photoanode. A simple and cheap hydrogenated amorphous silicon (a-Si:H) double junction solar cell has been used to provide additional bias. The advantage of using thin film silicon (TF-Si) based solar cells is that this photovoltaic (PV) technology meets the crucial requirements for the PV component in PEC-WSDs based on W:BiVO4 photoanodes. TF-Si PV devices are stable in aqueous solutions, are manufactured by simple and cheap fabrication processes and their spectral response, voltage and current density show an excellent match with the photoanode. This paper is mainly focused on the optimization of the TF-Si solar cell with respect to the remaining solar spectrum transmitted through the W:BiVO4 photoanode. The current matching between the top and bottom cells is studied and optimized by varying the thickness of the a-Si:H top cell. We support the experimental optimization of the current balance between the two sub-cells with simulations of the PV devices. In addition, the impact of the light induced degradation of the a-Si:H double junction, the so-called Staebler-Wronski Effect (SWE), on the performance of the PEC-WSD has been studied. The light soaking experiments on the a-Si:H/a-Si:H double junctions over 1000 hours show that the efficiency of a stand-alone a-Si:H/a-Si:H double junction cell is significantly reduced due to the SWE. Nevertheless, the SWE has a significantly smaller effect on the performance of the PEC-WSD.

Assessing elevated pressure impact on photoelectrochemical water splitting via multiphysics modeling.

Photoelectrochemical (PEC) water splitting is a promising approach for sustainable hydrogen production. Previous studies have focused on devices operated at atmospheric pressure, although most applications require hydrogen delivered at elevated pressure. Here, we address this critical gap by investigating the implications of operating PEC water splitting directly at elevated pressure. We evaluate the benefits and penalties associated with elevated pressure operation by developing a multiphysics model that incorporates empirical data and direct experimental observations. Our analysis reveals that the operating pressure influences bubble characteristics, product gas crossover, bubble-induced optical losses, and concentration overpotential, which are crucial for the overall device performance. We identify an optimum pressure range of 6-8 bar for minimizing losses and achieving efficient PEC water splitting. This finding provides valuable insights for the design and practical implementation of PEC water splitting devices, and the approach can be extended to other gas-producing (photo)electrochemical systems. Overall, our study demonstrates the importance of elevated pressure in PEC water splitting, enhancing the efficiency and applicability of green hydrogen generation.

Electrolyte selection toward efficient photoelectrochemical glycerol oxidation on BiVO4.

Glycerol, a primary by-product of biodiesel production, can be oxidized into various value-added chemicals, significantly enhancing the techno-economic value of photoelectrochemical (PEC) cells. Several studies have explored various photoelectrode materials and co-catalysts, but the influence of electrolytes on PEC glycerol oxidation has remained relatively unexplored despite its significance. Here, we explore the impact of various acidic (pH = 2) electrolytes, namely NaNO3, NaClO4, Na2SO4, K2SO4, and KPi, on PEC glycerol oxidation using nanoporous thin film BiVO4 as a model photoanode. Our experimental findings reveal that the choice of electrolyte anion and cation significantly affects the PEC performance (i.e., photocurrent, onset potential, stability, and selectivity towards value-added products) of BiVO4 for glycerol oxidation. To explain this interesting phenomenon, we correlate the observed performance trend with the ion specificity in the Hofmeister series as well as the buffering capacity of the electrolytes. Notably, NaNO3 is identified as the optimal electrolyte for PEC glycerol oxidation with BiVO4 when considering various factors such as stability and production rates for glycerol oxidation reaction (GOR) products, surpassing the previously favored Na2SO4. Glycolaldehyde emerges as the most dominant product with ∼50% selectivity in NaNO3. The general applicability of our findings is confirmed by similar observation in electrochemical (EC) GOR with a polycrystalline platinum anode. Overall, these results emphasize the critical role of electrolyte selection in enhancing the efficiency of EC/PEC glycerol oxidation.

An n-Si/n-Fe2O3 heterojunction tandem photoanode for solar water splitting.

Few metal oxide photoanodes are able to reduce protons to hydrogen because their conduction band minimum is located at too positive potentials. This can be remedied by biasing the photoanode with a photovoltaic cell placed behind the photoanode. The disadvantage of such a tandem device is the rather complicated structure. Here, we demonstrate a very simple monolithic heterojunction tandem photoanode based on n-Si and n-type α-Fe2O3. Detailed characterization of this system in a basic planar configuration reveals that the silicon generates a photovoltage of ∼0.3 V, and that the heterojunction functions as a D4 tandem device in which the absorption of two photons leads to one high-energy electron in the external circuit. No Fermi level pinning occurs at the Si/Fe2O3 interface, and the tandem photoanode is thermodynamically able to split water without the need for an external bias potential. This suggests that the n-Si/n-Fe2O3 heterojunction photoanode is a promising system for solar water splitting.

Water-splitting catalysis and solar fuel devices: artificial leaves on the move.

The development of new energy materials that can be utilized to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks in science today. Solar-powered catalytic water-splitting processes can be exploited as a source of electrons and protons to make clean renewable fuels, such as hydrogen, and in the sequestration of CO2 and its conversion into low-carbon energy carriers. Recently, there have been tremendous efforts to build up a stand-alone solar-to-fuel conversion device, the "artificial leaf", using light and water as raw materials. An overview of the recent progress in electrochemical and photo-electrocatalytic water splitting devices is presented, using both molecular water oxidation complexes (WOCs) and nano-structured assemblies to develop an artificial photosynthetic system.

Life cycle net energy assessment of sustainable H2 production and hydrogenation of chemicals in a coupled photoelectrochemical device.

Green hydrogen has been identified as a critical enabler in the global transition to sustainable energy and decarbonized society, but it is still not economically competitive compared to fossil-fuel-based hydrogen. To overcome this limitation, we propose to couple photoelectrochemical (PEC) water splitting with the hydrogenation of chemicals. Here, we evaluate the potential of co-producing hydrogen and methyl succinic acid (MSA) by coupling the hydrogenation of itaconic acid (IA) inside a PEC water splitting device. A negative net energy balance is predicted to be achieved when the device generates only hydrogen, but energy breakeven can already be achieved when a small ratio (~2%) of the generated hydrogen is used in situ for IA-to-MSA conversion. Moreover, the simulated coupled device produces MSA with much lower cumulative energy demand than conventional hydrogenation. Overall, the coupled hydrogenation concept offers an attractive approach to increase the viability of PEC water splitting while at the same time decarbonizing valuable chemical production.

Solar-driven upgrading of biomass by coupled hydrogenation using in situ (photo)electrochemically generated H2.

With the increasing pressure to decarbonize our society, green hydrogen has been identified as a key element in a future fossil fuel-free energy infrastructure. Solar water splitting through photoelectrochemical approaches is an elegant way to produce green hydrogen, but for low-value products like hydrogen, photoelectrochemical production pathways are difficult to be made economically competitive. A possible solution is to co-produce value-added chemicals. Here, we propose and demonstrate the in situ use of (photo)electrochemically generated H2 for the homogeneous hydrogenation of itaconic acid-a biomass-derived feedstock-to methyl succinic acid. Coupling these two processes offers major advantages in terms of stability and reaction flexibility compared to direct electrochemical hydrogenation, while minimizing the overpotential. An overall conversion of up to ~60% of the produced hydrogen is demonstrated for our coupled process, and a techno-economic assessment of our proposed device further reveals the benefit of coupling solar hydrogen production to a chemical transformation.

Selective photoreduction of nitric oxide to nitrogen by nanostructured TiO2 photocatalysts: role of oxygen vacancies and iron dopant.

Conventional TiO(2)-based photocatalysts oxidize NO(x) to nitrate species, which do not spontaneously desorb and therefore deactivate the catalyst. We show that the selectivity of this reaction can be changed by creating a large concentration of oxygen vacancies in TiO(2) nanoparticles through thermal reduction in a reducing atmosphere. This results in the photoreduction of nitric oxide (NO) to N(2) and O(2), species which spontaneously desorb at room temperature. The activity of the photoreduction reaction can be greatly enhanced by doping the TiO(2) nanoparticles with Fe(3+), an acceptor-type dopant that stabilizes the oxygen vacancies. Moreover, the photoinduced reduction of Fe(3+) to Fe(2+) provides a recombination pathway that almost completely suppresses the formation of NO(2) and thus enhances the selectivity of the reaction for N(2) formation. Gas chromatography confirms that N(2) and O(2) are formed in a stoichiometric ratio, and the activity for NO decomposition is found to be limited by the concentration of oxygen vacancies. A series of internally consistent reaction equations are proposed that describe all experimentally observed features of the photocatalytic process. The observed influence of oxygen vacancies on the activity and selectivity of photoinduced reactions may lead to new routes toward the design of highly selective photocatalysts.

Photocatalytic hydrogenation of acetophenone on a titanium dioxide cellulose film.

A previously developed sustainable immobilization concept for photocatalysts based on cellulose as a renewable support material was applied for the photocatalytic hydrogenation of acetophenone (ACP) to 1-phenyl ethanol (PE). Four different TiO2 modifications (P25, P90, PC105, and PC500) were screened for the reaction showing good performance for PC25 and PC500. PC500 was selected for a detailed kinetic study to find the optimal operating conditions, and to obtain a better understanding of the photocatalytic pathway in relation to conventional and transfer hydrogenation. The kinetic data were analyzed using the pseudo-first-order reaction rate law. A complete conversion was obtained for ACP concentrations below 1 mM using a 360 nm filter and argon as the purge gas within 2-3 hours. High oxygen concentrations slow down or prevent the reaction, and wavelengths below 300 nm lead to side-products. By investigating the temperature dependency, an activation energy of 22 kJ mol-1 was determined which is lower than the activation energies for conventional and transfer hydrogenation, because the light activation of the photocatalyst turns the endothermic to an exothermic reaction. PC500 was immobilized onto the cellulose film showing a 37% lower activity that remains almost constant after multiple use.

Low-bias photoelectrochemical water splitting via mediating trap states and small polaron hopping.

Metal oxides are promising for photoelectrochemical (PEC) water splitting due to their robustness and low cost. However, poor charge carrier transport impedes their activity, particularly at low-bias voltage. Here we demonstrate the unusual effectiveness of phosphorus doping into bismuth vanadate (BiVO4) photoanode for efficient low-bias PEC water splitting. The resulting BiVO4 photoanode shows a separation efficiency of 80% and 99% at potentials as low as 0.6 and 1.0 VRHE, respectively. Theoretical simulation and experimental analysis collectively verify that the record performance originates from the unique phosphorus-doped BiVO4 configuration with concurrently mediated carrier density, trap states, and small polaron hopping. With NiFeOx cocatalyst, the BiVO4 photoanode achieves an applied bias photon-to-current efficiency of 2.21% at 0.6 VRHE. The mechanistic understanding of the enhancement of BiVO4 properties provides key insights in trap state passivation and polaron hopping for most photoactive metal oxides.