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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Role of Hydrogen in Defining the n-Type Character of BiVO 4 Photoanodes

The roles of hydrogen impurity and oxygen vacancy defects on defining the conductivity, and hence photoelectrochemical (PEC) performance characteristics, of monoclinic scheelite bismuth vanadate (BiVO 4 ) are investigated using a combination of experiment and theory. We find that elemental hydrogen is present as an impurity in as-synthesized BiVO 4 and that increasing its concentration by annealing in H 2 at temperatures up to 290°C leads to near-complete elimination of majority carrier transport limitations, a beneficial shift in the photoanodic current onset potential, and improved fill factor. Magnetic resonance measurements reveal that hydrogen can be incorporated in at least two different chemical environments, which are assigned to interstitial and substitutional sites. Incorporation of hydrogen leads to a shift of the Fermi level toward the conduction band edge, indicating that n-type character is correlated with increased hydrogen content. This finding is in agreement with theory and reveals that hydrogen acts as a donor in BiVO 4 . Sub-bandgap photoluminescence is observed from as-synthesized material and is consistent with deep electronic states associated with oxygen vacancies. Hydrogen treatment leads to reduced emission from these states. These findings support the conclusion that hydrogen, rather than oxygen vacancies, is dominant in determining the n-type conductivity of BiVO 4 . These findings have important implications for controlling the electronic properties and functional characteristics of this promising photoanode material.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The Electronic Structure of Zirconium and Hafnium Monochalcogenides

High-level ab initio CCSD(T) and spin–orbit icMRCI+Q calculations were used to predict potential energy curves (PECs) for the lowest-lying states of ZrO, ZrS, HfO, and HfS. The prediction of the ground state is basis set dependent at the icMRCI+Q level for ZrO and ZrS due to the small singlet–triplet splitting between the lowest 1 Σ + and 3 Δ states. CCSD(T) with a spin orbit correction predicted the 1 Σ + ground state in agreement with experiment. New all-electron basis sets were developed for Hf to improve the results over those predicted by use of effective core potentials (ECPs) that subsume the 4f electrons into the definition of the core. The use of the new DK-4f basis sets rather than ECPs became more important for HfO and HfS where there is a lack of a good core–valence separation. icMRCI+Q, CCSD(T), and DFT calculations for the spectroscopic parameters of ZrO, ZrS, HfO, and HfS were benchmarked with available experimental data. Bond dissociation energies (BDEs) of these four systems were calculated at the Feller–Peterson–Dixon (FPD) level to be 762.1 (ZrO), 543.5 (ZrS), 803.8 (HfO), and 575.1 kJ/mol (HfS), in excellent agreement with experiment. The HfS BDE was remeasured using the R3PI method, providing an updated experimental measurement of D 0 (HfS) = 5.978 ± 0.002 eV = 576.8 ± 0.2 kJ/mol. This experimental value, combined with experimental measurements of the ionization energies of Hf and HfS, gives the cationic BDE of D 0 (Hf + -S) = 5.124 ± 0.002 eV = 494.4 ± 0.2 kJ/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Thorium Monosilicide, ThSi: An Experimental and Theoretical Study

The present theoretical and experimental combination study investigates the ThSi molecule in detail. Computationally, we utilized high-level multireference and coupled-cluster levels of theory conjoined with large correlation consistent basis sets to study a series of electronic and spin–orbit states of ThSi. Here, we report potential energy curves (PECs), electron configurations at equilibrium distances, spectroscopic constants, energetics, and spin–orbit coupling effects for 16 electronic states of ThSi. The studied 16 electronic states are arranged tightly within 0.9 eV, highlighting the complexity of the electronic spectrum of ThSi. The ground electronic state of ThSi is a single-reference 1 1 Σ + state that derives from the 1σ 2 2σ 2 1π 4 electronic configuration. The Ω = 0 + spin–orbit ground state of ThSi is composed of 1 1 Σ + (47%) and 13Π (44%) electronic states. Our measured bond energy (D0) of ThSi, obtained using resonant two-photon ionization (R2PI) spectroscopy is 3.146(4) eV, where the assigned error limit is given in parentheses in units of the last quoted digits. The computed D0 of ThSi (Ω = 0 + ) at the CBS-C-CCSD(T)-δT(Q)-δDK-δSO level (3.181 eV) is in good agreement with the experimental value. Our derived enthalpy of formation for ThSi, Δ f H 0K o (ThSi(g)), is 971.8(6.0) kJ/mol. Finally, we have performed density functional theory (DFT) calculations for ThSi(1 1 Σ + ) using 16 exchange correlation functionals that span multiple rungs of “Jacob’s ladder” of density functional approximation (DFA) to assess the DFT errors on D 0 , r e , and ω e of ThSi with respect to experimental and ab initio coupled-cluster values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Influence of Thermal Annealing on Free Carrier Concentration in (GaN) 1– x (ZnO) x Semiconductors

It has been previously demonstrated that the efficiency of (GaN) 1–x (ZnO) x semiconductors for solar water splitting can be improved by thermal annealing, though the origin of this improvement was not resolved. In the present work, it is shown that annealing reduces the free carrier (electron) concentration of (GaN) 1–x (ZnO) x . The time-, temperature-, and atmosphere-dependent changes were followed through two simple techniques: indirect diffuse reflectance measurements from 0.5 to 3.0 eV which show very high sensitivity to the free carrier response at the lowest energies and EPR measurements which directly probe the number of unpaired electrons. For the thermal annealing of investigated compositions, it is found that temperatures of 250 °C and below do not measurably change the free carrier concentration, a gradual reduction of the free carrier concentration occurs over a time period of many hours at 350 °C, and the complete elimination of free carriers happens within an hour at 550 °C. These changes are driven by an oxidative process which is effectively suppressed under actively reducing atmospheres (H 2 , NH 3 ) but which can still occur under nominally inert gases (N 2 , Ar). Surprisingly, it is found that the N 2 gas released during thermal oxidation of (GaN) 1–x (ZnO) x samples remains trapped within the solid matrix and is not expelled until temperatures of about 900 °C, a result directly confirmed through neutron pair-distribution fuction (PDF) measurements which show a new peak at the 1.1 Å bond length of molecular nitrogen after annealing. Preliminary comparative photoelectrochemical (PEC) measurements of the influence of free carrier concentration on photoactivity for water oxidation were carried out for a sample with x = 0.64. Samples annealed to eliminate free carriers exhibited no photoactivity for water oxidation, while a complex dependence on carrier concentration was observed for samples with intermediate free carrier concentrations. The methods demonstrated here provide an important approach for quantifying (and controlling) the carrier concentrations of semiconductors which are only available in the form of loose powders, as is commonly the case for oxynitride compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A Perspective into Operando Methods for Probing Catalytic Interfaces

Rational design of electrocatalysts for (photo)electrochemical (PEC) processes like hydrogen and oxygen evolution and CO2 reduction reactions is aided by the recent improvements in capabilities of operando measurements, where morphology, composition, and/or function are probed during active catalysis. Through operando microscopy and spectroscopy, structure, catalytic microenvironment, oxidation state, adsorbates, and products can be measured to gain a better understanding of catalyst behavior and suggest possible improvements. Visualizing evolving catalyst morphologies, surface compositions, and electrochemical behavior also helps address many fundamental research questions for a better understanding of catalytic mechanisms. Correlating morphology with chemical identity or functional behavior using a variety of innovative microscopy methods is particularly promising for guiding development of next generation catalysts, and there are also many recent examples of using AI and robotics tools to innovate and speed development. In this Perspective, advances made over the past few years in operando imaging of catalysts relevant to solar fuels will be explored, followed by an outlook on technological developments in instrumentation, sample design, and computational power that may be applied to this field.

Catalysts↗
DOE OSTI2024

Sputter-Coated TiO 2 Films as Passivation and Hole Transfer Layers for Improved Energy Conversion with Solar Fuel WO 3 /CuWO 4 Photoanodes

Atomic layer deposited (ALD) “leaky” TiO 2 have gained interest as charge-selective protection layers for semiconductor solar fuel electrodes. Here we demonstrate the use of sputter-deposited TiO 2 layers as hole selective contacts for WO 3 /CuWO 4 type 2 heterojunction water oxidation photoanodes for the first time. TiO 2 protection layers with varying thicknesses (2 to 128 nm) were deposited using the RF magnetron sputtering technique. The resulting TiO 2 films are amorphous based on Raman spectroscopy and powder XRD. Photoelectrochemical scans and Vibrating Kelvin probe photovoltage spectroscopy show that 2-8 nm TiO 2 layers nearly double the photocurrent to 0.97 mA cm -2 under AM 1.5 illumination (19% AQE at 350 nm), increase the surface photovoltage signal by 25%, and increase the WO 3 /CuWO 4 bandgap. These effects can be attributed to the selectivity of TiO 2 for photoholes. Additionally, SPV data suggest that TiO 2 overlayers suppress copper-based surface recombination defects. Reduced photocurrent and the photovoltage are seen in thicker TiO 2 films (16 to 128 nm) as a result of an increasing hole transfer resistance and because of light shading effects according to photoaction spectra. The TiO 2 films also improve the stability of the WO 3 /CuWO 4 photoelectrodes, allowing nearly constant O 2 evolution over 3 hours after an initial 20-35% loss. Overall, this work establishes RF magnetron sputtering as a useful method to install amorphous TiO 2 passivation layers for improved WO 3 /CuWO 4 solar fuel photoelectrodes. Furthermore, we show how the combination of PEC with SPV measurements provides insight into the function of the TiO 2 coatings.

CuWO4↗
DOE OSTI2018

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO 2

The inertness of the C–H bond in CH 4 poses significant challenges to selective CH 4 oxidation, which often proceeds all the way to CO 2 once activated. Selective oxidation of CH 4 to high-value industrial chemicals such as CO or CH 3 OH remains a challenge. Presently, the main methods to activate CH 4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH 4 oxidation exhibit limited control over the product selectivity, with CO 2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO 2 grown by atomic layer deposition (ALD), which features high concentrations of Ti 3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO 2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO 2 . Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO 2 reduction mechanisms. Our results not only present a new route to selective CH 4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Charge Transport at Ti-Doped Hematite (001)/Aqueous Interfaces

Solid-state transport and electrochemical properties of Ti-doped hematite (001) epitaxial thin films (6.0, 8.3, and 16.6 at% Ti) were probed to achieve a better understanding of doped hematite for photoelectrochemical (PEC) applications. Room temperature resistivity measurements predict a resistivity minimum near 10 at% Ti doping, which can be rationalized as maximizing charge compensating Fe2+ concentration and Fe3+ electron accepting percolation pathways simultaneously. Temperature dependent resistivity data are consistent with small polaron hopping, revealing an activation energy that is Ti concentration dependent and commensurate with previously reported values (≈ 0.11 eV). In contact with inert electrolyte, linear Mott-Schottky data at various pH values indicate that there is predominantly a single donor for Ti-doped hematite at 6.0 at% Ti and 16.6 at% Ti concentrations. Two slope Mott-Schottky data at pH extremes indicate the presence of a second donor or surface state in the 8.3 at% Ti-doped film, with an energy level ≈ 0.7 eV below the Fermi level. Mott-Schottky plots indicate pH and Ti concentration dependent flatband potentials of -0.4 to -1.1 V vs. Ag/AgCl, commensurate with previously reported data. Flatband potentials exhibited super-Nernstian pH dependence ranging from -69.1 to -101.0 mV/pH. Carrier concentration data indicate that the Fermi energy of the Ti-doped system is Ti concentration dependent, with a minimum of 0.15 eV near 10 at% Ti. These energy level data allow us to construct an energy band diagram for Ti-doped hematite electrode/electrolyte interfaces, and to determine a Ti-doping concentration t

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

p-Type Transparent Conducting Oxide/n-Type Semiconductor Heterojunctions for Efficient and Stable Solar Water Oxidation

Achieving stable operation of photoanodes used as components of solar water splitting devices is essential to realizing the promise of this renewable energy technology. It is demonstrated that p-type transparent conducting oxides (p-TCOs) can function both as a selective hole contact and corrosion protection layer for photoanodes used in light-driven water oxidation. Using NiCo 2 O 4 as the p-TCO and n-type Si as a prototypical light absorber, a rectifying heterojunction capable of light driven water oxidation was created. By placing the charge separating junction in the Si using a np + structure and by incorporating a highly active heterogeneous Ni-Fe oxygen evolution catalyst, efficient light-driven water oxidation can be achieved. In this structure, oxygen evolution under AM 1.5 G illumination occurs at 0.95 V vs RHE, and the current density at the reversible potential for water oxidation (1.23 V vs RHE) is >25 mA cm -2 . Stable operation was confirmed by observing a constant current density over 72 h and by sensitive measurements of corrosion products in the electrolyte. In situ Raman spectroscopy was employed to investigate structural transformation of NiCo 2 O 4 during electrochemical oxidation. The interface among the light absorber and p-TCO is crucial to produce selective hole conduction to the surface under illumination. For example, annealing to produce more crystalline NiCo 2 O 4 produces only small changes in its hole conductivity, while a thicker SiO x layer is formed at the n-Si/p-NiCo 2 O 4 interface, greatly reducing the PEC performance. The generality of the p-TCO protection approach is demonstrated by multihour, stable, water oxidation with n-InP/p-NiCo 2 O 4 heterojunction photoanodes.

Chen, Le↗
DOE OSTI2025

Tetracene Functionalized Si(111) Achieves Enhanced Solar-to-Chemical Energy Conversion via Molecular Acceptor States

The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage (I–V, dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Altogether, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.

Group theory↗
DOE OSTI2026

Observation of Transition from Rate Law to Butler–Volmer Controlled Water Oxidation Kinetics on Hematite Photoanodes

Despite its central role in photoelectrochemical (PEC) water splitting, the mechanistic pathway of water oxidation on metal oxides remains unresolved, with population-based and Butler–Volmer (BV) models offering distinct views on how surface valence band holes drive the reaction. Here, we bring together these two perspectives by combining operando photoinduced absorption (PIA) spectroscopy with photocurrent analyses on α-Fe 2 O 3 (hematite) photoanodes as a function of light intensity. We find a crossover from population-controlled, rate law water oxidation at low hole densities to a BV-like, potential driven regime at high densities, triggered by band edge unpinning once surface M–OH species are fully oxidized, and excess holes accumulate without compensation. This mechanistic transition unifies competing models of interfacial charge transfer and reveals design principles for optimizing water oxidation in metal oxide photoelectrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Indirect Bandgap and Optical Properties of Monoclinic Bismuth Vanadate

© 2015 American Chemical Society. Monoclinic scheelite bismuth vanadate (m-BiVO4) is a promising semiconductor photoanode for photoelectrochemical (PEC) water splitting. Despite considerable recent progress in achieving improved photocurrents and photovoltages, there remain open questions about the basic optoelectronic properties of this material. Indeed, there is disagreement about the nature of its fundamental bandgap, with theoretical predictions and some experimental observations pointing to an indirect bandgap and other experimental studies to a direct bandgap. Knowledge of this property is critical for understanding light absorption and photocarrier properties, as well as for establishing rational approaches to improved efficiency. Here, experimental spectroscopic techniques are used to resolve this issue and provide a fundamental portrait of the optical properties of the material. Resonant inelastic X-ray scattering proves conclusively that m-BiVO4 is an indirect bandgap semiconductor. These measurements are supported by UV-vis absorption spectroscopy and spectroscopic ellipsometry, which confirm this finding and also indicate the presence of a direct transition located at 200 meV above the indirect one. The spectral dependence of the optical constants is determined by development of a photophysical model for the ellipsometric data. Photogenerated carrier dynamics are probed by transient absorption spectroscopy, which reveals a relatively long lifetime compared to other commonly utilized metal oxide photoanodes and is attributed to the indirect nature of the fundamental gap. The combination of strong visible light absorption and relatively long excited state lifetime provides the basis for the high performance that has been achieved from BiVO4 photoanodes for water splitting.

Cooper, Jason K↗
DOE OSTI2015

Enabling unassisted solar water splitting by iron oxide and silicon

A solution for large-scale solar energy storage is photoelectrochemical (PEC) water splitting. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. We show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversible hydrogen electrode) is achieved. In conclusion, this result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.

25 ENERGY STORAGE↗
DOE OSTI2024

Absolute band-edge energies are over-emphasized in the design of photoelectrochemical materials

The absolute band-edge potentials of semiconductors, i.e., the conduction-band minimum, valence-band maximum, and their relative positions to solution redox potentials, are often invoked as design principles for photoelectrochemical (PEC) devices, especially for particulate photocatalysts. Here we show that reliance on these criteria is not necessary and limits the exploration of materials that will advance the fields of photoelectrochemistry, photochemistry, and photocatalysis. We discuss how i) band-edge energies are not singular parameters and instead shift with pH, electrolyte type, and surface chemistry; ii) the free energy of electrons and holes in comparison to that of solution redox couples dictates overall reaction spontaneity and thus reactivity; and iii) favorable charge-transfer kinetics can occur even when the relevant electrolyte redox potential(s) appear ‘outside’ the bandgap, enabled by the inversion or accumulation of electronic charge at the semiconductor surface. As a result, this discussion informs design principles for photocatalyst systems engineering for both one-electron redox reactions as well as for more complex multi-electron transfer reactions (e.g, H 2 evolution, H 2 O oxidation, CO 2 reduction).

14 SOLAR ENERGY↗
DOE OSTI2016

Hydrothermal growth of ZnO nanowire arrays: fine tuning by precursor supersaturation

In this paper, we develop a technique that fine tunes the hydrothermal growth of ZnO nanowires to address the difficulties in controlling their growth in a conventional one-pot hydrothermal method. In our technique, precursors are separately and slowly supplied with the assistance of a syringe pump, through the entire course of the growth. Compared to the one-pot method, the significantly lowered supersaturation of precursors helps eliminating competitive homogeneous nucleation and improves the reproducibility. The supersaturation degree can be readily tuned by the precursor quantity and injection rate, thus forming ZnO nanowire arrays of various geometries and packing densities in a highly controllable fashion. The precise control of ZnO nanowire growth enables systematic studies on the correlation between the material's properties and its morphology. Finally, in this work, ZnO nanowire arrays of various morphologies are studied as photoelectrochemical (PEC) water splitting photoanodes, in which we establish clear correlations between the water splitting performance and the nanowires' size, shape, and packing density.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Thin film photoelectrodes for solar water splitting

Photoelectrochemical (PEC) water splitting has been intensively studied in the past decades as a promising method for large-scale solar energy storage. Among the various issues that limit the progress of this field, the lack of photoelectrode materials with suitable properties in all aspects of light absorption, charge separation and transport, and charge transfer is a key challenge, which has attracted tremendous research attention. A large variety of compositions, in different forms, have been tested. This review aims to summarize efforts in this area, with a focus on materials-related considerations. Issues discussed by this review include synthesis, optoelectronic properties, charge behaviors and catalysis. In the recognition that thin-film materials are representative model systems for the study of these issues, we elected to focus on this form, so as to provide a concise and coherent account on the different strategies that have been proposed and tested. Because practical implementation is of paramount importance to the eventual realization of using solar fuel for solar energy storage, we pay particular attention to strategies proposed to address the stability and catalytic issues, which are two key factors limiting the implementation of efficient photoelectrode materials. To keep the overall discussion focused, all discussions were presented within the context of water splitting reactions. Finally, how the thin-film systems may be applied for fundamental studies of the water splitting chemical mechanisms and how to use the model system to test device engineering design strategies are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗