Oxidation State and Surface Reconstruction of Cu under CO2 Reduction Conditions from In Situ X-ray Characterization.

The electrochemical CO2 reduction reaction (CO2RR) using Cu-based catalysts holds great potential for producing valuable multi-carbon products from renewable energy. However, the chemical and structural state of Cu catalyst surfaces during the CO2RR remains a matter of debate. Here, we show the structural evolution of the near-surface region of polycrystalline Cu electrodes under in situ conditions through a combination of grazing incidence X-ray absorption spectroscopy (GIXAS) and X-ray diffraction (GIXRD). The in situ GIXAS reveals that the surface oxide layer is fully reduced to metallic Cu before the onset potential for CO2RR, and the catalyst maintains the metallic state across the potentials relevant to the CO2RR. We also find a preferential surface reconstruction of the polycrystalline Cu surface toward (100) facets in the presence of CO2. Quantitative analysis of the reconstruction profiles reveals that the degree of reconstruction increases with increasingly negative applied potentials, and it persists when the applied potential returns to more positive values. These findings show that the surface of Cu electrocatalysts is dynamic during the CO2RR, and emphasize the importance of in situ characterization to understand the surface structure and its role in electrocatalysis.

Electrochemical flow cell enabling operando probing of electrocatalyst surfaces by X-ray spectroscopy and diffraction.

The rational improvement of current and developing electrochemical technologies requires atomistic understanding of electrode-electrolyte interfaces. However, examining these interfaces under operando conditions, where performance is typically evaluated and benchmarked, remains challenging, as it necessitates incorporating an operando probe during full electrochemical operation. In this study, we describe a custom electrochemical flow cell that enables near-surface-sensitive operando investigation of planar thin-film catalysts at significant hydrogen evolution reaction (HER) rates (in excess of -100 mA cm-2) using grazing incidence X-ray methods. Grazing-incidence X-ray spectroscopy and diffraction were implemented on the same sample under identical HER conditions, demonstrating how the combined measurements track changing redox chemistry and structure of Cu thin-film catalyst surfaces as a function of electrochemical conditions. The coupling of these methods with improved mass transport and hydrodynamic control establishes a new paradigm for operando measurement design, enabling unique insights into the key fundamental processes occurring at the catalyst-electrolyte interface.

Hybrid photoelectrochemical and photovoltaic cells for simultaneous production of chemical fuels and electrical power.

Harnessing solar energy to drive photoelectrochemical reactions is widely studied for sustainable fuel production and versatile energy storage over different timescales. However, the majority of solar photoelectrochemical cells cannot drive the overall photosynthesis reactions without the assistance of an external power source. A device for simultaneous and direct production of renewable fuels and electrical power from sunlight is now proposed. This hybrid photoelectrochemical and photovoltaic device allows tunable control over the branching ratio between two high-value products of solar energy conversion, requires relatively simple modification to existing photovoltaic technologies, and circumvents the photocurrent mismatches that lead to significant loss in tandem photoelectrochemical systems comprising chemically stable photoelectrodes. Our proof-of-concept device is based on a transition metal oxide photoanode monolithically integrated onto silicon that possesses both front- and backside photovoltaic junctions. This integrated assembly drives spontaneous overall water splitting with no external power source, while also producing electricity near the maximum power point of the backside photovoltaic junction. The concept that photogenerated charge carriers can be controllably directed to produce electricity and chemical fuel provides an opportunity to significantly increase the energy return on energy invested in solar fuels systems and can be adapted to a variety of architectures assembled from different materials.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes.

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Defective TiO2 with high photoconductive gain for efficient and stable planar heterojunction perovskite solar cells.

Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100 h.

Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes.

Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability.

Modeling, simulation, and fabrication of a fully integrated, acid-stable, scalable solar-driven water-splitting system.

A fully integrated solar-driven water-splitting system comprised of WO3 /FTO/p(+) n Si as the photoanode, Pt/TiO2 /Ti/n(+) p Si as the photocathode, and Nafion as the membrane separator, was simulated, assembled, operated in 1.0 M HClO4 , and evaluated for performance and safety characteristics under dual side illumination. A multi-physics model that accounted for the performance of the photoabsorbers and electrocatalysts, ion transport in the solution electrolyte, and gaseous product crossover was first used to define the optimal geometric design space for the system. The photoelectrodes and the membrane separators were then interconnected in a louvered design system configuration, for which the light-absorbing area and the solution-transport pathways were simultaneously optimized. The performance of the photocathode and the photoanode were separately evaluated in a traditional three-electrode photoelectrochemical cell configuration. The photocathode and photoanode were then assembled back-to-back in a tandem configuration to provide sufficient photovoltage to sustain solar-driven unassisted water-splitting. The current-voltage characteristics of the photoelectrodes showed that the low photocurrent density of the photoanode limited the overall solar-to-hydrogen (STH) conversion efficiency due to the large band gap of WO3 . A hydrogen-production rate of 0.17 mL hr(-1) and a STH conversion efficiency of 0.24 % was observed in a full cell configuration for >20 h with minimal product crossover in the fully operational, intrinsically safe, solar-driven water-splitting system. The solar-to-hydrogen conversion efficiency, ηSTH , calculated using the multiphysics numerical simulation was in excellent agreement with the experimental behavior of the system. The value of ηSTH was entirely limited by the performance of the photoelectrochemical assemblies employed in this study. The louvered design provides a robust platform for implementation of various types of photoelectrochemical assemblies, and can provide an approach to significantly higher solar conversion efficiencies as new and improved materials become available.

A direct thin-film path towards low-cost large-area III-V photovoltaics.

III-V photovoltaics (PVs) have demonstrated the highest power conversion efficiencies for both single- and multi-junction cells. However, expensive epitaxial growth substrates, low precursor utilization rates, long growth times, and large equipment investments restrict applications to concentrated and space photovoltaics (PVs). Here, we demonstrate the first vapor-liquid-solid (VLS) growth of high-quality III-V thin-films on metal foils as a promising platform for large-area terrestrial PVs overcoming the above obstacles. We demonstrate 1-3 µm thick InP thin-films on Mo foils with ultra-large grain size up to 100 µm, which is ~100 times larger than those obtained by conventional growth processes. The films exhibit electron mobilities as high as 500 cm²/V-s and minority carrier lifetimes as long as 2.5 ns. Furthermore, under 1-sun equivalent illumination, photoluminescence efficiency measurements indicate that an open circuit voltage of up to 930 mV can be achieved, only 40 mV lower than measured on a single crystal reference wafer.

Embedded binary eutectic alloy nanostructures: a new class of phase change materials.

Phase change materials are essential to a number of technologies ranging from optical data storage to energy storage and transport applications. This widespread interest has given rise to a substantial effort to develop bulk phase change materials well suited for desired applications. Here, we suggest a novel and complementary approach, the use of binary eutectic alloy nanoparticles embedded within a matrix. Using GeSn nanoparticles embedded in silica as an example, we establish that the presence of a nanoparticle/matrix interface enables one to stabilize both nanobicrystal and homogeneous alloy morphologies. Further, the kinetics of switching between the two morphologies can be tuned simply by altering the composition.

Predicting the response of a submillimeter bolometer to cosmic rays.

Bolometers designed to detect submillimeter radiation also respond to cosmic, gamma, and x rays. Because detectors cannot be fully shielded from such energy sources, it is necessary to understand the effect of a photon or cosmic-ray particle being absorbed. The resulting signal (known as a glitch) can then be removed from raw data. We present measurements using an Americium-241 gamma radiation source to irradiate a prototype bolometer for the High Frequency Instrument in the Planck Surveyor satellite. Our measurements showed no variation in response depending on where the radiation was absorbed, demonstrating that the bolometer absorber and thermistor thermalize quickly. The bolometer has previously been fully characterized both electrically and optically. We find that using optically measured time constants underestimates the time taken for the detector to recover from a radiation absorption event. However, a full thermal model for the bolometer, with parameters taken from electrical and optical measurements, provides accurate time constants. Slight deviations from the model were seen at high energies; these can be accounted for by use of an extended model.