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At least 487 records · Page 27

In Situ Aerosol Detector

An affordable technology designed to facilitate extensive global atmospheric aerosol measurements has been developed. This lightweight instrument is compatible with newly developed platforms such as tethered balloons, blimps, kites, and even disposable instruments such as dropsondes. This technology is based on detection of light scattered by aerosol particles where an optical layout is used to enhance the performance of the laboratory prototype instrument, which allows detection of smaller aerosol particles and improves the accuracy of aerosol particle size measurement. It has been determined that using focused illumination geometry without any apertures is advantageous over using the originally proposed collimated beam/slit geometry (that is supposed to produce uniform illumination over the beam cross-section). The illumination source is used more efficiently, which allows detection of smaller aerosol particles. Second, the obtained integral scattered light intensity measured for the particle can be corrected for the beam intensity profile inhomogeneity based on the measured beam intensity profile and measured particle location. The particle location (coordinates) in the illuminated sample volume is determined based on the information contained in the image frame. The procedure considerably improves the accuracy of determination of the aerosol particle size.

Vakhtin, Andrei↗

The New Sun-Sky-Lunar Cimel CE318-T Multiband Photometer - A Comprehensive Performance Evaluation

This paper presents the new photometer CE318-T, able to perform daytime and night-time photometric measurements using the sun and the moon as light source. Therefore,this new device permits a complete cycle of diurnal aerosol and water vapour measurements valuable to enhance atmospheric monitoring to be extracted. In this study wehave found significantly higher precision of triplets when comparing the CE318-T master instrument and the Cimel AErosol RObotic NET work (AERONET) master (CE318-AERONET) triplets as a result of the new CE318-T tracking system. Regarding the instrument calibration, two new methodologies to transfer the calibration from a reference instrument using only daytime measurements (Sun Ratio and Sun-Moon gain factor techniques) are presented and discussed. These methods allow the reduction of the previous complexities inherent to nocturnal calibration. A quantitative estimation of CE318-T AOD uncertainty by means of error propagation theory during daytime revealed AOD uncertainties (u(sup D)(sub AOD)) for Langley-calibrated instruments similar to the expected values for other reference instruments (0.002-0.009). We have also found u(sup D)(sub AOD) values similar to the values reported in sun photometry for field instruments (approximately 0.015). In the case of the night-time period, the CE318-T-estimated standard combined uncertainty (u(sup N)(sub AOD)) is dependent not only on the calibration technique but also on illumination conditions and the instrumental noise. These values range from 0.011-0.018 for Lunar Langley-calibrated instruments to 0.012-0.021 for instruments calibrated using the Sun Ratio technique. In the case of moon-calibrated instruments using the Sun-Moon gain factor method and sun calibrated using the Langley technique, we found u(sup N)(sub AOD) ranging from 0.016 to 0.017 (up to 0.019 in 440 nm channel), not dependent on any lunar irradiance model. A subsequent performance evaluation including CE318-T and collocated measurements from independent reference instruments has served to assess the CE318-T performance as well as to confirm its estimated uncertainty. Daytime AOD evaluation, performed at Izana station from March to June 2014, encompassed measurements from a reference CE318-T, a CE318-AERONET master instrument, a Precision Filter Radiometer (PFR) and a Precision Spectroradiometer (PSR) prototype, reporting low AOD discrepancies between the four instruments (up to 0.006). The nocturnal AOD evaluation was performed using CE318-T- and starphotometer-collocated measurements and also by means of a day/night coherence transition test using the CE318-T master instrument and the CE318 daytime data from the CE318-AERONET master instrument. Results showed low discrepancies with the star photometer at 870 and 500 nm channels(less tna or equal to 0.013) and differences with AERONET daytime data (1 h after and before sunset and sunrise) in agreement with the estimated u(sup N)(sub AOD) values at all illumination conditions in the case of channels within the visible spectral range, and only for high moon's illumination conditions in the case of near infrared channels. Perceptible water vapour (PWV) validation showed a good agreement between CE318-T and Global Navigation Satellite System (GNSS) PWV values for all illumination conditions, within the expected precision for sun photometry. Finally, two case studies have been included to highlight the ability of the new CE318-T to capture the diurnal cycle of aerosols and water vapour as well as short-term atmospheric variations, critical for climate studies.

Barreto, Africa↗

Scattering By Relatively Small Oblate Spheroidal Drops of Water in the Rainbow Region: T-Matrix Results and Geometric Interpretation

Late in 1999 Michael Mishchenko carried out T-matrix calculations of light scattered by oblate spheroidal drops of water at Marston's request. The purpose of the investigation was to determine if the caustic features, known by that time to be visible in the far-field scattering near the primary rainbow region for horizontally illuminated relatively large drops, would also be present in T-matrix calculations of the scattering by small drops. The axis of rotational symmetry of the drop was taken to be vertical, and the illumination was taken to be horizontal. Scattering into the relevant angular region was evaluated for drop aspect ratios D/H = 1, 1.23, 1.311, and 1.37 where D denotes the equatorial diameter and H the vertical diameter. The results are limited to polarized monochromatic illumination with ka = 140 where a = D/2 and k = 2π/λ with λ being the wavelength of the illumination. As expected from geometrical analysis, a horizontal “V” shaped caustic is visible for D/H = 1.311. The T-matrix results, gray-tone intensity displays provided by Mishchenko, remain instructive.

Scattering by spheroids↗

Orion Cabin Lighting System: Filter Workaround for Maintaining Crew Circadian Entrainment

Introduction: Suboptimal crew circadian entrainment (CCE) is common and results in cumulative fatigue and reduced cognitive function. This may promote use of psychostimulants and hypnotics. The Orion Cabin Lighting System (OCLS) consists of 15 dimmable lamps circuited to several zones. The OCLS monochromatic white lamp design is insufficient for maintaining CCE. While blue light (480-nm) elicits peak wake-cycle response, it is a powerful disruptor of CCE. We propose OCLS lamp filters (OLFs) as a workaround for maintaining CCE. Methods: Preliminary OLFs testing utilized a tunable-white LED to serve as a baseline lamp in the NASA Lighting Lab’s controlled environment (prototype OCLS lamps were unavailable). Illuminance and spectral irradiances were measured with the NASA Lighting Lab’s spectroradiometer. ConOps is proposed for OLFs. Results: OLFs markedly attenuated 480-nm light and illumination with minimal mass/volume requirements. ConOps includes in-flight deployment of OLFs and reducing OCLS lamp intensity prior to bedtime. Pros: minimal mass/volume, no added power, and a simplistic design. Cons: manual twice-daily articulation of OLFs, undetermined frangibility/flammability/off-gassing and effects on thermal regulation, and untested task illumination or color fidelity in the Orion cabin. Discussion: While OLFs aptly attenuate 480-nm light from our tunable LED lamp in the Lighting Lab’s controlled environment, they remain untested within the Orion cabin on OCLS lamps. Future tests include Orion cabin illumination optimization for appropriate Lux delivery and ensuring task/color fidelity with OLFs deployed. Adequate OCLS cooling should be similarly assessed. Other safety testing includes OLF frangibility/flammability/off-gassing in an enriched-O 2 /hypobaric environment. Together, these data will demonstrate OLFs provide a viable workaround for maintaining CCE further ensuring mission safety and success.

Carlos Rene Dostal↗

Non-contact rapid reader system for reflective particle tags

A reflective particle tag reader system includes a read head assembly having a camera, illuminators, and a rigid frame portion for supporting the camera and the illuminators. The illuminators illuminate a focal point located opposite the camera where a reflective particle tag is placed. A computer in data communication with the camera receives and store images of the reflective particle tag that are acquired by the camera. The computer is programmed to process video images and to quantify a positional alignment parameter and an angular alignment parameter of the reader with respect to the reflective particle tag. A rapid burst of image frames is obtained in response to the positional alignment and the angular alignment parameters being within a predetermined tolerance and identity of the reflective tag is established between a first image set and a second image set.

42 ENGINEERING↗

Soft X-ray quantum efficiency of a commercial CMOS imaging sensor

The demonstrated performance and cost-effectiveness of complementary metal-oxide-semiconductor (CMOS) sensors make them a potentially attractive option for low-cost space-based X-ray observatories. We have previously reported on the performance of a commercially available backside-illuminated Sony IMX290LLR-C CMOS sensor and found it to offer X-ray spectral resolutions comparable to the charged coupled devices (CCDs) aboard Suzaku and Chandra and to have a sufficient radiation hardness for use in low Earth orbit. Here, in this work, we report on the quantum efficiency (QE) of this sensor, an essential metric for modeling the sensitivity of an instrument as an X-ray detector. Using the Advanced Photon Source at Argonne National Laboratory, we measure the soft X-ray QE of this CMOS sensor to be 0.28 ± 0.02 at a photon energy of 490.5 eV. This energy was chosen for its proximity to the astrophysically important O VII triplet emission lines (~574 eV) studied by the HaloSat mission. Although not surpassing that of the back-illuminated CCDs aboard Suzaku and Chandra, this QE compares favorably to that of the front-illuminated CCDs aboard the same observatories and is competitive with that of the silicon drift detectors used aboard HaloSat, making it a strong candidate for use on future X-ray small satellite (SmallSat) missions.

47 OTHER INSTRUMENTATION↗

Atomistic Probing of Defect-Engineered 2H-MoTe 2 Monolayers

Point defects dictate various physical, chemical, and optoelectronic properties of two-dimensional (2D) materials, and therefore, a rudimentary understanding of the formation and spatial distribution of point defects is a key to advancement in 2D material-based nanotechnology. In this work, we performed the demonstration to directly probe the point defects in 2H-MoTe 2 monolayers that are tactically exposed to (i) 200 °C-vacuum-annealing and (ii) 532 nm-laser-illumination; and accordingly, we utilize a deep learning algorithm to classify and quantify the generated point defects. We discovered that tellurium-related defects are mainly generated in both 2H-MoTe 2 samples; but interestingly, 200 °C-vacuum-annealing and 532 nm-laser-illumination modulate a strong n-type and strong p-type 2H-MoTe 2 , respectively. While 200 °C-vacuum-annealing generates tellurium vacancies or tellurium adatoms, 532 nm-laser-illumination prompts oxygen atoms to be adsorbed/chemisorbed at tellurium vacancies, giving rise to the p-type characteristic. This work significantly advances the current understanding of point defect engineering in 2H-MoTe 2 monolayers and other 2D materials, which is critical for developing nanoscale devices with desired functionality.

2H-MoTe 2↗

Light-enhanced oxygen degradation of MAPbBr 3 single crystal

Organometal halide perovskites are promising materials for optoelectronic applications, whose commercial realization depends critically on their stability under multiple environmental factors. In this study, a methylammonium lead bromide (MAPbBr 3 ) single crystal was cleaved and exposed to simultaneous oxygen and light illumination under ultrahigh vacuum (UHV). The exposure process was monitored using X-ray photoelectron spectroscopy (XPS) with precise control of the exposure time and oxygen pressure. It was found that the combination of oxygen and light accelerated the degradation of MAPbBr 3 , which could not be viewed as a simple addition of that by oxygen-only and light-only exposures. The XPS spectra showed significant loss of carbon, bromine, and nitrogen at an oxygen exposure of 10 10 Langmuir with light illumination, approximately 17 times of the additive effects of oxygen-only and light-only exposures. It was also found that the photoluminescence (PL) emission was much weakened by oxygen and light co-exposure, while previous reports had shown that PL was substantially enhanced by oxygen-only exposure. Measurements using a scanning electron microscope (SEM) and focused ion beam (FIB) demonstrated that the crystal surface was much roughened by the co-exposure. Furthermore, Density functional theory (DFT) calculations revealed the formation of superoxide and oxygen induced gap state, suggesting the creation of oxygen radicals by light illumination as a possible microscopic driving force for enhanced degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lasing dynamics of diode-pumped Yb – Er laser with a passive Q switch exposed to high-power external light

The temporal dynamics of diode-side-pumped Yb – Er laser, with a passive Co{sup 2+} : MgAl{sub 2}O{sub 4} Q switch illuminated by a light beam (total fluence of 0.15 – 0.16 J cm{sup −2}) from a semiconductor pulsed module, is investigated. It is shown that, using this external illumination, one can change the lasing onset delay and the time jitter ΔT{sub gi}. The dependence of ΔT{sub gi} on the interval between the instant of switching the illumination module on and the lasing peak position t{sub i} has a minimum at |t{sub i}| ≈ 10 μs. The decrease in ΔT{sub gi} with a change in |t{sub i}| from 90 to 10 μs indicates that instant of lasing peak occurrence for the Yb – Er laser is partially controlled by the pulse from the highly stable semiconductor module. If |t{sub i}| < 10 μs, the enhanced luminescence fluence in the cavity of Yb – Er laser exceeds 0.16 J cm{sup −2}; the light beam from the module does not affect much the lasing process in the ytterbium – erbium laser; and, as a consequence, the time jitter recovers the initial value. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Sedimentology of Martian Gravels from Mardi Twilight Imaging: Techniques

Quantitative sedimentologic analysis of gravel surfaces dominated by pebble-sized clasts has been employed in an effort to untangle aspects of the provenance of surface sediments on Mars using Curiosity's MARDI nadir-viewing camera operated at twilight Images have been systematically acquired since sol 310 providing a representative sample of gravel-covered surfaces since the rover departed the Shaler region. The MARDI Twilight imaging dataset offers approximately 1 millimeter spatial resolution (slightly out of focus) for patches beneath the rover that cover just under 1 m2 in area, under illumination that makes clast size and inter-clast spacing analysis relatively straightforward using semi- automated codes developed for use with nadir images. Twilight images are utilized for these analyses in order to reduce light scattering off dust deposited on the front MARDI lens element during the terminal stages of Curiosity's entry, descent and landing. Such scattering is worse when imaging bright, directly-illuminated surfaces; twilight imaging times yield diffusely-illuminated surfaces that improve the clarity of the resulting MARDI product. Twilight images are obtained between 10-30 minutes after local sunset, governed by the timing of the end of the no-heat window for the camera. Techniques were also utilized to examine data terrestrial locations (the Kau Desert in Hawaii and near Askja Caldera in Iceland). Methods employed include log hyperbolic size distribution (LHD) analysis and Delauney Triangulation (DT) inter-clast spacing analysis. This work extends the initial results reported in Yingst et al., that covered the initial landing zone, to the Rapid-Transit Route (RTR) towards Mount Sharp.

sedimentologic↗

Imaging Photonic Resonances within an All‐Dielectric Metasurface via Photoelectron Emission Microscopy

Dielectric metasurfaces, through volume‐type photonic resonances, enable precise control of light‐matter interactions for applications including imaging, holography, and sensing. The application space of dielectric metasurfaces has extended from infrared to visible wavelengths by incorporating high refractive index materials, such as titanium dioxide (TiO 2 ). Understanding the fundamental and fabrication limits for these applications requires metrology with nanoscale resolution, sensitivity to electromagnetic fields within the meta‐atom volume, and far‐field excitation. In this work, photoelectron emission microscopy (PEEM) is used to image field distributions of photonic resonances in a TiO 2 metasurface excited with far‐field, visible‐wavelength illumination. The local volumetric field variations within the meta‐atoms are analyzed as a function of illumination angle and polarization by comparing photoelectron images to finite‐difference time‐domain simulations. This study determines the inelastic mean free path of very low‐energy (<1 eV) photoelectrons to be 35 ± 10 nm, which is comparable to the meta‐atom height thereby highlighting PEEM sensitivity to resonances within the volume. Additionally, the simulations reveal high sensitivity of PEEM images to an in‐plane component of the illumination k ‐vector. These results demonstrate that photoelectron imaging with subwavelength resolution offers unique advantages for examining light‐matter interactions in volume‐type (as opposed to surface) photonic modes within dielectric nanophotonic structures.

electron inelastic mean free path↗

Degradation and Accelerated Recovery of Surface Passivation in n+, p+, and Intrinsic Poly-Si/SiOx Passivating Contacts for Silicon Solar Cells

We report on the degradation and recovery of surface passivation of fired poly-Si/SiOx passivating contacts with hydrogen containing Al2O3 during annealing in the dark and under illumination. Upon firing to a peak temperature of 670 degrees C, the iVoc for symmetric test structures with n+, p+, and intrinsic poly-Si/SiOx contacts decreases due to a loss of surface passivation. Upon further annealing over the temperature range of 200-350 degrees C in the dark, depending on the type of doping, the surface passivation either shows further degradation followed by recovery, or direct recovery to the initial iVoc. Annealing at higher temperatures and/or higher illumination intensities accelerates the kinetics for both degradation and recovery processes. We show that the degradation and recovery processes are thermally activated and proceed identically in subsequent firing and annealing steps showing their cyclic nature. We present a series reaction model to explain the kinetics of degradation and recovery processes for n+ and intrinsic poly-Si/SiOx contacts. By fitting the model's rate expressions to the data, the determined effective activation energy barriers for degradation and recovery for n+ poly-Si/SiOx contacts in the dark are 1.24 and 1.51 eV, which are lowered under 7.5 Suns illumination to 0.76 and 1.15 eV, respectively.

14 SOLAR ENERGY↗

Benchmarking image processing techniques for porosity measurement in polymer additive manufacturing: Review and experimental analysis

An image processing workflow is proposed for porosity measurement in polymer additive manufacturing. Various techniques, including global and local thresholding, region growing, and K-means clustering, were applied to microscopic images of carbon fiber reinforced acrylonitrile butadiene styrene (CF-ABS) and benchmarked for their ability to accurately measure porosity. Global methods included Otsu, minimum error, iterative, and entropy-based thresholding, while local methods included Niblack, Bernsen, Sauvola, and Bradley-Roth algorithms. Artificial uneven illumination was introduced to test local adaptive thresholds. Results showed significant differences in porosity values across methods. Otsu, region growing, and K-means clustering excelled under uniform illumination, while Sauvola and Bradley-Roth performed better with uneven illumination. Comparison with X-ray computed tomography (XCT) revealed slightly lower porosity values (2.55 %) than optimized methods (2.73–2.79 %) due to XCT's lower resolution excluding smaller pores. While XCT offers finer pore detection, it limits sample volume and underestimates porosity due to spatial variation. Validation using artificial grayscale images with 5 % porosity confirmed that Otsu, Bradley-Roth, region growing, and Sauvola algorithms produced accurate results. Although tested on a single material system, these methods can be adapted to others with optimization. In conclusion, given XCT's high computational and time costs, this study highlights suitable image processing techniques as cost-effective alternatives for porosity analysis in polymer composites.

Additive manufacturing↗

Investigating feasible light configurations for fish restoration: an ethological insight

Light environment significantly impacts the effectiveness of fish population restoration in developed watersheds, subserving fish passage reconstruction in hydraulic complex and habitat rehabilitation. To develop an interior connection between light-related fish response from the laboratory and field fish conservation practice, we employed a new indexing system, consisting of phototaxis rate, relative swimming speed (RSS), and optic evasion coefficient (OEC), to quantify the light-induced behaviors in Ptychobarbus kaznakovi, a representative rare cyprinid in Tibet, China, at four experimental illuminance levels (15 lx, 30 lx, 60 lx, 120 lx) and four wavelengths (red, yellow, green, blue). The fish showed negative phototaxis at all given illuminances and wavelengths. Under red light, the OEC increased significantly from 0.642 at 15 lx to 0.782 at 30 lx (P = 0.029), while the RSS decreased significantly from 3.752 to 2.383 (P < 0.001). Behaviorally, the fish shifted from sprint to wandering around, indicating the alteration of dominant physiological activity from behavioral stress response to negative phototaxis. Under the green treatment, P. kaznakovi swam around quickly and presented slight negative phototaxis, and OEC values were uniform among all illuminances, probably because of the similarity of green light to the ambient color of the habitat. Accordingly, ecologists and fisheries practitioners can utilize red light to exclude fish from dangerous waters and green light to guide them to ideal habitats, laying the necessary groundwork for the light-driven fish recovery effort. Furthermore, the appropriate light configuration can yield economic benefits through the tradeoff among fish protection, power generation, and investment costs.

Lin, Chenyu↗

Electro and electro-photo plasticity of CdZnTeSe and CdZnTe

In this work, we studied the influence of applied bias on of the Vickers microhardness HV 0.025 of CdZnTeSe and CdZnTe semi-insulating samples without and with the illumination of light at 870 nm. We observed that a small applied bias results in the hardening of the material. The effect is strongest at a bias of ± 0.5 V and is further strengthened by additional illumination. We suggest that the observed positive electro and electro-photo plastic effects in CdZnTeSe and CdZnTe can be explained by an increase in the concentration of free electrons and holes injected from contacts in a biased sample or generated by illumination. These free carriers can be trapped at dislocations and induce a reconstruction of bonds at the dislocation core. The necessity to break the bonds before dislocation glide results in an increase of microhardness.

36 MATERIALS SCIENCE↗

Experimental demonstration and performance evaluation of a complex fenestration system for daylighting and thermal harvesting

Two significant design strategies for mitigating building energy consumption are daylight redirection and solar energy harvesting. Effective daylighting implementation enhances the amount of useful natural light within a space and offsets the need for electric lighting. Solar energy harvesting systems can mitigate energy costs from mechanical systems by managing incoming thermal loads or capturing solar energy that can be used to supplement thermal systems in the building. While there are many available façade-based technologies that can perform daylighting or solar thermal energy harvesting, there remains a limitation in available systems that can perform both of them simultaneously. This paper, describes the design and experimental demonstration of a Liquid Filled Prismatic Louver (LFPL) system, which combines both energy-saving strategies. The LFPL system was installed in a south-facing room in New York City and evaluated for indoor daylight penetration and potential for thermal energy harvesting. Daylight redirection is achieved through the prismatic louver geometry and proper orientation, whereas thermal energy harvesting is achieved through IR absorption from the liquid (e.g., water) within the prisms. Daylighting performance was evaluated by illuminance measurements at key locations within the space, whereas thermal harvesting performance was evaluated through temperature measurements and thermal imaging analysis. We show that the LFPL system, with all prismatic elements oriented at the same angle, achieve a 2-fold and 8-fold enhancement in daylight redirection to the ceiling, for prism orientations of 10° and 20°, respectively. We also demonstrate the system’s capability to adjust to specific lighting needs, within the space, through the dynamic individual orientation of prismatic elements; thus, achieving a concentrated ceiling illuminance enhancement of ~100 times and ~200 times at 2.5 and 4.3 m away from the window sill, providing workplane illuminance enhancement of 6 and 2 times more than in the case of the control room with regular windows. Furthermore, we illustrate a reduction of potential heating loads at locations close to the window from the combination of infrared absorption in the water volume and the redirection of the incoming solar radiation, leading to a reduction of the workplane temperature by an average of 7–10 °C.

14 SOLAR ENERGY↗

Lighting and visual comfort performance of commercially available tubular daylight devices

Tubular daylight devices (TDDs) require a much smaller roof opening than conventional skylights and, because of their highly reflective tube, they can deliver daylight farther away from the building envelope. This can provide lighting energy savings, increasing resilience in new and existing buildings. Different types and configurations are available amongst commercially available TDDs, including domes/diffusers with varying optical properties and the diameter of the TDD. This paper presents a comprehensive experimental evaluation of the lighting and visual comfort performance of multiple configurations of commercially available TDDs, varying dome type (prismatic and clear), diffuser type (Fresnel and prismatic), and diameter (53 and 35 cm), under a range of environmental conditions (different times of day/year, sky cover). Based on illuminance measurements, estimated lighting energy use is also presented. Results indicate that, for clear sky, light levels increase and energy use decreases with solar altitude (e.g., 16 Wh/m 2 daily energy use intensity on a high maximum daily solar altitude (MDSA) day and 34 Wh/m 2 on a low MDSA day) and TDD diameter (e.g., 34 Wh/m 2 and 69 Wh/m 2 for 53 cm and 35 cm TDDs, respectively, for low MDSA). The daily illuminance profile is more rounded for prismatic domes and has higher peaks for clear domes; this translates into a somewhat higher average daily useful daylight illuminance (DUDI) for prismatic domes (86 %) when compared to clear domes (80 %). No clear impact of diffuser type was apparent. In conclusion, measurements indicated no discomfort glare for any of the conditions tested.

14 SOLAR ENERGY↗

Understanding and Controlling the Performance-Limiting Steps of Catalyst-Modified Semiconductors

Understanding and controlling factors that restrict the rates of fuel-forming reactions are essential to designing effective catalyst-modified semiconductors for applications in solar-to-fuel technologies. Herein, we describe GaAs semiconductors featuring a polymeric coating that contains cobaloxime-type catalysts for photoelectrochemically powering hydrogen production. The activities of these electrodes (limiting current densities >20 mA cm –2 under 1-sun illumination) enable identification of fundamental performance-limiting bottlenecks encountered at relatively high rates of fuel formation. Experiments conducted under varying bias potential, pH, illumination intensity, and scan rate reveal two distinct mechanisms of photoelectrochemical hydrogen production. At relatively low polarization and pH, the limiting photoactivity is independent of illumination conditions and is attributed to a mechanism involving reduction of substrate protons. At relatively high polarization or pH, the limiting photoactivity shows a linear response to increasing photon flux and is attributed to a mechanism involving reduction of substrate water. Furthermore, this work illustrates the complex interplay between transport of photons, electrons, and chemical substrates in photoelectrosynthetic reactions and highlights diagnostic tools for better understanding these processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗