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RADAI: A Large-Scale Realistic Dataset for Radiation Detection Algorithm Development

Open, realistic datasets are essential for developing and benchmarking radiation detection algorithms, yet they remain scarce. The Radiological Anomaly Detection and Identification (RADAI) project was develop to create datasets that meet the training and testing needs for sophisticated radiation detection algorithms. The RADAI dataset is a large-scale synthetic resource that integrates high-fidelity Monte Carlo simulations with realistic urban scenarios to capture both background variability and source signatures. RADAI models construction-material NORM, people and vehicles, urban clutter, and dynamic environmental effects such as cosmic-ray and rain-induced transients, and they provide list-mode detector data with motion and response modeling suitable for algorithm training and evaluation. The RADAI project resulted in three publicly-released complementary datasets together with an online scoring portal for standardized performance assessment and an open software toolkit that supports data access, augmentation, model development, and evaluation. These resources enable reproducible comparisons across methods and promote rigorous studies at the scale required by contemporary machine learning. By grounding algorithm development in realistic, well-documented conditions, RADAI supports progress toward more robust detection, identification, and localization in complex urban environments.

Ghawaly, James M. [Division of Computer Science an

Rapid Assessment of Sulfate Resistance in Mortar and Concrete

Extensive research has been conducted on the sulfate attack of concrete structures; however, the need to adopt the use of more sustainable materials is driving a need for a quicker test method to assess sulfate resistance. This work presents accelerated methods that can reduce the time required for assessing the sulfate resistance of mixtures by 70%. Class F fly ash has historically been used in concrete mixtures to improve sulfate resistance. However, environmental considerations and the evolving energy industry have decreased its availability, requiring the identification of economically viable and environmentally friendly alternatives to fly ash. Another challenge in addressing sulfate attack durability issues in concrete is that the standard sulfate attack test (ASTM C1012) is time-consuming and designed for only standard mortars (not concrete mixtures). To expedite the testing process, accelerated testing methods for both mortar and concrete mixtures were adopted from previous work to further the development of the accelerated tests and to assess the feasibility of testing the sulfate resistance of mortar and concrete mixtures rapidly. This study also established criteria for interpreting sulfate resistance for each of the test methods used in this work. A total of 14 mortar mixtures and four concrete mixtures using two types of Portland cement (Type I and Type I/II) and various supplementary cementitious materials (SCMs) were evaluated in this study. The accelerated testing methods significantly reduced the evaluation time from 12 months to 21 days for mortar mixtures and from 6 months to 56 days for concrete mixtures. The proposed interpretation method for mortar accelerated test results showed acceptable consistency with the ACI 318-19 interpretations for ASTM C1012 results. The interpretation methods proposed for the two concrete sulfate attack tests demonstrated excellent consistency with the ASTM C1012 results from mortar mixtures with the same cementitious materials combinations. Metakaolin was shown to improve sulfate resistance for both mortar and concrete mixtures, while silica fume and natural pozzolan had a limited impact. Using 15% metakaolin in mortar or concrete mixtures with Type I/II cement provided the best sulfate resistance.

Chemistry

Battery Failure Databank

The Battery Failure Databank contains thermal runaway results gathered from nearly 300 small format fractional thermal runaway calorimetry (S-FTRC) experiments. A majority of these experiments were conducted at synchrotron facilities where high-speed x-ray videography was conducted of the cell while tested inside of the S-FTRC. The databank is a two-component system which consists of a Microsoft ExcelTM spreadsheet which provides S-FTRC results in tabular format and a radiographic video library containing the high-speed x-ray videos. Overall, the databank provides thermal results from S-FTRC experiments conducted on a mixture of commercially available lithium-ion (Li-ion) cells and specialized Li-ion test cells with varying cell format (18650, 21700, and D-cell) and trigger mechanism (heaters, heaters plus internal short circuiting device, and nail penetration). The radiography video component provides insight into the initiation and propagation of TR in the cells, in addition to consequences of TR measured by the FTRC. Fractions of mass ejected for the cell types are separated into regimes based on the different failure modes of the cells, such as purely venting, partial ejection, and total ejection. With knowledge of the rate and characterization of the internal degradation of the cells during TR, and the amounts of mass ejected and unrecovered, the extent of TR, and therefore the mitigation of TR, is revealed relative to cell types and failure modes.

Lithium-ion battery

An Overview of Experiments and Modeling of Polysiloxane-Coated Thermal Protection Systems for Missions to Mars, Titan, and Beyond.

Phenolic Impregnated Carbon Ablator (PICA) gained heritage during the historic Stardust mission, where it successfully returned samples from a comet’s tail and has since been instrumental in delivering payloads to the surface of Mars [1-3]. Most recently, PICA enabled the safe return of samples collected from asteroid Bennu as part of the OSIRIS-REx mission. This rich legacy underscores PICA’s critical role in allowing NASA’s most ambitious exploration missions. However, the friable nature of its phenolic phase presents challenges during handling and pre-launch activities. To mitigate this issue, PICA is coated with a polysiloxane resin system, which serves to suppress particulate dispersion and thereby safeguard spacecraft components. A comprehensive understanding of the polysiloxane resin’s behavior is imperative, as it profoundly shapes the material response of PICA during atmospheric entry by influencing its thermal and oxidative stability. This influence extends to thermocouple plugs embedded within thermal protection systems. These plugs have demonstrated their significance in missions such as Mars Science Laboratory (MSL) and Mars 2020, where the MEDLI and MEDLI2 instrumentation suites delivered in-valuable insights into the performance of thermal protection systems during entry into the Martian atmosphere [4]. Looking ahead, missions such as Dragonfly, set to descend into Titan’s dense atmosphere, aim to leverage advanced sensor technologies to further refine our understanding of thermal protection response [5]. Moreover, thermocouple plugs play an essential role in validating cutting-edge material response models, such as those pioneered under NASA’s Entry Systems Modeling Project (ESM), designed, in-part, to predict the operational integrity of thermal protection systems under the extreme stresses of atmospheric entry. To achieve these modeling goals, ground-based experiments are crucial to provide the foundational data necessary for developing and refining these predictive tools. To this end, an extensive test campaign was conducted at the Hypersonic Materials Environmental Test System (HyMETS) to investigate the high-temperature behavior of the polysiloxane resin in an air environment [6]. These experiments revealed critical phenomena, including the formation of a silicon oxycarbide layer that enhances oxidation resistance, moderates surface temperatures, and alters in-depth thermal response. Building on these findings, subsequent tests were designed to simulate atmospheric entry conditions in reactive gases, such as CO2 and N2, to mimic the environments of Mars and Titan, respectively, as well as non-reactive gases representing the atmospheres of the Ice Giants (Neptune and Uranus). A heating rate dependent decomposition mechanism has been identified for the polysiloxane resin under oxidizing conditions (Fig. 1). In the initial stage, the resin and the underlying thermal protection system undergo pyrolysis, rapidly generating a thin amorphous silicon oxycarbide interwoven with carbonaceous char and residual fibers from PICA. During the second stage, the nascent oxide layer establishes a robust, oxidation-resistant thermal barrier coating, which significantly impedes heat transfer to the underlying carbonaceous char, resulting in a stagnation of the surface temperature. A key factor contributing to this thermal resistance is the low recombination efficiency of atomic oxygen (γ), which further diminishes the heat load on the material’s interior layers [7]. Moreover, as the surface temperature stagnates, the silicon oxycarbide phase separates into distinct regions of silica and free graphite. Ultimately, when the heat flux reaches a critical threshold, a third stage is triggered, leading to the breakdown of the coating through carbothermal reduction, exposing the underlying char layer. This exposure leads to a dramatic surface temperature spike, driven by highly exothermic reactions between atomic oxygen and the char layer, further accelerating material degradation. A detailed mass and heat transfer model of PICA coated with polysiloxane resin was implemented in the Porous material Analysis Toolbox based on OpenFOAM, PATO [8]. The initial stage was considered negligible in this model because the resin decomposition occurs rapidly within a thin surface layer. Instead, the coating was directly considered as an oxygen-resistant thermal barrier coating. For the second stage, the thin amorphous silicon oxycarbide was treated as a pure silica surface to simplify the thermochemical behavior. The model ac-counts for surface equilibrium processes using representative elements of the coating-environment system. For the third stage, specific boundary conditions were developed to estimate the onset and progression of the coating removal. Two-dimensional material response simulations were conducted to compare uncoated and coated PICA using boundary conditions calibrated with HyMETS data. Fig. 2 illustrates that the simulations closely align with experimental data, successfully reproducing measured temperature profiles. This work will include the latest advancements in the coating model, including the calibration of recombination of atomic oxygen at the surface during the second phase. These simulated results will be further validated against additional CO2 data points from HyMETS, reinforcing the models’ predictive capabilities. These mechanisms and their effects on thermal protection systems, including thermochemical behavior and thermocouple probe performance in extreme environments, provide crucial insights for optimizing spacecraft designs that safeguard scientific payload and ensure mission success in future planetary exploration endeavors.

Active Oxidation

First in operando transient grating spectroscopy measurements on tungsten during high flux plasma operation in PISCES-RF

This work details the construction and first in operando transient grating spectroscopy measurements conducted on PISCES-RF during plasma operation. A preliminary study on a tungsten sample with varied plasma species (Ar and D 2 ), ion flux (4 × 10 21 to 6 × 10 22 ion/m 2 /s), ion energy (5 to 80 eV), and surface temperature (20 to 200 °C) is presented. Prior to plasma exposure, the thermal diffusivity and surface acoustic wave (SAW) speed, (6.9 ± 0.2) × 10 −5 m 2 /s and (2.66 ± 0.02) km/s, were measured in situ with a thermal grating period of 12.5 μm. During Ar plasma exposure, these two quantities vary according to the sample surface temperature. At low flux and varied ion energy, D 2 plasma exposure also results in thermal diffusivity and SAW speed varying with surface temperature alone. At high flux, D 2 plasma exposure results in no convincing change to the thermal diffusivity, but the SAW speed is reduced. After returning to 20 °C, post plasma exposures, the thermal diffusivity and SAW speed almost recover to the initial value prior to exposure.

Surface acoustic wave SAW

Erosion, Corrosion and Foreign Object Damage Effects in Gas Turbines [Les consequences de l'endommagement des turbines I gaz par erosion, corrosion et objets étrangers]

The Conference Proceedings contains 31 papers presented at the Propulsion and Energetics Panel Symposium on Erosion, Corrosion and Foreign Object Damage Effects in Gas Turbines which was held from 25-28th April 1994, in Rotterdam, The Netherlands. The Technical Evaluation Report and the Keynote Address are included at the beginning and discussions follow most papers. The Symposium was arranged in the following Sessions: Operational Experience and Requirements (7); Deposition and Erosion (7); Foreign Object Damage (5); Coatings, Repairs and Materials Aspects - 1 (4); Coatings, Repairs and Materials Aspects - 2 (7); and Testing and Certification Procedures (1).

Deposition

Ground Slope Effects on Lander Radiator Performance

Two sensitivity studies were performed to examine the drop in radiator heat rejection from slopes. Study #1 used a 5.5m tall reduced order asset to represent a small-lander/rover. Study #2 used a 20m asset represent a tall lander. The assets had body mounted horizontal, 45º inward-tilted, and vertical radiator orientations. The impact of slopes on different radiator orientations and on radiators pointing different directions (i.e., slope verses sun) was investigated. The studies were conducted at a polar location of -82.5ºS to capture the incident solar flux at the northmost, and therefore the hottest, range of potential Artemis landing sites (Mons Mouton Plateau).

Lunar Slope

Barium Fluoride as a Standard Reference Material for Infrared Refractometry

This work proposes a standard reference material (SRM) for measurements of refractive index in the infrared spectral region (1–12 μm). The purpose of this material is to enable cross-method comparison of refractive index data obtained through minimum deviation, ellipsometry, interferometry, and prism coupling techniques. This will allow vendors and metrology laboratories, regardless of which technique they employ, to certify that their measurements meet required levels of accuracy, precision, and repeatability. Drawing on foundational work by Tilton at the National Bureau of Standards, a figure of merit for candidate SRM materials is outlined, and three materials are selected for further evaluation. Ultimately, barium fluoride is proposed as the most suitable SRM for the infrared spectral region, based on its broad transmission range, chemical and mechanical stability, low temperature dependence of refractive index, and well-characterized dispersion behavior.

Andrew Howe

Multifrequency, Multipolarization External Calibration of the SIR-C/X-SAR Radars

Progress and the future plans for the following objectives are discussed: (1) Assess the accuracy at which the SIR-C/X-SAR standard data products can be calibrated through the use of ground calibrators to estimate the end-to-end system polarization calibration constants (or distortion parameters) and incorporate the constants into the data processing; (2) Study the cross-calibration between three multipolarization systems: SIR-C, the National Aeronautics and Space Administration/Jet Propulsion Laboratory (NASA/JPL) DC-8 SAR, and the University of Michigan ground-based polarimetric scatterometer; (3) Evaluate the calibration "stability" of SIR-C/X-SAR (measured by variations in the calibration constants) over the range swath width and over a specified distance in azimuth. Variations over a 12-hour period (between ascending and descending passes) will also be studied; and (4) Develop a cost-effective calibration plan including development of inexpensive polarimetric active calibrators.

Anthony Freeman

Tree tensor network hierarchical equations of motion based on time-dependent variational principle for efficient open quantum dynamics in structured thermal environments

In this work, we introduce an efficient method, TTN-HEOM, for exactly calculating the open quantum dynamics for driven quantum systems interacting with highly structured bosonic baths by combining the tree tensor network (TTN) decomposition scheme with the bexcitonic generalization of the numerically exact hierarchical equations of motion (HEOM). The method yields a series of quantum master equations for all core tensors in the TTN that efficiently and accurately capture the open quantum dynamics for non-Markovian environments to all orders in the system–bath interaction. These master equations are constructed based on the time-dependent Dirac–Frenkel variational principle, which isolates the optimal dynamics for the core tensors given the TTN ansatz. The dynamics converges to the HEOM when increasing the rank of the core tensors, a limit in which the TTN ansatz becomes exact. We introduce TENSO, tensor equations for non-Markovian structured open systems, as a general-purpose Python code to propagate the TTN-HEOM dynamics. We implement three general propagators for the coupled master equations: two fixed-rank methods that require a constant memory footprint during the dynamics and one adaptive-rank method with a variable memory footprint controlled by the target level of computational error. We exemplify the utility of these methods by simulating a two-level system coupled to a structured bath containing one Drude–Lorentz component and eight Brownian oscillators, which is beyond what can presently be computed using the standard HEOM. Our results show that the TTN-HEOM is capable of simulating both dephasing and relaxation dynamics of driven quantum systems interacting with structured baths, even those of chemical complexity, with an affordable computational cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Radiative divertor detachment and impurity transport with nitrogen and neon seeding in KSTAR H-mode plasmas

Achieving core-edge compatible divertor detachment is a critical requirement for stable operation in future fusion devices. This study compares nitrogen and neon seeding in KSTAR H-mode plasmas with carbon walls, combining experiments and SOLPS-ITER modelling to evaluate their radiative dissipation and core-edge compatibility. Experimentally, N seeding achieved stronger divertor detachment, with larger reductions in target particle and heat fluxes, a higher divertor radiation fraction, and a lower core radiation fraction than Ne. In contrast, Ne seeding triggered a significant rise in core radiation followed by H–L back transitions, limiting the maximum total radiated power fraction to roughly half that of N. SOLPS-ITER simulations reproduced the experimental trends and revealed that the better core-edge compatibility of N arises from its higher divertor retention in addition to its higher cooling factor. The relative positions of the stagnation points of impurity poloidal velocity and ionization sources did not explain the different divertor compression. Instead, in the present modelling, the higher impurity parallel particle flux, resulting from the higher parallel impurity velocity, explains the stronger nitrogen impurity compression in the divertor region. The parallel temperature distribution with N was more favourable for achieving higher impurity parallel velocity than with Ne, because the impurity velocity is governed by modifications of the main ion flow due to friction and thermal forces, both of which strongly depend on the temperature. Ultimately, this behaviour is attributed to the strongly divertor-localized radiation of N. These results demonstrate that N is more effective than Ne in achieving radiative divertor detachment while maintaining low core contamination in KSTAR, consistent with observations in other present tokamaks.

KSTAR

Conclusions of a Cryogenic Motor Configuration Study for Aircraft Propulsion

Cryogenic electric machines are a promising technology for multi megawatt electric aircraft drivetrains. Superconducting stators that make use of low AC loss superconducting wires are considered to be a key component for these cryogenic machines. This paper shares the lessons learned from a design study that evaluated several configurations of a 5 MW cryogenic motor for this application. The lessons are drawn from a qualitative study of 16 configurations and a quantitative study of 8 down selected configurations. The quantitative study involved using analytical calculations (electromagnetic, thermofluid, mechanical, and motor sizing) to determine each configuration’s Pareto front of total efficiency and total specific power. The conclusions from a preliminary assessment of different stator conductors (superconductors and cryogenic metals) are also presented. One motor configuration is down selected for future detailed design and demonstration at the multi megawatt level.

Electrified aircraft propulsion

RG-CAT: Detection pipeline and catalogue of radio galaxies in the EMU pilot survey

Abstract We present source detection and catalogue construction pipelines to build the first catalogue of radio galaxies from the 270$\rm deg^2$pilot survey of the Evolutionary Map of the Universe (EMU-PS) conducted with the Australian Square Kilometre Array Pathfinder (ASKAP) telescope. The detection pipeline uses Gal-DINO computer vision networks (Gupta et al. 2024, PASA, 41, e001) to predict the categories of radio morphology and bounding boxes for radio sources, as well as their potential infrared host positions. The Gal-DINO network is trained and evaluated on approximately 5 000 visually inspected radio galaxies and their infrared hosts, encompassing both compact and extended radio morphologies. We find that the Intersection over Union (IoU) for the predicted and ground-truth bounding boxes is larger than 0.5 for 99% of the radio sources, and 98% of predicted host positions are within$3^{\prime \prime}$of the ground-truth infrared host in the evaluation set. The catalogue construction pipeline uses the predictions of the trained network on the radio and infrared image cutouts based on the catalogue of radio components identified using theSelavysource finder algorithm. Confidence scores of the predictions are then used to prioritiseSelavycomponents with higher scores and incorporate them first into the catalogue. This results in identifications for a total of 211 625 radio sources, with 201 211 classified as compact and unresolved. The remaining 10 414 are categorised as extended radio morphologies, including 582 FR-I, 5 602 FR-II, 1 494 FR-x (uncertain whether FR-I or FR-II), 2 375 R (single-peak resolved) radio galaxies, and 361 with peculiar and other rare morphologies. Each source in the catalogue includes a confidence score. We cross-match the radio sources in the catalogue with the infrared and optical catalogues, finding infrared cross-matches for 73% and photometric redshifts for 36% of the radio galaxies. The EMU-PS catalogue and the detection pipelines presented here will be used towards constructing catalogues for the main EMU survey covering the full southern sky.

Astronomy & Astrophysics

Building Operation Model (Morpheus) for Dallas Fort Worth Airport (CRADA CRD-19-16301 Final Report)

The primary objective of this project was to leverage digital twin technology to enhance the design and operation of DFW Airport terminals and their associated energy systems. To achieve this, Morpheus, a building digital twin, was developed to guide improvements in airport operations, specifically targeting reductions in peak power demand and overall energy consumption.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI

General Purpose Data-Driven Monitoring for Space Operations

As modern space propulsion and exploration systems improve in capability and efficiency, their designs are becoming increasingly sophisticated and complex. Determining the health state of these systems, using traditional parameter limit checking, model-based, or rule-based methods, is becoming more difficult as the number of sensors and component interactions grow. Data-driven monitoring techniques have been developed to address these issues by analyzing system operations data to automatically characterize normal system behavior. System health can be monitored by comparing real-time operating data with these nominal characterizations, providing detection of anomalous data signatures indicative of system faults or failures. Data-driven techniques have a number of advantages over other methods for monitoring complex space vehicles. Unlike model-based systems, the developer does not need to understand or encode the internal operation of the system. The knowledge required to monitor the system is automatically derived from archived data from system operation. Unlike rule-based systems, data-driven systems do not require system analysts to define nominal relationships among sensors. Analysts can and often do determine these relationships for a system with few sensors; it is more difficult to analytically determine the nominal relationship among a large number of sensors. Data-driven techniques are not limited to low-dimensional spaces and work as effectively with dozens of parameters as they do with a few. Knowledge bases formed by data-driven techniques are also easy to update. As the operating envelope of the monitored system is expanded, data-driven techniques can be quickly retrained to incorporate the new behavior into the knowledge base. The expertise and time-consuming process of updating a model or rule base to maintain consistency with the new operation is not required. The Inductive Monitoring System (IMS) is a data-driven system health monitoring software tool that has been successfully applied to several aerospace applications. IMS uses a data mining technique called clustering to analyze archived system data and characterize normal interactions between parameters. This characterization, or model, of nominal operation is stored in a knowledge base that can be used for real-time system monitoring or analysis of archived events. System data is compared with the nominal IMS model to produce a measure of how well current system behavior matches the normal behavior defined by the training data. Significant deviations from the nominal system model can provide alerts to system malfunctions or precursors of significant failures. The scope of IMS based data-driven monitoring applications continues to expand with current development activities. Successful IMS deployment in the International Space Station (ISS) flight control room to monitor ISS attitude control systems has led to applications in other ISS flight control disciplines, such as thermal control. It has also generated interest in data-driven monitoring capability for Constellation, NASA's program to replace the Space Shuttle with new launch vehicles and spacecraft capable of returning astronauts to the moon, and then on to Mars. Several projects are currently underway to evaluate and mature the IMS technology and complementary tools for use in the Constellation program. These include an experiment on board the Air Force TacSat-3 satellite, and ground systems monitoring for NASA's Ares I-X and Ares I launch vehicles. The TacSat-3 Vehicle System Management (TVSM) project is a software experiment to integrate fault and anomaly detection algorithms and diagnosis tools with executive and adaptive planning functions contained in the flight software on-board the Air Force Research Laboratory TacSat-3 satellite. The TVSM software package will be uploaded after launch to monitor spacecraft subsystems such as power and guidance, navigation, and control (GN&C). It will analyze data in real-time to demonstrate detection of faults and unusual conditions, diagnose problems, and react to threats to spacecraft health and mission goals. The experiment will demonstrate the feasibility and effectiveness of integrated system health management (ISHM) technologies with both ground and on-board experiments. Initially, the TVSM software will run open loop, providing system health information and recommendations to ground operators, without automatically performing fault-mitigating corrective actions. After the end of the satellite's mission, closed loop tests combining TVSM monitoring and diagnosis with reactive capabilities by the flight software will be performed. In addition to monitoring for long periods of actual operation, the experiment will include fault injection into TacSat-3 data as well as commanded operations to test and evaluate automatic ISHM monitoring and recovery under controlled conditions.

Satellites

Spacecraft Disposal Rosetta Stone: Parametric Tool for Orbital Lifetime, Disposal, and Cost Assessment

This Technical Memorandum documents a simplified, parametric method for evaluating spacecraft orbital lifetime, disposal compliance, and disposal-related cost impacts during early mission formulation and preliminary design. The method captures the dominant drivers of orbital decay—effective ballistic coefficient, operating altitude, and solar-cycle variability—using conservative bounding assumptions. Solar maximum conditions are used to bound achievable mission lifetime, while solar minimum conditions are used to bound disposal timelines and compliance with orbital debris requirements. A single tabulated dataset provides orbital lifetime under both solar-cycle extremes together with representative disposal ΔV required to ensure compliant disposal, enabling rapid assessment of disposal feasibility, cost sensitivity, and system-level impacts prior to committing to higher-fidelity analyses.

Orbital debris mitigation

Ejecta Management in a Safe Lithium Ion Battery Design

As lithium-ion battery energy densities continue to rise, managing the heat and pressure generated during failure events has become increasingly critical. Safety systems must effectively relieve pressure without releasing sparks, flames, or particulate matter, requiring robust filtration solutions. The challenge is compounded by the reduced free volume available for gas expansion in high-density designs, which increases the demands on these filters. While significant progress has been made through experimental studies and modeling efforts to understand the behavior of ejecta during battery failures, there remains a pressing need for practical, rule-of-thumb sizing parameters. These parameters would help correlate high-energy waste streams with appropriate filter design, ensuring reliable containment and safety. This talk will explore recent experimental findings in this area and discuss the potential pathways for developing these essential sizing guidelines.

Ejecta Management

Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. Furthermore, the results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.

Catalysts