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At least 1,621 records · Page 90

The Effects of Sweeping Jet Actuator Parameters on Flow Separation Control

A parametric experimental study was performed with sweeping jet actuators (fluidic oscillators) to determine their effectiveness in controlling flow separation on an adverse pressure gradient ramp. Actuator parameters that were investigated include blowing coefficients, operation mode, pitch and spreading angles, streamwise location, aspect ratio, and scale. Surface pressure measurements and surface oil flow visualization were used to characterize the effects of these parameters on the actuator performance. 2D Particle Image Velocimetry measurements of the flow field over the ramp and hot-wire measurements of the actuator's jet flow were also obtained for selective cases. In addition, the sweeping jet actuators were compared to other well-known flow control techniques such as micro-vortex generators, steady blowing, and steady vortex-generating jets. The results confirm that the sweeping jet actuators are more effective than steady blowing and steady vortex-generating jets. The results also suggest that an actuator with a larger spreading angle placed closer to the location where the flow separates provides better performance. For the cases tested, an actuator with an aspect ratio, which is the width/depth of the actuator throat, of 2 was found to be optimal. For a fixed momentum coefficient, decreasing the aspect ratio to 1 produced weaker vortices while increasing the aspect ratio to 4 reduced coverage area. Although scaling down the actuator (based on the throat dimensions) from 0.25 inch x 0.125 inch to 0.15 inch x 0.075 inch resulted in similar flow control performance, scaling down the actuator further to 0.075 inch x 0.0375 inch reduced the actuator efficiency by reducing the coverage area and the amount of mixing in the near-wall region. The results of this study provide insight that can be used to design and select the optimal sweeping jet actuator configuration for flow control applications.

Koklu, Mehti↗

Image-Optimized Coronal Magnetic Field Models

We have reported previously on a new method we are developing for using image-based information to improve global coronal magnetic field models. In that work we presented early tests of the method which proved its capability to improve global models based on flawed synoptic magnetograms, given excellent constraints on the field in the model volume. In this follow-up paper we present the results of similar tests given field constraints of a nature that could realistically be obtained from quality white-light coronagraph images of the lower corona. We pay particular attention to difficulties associated with the line-of-sight projection of features outside of the assumed coronagraph image plane, and the effect on the outcome of the optimization of errors in localization of constraints. We find that substantial improvement in the model field can be achieved with this type of constraints, even when magnetic features in the images are located outside of the image plane.

Jones, Shaela I.↗

Finite Element Model Tuning using Analytical Sensitivity Values

This paper presents an efficient approach for tuning finite element models to match the measured ground vibrationtest and proof test data. Frequencies, mode shapes, total weight, location of the center of gravity, and staticdeformation computed from the finite element model are matched to the measured data. The model tuningprocedure used in this work is based on solving an optimization problem in which the errors for the consideredmetrics, between the finite element prediction and the measured data, are minimized. Analytical sensitivity values ofperformance indices are computed using the NASTRAN-generated sensitivity values together with the in-housecomputer programs, which allow for faster computational time and the use of gradient-based optimizers. The methodis applied to the Aerostructures Test Wing 4 model. The study shows that the military standard and the NASAstandard for comparing analytical and experimental modal data are all satisfied. The final finite element modelcorrelates well with the test data. The flutter speed decreases by 8.91% after model tuning compared with the original Aerostructures Test Wing 4 design.

Chan-gi Pak↗

Entry, Descent, and Landing Analysis for the OSIRIS-REx Sample Return Capsule

The Origins, Spectral Interpretation, Resource Identification, and Security – Regolith Explorer (OSIRIS-REx) sample return capsule (SRC) returned to Earth on September 24, 2023, safely landing in the Utah Test and Training Range (UTTR). To ensure a safe and successful landing, a pair of high-fidelity EDL simulations, based on the Program to Optimize Simulated Trajectories (POST) architecture, were used to regularly assess the latest orbit determination (OD) solution from the navigation team, making predictions on Entry, Descent, and Landing (EDL) performance and SRC landing location. The results from these analyses fed into the decision processes for the final trajectory correction maneuvers (TCM’s) and SRC release. The models and methods of analysis will be discussed and a comparison of the final pre-entry landing prediction against the observed landing location will be presented along with an assessment of the best estimates of day-of-entry environmental conditions.

Scott R Francis↗

Equity-driven Planning of Distributed Solar PV using Optimal Transport

Typically, distribution system planning processes do not explicitly incorporate energy equity considerations, such as identifying consumers most affected by energy costs and determining how investments in the distribution system can address existing energy burden imbalances. This paper proposes a novel optimal transport (OT)-based method to improve the energy burden distribution of consumers. The approach involves the strategic siting and sizing of solar PV in order to assist customers with high energy burden and improve the overall energy burden distribution of the community. The desired energy burden distribution is defined using the equal distribution equivalent (EDE) concept. The OT-based method is then used to estimate the distributed solar PV capacity to be installed at various locations and the tariffs to be adjusted, all while improving the energy burden distribution and providing valuable insights into distributed generation (DG) planning. The results on IEEE 37 bus test system demonstrate how DG planning, considering EDE and OT, can help reduce the energy burden of low-income consumers. Additionally, the approach also reveals optimal tariff adjustments needed to ensure revenue neutrality for distribution utilities.

Optimal transport, equal distribution equivalent, ↗

Subtask 1.5 – CO2 Injection Monitoring with an Optimized Scalable, Automated, Semipermanent Seismic Array

The scalable, automated, semipermanent seismic array (SASSA) method is a flexible and relatively cost-effective surface geophysical method for regular time-lapse monitoring of the movement of injected carbon dioxide (CO2) in a reservoir for CO2 enhanced oil recovery (EOR) or geologic CO2 storage operations. It has the advantages of a low-environmental-footprint while monitoring regions of a reservoir from the surface without the need for a regular grid distribution of receivers. Automated data collection is possible. As only time-lapse amplitude changes at the reservoir level due to CO2 movement within the reservoir are monitored, the turnaround time to deliver results from the SASSA method can be short, without the need for long, time-consuming data-processing workflows. As data is collected and processed, incremental information can be provided to the field operator. The Energy & Environmental Research Center (EERC) conducted a SASSA field test from September 2018 to November 2020 in a portion of the Bell Creek Field in Montana, which implemented new CO2 EOR field activities during the study period. Lessons learned from a proof-of-concept study were incorporated to improve the data quality of the SASSA method and demonstrate the viability of the technology. The EERC implemented several enhancements to improve data quality, including 1) an iterative survey design, which allowed placing the receivers in strategic locations where the movement of the CO2 in the reservoir could be tracked with minimum interference by the cultural noise in the study area; 2) the use of powerful seismic sources in the form of surface orbital vibrators, and 3) data acquisition during optimal periods. History-matched reservoir simulation was performed to predict gas saturation and pressure response induced by CO2 injection in the study area. The results were compared with the SASSA-measured responses to CO2 injection as a partial validation technique. A match between the two methods was observed for most of the SASSA points predicted to have intersected a CO2 saturation change. The validated results provide confidence that the SASSA method can be used independently as a CO2 saturation monitoring technique. As data are collected and processed, incremental information can be provided to the field operator. The critical components of the SASSA workflow for a successful application of the method are the following: Iterative survey design with information about CO2 injection activities from the oilfield operator. A detailed CO2 injection plan is the key driver to select the strategic monitoring location of the SASSA sensors. After this information is incorporated in the initial distribution of sources and receivers in the study area, high-resolution satellite images are used to identify ground locations not affected by cultural noise sources, such as power lines, pipelines/flow lines, or roadways. In the next iteration of the survey design, a scouting trip to the study area is needed to understand more details of the noise sources identified in the previous step and the intensity of the field activities that can also generate noise during the monitoring. Integrating the information from the scouting trip into the survey design to select the optimum source and receiver locations is the final step. Noise attenuation. The variety of noise types during seismic monitoring of an oil field is enormous. Tailored noise characterization and processing at a node-by-node level can enhance the performance and sensitivity of the SASSA technique. Future advancements that could improve the efficiency and application of the SASSA technology include: Gaining a better understanding of the noise field produced by the seismic source to aid the choice of receiver location. Surface noise from the source can overwhelm the small signal changes due to CO2 that the SASSA method measures. Improved data-processing workflow to automatically analyze and adapt to dynamic noise conditions associated with industrial settings. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE- FE0024233.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

TREAT Neutronics Analysis and Design Support, Part I: Multi-SERTTA

Experiment vehicle design is necessary in preparation for Transient Reactor Test (TREAT) facility restart and the resumption of transient testing to support Accident Tolerant Fuel (ATF) characterization and other future fuels testing requirements. Currently the most mature vehicle design is the Multi-SERTTA (Static Environments Rodlet Transient Test Apparatuses), which can accommodate up to four concurrent rodlet-sized specimens under separate environmental conditions. Robust test vehicle design requires neutronics analyses to support design development, optimization of the power coupling factor (PCF) to efficiently maximize energy generation in the test fuel rodlets, and experiment safety analyses. Calculations were performed to support analysis of a near-final design of the Multi-SERTTA vehicle, the design process for future TREAT test vehicles, and establish analytical practices for upcoming transient test experiments. Models of the Multi-SERTTA vehicle containing typical PWR-fuel rodlets were prepared and neutronics calculations were performed using MCNP6.1 with ENDF/B-VII.1 nuclear data libraries. Calculation of the PCF for reference conditions of a PWR fuel rodlet in clean water at operational temperature and pressure provided results between 1.10 and 1.74 W/g-MW depending on the location of the four Multi-SERTTA units with the stack. Basic changes to the Multi-SERTTA secondary vessel containment and support have minimal impact on PCF; using materials with less neutron absorption can improve expected PCF values, especially in the primary containment. An optimized balance is needed between structural integrity, experiment safety, and energy deposition in the experiment. Type of medium and environmental conditions within the primary vessel surrounding the fuel rodlet can also have a significant impact on resultant PCF values. The estimated reactivity insertion worth into the TREAT core is impacted more by the primary and secondary Multi-SERTTA vehicle structure with the experiment content and contained environment having a near negligible impact on overall system reactivity. Additional calculations were performed to evaluate the peak-to-average assembly powers throughout the TREAT core, as well as the nuclear heat generation for the various structural components of the Multi-SERTTA assembly. Future efforts include the evaluation of flux collars to shape the PCF for individual Multi-SERTTA units during an experiment such as to achieve uniformity in test unit environmental conditions impacted by the non-uniform axial flux/power profile of TREAT. Upon resumption of transient testing, experimental results from both the Multi-SERTTA and Multi-SERTTA-CAL will be compared against calculational results and methods for further optimization and design strategies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

TREAT neutronics analysis and design support, Part I: Multi-SERTTA

Experiment vehicle design is necessary in preparation for Transient Reactor Test (TREAT) facility restart and the resumption of transient testing to support Accident Tolerant Fuel (ATF) characterization and other future fuels testing requirements. Currently the most mature vehicle design is the Multi-SERTTA (Static Environments Rodlet Transient Test Apparatuses), which can accommodate up to four concurrent rodlet-sized specimens under separate environmental conditions. Robust test vehicle design requires neutronics analyses to support design development, optimization of the power coupling factor (PCF) to efficiently maximize energy generation in the test fuel rodlets, and experiment safety analyses. Calculations were performed to support analysis of a near-final design of the Multi-SERTTA vehicle, the design process for future TREAT test vehicles, and establish analytical practices for upcoming transient test experiments. Models of the Multi-SERTTA vehicle containing typical PWR-fuel rodlets were prepared and neutronics calculations were performed using MCNP6.1 with ENDF/B-VII.1 nuclear data libraries. Calculation of the PCF for reference conditions of a PWR fuel rodlet in clean water at operational temperature and pressure provided results between 1.10 and 1.73 W/g-MW depending on the location of the four Multi-SERTTA units with the stack. Basic changes to the Multi-SERTTA secondary vessel containment and support have minimal impact on PCF; using materials with less neutron absorption can improve expected PCF values, especially in the primary containment. An optimized balance is needed between structural integrity, experiment safety, and energy deposition in the experiment. Type of medium and environmental conditions within the primary vessel surrounding the fuel rodlet can also have a significant impact on resultant PCF values. The estimated reactivity insertion worth into the TREAT core is impacted more by the primary and secondary Multi-SERTTA vehicle structure with the experiment content and contained environment having a near negligible impact on overall system reactivity. Additional calculations were performed to evaluate the peak-to-average assembly powers throughout the TREAT core, as well as the nuclear heat generation for the various structural components of the Multi-SERTTA assembly. Future efforts include the evaluation of flux collars to shape the PCF for individual Multi-SERTTA units during an experiment such as to achieve uniformity in test unit environmental conditions impacted by the non-uniform axial flux/power profile of TREAT. Upon resumption of transient testing, experimental results from both the Multi-SERTTA and Multi-SERTTA-CAL will be compared against calculational results and methods for further optimization and design strategies. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Identification of optimal landforms to reduce impacts on the landscape using LiDAR for hosting a new highway

Highlights: •New territorial indicators were designed to quantify landscape impacts. •Reduction of visual impacts caused by new roads from planning and design stages. •LIDAR and 3D realistic views were considered to locate observer's views. •Bands of less cumulative impact were obtained as guides for highway tracing. •Preventive and corrective measures for impact mitigation were located.

54 ENVIRONMENTAL SCIENCES↗

Static aeroelastic analysis and tailoring of missile control fins

A concept for enhancing the design of control fins for supersonic tactical missiles is described. The concept makes use of aeroelastic tailoring to create fin designs (for given planforms) that limit the variations in hinge moments that can occur during maneuvers involving high load factors and high angles of attack. It combines supersonic nonlinear aerodynamic load calculations with finite-element structural modeling, static and dynamic structural analysis, and optimization. The problem definition is illustrated. The fin is at least partly made up of a composite material. The layup is fixed, and the orientations of the material principal axes are allowed to vary; these are the design variables. The objective is the magnitude of the difference between the chordwise location of the center of pressure and its desired location, calculated for a given flight condition. Three types of constraints can be imposed: upper bounds on static displacements for a given set of load conditions, lower bounds on specified natural frequencies, and upper bounds on the critical flutter damping parameter at a given set of flight speeds and altitudes. The idea is to seek designs that reduce variations in hinge moments that would otherwise occur. The block diagram describes the operation of the computer program that accomplishes these tasks. There is an option for a single analysis in addition to the optimization.

Mcintosh, S. C., Jr.↗

SU-F-T-186: A Treatment Planning Study of Normal Tissue Sparing with Robustness Optimized IMPT, 4Pi IMRT, and VMAT for Head and Neck Cases

Purpose: We performed a retrospective dosimetric comparison study between the robustness optimized Intensity Modulated Proton Therapy (RO-IMPT), volumetric-modulated arc therapy (VMAT), and the non-coplanar 4? intensity modulated radiation therapy (IMRT). These methods represent the most advanced radiation treatment methods clinically available. We compare their dosimetric performance for head and neck cancer treatments with special focus on the OAR sparing near the tumor volumes. Methods: A total of 11 head and neck cases, which include 10 recurrent cases and one bilateral case, were selected for the study. Different dose levels were prescribed to tumor target depending on disease and location. Three treatment plans were created on commercial TPS systems for a novel noncoplanar 4π method (20 beams), VMAT, and RO-IMPT technique (maximum 4 fields). The maximum patient positioning error was set to 3 mm and the maximum proton range uncertainty was set to 3% for the robustness optimization. Line dose profiles were investigated for OARs close to tumor volumes. Results: All three techniques achieved 98% coverage of the CTV target and most photon plans had less than 110% of the hot spots. The RO-IMPT plans show superior tumor dose homogeneity than 4? and VMAT plans. Although RO-IMPT has greater R50 dose spillage to the surrounding normal tissue than 4π and VMAT, the RO-IMPT plans demonstrate better or comparable OAR (parotid, mandible, carotid, oral cavity, pharynx, and etc.) sparing for structures closely abutting tumor targets. Conclusion: The RO-IMPT’s ability of OAR sparing is benchmarked against the C-arm linac based non-coplanar 4π technique and the standard VMAT method. RO-IMPT consistently shows better or comparable OAR sparing even for tissue structures closely abutting treatment target volume. RO-IMPT further reduces treatment uncertainty associated with proton therapy and delivers robust treatment plans to both unilateral and bilateral head and neck cancer patients with desirable treatment time.

60 APPLIED LIFE SCIENCES↗

HPC for Optimizing Process Parameters to Control Material Evolution in Seamless Induction Hardening of Wind Turbine Main Shaft Bearings

Work proposed in this project focused on understanding the effect of martensitic transformation in the steel on the potential for cracking during seamless induction hardening (SIH) as a function of process conditions to allow the process to optimally scale up. Large-scale, three-dimensional phase-field simulations of martensitic transformation were performed using MEUMAPPS-SS (Microstructure Evolution Using Massively Parallel Phase-field Simulations – Solid State) code developed at Oak Ridge National Laboratory. The simulations were guided by location-specific thermal history generated by experimental measurements of time-temperature history generated at The Timken Company. The simulations were able to capture the morphological evolution of the martensite variants in an Fe-1.0C-1.5Cr steel based on the Nishiyama-Wasserman (NW) orientation relationship. The simulations were also able to quantify the stress-state at the interface between impinging martensite variants. The simulations indicated that the magnitude of the various stress and strain components were dependent on the sizes of the impinging plates with a reduction in these quantities with reduced plate size in agreement with experimental findings. The results obtained from the simulations will be used to guide the optimization of the alloy thermal conditions to eliminate quench cracking during SIH of bearing steels.

99 GENERAL AND MISCELLANEOUS↗

HPC for optimizing process parameters to control material evolution in seamless induction hardening of wind turbine main shaft bearings

Work proposed in this project focused on understanding the effect of martensitic transformation in the steel on the potential for cracking during seamless induction hardening (SIH) as a function of process conditions to allow the process to optimally scale up. Large-scale, three-dimensional phase-field simulations of martensitic transformation were performed using MEUMAPPS-SS (Microstructure Evolution Using Massively Parallel Phase-field Simulations – Solid State) code developed at Oak Ridge National Laboratory. The simulations were guided by location-specific thermal history generated by experimental measurements of time-temperature history generated at The Timken Company. The simulations were able to capture the morphological evolution of the martensite variants in an Fe-1.0C-1.5Cr steel based on the Nishiyama-Wasserman (NW) orientation relationship. The simulations were also able to quantify the stress-state at the interface between impinging martensite variants. The simulations indicated that the magnitude of the various stress and strain components were dependent on the sizes of the impinging plates with a reduction in these quantities with reduced plate size in agreement with experimental findings. The results obtained from the simulations will be used to guide the optimization of the alloy thermal conditions to eliminate quench cracking during SIH of bearing steels.

17 WIND ENERGY↗

Distributed energy management for community microgrids considering network operational constraints and building thermal dynamics

A distributed energy management system for community microgrids is developed here. Unlike a centralized optimization-based energy management system, it schedules distributed energy resources and energy storage systems, as well as residential appliances, indirectly through iterative interaction between the microgrid central controller and home energy management systems, based on price signals. In each iteration, the microgrid central controller adjusts the scheduling of distributed energy resources and energy storage systems at the microgrid level. Meanwhile, the home energy management system of each house adjusts the scheduling of residential appliances. Then, the energy price at each bus is updated according to the unbalanced power between generation and demand. The optimization converges when the unbalanced power of all buses is close to zero, i.e., the microgrid central controller and home energy management systems reach an agreement on the energy price and generation/consumption. In particular, a detailed thermal dynamic model of the house is integrated into the HEMS scheduling for intelligent control of the heating, ventilation, and air-conditioning system by customers. Lastly, the distribution network is also considered to make the energy price signal locational. Results of case studies validate the efficacy of the proposed distributed energy management system.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Sub-Optimal Control of Nonlinear Flexible Space Structures

A simple yet effective method is presented for the on-line vibration control of nonlinear distributed parameter systems, with constant or time-varying properties, responding to a wide class of dynamic environments. The control procedure uses pulse generators located at selected positions throughout a given system. The degree of system oscillation near each controller determines the controller's activation time and pulse amplitude. The direct method of Liapunov is used to establish that the response of the controlled nonlinear system is Lagrange stable. Analytical and experimental studies of a wing-like plate demonstrate the feasibility, reliability, and robustness of the proposed vibration-suppression method.

Dehghanyar, T. J.↗

The Advanced Mixed Waste Treatment Project: Optimizing use of This National Asset to Treat Challenging Radioactive Waste From Other Department of Energy Sites - 16064

The U.S. Department of Energy's (DOE) Advanced Mixed Waste Treatment Project (AMWTP) is a world-class radioactive waste treatment facility with a highly experienced and innovative workforce located at the Idaho National Laboratory (INL). The AMWTP's state-of-the-art capabilities include a 62-ton super-compactor, remote cutting and sorting, macro-encapsulation systems, assay units, drum repackaging, waste characterization, and payload assembly and loading. Since operations began in 2003, the facility has been the largest shipper for contact-handled (CH) transuranic (TRU) waste to the Waste Isolation Pilot Plant (WIPP). It has successfully processed over 56,000 cubic meters (m{sup 3}) of CH TRU waste and mixed low-level waste (MLLW) from the Idaho Site and approximately 700 m{sup 3} of CH TRU waste from 15 other DOE sites. While the AMWTP is nearing successful completion of its Idaho mission, other DOE environmental cleanup sites will require safe and proven capabilities to treat, package, characterize, and certify legacy radioactive waste inventories well into the next decade. In addition, DOE's national security, nuclear energy, and science programs need sustainable treatment capabilities to support ongoing and new missions. The AMWTP could continue to serve a vital role beyond its current Idaho mission to help address these larger DOE needs. To this end and in recognition that AMWTP's current priority is to complete the processing and removal of Idaho waste, DOE's Office of Environmental Management has initiated strategic planning to assess the feasibility of continued AMWTP operations to treat challenging radioactive waste from other generator sites consistent with existing regulatory agreements. This paper describes AMWTP's unique capabilities and identifies potential benefits, opportunities, and possible solutions to packaging and transportation challenges to fully use AMWTP as a national asset. A panel discussion of subject matter experts with audience participation would help to inform DOE's strategic planning on how best to use this national asset into the future. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A novel machine learning-based optimization algorithm (ActivO) for accelerating simulation-driven engine design

A novel design optimization approach (ActivO) that employs an ensemble of machine learning algorithms is presented. The proposed approach is a surrogate-based scheme, where the predictions of a weak leaner and a strong learner are utilized within an active learning loop. The weak learner is used to identify promising regions within the design space to explore, while the strong learner is used to determine the exact location of the optimum within promising regions. For each design iteration, exploration is done by randomly selecting evaluation points within regions where the weak learner-predicted fitness is high. The global optimum obtained by using the strong learner as a surrogate is also evaluated to enable rapid convergence once the most promising region has been identified. First, the performance of ActivO was compared against five other optimizers on a cosine mixture function with 25 local optima and one global optimum. In the second problem, the objective was to minimize indicated specific fuel consumption of a compression-ignition internal combustion (IC) engine while adhering to desired constraints associated with in-cylinder pressure and emissions. In this work, the efficacy of the proposed approach is compared to that of a genetic algorithm, which is widely used within the internal combustion engine community for engine optimization, showing that ActivO reduces the number of function evaluations needed to reach the global optimum, and thereby time-to-design by 80%. Furthermore, the optimization of engine design parameters leads to savings of around 1.9% in energy consumption, while maintaining operability and acceptable pollutant emissions.

97 MATHEMATICS AND COMPUTING↗

Aliovalent gallium dopants remove Ti 3+ defects and improve photocatalytic and photoelectrochemical water oxidation properties of LaTiO 2 N

LaTiO 2 N is a promising semiconductor for the water splitting reaction due to its 2.1 eV band gap and stability against corrosion. However, its solar energy conversion is limited by Ti 3+ recombination defects introduced during ammonolysis. Here we show for the first time that Ti 3+ defects in LaTiO 2 N can be suppressed with incorporation of 2, 5, and 10% aliovalent gallium (Ga 3+ ) dopants during synthesis via the layered La 2 Ti 2 O 7 intermediate. Electron paramagnetic resonance (EPR) spectroscopy on the solid powders confirms a reduction in the Ti 3+ donor density from 2.97 × 10 17 cm −3 for the non-doped material to ∼6.24 × 10 16 cm −3 for 5% Ga-doped LaTiO 2 N. The remaining Ti 3+ defects are concentrated near the LaTiO 2 N surface, according to X-ray photoelectron spectroscopy. The defect reduction shifts the optical absorption edge from 2.02 to 2.09 eV and eliminates a broad absorption band at 1050 nm from the optical absorption spectra. It also removes a 1.0–1.7 eV sub-band gap photovoltage signal from surface photovoltage spectra. This suggests that empty Ti 3+ d-orbitals are located 1.0–1.7 eV above the LaTiO 2 N valence band edge. Removing these recombination states with increasing Ga 3+ content enhances the photoconversion efficiency of LaTiO 2 N during water oxidation. The optimized 2 wt% CoO x -loaded 5% Ga-doped LaTi O2 N material has a 16% AQE (400 nm) for O 2 production from aqueous silver nitrate solution and a ∼2.1 mA cm −2 water oxidation photocurrent at 1.23 V under 100 mW cm −2 Xe arc lamp illumination. The water oxidation photocurrent is stable during a 50 min test, and the Faraday efficiency for O 2 generation is 97%, confirming short-term corrosion stability of LaTiO 2 N. Altogether, these results provide a better understanding of the distribution, concentration, and impact of Ti 3+ defects on the optical, photovoltage, and photoelectrochemical properties of LaTiO 2 N. In combination with other defect control strategies, aliovalent Ga 3+ doping can help bring the solar energy conversion efficiency of LaTiO 2 N closer to the theoretical limit.

Wang, Li [University of California, Davis, CA (Uni↗