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Results for “multiple cycles”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Integrated solid-state rapid thermo-cycling system

Techniques, systems, and devices are disclosed for implementing a portable lab system for PCR testing. An example method for operating an integrated thermal cycling system includes depositing samples into the integrated thermal cycling system that includes a thermal cycling device and an electronic interface. The thermal cycling device includes multiple wells to receive the samples to be thermally cycled, a thermoelectric cooling (TEC) element connected to the multiple wells, a substrate on which the TEC element is positioned, and a controller coupled to the TEC element. The multiple wells are positioned within the substrate that includes a thermally conductive ground positioned between adjacent wells. Supplying power to the integrated thermal cycling system, via the electronic interface, allows the multiple wells to exchange heat with the substrate and for each well to operate independently from other wells.

Beer, N. Reginald↗
DOE OSTI2022

On the prospects of optical cycling in diatomic cations: effects of transition metals, spin–orbit couplings, and multiple bonds

Molecules with optical cycling centers (OCCs) are highly desirable in the context of fundamental studies as well as applications (e.g., quantum computing) because they can be effectively cooled to very low temperatures by repeated absorption and emission (hence, cycling). Charged species offer additional advantages for experimental control and manipulation. Here, we present a systematic computational study of a series of diatomic radical-cations made of a d-block metal and a p-block ligand, that are isoelectronic (in their valence shell) to the successfully laser-cooled neutral molecules. Using high-level electronic structure methods, we characterize state and transition properties of low-lying electronic states and compute Franck-Condon factors. The computed branching ratios and radiative lifetimes reveal that the electronic transitions analogous to those successfully used in the laser cooling of neutral molecules are less than optimal in the cations. We propose alternative transitions suitable for optical cycling and highlight trends that could assist future designs of OCCs in charged or neutral molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Toward Ultracold Organic Chemistry: Prospects of Laser Cooling Large Organic Molecules

Ultracold organic chemistry enables studies of reaction dynamics and mechanisms in quantum regime. Access to ultracold molecules hinges on the ability to efficiently scatter multiple photons via quasi-closed cycling transitions. Optical cycling in polyatomic molecules is challenging due to their complex electronic structure. Using equation-of-motion coupled-cluster calculations, we demonstrate that an alkaline earth metal attached to various aromatic ligands (such as benzene, phenol, cyclopentadienyl, and pyrrolide) offer nearly closed cycling transitions with only a few additional repump lasers. Here, we also show that aromatic ligands such as benzene can accommodate multiple cycling centers in various geometrical arrangements, opening new avenues in quantum information science, precision measurements, and ultracold chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

An Open-Source Coupling for Depletion During Fuel Cycle Modeling

Fuel depletion is an important aspect of fuel cycle modeling, allowing a user to account for how loaded fuel compositions affect in-core and spent fuel compositions and their related fuel cycle metrics. Therefore, multiple methods have been developed to account for depletion within fuel cycle simulations. This work adds to that list of methods by introducing an open-source coupling between C$\scriptsize{YCLUS}$ and OpenMC to perform fuel depletion during a fuel cycle simulation, called OpenMCyclus. This work explains the methodology of OpenMCyclus and presents a benchmark comparison between the performance of OpenMCyclus and another C$\scriptsize{YCLUS}$ archetype that uses recipes to define spent fuel compositions. In conclusion, the development of this coupling expands the functionalities possible through C$\scriptsize{YCLUS}$ by providing real-time fuel depletion that is reactor agnostic and open source.

C$\scriptsize{YCLUS}$↗
DOE OSTI2024

Multiple Functional Bonds Integrated Interphases for Long Cycle Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have garnered significant interest as one of the most promising energy suppliers for power grid energy storage. However, the poor electrode/electrolyte interfacial stability leads to continual electrolyte decomposition and transition metal dissolution, resulting in rapid performance degradation of SIBs. In this work, we propose a strategy integrating multiple functional bonds to regulate electrode/electrolyte interphase by triple-coupling of succinonitrile (SN), sodium hexafluorophosphate (NaPF 6 ) and fluorinated ethylene carbonate (FEC). Theoretical calculation and experiment results show that the solvation structure of Na + and ClO 4 – is effectively reconfigured by the solvated FEC, SN and PF 6 – in PC-based carbonate electrolyte. The newly developed electrolyte demonstrates increased Na + -FEC coordination, weakened interaction of Na + -PC and participation of SN and PF 6 – anions in solvation, resulting in the formation of a conformal interfacial layer comprising of sodium oxynitrides (NaN x O y ), sodium fluoride (NaF) and phosphorus oxide compounds (NaP x O y ). Consequently, a 3 Ah pouch full cell of hard carbon//NaNi 1/3 Fe 1/3 Mn 1/3 O 2 exhibits an excellent capacity retention of 90.4 % after 1000 cycles. Detailed postmortem analysis of interface chemistry is further illustrated by multiple characterization methods. Finally, this study provides a new avenue for developing electrolyte formulations with multiple functional bonds integrated interphases to significantly improve the long-term cycling stability of SIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Multiple microbial guilds mediate soil methane cycling along a wetland salinity gradient

ABSTRACT Estuarine wetlands harbor considerable carbon stocks, but rising sea levels could affect their ability to sequester soil carbon as well as their potential to emit methane (CH 4 ). While sulfate loading from seawater intrusion may reduce CH 4 production due to the higher energy yield of microbial sulfate reduction, existing studies suggest other factors are likely at play. Our study of 11 wetland complexes spanning a natural salinity and productivity gradient across the San Francisco Bay and Delta found that while CH 4 fluxes generally declined with salinity, they were highest in oligohaline wetlands (ca. 3-ppt salinity). Methanogens and methanogenesis genes were weakly correlated with CH 4 fluxes but alone did not explain the highest rates observed. Taxonomic and functional gene data suggested that other microbial guilds that influence carbon and nitrogen cycling need to be accounted for to better predict CH 4 fluxes at landscape scales. Higher methane production occurring near the freshwater boundary with slight salinization (and sulfate incursion) might result from increased sulfate-reducing fermenter and syntrophic populations, which can produce substrates used by methanogens. Moreover, higher salinities can solubilize ionically bound ammonium abundant in the lower salinity wetland soils examined here, which could inhibit methanotrophs and potentially contribute to greater CH 4 fluxes observed in oligohaline sediments. IMPORTANCE Low-level salinity intrusion could increase CH4 flux in tidal freshwater wetlands, while higher levels of salinization might instead decrease CH4 fluxes. High CH4 emissions in oligohaline sites are concerning because seawater intrusion will cause tidal freshwater wetlands to become oligohaline. Methanogenesis genes alone did not account for landscape patterns of CH4 fluxes, suggesting mechanisms altering methanogenesis, methanotrophy, nitrogen cycling, and ammonium release, and increasing decomposition and syntrophic bacterial populations could contribute to increases in net CH4 flux at oligohaline salinities. Improved understanding of these influences on net CH4 emissions could improve restoration efforts and accounting of carbon sequestration in estuarine wetlands. More pristine reference sites may have older and more abundant organic matter with higher carbon:nitrogen compared to wetlands impacted by agricultural activity and may present different interactions between salinity and CH4. This distinction might be critical for modeling efforts to scale up biogeochemical process interactions in estuarine wetlands.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Registration of ‘Cedar Creek’ switchgrass

‘Cedar Creek’ (Reg. no. CV-290, PI 700113) switchgrass (Panicum virgatum L.) was selected for increased winter survivorship for three cycles, using surviving plants from ‘Kanlow’. The first two cycles were conducted at multiple locations in Wisconsin, and the third cycle was conducted at the Cedar Creek Ecosystem Science Reserve, East Bethel, MN. All seed production and increases were conducted by either Illinois State University or the University of Illinois. Field evaluations of the third-cycle population were conducted at five locations in Wisconsin between 2017 and 2021, located within USDA hardiness zones 3–5. Field experiments were planted in both 2016 and 2017. Averaged over the five locations and all trial years, Cedar Creek had 91% ground cover, compared with 96% for Cave-in-Rock, 95% for Shawnee, and 91% for Liberty. Biomass yield of Cedar Creek averaged 12.17 Mg ha –1 , which was 20% higher than Liberty, 30% higher than Cave-in-Rock, 31% higher than Shawnee, and 520% higher than Kanlow. Cedar Creek is a high-biomass lowland-type of switchgrass and is the first lowland-type adapted to USDA hardiness zones 3–5. Cedar Creek was released to the public by USDA-ARS in 2021.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Process Cycle Modeling with AI

Here a convoluted process model-filtering technique is presented that can build and successfully train the structural property artifacts of materials after multiple heat treatment cycles.

Romanov, Vyacheslav↗
DOE OSTI2020

Activation Energy for Solder Bond Degradation: Thermal Cycling of Field-aged Modules at Multiple Upper Temperatures

The reliability of solder joints in the solar cell metallization-interconnect system influences the lifetime of photovoltaic modules. Two field-aged modules-one with Sn 62 Pb 36 Ag 2 solder at the solder joints (Solarex MSX 60), and the other with the standard Sn 60 Pb 40 solder (Siemens M55)-were subjected to a modified thermal cycling (TC) test of IEC 61215. Three sections in each module were maintained at 85 degrees C, 95 degrees C, and 105 degrees C during the 15-minute high temperature dwell time. Current equivalent to the module short-circuit current was injected through the module when the chamber temperature was above 25 degrees C to simulate regular field operation. This novel approach aims to induce thermomechanical fatigue (TMF) at the solder joints and intermetallic compound (IMC) formation at the metal/solder interfaces. The activation energy (E a ) for solder bond degradation was calculated based on the series resistance (R s ) increase in TC testing rather than power drop to avoid the effect of confounding variables. Module-level R s increase in MSX 60 module after TC800 cycles and in M55 module after TC400 cycles was 1.22% and 183.7%, respectively. The E a determined for the module with 2wt% Ag is 0.24 eV and for that with the standard solder is 0.27 eV. The solder bond degradation seems to have been driven by TMF rather than IMC formation for both modules.

14 SOLAR ENERGY↗
DOE OSTI2025

Effect of pressure cycling and compression rate on the bcc-hcp transition in an FeNi alloy

Here, we investigate the body-centered cubic (bcc) to hexagonal close-packed (hcp) phase transition in Fe-10wt. %Ni alloy, combining pressure cycling and fast compression with time-resolved synchrotron x-ray diffraction in a dynamic diamond anvil cell. Three pressure cycles were conducted with compression rates ranging from 0.1 to nearly 10 3 GPa/s. During the first cycle with the slowest compression, the observed orientations in the bcc and hcp phases are consistent with the Burgers mechanism, followed by c-axis rotation of the hcp phase consistent with {$10$ $\bar{1}2$} twinning. During the following cycles with fast compression at 10 2 –10 3 GPa/s, the hcp phase exhibits negligible c-axis rotation with a nearly constant c/a ratio of ∼1.61 up to ∼30 GPa, indicating suppression of plastic deformation (especially, twinning) due to sample confinement from the gasket. Notably, the onset pressure of the transition decreases with additional pressure cycling and faster compression, which normally leads to over-pressurization. This suggests that defects or shear induced from the pressure cycling reduces the transition kinetics even during fast compression. These insights into the deformation and transition behavior in an FeNi alloy under multiple dynamic loading cycles can offer guidance for future design of advanced structural alloys and improve our understanding of planetary core processes.

FeNi alloy↗
DOE OSTI2023

Using root and soil traits to forecast woody encroachment dynamics in mesic grassland

Grasslands are a widespread and globally important biome providing key ecosystem services including C storage and regulation of the water cycle. Grasslands face multiple threats, including changes in drought intensity and woody encroachment - a process that results in increased woody plant abundance corresponding with decreased herbaceous plant abundance. The combination of reduced soil moisture and shifts in plant dominance from herbaceous to woody are likely to alter C pools in the soil profile. We currently do not have the capacity to predict either the magnitude or rates of change in these C pools. In order to predict changes in grassland vegetation structure and the associated impacts on C cycling requires greater understanding of changes in soil C pools at multiple soil depths, and the responses of these pools to changes in precipitation. To support and perform this parameterization of Land Surface Models, we performed detailed investigations of root (anatomical and physiological) and soil traits (microbial function) at varying soil depths, to capture the belowground impacts of changing dominant plant growth forms (grasses to shrubs) and the impacts of frequent drought.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Sensitivity and Uncertainty Quantification of Transition Scenario Simulations

This report documents the first collective attempt at developing and applying capabilities to quantify uncertainties, assess parametric sensitivities, and optimize multiple parameters and metrics in fuel cycle simulations generated by the SA&I Campaign. To do this, external codes that were designed to perform sensitivity analysis and uncertainty quantification (SA&UQ) needed to be coupled to the SA&I Campaign’s nuclear fuel cycle simulators (NFCS). In FY20, two approaches were pursued: 1) coupling Cyclus to an ORNL-internal code called MOT (Metaheuristic Optimization Tool) and 2) coupling DYMOND to the opensource SA&UQ tool kit Dakota. The primary objective of having these NFCS/SA&UQ coupled capabilities is to better inform DOE-NE and other stakeholders on the results generated from the NFCS. For a given set of fuel cycle strategies, policies, and technology assumptions that make up a fuel cycle scenario, these NFCS have traditionally been used by the SA&I Campaign to provide quantitative answers in terms of year-by-year mass flows, infrastructure requirements, costs, etc. With these newly developed coupled capabilities, the SA&I Campaign can now efficiently simulate hundreds or thousands of these scenarios, sample large ranges of parameters and assumptions, and use the unique features of the SA&UQ tools to process the data. This enables providing answers with known and propagated uncertainties, determining the sensitivity of important metrics to different parameters and assumptions, quantifying how much fuel cycle and technology parameters impact each other, and producing optimized fuel cycle strategies for single and multiple variables. To demonstrate these new capabilities, the Cyclus/MOT was used to model several scenarios ranging from simple fleet retirements to transitions to advanced reactors. Specifically, for a transition scenario from LWRs to SFRs and advanced LWRs, uncertainty quantification, sensitivity analysis, and optimization studies were applied to cases involving single and multiple parameter (input) and single and multiple metric (output) variations. In addition, a similar transition scenario was modeled to demonstrate how to optimize the reprocessing capacity parameter to minimize two performance metrics while taking into account uncertainties from two other parameters. Lastly, a depletion module based on SCALE/ORIGEN was added in Cyclus to simulate the third scenario that was designed to quantify the impact of the modeling assumption that all LWR used nuclear fuel have the same burnup. The newly developed DYMOND/Dakota capability was also applied to a transition scenario from the existing fleet to small modular reactors and fast reactors. This particular scenario involves not only explicit isotopic depletion via ORIGEN-2, but also includes multirecycling and utilizing the criticality search feature to determine the fresh fuel composition of recycled fuel, a feature unique to the DYMOND NFCS. A large database of simulations were run with 4 main parameters that were sampled: start date of reprocessing, reprocessing capacity, energy demand growth rate, and advanced reactor share of the fleet. The 4 main metrics were uranium consumption, enrichment requirements, waste generation, and levelized cost of electricity using data from the Cost Basis Report. The demonstrated SA&UQ results include those that inform on how to choose parameters to avoid “failed” scenarios, Sobol’ indices that inform on the importance of various parameters individually and synergistically, and Analysis of Variance (ANOVA) studies that decompose parameter ranges into groups and informs on whether variations are statistically significant.

Feng, B.↗
DOE OSTI2025

Simulating evaporative wet and dry cycles in Gale crater, Mars using thermochemical modeling techniques

The aim of this work is to provide a model‐backed hypothesis for the formation of evaporites—sulfates, borates—in Gale crater using thermochemical modeling to determine constraints on their formation. We test the hypothesis that primary evaporites required multiple wet–dry cycles to form, akin to how evaporite assemblages form on Earth. Starting with a basalt‐equilibrated Mars fluid, Mars‐relevant concentrations of B and Li were added, and then equilibrated with Gale lacustrine bedrock. We simulated the cycles of evaporation followed by groundwater recharge/dilution to establish an approximate minimum number of wet–dry cycles required to form primary evaporites. We determine that a minimum of 250 wet–dry cycles may be required to start forming primary evaporites that consist of borates and Ca‐sulfates. We estimate that ~14,250 annual cycles (~25.6 k Earth years) of wet and dry periods may form primary borates and Ca‐sulfates in Gale crater. These primary evaporites could have been remobilized during secondary diagenesis to form the veins that the Curiosity rover observes in Gale crater. No Li salts form after 14,250 cycles modeled for the Gale‐relevant scenario (approximately 10 6 cycles would be needed) which implies Li may be leftover in a groundwater brine after the time of the lake. No major deposits of borates are observed to date in Gale crater which also implies that B may be leftover in the subsequent groundwater brine that formed after evaporites were remobilized into Ca‐sulfate veins.

58 GEOSCIENCES↗
DOE OSTI2022

Frozen storage of proteins: Use of mannitol to generate a homogenous freeze-concentrate

Therapeutic proteins may be subjected to several freeze–thaw cycles throughout manufacturing and storage. The protein solution composition and the freezing conditions may lead to incomplete ice crystallization in the frozen state. This can also result in freeze-concentrate heterogeneity characterized by multiple glass transition temperatures and protein destabilization. The overall objective was to investigate the potential advantages of including a crystallizing excipient (mannitol) along with a sugar (sucrose or trehalose) for frozen storage. Here, this study showed that the addition of mannitol, a readily crystallizing excipient, facilitated ice crystallization. Inclusion of an isothermal hold during cooling (annealing) maximized the mannitol crystallization and resulted in a homogenous freeze-concentrate of a constant composition characterized by a single glass transition temperature. The role of freezing rate and annealing on both mannitol and ice crystallization were discerned using high intensity synchrotron radiation. The addition of sucrose or trehalose, at an appropriate concentration, stabilized the protein. The mannitol to sugar ratio (3:1 or 1:1, 5 % w/v) was optimized to selectively cause maximal crystallization of mannitol while retaining the sugar amorphous. Human serum albumin (1 mg/mL) in these optimized and annealed compositions did not show any meaningful aggregation, even after multiple freeze–thaw cycles. Thus, in addition to a sugar as a stabilizer, the use of a crystallizing excipient coupled with an annealing step can provide an avenue for frozen storage of proteins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

American cities in a time of global environmental change: the case of the Baltimore Social-Environmental Collaborative

The Baltimore Social-Environmental Collaborative (BSEC) Urban Integrated Field Laboratory seeks a new paradigm for urban climate research. Motivated by deep uncertainties in urban climate and the future of urban systems, BSEC works collaboratively across institutions and stakeholder groups to co-generate the science needed to advance energy security and resilience to extreme events across the city of Baltimore, Maryland, USA, and to do so in a manner that can inform similar efforts in other cities. BSEC begins with stakeholder priorities (health, affordable energy, etc) and designs observation networks and models to deliver climate science to address them. This takes the form of an iterative collaborative cycle, in which an initial research strategy is repeatedly updated in conversation with community partners, and researchers and stakeholders learn from each other. To date, this cycle has included multiple rounds of collaborative deliberation on urban heat mitigation, in which a multicriteria decision tool has been updated with more community-relevant spatial structure and modified optimization metrics. The guiding objective of this cycle is to inform potential ‘secure and resilient pathways’ for energy and infrastructure. In doing so, BSEC addresses fundamental urban science questions in natural and social sciences. It also tests our ability to integrate this science in a manner that advances participatory decision-making for urban resilience.

climate↗
DOE OSTI2020

Improved recovery of cell-cycle gene expression in Saccharomyces cerevisiae from regulatory interactions in multiple omics data

Gene expression is regulated by DNA-binding transcription factors (TFs). Together with their target genes, these factors and their interactions collectively form a gene regulatory network (GRN), which is responsible for producing patterns of transcription, including cyclical processes such as genome replication and cell division. However, identifying how this network regulates the timing of these patterns, including important interactions and regulatory motifs, remains a challenging task. Results We employed four in vivo and in vitro regulatory data sets to investigate the regulatory basis of expression timing and phase-specific patterns cell-cycle expression in Saccharomyces cerevisiae . Specifically, we considered interactions based on direct binding between TF and target gene, indirect effects of TF deletion on gene expression, and computational inference. We found that the source of regulatory information significantly impacts the accuracy and completeness of recovering known cell-cycle expressed genes. The best approach involved combining TF-target and TF-TF interactions features from multiple datasets in a single model. In addition, TFs important to multiple phases of cell-cycle expression also have the greatest impact on individual phases. Important TFs regulating a cell-cycle phase also tend to form modules in the GRN, including two sub-modules composed entirely of unannotated cell-cycle regulators ( STE12-TEC1 and RAP1-HAP1-MSN4 ). Conclusion Our findings illustrate the importance of integrating both multiple omics data and regulatory motifs in order to understand the significance regulatory interactions involved in timing gene expression. This integrated approached allowed us to recover both known cell-cycles interactions and the overall pattern of phase-specific expression across the cell-cycle better than any single data set. Likewise, by looking at regulatory motifs in the form of TF-TF interactions, we identified sets of TFs whose co-regulation of target genes was important for cell-cycle expression, even when regulation by individual TFs was not. Overall, this demonstrates the power of integrating multiple data sets and models of interaction in order to understand the regulatory basis of established biological processes and their associated gene regulatory networks.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

VERA-Grizzly Ex-Core Calculations: Watts Bar Unit 1 Cycles 1-2

The critical structures that comprise light-water reactor (LWR) nuclear power plants are subjected to operating environments that can challenge their integrity. Structures in close proximity to the reactor core, such as the reactor pressure vessel (RPV) and the biological shield wall, are subjected to high levels of radiation emanating from the core, as well as elevated temperatures. As the US fleet of operating LWRs ages, the effects of these operating environments on the integrity of these structures must be considered to ensure their continued safe operation. Extending the lifetime of commercial reactors and maintaining the aging reactor fleet require accurate prediction of the exposure of ex-core components to neutron and photon radiation. In particular, concrete degradation studies must be performed to evaluate the safety and long-term operation of reactors with lifetime extensions. The concrete reactor bioshield is important for providing radiological protection during operation and must last for the entire lifetime of the reactor. Recent interest in lifetime extensions furthers the need to accurately simulate concrete material degradation in the reactor bioshield. As a result of this need, the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program has funded this study to couple its tools, Virtual Environment for Reactor Applications (VERA) and Grizzly. VERA allows users to set up models to calculate time-dependent and fully coupled solutions (with thermal feedback) for ex-core quantities of interest such as vessel and coupon fluence and detector responses for multiple statepoints and cycles. Grizzly is a finite-element application based on the Multiphysics Object Oriented Simulation Environment (MOOSE) framework that is used to enable aging materials calculations. This report highlights the work performed to calculate the fluence in the vessel and concrete for Watts Bar Nuclear Plant Unit 1 (WBN1) Cycles 1 and 2. The fluences obtained from VERA were successfully transferred to Grizzly using a Python script. Four simulations were run with Grizzly: (1) the Mazars model with the initial Young’s modulus being the instantaneous modulus, (2) the Mazars model with the initial Young’s modulus being the delayed modulus, (3) the Mazars model with the initial Young’s modulus being the delayed modulus with the addition of the effects of micro-damage caused by irradiation, and (4) the Mazars model with the initial Young’s modulus being the instantaneous modulus, and with the addition of micro-damage and creep. Details regarding the methods used to obtain the fluence and the statistical errors associated with the VERA Monte Carlo Shift calculations are discussed in greater detail in this report. The results obtained from the four Grizzly models are also presented in this report.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2024

Visible Light Photolysis at Single Atom Sites in Semiconductor Perovskite Oxides

Designing catalysts with well-defined active sites with chemical functionality responsive to visible light has significant potential for overcoming scaling relations limiting chemical reactions over heterogeneous catalyst surfaces. Visible light can be leveraged to facilitate the removal of strongly bound species from well-defined single cationic sites (Rh) under mild conditions (323 K) when they are incorporated within a photoactive perovskite oxide (Rh-doped SrTiO 3 ). CO, a key intermediate in many chemistries, forms stable geminal dicarbonyl Rh complexes (Rh + (CO) 2 ), that could act as site blockers or poisons during a catalytic cycle. For the first time, we demonstrate that CO removal can occur at mild temperatures (323 K) under low-energy red light (635 nm) irradiation, which is not possible for supported isolated-site Rh catalysts (0.2 wt % Rh/γ-Al 2 O 3 ). Photolysis of supported Rh + (CO) 2 complexes (e.g., 0.2 wt % Rh/γ-Al 2 O 3 ) has been demonstrated but is limited to high energy UV photons. Rigorous kinetic experiments elucidate disparate mechanisms for CO photodepletion from Rh-doped SrTiO 3 and supported isolated site Rh/γ-Al 2 O 3 . CO photodepletion from supported isolated site Rh/γ-Al 2 O 3 involves a direct metal to ligand charge transfer mechanism, whereas Rh-doped SrTiO 3 is governed by electron–hole pair formation in the perovskite. In this work, we show that under visible, low-energy red light, surface Rh species in Rh-doped SrTiO 3 introduce midgap energy states above the valence band that facilitate electronic excitations leading to surface CO removal. Isolated Rh sites in Rh-doped SrTiO 3 also exhibit exceptional stability under multiple CO photodepletion cycles. Overall, incorporating single sites into photoactive perovskite oxides is an effective strategy to influence surface chemistries with visible light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗