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At least 415 records · Page 23

Dataset for Evaluation of Extreme Weather Impacts on Utility-Scale Photovoltaic Plant Performance in the United States

This dataset is a fusion of three data types (operations and maintenance tickets, weather data, and production data) that was used to support machine learning analysis and evaluation of drivers for low performance at photovoltaic (PV) sites during compound, extreme weather events. After being processed with machine learning, the data was used in the "Evaluation of Extreme Weather Impacts on Utility-scale Photovoltaic Plant Performance in the United States" manuscript. Additional details are captured in the associated manuscript.

AI↗

Diploid genomic architecture of Nitzschia inconspicua, an elite biomass production diatom

Abstract A near-complete diploid nuclear genome and accompanying circular mitochondrial and chloroplast genomes have been assembled from the elite commercial diatom species Nitzschia inconspicua . The 50 Mbp haploid size of the nuclear genome is nearly double that of model diatom Phaeodactylum tricornutum , but 30% smaller than closer relative Fragilariopsis cylindrus . Diploid assembly, which was facilitated by low levels of allelic heterozygosity (2.7%), included 14 candidate chromosome pairs composed of long, syntenic contigs, covering 93% of the total assembly. Telomeric ends were capped with an unusual 12-mer, G-rich, degenerate repeat sequence. Predicted proteins were highly enriched in strain-specific marker domains associated with cell-surface adhesion, biofilm formation, and raphe system gliding motility. Expanded species-specific families of carbonic anhydrases suggest potential enhancement of carbon concentration efficiency, and duplicated glycolysis and fatty acid synthesis pathways across cytosolic and organellar compartments may enhance peak metabolic output, contributing to competitive success over other organisms in mixed cultures. The N. inconspicua genome delivers a robust new reference for future functional and transcriptomic studies to illuminate the physiology of benthic pennate diatoms and harness their unique adaptations to support commercial algae biomass and bioproduct production.

09 BIOMASS FUELS↗

Magnetic Nanoparticle Extraction of Lithium from Produced Waters: CRADA 483 [Abstract only]

In this project, we will synthesize, evaluate, and screen a set of new sorbents that have high capacity and selectivity for lithium. Sorbent performance will be evaluated by conducting Li extraction tests with produced water samples supplied by ConocoPhillips Company, Moselle Technologies, and Cascade Natural Resources. The best performing of these sorbents based on Li uptake capacity and selectivity will be produced as a magnetic nanoparticle and subjected to extended cycle testing in our laboratory bench-scale magnetic separator system. Moselle has acquired an exclusive license to the background IP associated with this magnetic nanoparticle mineral extraction technology and wishes to foster implementation of the technology in the oil & gas industry through this CRADA. Moselle will support PNNL in the design of a commercial-scale magnetic separator system tailored for lithium production. The goal is to collect sufficient information to support a decision by our industry partners to invest in a subsequent field demonstration at one of our partner’s field sites as a prerequisite to advancing this technology towards commercialization.

36 MATERIALS SCIENCE↗

Effects of Gasoline Composition and Operating Parameters on the Response of End-Gas Autoignition to Nitric Oxide in a Lean-Burn DI-SI Engine

Lean operation of spark-ignition engines can lead to engine thermal efficiency gains and lower NOx emissions due to reduced combustion temperatures. Yet, lean operation could still face challenges in end-gas autoignition and knock generation due to higher intake pressures and trapped NO in the residual gas. Here, this study evaluates the impact of NO on end-gas autoignition for two gasoline fuels with similar octane rating but different composition: high cycloalkane fuel (HCA) and high olefin fuel (HO). Experiments were performed at stoichiometric and lean (λ = 2) conditions and at two engine speeds of 1400 rpm and 2000 rpm. Accompanying chemical kinetics simulations in CHEMKIN revealed that the mechanisms controlling the effect of NO on autoignition are similar λ = 2 and λ = 1, with NO + HO 2 = NO 2 + OH being the main pathway for enhancing reactivity by promoting low-temperature heat release (LTHR). The compositionally different fuels reacted differently to NO seeding and engine speed, and differences were augmented at λ = 2 compared to λ = 1 as the end-gas autoignition shifted to the low temperature regime. HO, which has inherent low temperature chemistry, was strongly impacted by engine speed at low NO seeding levels, with no noticeable peak of LTHR detected at 2000 rpm. On the other hand, LTHR of HCA was marginally affected by shortened residence time at higher engine speed as NO + HO 2 reaction was not greatly affected by shorter time scales, since HO 2 production was sustained even at 2000 rpm to support OH generation from NO + HO 2 . Contrary to HO, HCA exhibited greater sensitivity to NO seeding, as the increased OH production at higher NO concentrations offset the OH-quenching effect of cyclopentane, which accounts for 28.6% of HCA’s composition. Consequently, a sensitivity analysis revealed that fuels with weak inherent low-temperature chemistry, like HCA, are likely to be more sensitive to variations in NO concentration and charge temperature, whereas fuels with strong low temperature chemistry are more sensitive to variations in end-gas λ and intake pressure.

Energy↗

BioTransformer 3.0 – A Web Server for Accurately Predicting Metabolic Transformation Products

BioTransformer 3.0 is a freely available web server that supports accurate, rapid and comprehensive in silico metabolism prediction. It combines machine learning approaches with a rule-based system to predict small-molecule metabolism in human tissues, the human gut as well as the external environment (soil and water microbiota). Simply stated, BioTransformer takes a molecular structure as input (SMILES or SDF) and outputs an interactively viewable/sortable table of the predicted metabolites or transformation products (SMILES, PNG images) along with the enzymes that are predicted to be responsible for those reactions and richly annotated downloadable files (CSV and JSON). The entire process typically takes a few seconds. Previous versions of BioTransformer focused exclusively on predicting the metabolism of xenobiotics (such as plant natural products, drugs, cosmetics and other synthetic compounds) using a limited number of pre-defined steps and somewhat limited rule-based methods. BioTransformer 3.0, uses much more sophisticated methods and incorporates new databases, new constraints and new prediction modules to not only more accurately predict the metabolic transformation products of exogenous xenobiotics but also the transformation products of endogenous metabolites, such as amino acids, peptides, carbohydrates, organic acids, and lipids. BioTransformer 3.0 can also support customized sequential combinations of these transformations along with multiple iterations to simulate multi-step human and/or environmental biotransformation events. Performance tests indicate that BioTransformer 3.0 is 40-50% more accurate, much less prone to combinatorial “explosions” and far more comprehensive in terms of metabolite coverage/capabilities than previous versions of BioTransformer.

59 BASIC BIOLOGICAL SCIENCES↗

Radioisotope Science and Technology Division FY 2025 Core R&D Summary Report: Competitive Projects, Postdoctoral Researchers, and Student Interns

R&D efforts in support of the Oak Ridge National Laboratory (ORNL) Isotope Program Radioisotope Portfolio are led by the Radioisotope Science and Technology Division (RSTD). In addition to supporting the ORNL Isotope Program Radioisotope Portfolio, RSTD supports a portfolio of research related to fundamental properties of radioisotopes and radioisotope applications, including diagnostic and therapeutic uses of medical radioisotopes, radioisotopes for national security, and the production of 238 Pu for the National Aeronautics and Space Administration (NASA) and US Department of Energy (DOE) Office of Nuclear Energy. RSTD is organized into functional science and engineering groups, with most staff members supporting multiple programs. The goal of this organization is to enable synergy between programs such that R&D advances coming from other programs may provide benefit to the ORNL Isotope Program. R&D within RSTD is focused around addressing five grand challenges, as documented in the strategic plan for the DOE Office of Isotope R&D and Production, or DOE Isotope Program (IP), Radioisotope Production R&D activities at ORNL: 1. Maximizing the scientific output of radioisotope transmutation resources, 2. Maximizing the scientific output of radioisotope processing resources, 3. Minimizing waste and having optimal waste disposition, 4. Focusing on product quality and reliability, and 5. Expanding the use of beneficial isotopes. The ORNL Core R&D program, one of the primary R&D components within the ORNL Isotope Program Radioisotope Portfolio, ranges from benchtop to demonstration activities, with a focus on researching enhanced production techniques, developing emerging isotopes, and developing the talent pipeline for radioisotope science and technology. Projects within the Core R&D Program are led primarily by RSTD staff members. In supporting enhanced production techniques, the Core R&D program presents an opportunity to fund novel R&D that might not be tied to a specific radioisotope product but still presents a high potential for broad applicability in the longer term. In supporting the development of emerging isotopes, the Core R&D program develops high-priority isotopes that are not able to be fully supported through production funds.

07 ISOTOPE AND RADIATION SOURCES↗

Scaling from Flux Towers to Ecosystem Models: Regional Constraints on Carbon Cycle Processes from Atmospheric Carbonyl Sulfide (Final Report)

DOE supported research suggests that gross primary productivity (GPP) is largely underestimated by global earth system models [Welp et al., 2011], reflecting the persistent challenge in extrapolating from local-scale GPP observations to global-scale earth system models. This poor understanding of GPP at large spatial scales is of particular concern in tropical forests. In tropical forests, some earth systems models forecast a powerful feedback between a warming climate and a decline in GPP resulting in forest dieback. While this simulated feedback is intensely debated, we lack robust large-scale constraints on GPP that are needed to resolve this debate. In particular, carbon dioxide measurements provide valuable information on net carbon flux, but not on the gross flux associated with GPP. Here we conducted a study of regional-to-global scale GPP using atmospheric carbonyl sulfide to provide a new constraint on GPP mechanisms in earth system models. Our project activities integrated modeling, in situ measurement, and remote sensing techniques to resolve GPP for the Amazon as well as global scale trends. The results of this work included initiating airborne carbonyl sulfide monitoring in the Amazon, training for postdocs and graduate students at a Hispanic Serving Institution, fundamental advances in carbonyl sulfide budgets [e.g. Hilton et al., Nature Climate Change, 2017], and high-profile publications that focused on GPP trends for the Amazon [Stinecipher et al., GRL, 2022] and global historical GPP trends [Campbell, et al., Nature, 2017]. Based on the suggestion of our DOE program manager, we published a state-of-the-science commentary to the scientific community on GPP monitoring with COS [Campbell et al., EOS, 2017] which was selected as the cover story. DOE support was acknowledged in all reports. The importance of this research to understanding climate change was communicated to the general public through community seminars (Rotary, Public Libraries, State Parks), an op-ed (SF Chronicle), and interviews in the mass media including two stories in the New York Times (4/5/17; 7/30/18), one of which was especially widely read after it was featured in the New York Time’s Quote of the Day.

54 ENVIRONMENTAL SCIENCES↗

FacultyHack Events: Faculty-Focused Hackathons for High-Performance Computing Curriculum Development

Broadening participation initiatives are important for engaging underrepresented groups in science, technology, engineering, and math (STEM). Such initiatives help foster supportive and inclusive work environments that promote creativity and productivity. While there are initiatives that aim to engage students and faculty, opportunities remain to improve faculty support. Hackathons have proved to be a useful approach for student engagement. There are, however, limited insights into whether and how such events would also work for faculty aiming to develop curricula. This paper discusses the design of a faculty-focused hackathon event, FacultyHack, for curriculum development. We outline the logistics and structure for two past FacultyHack events, detail changes between events, and describe potential improvements and lessons learned.

Holmen, John [ORNL] (ORCID:0000000259342641)↗

Detailed characterization of a PWR fuel rod at high burnup in support of LOCA testing

Experimental investigations of the fuel microstructure and volatile fission products along the pellet of a high burnup specimen (local burnup 76 GWd/tHM) have been conducted to support future transient testing. Detailed microscopy examinations have been carried out at different length scales. Transmission electron microscopy has highlighted a significant amount of damage across the entire radius with the formation of networks of dislocations. The optical and scanning electron microscopy determined the formation of three zones in the pellet with different characteristics. An intermediate region with no grain subdivision, lower porosity than the central zone porosity and high retained fission gas in nanometric bubbles and in the matrix was present between r/r0 ˜ 0.55 and 0.8. The high retention of gas in this region might suggest that the region will be prone to fine fragmentation, in addition to the HBS. An abrupt transition in the structure was observed at mid radius, with a third region developing from the mid radius to the pellet center. In this part of the pellet, metallic and grey phases with size between hundreds of nanometers and a few micrometers have formed at grain boundaries. The majority of fission gas has been released from the grain matrix and the original grains have polygonised, forming sub-grain domains separated by low-angle grain boundaries. No final explanation can be given for the polygonization occurring in the center, but on the basis of the irradiation history and the analysis of all the post irradiation examination (PIE) data, it is postulated that the polygonization within the original grains is an effect of dynamic recovery occurring at high temperature in the fuel center.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Guideline 36 Conformance Test v2.0

ASHRAE Guideline 36 provides guidance for how typical commercial building HVAC systems should be controlled to reduce energy costs and improve the indoor environmental quality for occupants. An industry-led effort is developing test scripts for how control manufacturers can test that the control logic in their control products follows Guideline 36. This software intends to support that effort in two ways. First, by providing a testbed for control manufacturers to run the test scripts against their own control products and compare their generated results to the expected results provided by the test scripts. Second, by providing a testbed that can be used during the development of test scripts to rapidly and repeatably verify they exercise Guideline 36 logic as desired and generate accurate expected results that control products can be compared to. An initial version of the software has already been developed and released open-source by a previous CEC-funded project that implemented the first use case (https://github.com/LBNL-ETA/guideline36_conformance_test/blob/master/LICENSE.txt), while this software disclosure will add the functionality of the second use case, as well as update the software where needed, all open-source. We intend to extend and contribute to the existing open-source software repository.

Blum, David [Lawrence Berkeley National Laboratory↗

Seasonal Precipitation Classification during Surface Atmosphere Integrated Field Laboratory Campaign

The Surface Atmosphere Integrated Field Laboratory (SAIL) campaign, conducted from September 2021 to June 2023 in Crested Butte, Colorado, aimed to characterize precipitation processes in the Upper Colorado River Basin (UCRB). This increased observations of snowfall accumulation in this hydrologically significant watershed would be useful for quantitative precipitation estimates (QPE). Therefore, the Surface Quantitative Precipitation Estimate (SQUIRE) product was developed using the ARM-supported Colorado State University (CSU) X-band Precipitation Radar. Although SQUIRE will be only released for snowfall, by categorizing precipitation types, users can effectively utilize relevant datasets under diverse meteorological conditions. Moreover, the dataset facilitates validation of the QPE product and the analysis of seasonal variations in precipitation types at the surface. Hydrometeors classes are organized based on their phase and physical characteristics mapping the CSU (both winter Summer) and Py-ART classifications into four groups. 1. Liquid Precipitation: includs drizzle, rain, and large raindrops. 2. Frozen Snow and Ice : Pure Snow, combining ice crystals, aggregates, and vertically oriented ice structures. 3. Dense and Large frozen hydrometeors: including low- and high-density graupel and dry hail. 4.Melting: Wet Snow and Melting Hail, hydrometeors exhibiting both liquid and frozen characteristics.

54 ENVIRONMENTAL SCIENCES↗

Linking soil biodiversity and ecosystem function in a Neotropical savanna

Conserving the remaining savanna ecosystems in the Brazilian savanna (Cerrado) — a global biodiversity hotspot that stores carbon and provides water to a large portion of South America — requires understanding the ecological processes maintaining their function. Nutrient cycling supports savanna function via plant litter production and decomposition by soil fauna, releasing nutrients for plant and soil organism uptake. Soil biodiversity and biogeochemistry linkages with litter dynamics in Neotropical savannas under a changing climate are poorly understood. Here, in this study, we combined two years of rainfall seasonality, leaf and wood litter production and decomposition with soil epigeic fauna abundance — the number of ground-surface dwelling invertebrates collected through pitfall traps — taxa richness, Shannon's diversity and Pielou's evenness, and 16 soil biogeochemical variables measured in 12 plots of preserved savanna. Rainfall seasonality modulated the mean soil epigeic fauna diversity and evenness across all plots, which were highest in the rainy season, in contrast to litterfall rates, which peaked in the dry season. In the dry season (April to September), the Formicidae family was the most abundant with 50% of all individuals, while in the rainy season (October to March), the Isoptera order was the most abundant with approximately 39% of individuals. Wood litter decomposition grouped with annual Hemiptera abundance, co-varying with soil epigeic fauna diversity and evenness per plot and against soil fertility variables. Leaf litter decomposition co-varied with the total epigeic fauna abundance and soil pH. We speculate that the specific need to decompose wood litter may be associated with a greater need for diversity than an abundance of soil epigeic fauna. Our work highlights the role of rainfall seasonality on soil biodiversity and physicochemistry, which is also tightly linked with litter production and decomposition. This study advances our understanding of the mechanisms governing nutrient cycling in savanna ecosystems on nutrient-impoverished soils, with implications for achieving sustainable conservation and restoration goals.

59 BASIC BIOLOGICAL SCIENCES↗

Unlocking the biofuel power of cover crop in Washington State: Enhancing potential through hydrothermal liquefaction

This study evaluates cover crops in Washington State (WA) as a renewable feedstock for hydrothermal liquefaction (HTL), supported by techno-economic (TEA) and life cycle (LCA) analysis. In the Pacific Northwest, fallow land is the common winter practice, generating no income for farmers. Over three years, field trials at two representative sites—Puyallup (cool, wet) and Othello (irrigated, no-till)tested triticale, hairy vetch, crimson clover, winter pea, and fava bean preceding cash crops. Biomass yields, composition, soil impacts, and net revenue were assessed across removal treatments. HTL conversion produced 32–37 wt% biocrude, lower than 48 wt% for sewage sludge, with modeled cradle-to-grave carbon intensities of 26–31 g CO 2 e/MJ and minimum fuel selling prices (MFSP) of $\$$6.75–$\$$7.18 per gallon gasoline equivalent (GGE), comparable to other lignocellulosic feedstocks. No significant changes were observed in soil carbon, nitrogen, or subsequent cash crop yields after cover crop removal. Farmer profitability was possible, particularly for triticale and hairy vetch at $\$$60 per dry ton. To address seasonal variability, blending with wastewater sludge was evaluated. All scenarios delivered >70 % carbon intensity reductions relative to fossil fuels, and with Renewable Identification Number (RIN) credits, MFSPs below $\$$2.5 GGE were achievable. These results demonstrate that cover crops can generate new revenue streams for farmers while serving as a flexible, low-carbon feedstock. Integrating cover crops with waste biomass offers a practical pathway to expand the bioeconomy and support year-round renewable fuel production.

Biofuels↗

Ten questions concerning Large Language Models (LLMs) for building applications

Large Language Models (LLMs) are emerging as powerful AI tools capable of transforming how building information is collected, processed, analyzed, and applied across diverse research areas. Their capabilities can help building operators, facility managers and other stakeholders such as designers, architects and engineers by providing actionable insights for decision-making across planning, construction, operations, and maintenance of buildings and facilities. This paper explores ten key questions concerning the role of LLMs in shaping sustainable, intelligent, and human-centric buildings. From fundamental definitions to advanced applications, we examine how LLMs facilitate decision-making across the life cycle of buildings and energy systems. LLMs can enhance life cycle assessments (LCA), building energy simulations, and real-time data integration, empowering more efficient and adaptive human-AI environments. They can also contribute to streamlining regulatory compliance, improving post-occupancy evaluations, and fostering more inclusive and participatory design processes. Additionally, this paper addresses the ethical challenges posed by LLMs, such as bias, data privacy, and environmental impacts, and explores their potentials in advancing intelligent digital twins (DT) for ongoing building operations and maintenance. Built upon our applied research using LLMs and the review of tools, datasets, and research gaps, we provide a forward-looking perspective on how LLMs can drive innovation, collaboration, and productivity in the built environment while supporting ethical and effective implementation.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Decarbonization of the Chemical Industry Through Electrification: Barriers and Opportunities

The chemical industry is a major source of economic productivity and employment globally and among the top 3 industrial sources of greenhouse gas (GHG) emissions, along with steel and cement. As global demand for chemical products continues to grow, there is an urgency to develop and deploy sustainable chemical production pathways and to reconsider continued investment in current emission-intensive production technologies. This perspective describes the challenges and opportunities to decarbonize the chemical industry via electrification powered by low-carbon electricity supply, both in the near term and long term, and it discusses four technological pathways ranging from the more mature direct substitution of heat with electricity and use of hydrogen to technologically less mature, yet potentially more selective, approaches based on electrochemistry and plasma. Finally, we highlight the key elements of integrating an electrified industrial process with the power sector to leverage process flexibility to reduce energy costs of chemical production and provide valuable power grid support services. Unlocking such plant-to-grid coordination and the four electrification pathways has significant potential to facilitate rapid and deep decarbonization of the chemical industry sector.

chemical synthesis↗

Establishing the Role of Metal, Interface, and Vacancy Sites in Pt/TiO 2 -Catalyzed Acetic Acid Hydrodeoxygenation

Catalytic hydrodeoxygenation (HDO) following catalytic fast pyrolysis (CFP) offers an approach to convert the vapor-phase product of biomass pyrolysis to a stable bio-oil product by reducing the oxygen content. Fundamental insights into the HDO of carboxylic acids, which are a corrosive and acidic CFP product, on promising catalyst materials, such as Pt/TiO 2 , are needed to inform the design of multifunctional HDO catalysts with improved carbon efficiency. In this contribution, density functional theory (DFT) calculations were used to assess the role of Pt-metal and Pt-TiO 2 -interface sites on acetic acid HDO (AA-HDO), and to determine the effect of interfacial oxygen vacancies at the Pt-TiO 2 interface, by calculating the reaction energetics for key AA-HDO surface intermediates and elementary steps on each site type. Pt-metal sites, modeled via Pt(111), preferred to form undesired decarboxylation products (CH 4 and CO 2 ), whereas Pt-TiO 2 -interface sites, modeled via an anatase-supported Pt nanowire, favored the formation of desired deoxygenation products (acetaldehyde and ethane). Interfacial-vacancy sites lowered the activation energy barrier for the first C-O bond-scission step in AA-HDO, predicted to be the rate-limiting step for AA-HDO at the Pt-TiO 2 interface in the absence of a vacancy. These atomistic insights reveal the importance of metal-metal oxide interface sites in AA-HDO selectivity and can be used to inform the rational design of improved HDO catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Transformation of SiH 4 to a Molecular L(H) 2 Co=Si=Co(H) 2 L Silicide Complex

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si–H bond activations in SiH 4 at the metal centers of 14-electron LCo I fragments (L = Tp", HB(3,5-diisopropylpyrazolyl) 3 – ; [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl)). Upon exposure of (Tp"Co) 2 (μ-N 2 ) (1) to SiH 4 , a mixture of (Tp"Co) 2 (μ-H) (2) and (Tp"Co) 2 (μ-H) 2 (3) was formed and no evidence for Si–H oxidative addition products was observed. In contrast, [BP 2 tBu Pz]-supported Co complexes led to Si–H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP 2 tBu Pz]Co) 2 (μ-N 2 ) (5) with SiH 4 gave the dicobalt silicide complex [BP 2 tBu Pz](H) 2 Co=Si=Co(H) 2 [BP 2 tBu Pz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. Here, the effect of the [BP 2 tBu Pz] ligand on Co–Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP 2 tBu Pz]Co(L) x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH 4 , despite the lack of significant Si–H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of Me x SiH 4–x (x = 1–3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of Ni-Catalyzed Photochemical Halogen Atom-Mediated C(sp 3 )–H Arylation

Within the context of Ni photoredox catalysis, halogen atom photoelimination from Ni has emerged as a fruitful strategy for enabling hydrogen atom transfer (HAT)-mediated C(sp 3 )–H functionalization. Despite the numerous synthetic transformations invoking this paradigm, a unified mechanistic hypothesis that is consistent with experimental findings on the catalytic systems and accounts for halogen radical formation and facile C(sp 2 )–C(sp 3 ) bond formation remains elusive. We employ kinetic analysis, organometallic synthesis, and computational investigations to decipher the mechanism of a prototypical Ni-catalyzed photochemical C(sp 3 )–H arylation reaction. Our findings revise the previous mechanistic proposals, first by examining the relevance of SET and EnT processes from Ni intermediates relevant to the HAT-based arylation reaction. Our investigation highlights the ability for blue light to promote efficient Ni–C(sp 2 ) bond homolysis from cationic Ni III and C(sp 2 )–C(sp 3 ) reductive elimination from bipyridine Ni II complexes. However interesting, the rates and selectivities of these processes do not account for the productive catalytic pathway. Instead, our studies support a mechanism that involves halogen atom evolution from in situ generated Ni II dihalide intermediates, radical capture by a Ni II (aryl)(halide) resting state, and key C–C bond formation from Ni III . Oxidative addition to Ni I , as opposed to Ni 0 , and rapid Ni III /Ni I comproportionation play key roles in this process. Furthermore, the findings presented herein offer fundamental insight into the reactivity of Ni in the broader context of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗