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At least 253 records · Page 14

Tandem particle-slurry batch reactors for solar water splitting (Final Scientific/Technical Report)

Economically, particle slurry reactors are projected to be one of the most promising technologies for solar photoelectrochemical hydrogen production, according to a 2009 techno-economic analysis commissioned by the US DOE and performed by Directed Technologies, Inc. The Fuel Cell Technologies Office’s Multi-Year Research, Development and Demonstration (MYRD&D) goals and targets are to reduce the cost of H 2 produced from renewable sources at the plant gate (i.e. not including delivery, dispensing, or storage) to < $2.00/gge, equivalent to ~$2.00/kg H 2 . Research results from our techno-economic modeling research suggest that this target could be met using particle slurry reactors assuming STH efficiencies in the range of 5 – 10%, materials lifetimes of < 1 year, and nanoparticles that cost up to 20 times more than projected costs of TiO 2 -coated Fe 2 O 3 nanoparticles. Although most large worldwide research efforts directed at solar photoelectrochemical hydrogen production focus on wafer-based designs, the projected lower cost for a particle slurry reactor at these disparate projected STH efficiencies clearly suggests that particle slurry reactors could be a scalable and deployable technology, assuming several challenges are overcome. These major technological challenges include the demonstration of a vertically-stacked-vessel architecture that is capable of operating sustainably while mostly relying on diffusion and natural convection to mix the redox shuttles between the vessels, and the demonstration that photocatalyst particles can operate at an overall 1% STH efficiency or larger when incorporated into this two-vessel design. Our research adds to the understanding of photocatalytic reactors for solar water splitting through numerical modeling results and experimental results. Numerical models were developed to simulate relevant device physics including particle and reactor dimensions which affect optical, transport, and rheological properties, electrocatalytic and photovoltaic properties of particles at various temperatures, and properties of redox shuttles and separators. Moreover, theoretical maximum solar-to-hydrogen efficiencies for ensembles of particles like in photocatalyst reactors were modeled and simulated and shown to equal or exceed those of photoelectrochemical designs under most scenarios. These results help determine constraints on the reactor that will enable more optimal designs for future prototypes. In parallel, experiments were performed to identify the most effective redox shuttles and to empirically validate the numerical models and simulations. Toward the latter, state-of-the-art light-absorbing particles and electrocatalysts were synthesized and characterized physically and photoelectrochemically for water electrolysis and redox chemistry with redox shuttles in the form factor of mesoporous electrodes and free-floating particles. The most promising materials candidates were used in a suspension reactor to evaluate performance toward photocatalytic H 2 production and results from the two measurements were compared. Predominantly, state-of-the-art cocatalyst-modified Rh-doped SrTiO 3 and BiVO 4 particles were further characterized to assess for their ability to perform visible-light-driven H 2 and O 2 evolution, respectively, and results were similar to those reported for the state-of-the-art in the peer-reviewed literature. Outcomes from this work inform the public of the effectiveness and promise of solar photocatalytic water splitting for clean and renewable hydrogen production. This work may also help increase research interest and funding for photocatalysis projects, which will accelerate development of a technology that will benefit the public by generating fuel while emitting few greenhouse gases and pollutants.

08 HYDROGEN↗

Artificial Photosynthesis with Next Generation Molecular Catalysts

The objective of this project was to develop a new class of molecular photocatalysts for CO 2 reduction that will enable breakthrough advances in artificial photosynthesis. A major limitation of existing photocatalytic assemblies is that only a small fraction of absorbed photons are converted into fuel due to inefficiencies in electron transport between the different system components. In the case of molecular catalysts for reduction of CO 2 , highly reducing electron equivalents are required for catalysis. As a result, the electron flux between the photosensitizer and CO 2 reduction catalyst is heavily biased towards the photosensitizer. One method to direct the electron flux towards productive photocatalysis is to design molecular catalysts for CO 2 reduction that operate at more favorable potentials than existing catalysts. The conventional approach is to tune the potential of the catalyst through selection of the supporting ligands, however, this only leads to incremental improvements due to the existence of an unfavorable scaling relationship between the rate and potential of catalysis. Our hypothesis is that the catalytic rate and potential can be simultaneously enhanced using bimetallic catalysts in which one metal improves the potential of catalysis and the second metal increases the rate of catalysis. During the course of this project, a few studies reported some success in improving photocatalytic CO 2 reduction with heterobimetallic complexes, demonstrating the potential of this approach to catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic and Vibrational Coherence in Heterogeneous Electron Transfer (Final Report)

Interfacial electron transfer reactions constitute key physical phenomena central to a variety of energy related transport and conversion processes such as catalysis, photocatalysis, photovoltaics, energy storage, molecular electronics, etc. Heterogeneous material systems like organic/inorganic interfaces are of particular interest because they provide great potential to tailor properties according to application specific requirements. While electron transfer dynamics has been studied intensively in heterogeneous systems many questions remain unanswered. The significance of electronic-vibrational coupling and coherence is one aspect that has yet to be fully explored. The objective of this project is to develop and implement new ultrafast spectroscopic techniques based on pump four-wave mixing spectroscopy (pump-FWM) for studying the dynamics of vibrational coupling and coherence in heterogeneous electron transfer (HET) at molecule/semiconductor interfaces. The implementation of the spectroscopic setup allows to explore different four-wave mixing techniques and thus to identify a suitable approach to study the significance of vibrational as well as electronic coherence in HET.

14 SOLAR ENERGY↗

Nanoscale Imaging of Optical-Frequency Plasmonic Energy Transfer in Individual Nanoparticles and their Assemblies

The nonradiative transfer of energy from plasmonic metal nanostructures to their neighboring environments is a rapidly expanding research area because of its tremendous potential impact on photovoltaics and photocatalysis. Despite the significant progress achieved via optical spectroscopies, understanding the differing and competing energy transfer pathways available to these systems still presents a major challenge due to a lack of insight into their nanoscale optical responses. With the atom-scale spatial resolving power of the electron microscope and its ability to probe optical transitions, electron spectroscopies like EELS are uniquely suited for these challenges. Our proposal addressed STEM/EELS techniques (Camden) to directly measure and even control energy transfer pathways in hybrid plasmon-resonator systems and leveraged detailed theoretical models combined with simulation (Masiello) to understand the essential underlying physics. In particular, the outcome of our proposed studies deepened the fundamental understanding of how surface plasmons shed energy to their environment and the practical knowledge gained here will influence the design of future high-efficiency solar energy-harvesting devices and photocatalysts capable of operating throughout the visible and the infrared.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Solar Fuels Nexus: Molecules and Materials for Light-Driven Catalysis

The American Chemical Society (ACS) selects two groups of graduate students each year to plan and host a one-day symposium at each national meeting (both fall and spring).This year our Graduate Student Symposium Planning Committee (GSSPC), composed of seven students from four universities, proposal entitled “A Solar Fuels Nexus: Molecules and Materials for Light-Driven Catalysis” was selected for the “Crossroads in Chemistry” ACS Meeting that will take place March 23-26, 2023 in Indianapolis, IN. All members of our GSSPC are affiliated with the DOE Fuels from Sunlight Energy Innovation Hub, with two from the Liquid Sunlight Alliance (LiSA) and five from the Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE). Here we request funds to support this symposium. This symposium will highlight research progress and perspectives in the solar fuels generation field and seeks to advance the four priority research objectives (PROs) established by the Department of Energy’s Office of Basic Energy Sciences (DOE-BES) Roundtable Report that are also central to many research goals within LiSA and CHASE. The symposium will consist of research presentations from 10 invited senior researcher speakers on topics such as molecular catalyst design, computational modeling of electron transfer systems, microenvironmental effects on CO2 reduction and H2O oxidation catalysis, and intelligent design of semiconductor interfaces with ample time for discussions. These research topics fit very well with the Solar Photochemistry supported research areas of “light-driven electron and energy transfer in condensed phase and interfacial molecular systems,” “electrocatalysis and photocatalysis of solar fuels reactions,” and “semiconductor photoelectrochemistry.” More broadly, this symposium seeks to advance the DOE-BES’s mission to: “support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules” by providing a diverse atmosphere where such research will be disseminated, discussed, and debated. There will be a strong focus on Diversity, Equity, and Inclusivity (DEI) in our symposium. Of our 10 speakers, 7 will be from underrepresented demographics in STEM, including 5 who identify as women. Furthermore, we have representatives from academia accompanied by one national lab scientist and one officer from the Office of Fossil Energy and Carbon Management at the DOE. All speakers will be holding a short DEI moment ahead of their talks. In order to support the career development of attending early career scientists, we will also be hosting a luncheon specifically for graduate students and postdocs to provide them opportunities to network with the distinguished speakers and other attendees. DOE funds for this symposium will be used to support the attendance and participation of 15 graduate students from US institutions by defraying travel and registration costs. These funds will promote engagement and conversation between early career scientists in the solar fuels field, while disseminating solar fuels research funded by and relevant to the DOE.

30 DIRECT ENERGY CONVERSION↗

Probing the Sustainable Reduction of CO 2 , N 2 and NO 3 to Fuels and Chemicals using Non-Traditional Porphyrinoid Catalysts

For the last several decades, numerous strategies have been proposed to be able to interconvert electricity and commodity fuels for transportation and other applications. Even as solar and wind energy become more widely available, these renewable energy sources are not always available where the population is most dense or during peak times of energy demand. One plausible solution to the issue of electricity storage and transport is to use electricity to drive the formation of high-energy compounds and chemical fuels. As a result, the electrochemical conversion of CO 2 into chemical fuels has received major attention as a multi-pronged approach for electricity coversion, storage, and transport. Similar strategies are also attractive for conversion of N 2 and NO x into value added compounds such as ammonia. Metalloporphyrin and metallocorrole complexes are comprised of aromatic tetrapyrrole scaffolds and have been extensively studied as homogeneous catalysts for critical catalytic processes like the electrochemical CO 2 reduction reaction (eCO 2 RR) to generate CO as feedstock for the Fischer–Tropsch process to generate a variety of hydrocarbons as chemical fuels. Despite their significance and impact, efficiently driving such catalytic reduction processes is challenging for multiple reasons. Such processes require multiple-electron transfer events, as opposed to single-electron redox chemistry that forms high-energy singly-reduced intermediates. In addition, these electron transfer events must be coupled to proton-transfer steps and avoid application of high overpotentials where proton (H + ) reduction to generate H 2 (as well as other side-reactions) can lower the selectivity and energy efficiency of the eCO 2 RR process. Certain Fe(III) aromatic tetrapyrroles (e.g., porphyrins and corroles) have been reported to overcome these challenges, but are often difficult to synthesize and modify, and have a tendency to support single-electron redox chemistry at the metal as opposed to multielectron redox involving the ligand and metal in concert. Other families of tetrapyrroles in which all four meso-carbons are reduced (i.e., sp 3 -hybridized) are also known in the literature. These non-aromatic tetrapyrroles are known as porphyrinogens and support multi-electron redox chemistry which has been elaborated by several groups, prompting researchers to consider whether these scaffolds may improve the kinetics and efficiencies of multi-electron steps attendant to activation of thermodynamically stable small-molecule substrates such as CO 2 , N 2 , NO 3 − , and NO 2 − . Although porphyrinogens support multi-electron redox properties, the four sp 3 -hybridized meso-carbons inherent to the tetrapyrrole core completely disrupt π-conjugation between pyrrolic units, which compromises the photochemical properties of porphyrinogens in comparison to that of traditional porphyrinoids. Moreover, the highly reducing nature of porphyrinogens predisposes these platforms to extreme air and water sensitivity. Accordingly, such metalated porphyrinogens are often pyrophoric and/or incompatible with many common organic solvents (CH 2 Cl 2 , CHCl 3 , CH 3 CN, EtOAc, etc.). Hence, reports of efficient small-molecule activation or catalysis supported by porphyrinogens have been limited. To overcome the instability of porphyrinogens while retaining the scaffold’s attractive multi-electron redox properties, we have directed attention to establishing less-well studied groups of non-aromatic tetrapyrroles (i.e., phlorins, biladienes, and isocorroles). These non-traditional tetrapyrroles each contain just a single sp 3 -hybridized meso-carbon, which ablates the platforms aromaticity but still provides an extended π-framework. In addition to developing innovative platforms that may be used to sustainably generate value-added chemicals, fuels, and ammonia via either photo- or electrocatalytic approaches our work also has significantly broadened our understanding of how to prepare and modulate the properties of non-aromatic tetrapyrroles for other applications. Our efforts entailed a synergistic partnership and active collaborations with Drs. David C. Grills and Mehmed Z. Ertem (both of Brookhaven National Lab) to better characterize isocorroles (and related non-aromatic tetrapyrroles) using a variety of advanced spectroscopic and theoretical methods. Our combined efforts have shown that the combination of properties that isocorroles (and related tetrapyrroles) provide results in good chemical stability paired with unique redox and photochemical characteristics that are not typically supported by simple and/or unadorned aromatic tetrapyrroles. Beside redox chemistry, the photochemistry of isocorroles and other non-aromatic tetrapyrroles containing one sp 3 -hybridized meso-carbon is also appealing due to their absorption in the long-visible to near-IR regions, which are essential for photocatalysis and related applications that benefit from direct excitation at these wavelengths. The results reported vastly improve our understanding of non-aromatic tetrapyrrole synthesis, properties and utility for activation of small molecule substrates such as O 2 and CO 2 in the presence of weak cationic organic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Support for U.S. Participants at the 18 th International Congress on Catalysis

The 18 th International Congress on Catalysis (ICC) was held Lyon, France on July 14-19, 2024. It provided a premier technical gathering in surface and organometallic catalysis, industrial homogeneous and heterogeneous catalysis, electrocatalysis, photocatalysis, and catalysis in condensed media. This meeting brough together participants from academia, industry, and national laboratories. The organization that overseed this meeting was the Council of the International Congress on Catalysis. This international committee has over 27 signature countries. The United States is represented in the Council of the International Congress on Catalysis through two permanent representatives. These representatives are elected by the Board of Directors of the North American Catalysis Society (NACS), an organization which coordinates and overseas the activities of 12 largely autonomous clubs within the United States, Canada, and Mexico. The critical importance of catalysis is reflected by the fact that 25-30% of all manufactured goods in the United States involve at least one catalytic step. Because advances in a large number of catalytic processes, which are crucial to U.S. interests, were presented at this meeting, it was important to ensure participation from both the U.S. academic and the industrial sectors.

02 PETROLEUM↗

Fundamental Research Aimed at Diverting Excess Reducing Power in Photosynthesis to Orthogonal Metabolic Pathways

Photosystems are incredible biological machines that use sunlight to drive the conversion of carbon dioxide to sugar. The amount of sunlight available for photosynthesis sometimes exceeds the amount of energy plants can use. This excess energy has to be safely dissipated through non-productive biological processes. The ultimate goal of this project is to understand whether we can utilize that otherwise unused excess energy. In our previous work, we showed that, in principle, it is possible to attach a catalyst to photosystem I and generate H2 using light. Our current strategy is to genetically fuse parts of the photosystem I complex with a recently discovered oxygen-tolerant [FeFe] hydrogenase. Our rationale is that such chimeric proteins may potentially result in the natural incorporation of the photosystem I-hydrogenase link using the inherent genetic machinery of the cell. In this project, we aim to verify that light-driven hydrogen production in this construction is possible. Throughout the project, we designed nanoconstructs that showcase the plausibility of this technology, at least in vitro. We take advantage of these constructs to investigate details of the coupling between photosystem I and a H2-producing enzyme called [FeFe] hydrogenase. This part of the project reveals details of the electron transfer between photosystem I and the attached hydrogenase, providing information that can lead to new strategies for improved biological photocatalysis. We also researched efficient and robust tethering of the [FeFe] hydrogenase to photosystem I in cyanobacteria. This work will highlight successful design strategies to guide the future development of photosynthetic biohybrids. Uncovering the principles governing the utilization of otherwise unusable energy significantly further our understanding of cyanobacterial photosynthesis. The work proposed establishes the feasibility of diverting excess energy under high light conditions to orthogonal enzymatic pathways and set design rules for efficient utilization of such a strategy for scientific and industrial applications in biosensing, renewable energy, and high-value chemicals production. The work addresses the DOE-BES Photosynthetic Systems program goal to develop a multidimensional understanding of photosystems that would provide specific metrics that instruct strategies for improving biological photosynthesis and for guiding the future development of bioreactors and biomimetic energy systems.

Photosynthetic systems, hydrogenase, cyanobacteria↗

Triggering cell death in cancers using self-illuminating nanocomposites

Bioinspired photocatalysis has resulted in efficient solutions for many areas of science and technology spanning from solar cells to medicine. Here we show a new bioinspired semiconductor nanocomposite (nanoTiO 2 DOPA-luciferase, TiDoL) capable of converting light energy within cancerous tissues into chemical species that are highly disruptive to cell metabolism and lead to cell death. This localized activity of semiconductor nanocomposites is triggered by cancer-generated activators. Adenosine triphosphate (ATP) is produced in excess in cancer tissues only and activates nearby immobilized TiDoL composites, thereby eliminating its off-target toxicity. The interaction of TiDoL with cancerous cells was probed in situand in real-time to establish a detailed mechanism of nanoparticle activation, triggering of the apoptotic signaling cascade, and finally, cancer cell death. Activation of TiDoL with non-cancerous cells did not result in cell toxicity. Exploring the activation of antibody-targeted semiconductor conjugates using ATP is a step toward a universal approach to single-cell-targeted medical therapies with more precision, efficacy, and potentially fewer side effects.

60 APPLIED LIFE SCIENCES↗

Atmospheric Pressure Plasma Deposition of TiO2: A Review

Atmospheric pressure plasma (APP) deposition techniques are useful today because of their simplicity and their time and cost savings, particularly for growth of oxide films. Among the oxide materials, titanium dioxide (TiO2) has a wide range of applications in electronics, solar cells, and photocatalysis, which has made it an extremely popular research topic for decades. Here, we provide an overview of non-thermal APP deposition techniques for TiO2 thin film, some historical background, and some very recent findings and developments. First, we define non-thermal plasma, and then we describe the advantages of APP deposition. In addition, we explain the importance of TiO2 and then describe briefly the three deposition techniques used to date. We also compare the structural, electronic, and optical properties of TiO2 films deposited by different APP methods. Lastly, we examine the status of current research related to the effects of such deposition parameters as plasma power, feed gas, bias voltage, gas flow rate, and substrate temperature on the deposition rate, crystal phase, and other film properties. The examples given cover the most common APP deposition techniques for TiO2 growth to understand their advantages for specific applications. In addition, we discuss the important challenges that APP deposition is facing in this rapidly growing field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of High Surface Area Microporous ZnO from ZnO/Carbon Sacrificial Composite Monolith Template

Fabrication of porous materials from the standard sacrificial template method allows metal oxide nanostructures to be produced and have several applications in energy, filtration and constructing sensing devices. However, the low surface area of these nanostructures is a significant drawback for most applications. Here, we report the synthesis of ZnO/carbon composite monoliths in which carbon is used as a sacrificial template to produce zinc oxide (ZnO) porous nanostructures with a high specific surface area. The synthesized porous oxides of ZnO with a specific surface area of 78 m2/g are at least one order of magnitude higher than that of the ZnO nanotubes reported in the literature. The crucial point to achieving this remarkable result was the usage of a novel ZnO/carbon template where the carbon template was removed by simple heating in the air. As a high surface area porous nanostructured ZnO, these synthesized materials can be useful in various applications including catalysis, photocatalysis, separation, sensing, solar energy harvest and Zn-ion battery and as supercapacitors for energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Control of Photocatalytic Proton Reduction through the Mechanical Actuation of a Hydrogel Host Matrix

This paper describes a photocatalytic hydrogen evolution system that is dynamically and reversibly responsive to the pH of the surrounding solution through actuation of a micro-hydrogel (microgel) matrix that hosts the photocatalysts (CdSe/CdS nanorods). Here, the reversible actuation occurs within 0.7 s (swelling) and 1.7 s (contraction). A ΔpH of 0.01 relative to the pK a of the tertiary amine on the microgel polymer (7.27) results in a reversible change in the average diameter of the microgel hosts by a factor of 2.5 and a change in the photocatalytic turnover frequency (TOF) by a factor of five. Kinetic isotope effect and photoluminescence quenching experiments reveal that the scavenging of the photoexcited hole by sulfite ions is the rate-limiting step and leads to the observed response of the TOF to pH through actuation of the microgel. Molecular dynamics simulations quantify a greater local concentration of sulfite hole scavengers for pH < pK a .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Active Rutile TiO 2 Nanocrystalline Photocatalysts

The controllable synthesis of rutile TiO 2 single crystal particles with the preferential orientation of {111} facets still remains a scientific and technological challenge. Here, we developed a facile route for fabrication of rutile TiO 2 nanorod crystals (RTiO 2 NRs) having high ratios of oxidative {111} to reductive {110} surfaces. RTiO 2 NRs were synthesized using a peroxo-titanium complex (PTC) approach, which was controlled by changing the Ti/H 2 O 2 ratio. The thus obtained RTiO 2 NRs revealed a high tendency to agglomerate through orientation-dependent attachment along the {110} facets. This resulted in an increased {111}/{110} surface ratio and led to a markedly improved photocatalytic activity of RTiO 2 NR aggregates. The reported findings illustrate the rich potential of the herein proposed facile and energy-efficient synthesis of nanostructured rutile TiO 2 -based photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shapeshifting Nanocatalyst for CO2 Conversion

The conversion of CO2 into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO2 reduction reaction (CO2RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO2 reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu+ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO2 photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO2 conversion.

CO2 reduction reaction↗

Dicyanobenzothiadiazole (DCBT) Organic Dye as a Visible Light Absorbing Strong Photoinduced Oxidant with a 16 Microsecond Long–Lived Excited State

Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long–lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6–dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady–state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. Finally, the long–lived excited state photosensitizer is well–suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water–soluble photosensitizer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering a Non–Natural Photoenzyme for Improved Photon Efficiency

We developed a novel HTS engineering platform to optimize photoenzymatic activity. The improvements in variants were correlated to an increase in enzymatic photon efficiency. Here, transient absorption spectroscopy revealed a shift from a stepwise to a concerted mechanism. The platform was expanded to improve the synthesis of γ, δ, ϵ-lactams, and acyclic amides.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Abstract C−H amination and amidation by catalytic nitrene transfer are well‐established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C−H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd−N) with a diradical nitrogen ligand that is singly bonded to Pd II . Despite the subvalent nitrene character, selective C−H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N 3 SiMe 3 . Based on these results, a photocatalytic protocol for aldehyde C−H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C−H nitrogen atom transfer offers facile access to primary amides after deprotection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗