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At least 703 records · Page 39

Crossover as Determinant for Safety and Performance Tradeoffs in Proton Exchange Membrane Water Electrolyzers

Hydrogen (H2) crossover is a pressing challenge constraining safe and efficient operation of proton exchange membrane water electrolyzers (PEMWEs) especially amongst strides to employ thinner membranes, which enables improved energy efficiency, and elevated cathode pressures, that reduces the energy burden on downstream compressors. Here, we develop a microstructure-aware multicomponent reactive-transport framework that resolves dissolved and gaseous H2 transport pathways and mechanistically links electrode architecture to crossover related safety and performance. We show that operability is co-governed by the cathode catalyst layer (CCL) and the anode porous transport layer (APTL) which sets the H2 crossover flux and the egress capacity respectively. Elevated Pt/C ratio in the CCL suppresses crossover flux by up to 23% while a higher APTL porosity lowers H2 in O2 fraction by 0.6% in the anode effluent. We condense the findings into (cathode pressure-current density) maps overlaid with safety limits and performance targets and ultimately define two safety-performance unified metrics to gauge the size and quality of the operating window. Given the push towards higher pressure and deeper turndown for renewable integration, this study provides mechanistic design guidance to prevent crossover-induced safety risks while preserving the desired performance.

Electrolysis↗

Scale-Up of Electrode Coating and Flow-Field for Commercial Hydrogen Peroxide Electrolyzer: Cooperative Research and Development Final Report, CRADA Number CRD-17-00687

Hydrogen peroxide is currently produced at central chemical plants via the anthraquinone oxidation process. This process produces environmental pollutants that are costly to remediate, requires hazardous long distance shipping of highly concentrated peroxide (50% or 70%), and necessitates extra handling costs related to storage and dilution. Peroxygen Systems, Inc. (PSi) is developing breakthrough technology for on-site hydrogen peroxide production. PSi’s on-site on-demand electrolyzer can reduce the cost of producing hydrogen peroxide by 50%, while also completely eliminating the cost and safety issues associated with shipping and handling of high concentration hydrogen peroxide. The challenge for PSi is scaling. To support the next step toward commercialization (customer pilot tests), scaling the prototype into larger single cells and 20-40 cell stacks is required. In addition to internal hardware and flow-field design efforts at PSi, NREL will address three critical problems for this scale-up effort: (1) demonstrating a large scale roll-to-roll (R2R) process to coat uniform electrode materials for 100 cm2 and 500 cm2 stack testing, (2) demonstrating an in-line diagnostic to achieve better electrode quality control, and (3) performing in situ cell/stack testing to better understand and optimize the performance of the flow field design.

28 EE - Advanced Manufacturing Office (EE-5A)↗

Fluidized-Bed Gasification of Coal-Biomass-Plastics for Hydrogen Production

Coal is one of the most abundant fossil energy resources in the United States and in the world. The recoverable reserves in the United States are estimated to be about 252 billion tons – more than 350 years of supply at current rates of usage. However, the share of coal in total primary energy consumption in the US has been declining over the years. The decline of coal is mainly attributed to cheap natural gas and precipitous declines in the cost of electricity production from renewable technologies such as wind and solar. Coal can potentially be used if it is coupled with carbon-neutral feedstock such as biomass-agricultural residues, forest biomass, and forest residues. Co-gasification of coal and biomass can become a negative carbon emission technology if the carbon dioxide (CO 2 ) is captured and sequestered. Although the biomass gasification process has a lot of similarities to coal gasification, the large-scale adaptation of power production sourced from biomass has not come to fruition. The main reason is that the power production from biomass is still expensive when compared with natural gas or coal power technologies. To address the feedstock cost, one approach is to use low-cost feedstocks, such as municipal solid wastes (MSW) or plastics, for gasification. Gasification involves the partial oxidation of coal and/or biomass feedstocks to produce a combustible fuel called synthesis gas (syngas) which is composed of carbon monoxide (CO), hydrogen (H 2 ), CO 2 , methane (CH 4 ), nitrogen (N 2 ), water (H 2 O), and other compounds that might be considered as contaminants. Raw syngas from gasification must go through multiple steps to produce high-purity hydrogen. The specific steps depend upon the quality (gas composition, contaminants, and their concentration) and condition (pressure and temperature) of syngas. The long-term goal of the project was to utilize coal and plastics together with biomass to produce energy and fuels using a gasification platform while reducing greenhouse gas emissions. The main objective of this research was to examine gasification performance in a laboratory-scale fluidized-bed gasifier for hydrogen production. The specific objectives of the research were to: (i) study coal-plastic-biomass mixture flowability for consistent feeding in the gasifier; (ii) understand the gasification behavior of the mixture in steam and oxygen environments; (iii) perform thermal property characterization of ash and slag from the mixture feedstock and refractory-ash interface of the mixture under gasification conditions; and (iv) develop process models to determine the technology needed for syngas cleanup and contaminants. The study found that there was no apparent segregation when biomass, coal, and waste plastics were mixed together during feeding. Although there were differences in hydrogen production when individual feedstock were fed, the hydrogen concentration remained almost constant with various blends. Therefore, blending waste plastics with biomass and coal, which are all abundant, is a better approach for energy production. Results of the techno-economic analysis suggested that integration of advanced gasification (GTI’s R-GAS™) and syngas cleanup and conditioning technologies (RTI’s WDP and AFWGS) for clean hydrogen production resulted in substantial benefits, including significant capital cost and operating cost reductions. Advanced technologies resulted in 16% reduction in the hydrogen production cost (COH) from 2.94 $\$$/kg to 2.47 $\$$/g, with further scope for optimization and cost reduction. These advanced technologies also result in lower emissions, and improved energy efficiency.

01 COAL, LIGNITE, AND PEAT↗

Recycled Paper as a Source of Renewable Jet Fuel in the United States

Converting biomass into jet fuel involves more than the core chemical process. The overall process includes the logistics of harvesting and transporting the biomass, handling and preparing the material for processing, and processing and disposal of waste. All of these activities contribute to cost. Controlling cost involves more than developing efficient process chemistry. Choice of feedstock also has a significant impact on process economics. We consider chemical conversion of paper from municipal solid waste as a feedstock for the production of jet fuel and diesel. Paper has a significantly higher cellulose content than raw lignocellulosic biomass such as corn stover, so it requires less pretreatment to convert it into hydrocarbons than lignocellulosic biomass. Our techno-economic analysis showed that the cost of converting paper waste into jet fuel is about $1.00/gal less than jet fuel produced from corn stover. Although the cost of recycling paper into jet fuel is less than producing it from corn stover, the process is not competitive with petroleum. We estimated a minimum selling price of $3.97/gal for paper-derived jet fuel. Our sensitivity studies indicated that the biggest economic obstacle is the cost of cellulose hydrolysis. Direct hydrogenation of paper to sugar alcohols combined with increased economy of scale could make recycling paper jet fuel competitive.

09 BIOMASS FUELS↗

Dynamic oxidation of (Mn,Co) 3 O 4 -Coated interconnects for solid oxide electrolysis cells

Solid oxide electrolysis cell stacks are expected to experience dynamic conditions when using renewable electricity derived from wind or solar power. To address this scenario, (Mn,Co) 3 O 4 (MCO)-coated Crofer 22 APU interconnect coupons are subjected to thermal cycling, and intermittent current density, with gas compositions relevant to high-temperature electrolysis (elevated steam:hydrogen ratio and oxygen content). Defects are also intentionally introduced in the MCO coating, to assess whether the difference in oxidation properties of the adjacent coated and uncoated (defective) surfaces causes sufficient stress to damage the protective oxide scale. Specimens with defects are subjected to oxidation for 1000 h at 800 °C, or thermal cycling. Before thermal cycling, some specimens are pre-oxidized to create a thick oxide scale to mimic the scale thickness expected after ~30 kh operation. In all cases, the coating and oxide scale remain well adhered with no cracking observed. Area-specific resistance (ASR) is monitored in both single-atmosphere and dual-atmosphere conditions, and the ASR is stable and is not impacted by dynamic cycling of the current density. Finally, this work provides confidence that the MCO coated interconnect will function as needed in dynamic operation conditions, even with coating defects.

08 HYDROGEN↗

Assessment of Heavy-Duty Fueling Methods and Components-Modeling and Analysis

The goal of the Assessment of Heavy-Duty Fueling Methods and Components project was to comprehensively assess heavy-duty (HD) fuel cell electric vehicle fueling protocols and their effects on techno-economic assessments (TEA) and total cost of ownership (TCO). The project leveraged and built upon ongoing international HD fueling protocols and fueling component development activities to deliver component performance assessments, modeling tools and methods evaluations, TEA of industry-selected protocol structures, and experimental validations of the strategies at the station scale. The effects of the protocols on the fueling times, station costs, and TCO were explored. Fueling time, which was influenced by temperature and protocol selection, had a large impact on the station cost due to component sizing and satisfying hourly demand. As the fleet size increased, the station cost was shown to exponentially decrease by achieving economies of scale. Technology year and fuel economy were the largest contributors to the TCO; however, the choice of fueling protocol had a minor impact on the TCO.

33 ADVANCED PROPULSION SYSTEMS↗

Strategies for Continuous Balancing in Future Power Systems with High Wind and Solar Shares

The use of wind power has grown strongly in recent years and is expected to continue to increase in the coming decades. Solar power is also expected to increase significantly. In a power system, a continuous balance is maintained between total production and demand. This balancing is currently mainly managed with conventional power plants, but with larger amounts of wind and solar power, other sources will also be needed. Interesting possibilities include continuous control of wind and solar power, battery storage, electric vehicles, hydrogen production, and other demand resources with flexibility potential. The aim of this article is to describe and compare the different challenges and future possibilities in six systems concerning how to keep a continuous balance in the future with significantly larger amounts of variable renewable power production. A realistic understanding of how these systems plan to handle continuous balancing is central to effectively develop a carbon-dioxide-free electricity system of the future. The systems included in the overview are the Nordic synchronous area, the island of Ireland, the Iberian Peninsula, Texas (ERCOT), the central European system, and Great Britain.

14 SOLAR ENERGY↗

Identifying Opportunities and Recommendations for the Integration of Advanced Reactors for Industrial Heat and Electricity Users

Nuclear power in the United States has been used traditionally to provide baseload electric power to the grid. Advancements in nuclear power to create smaller and safer reactors have renewed interest in nuclear as a source of both heat and electricity for a variety of applications. There is great interest in coupling nuclear reactors with industrial applications because nuclear power is a low carbon energy source that can be utilized for process heating, hydrogen generation, on-site electricity demand, and more. Idaho National Laboratory is developing guidelines to identify and assist industrial heat and electricity decarbonization by integrating with nuclear power plants (NPPs) to provide clean, abundant, and dispatchable energy. Considerations include specific industrial hazards which impact NPP siting, heat transport requirements and associated technologies, and implementation feasibility based on site-specific demand profiles. To assess integration feasibility, facility process models are developed based on real data obtained from a survey of baseline requirements and process information from industrial facilities in the United States. An assessment of safety and siting requirements is also performed to determine how nuclear industrial pairings could meet licensing requirements for NPPs. In addition, site characterization of an industrial plant is essential to determining the feasibility and suitable integration methods for each industry. Characterization includes facility distance from the nearest population center, site size, rail or water transport availability, and proximity to undeveloped land. These characteristics are important to determine reactor- or industry-side design requirements for safe, efficient operation. The siting and technical data assessment will reveal opportunities for single-use nuclear integration and co-location opportunities for industries to share benefits from a single reactor. In addition to existing facilities, this “energy-park” style cooperation could include new construction like data centers which can cost-share energy investments or provide a stable demand-and-revenue stream to the investor. Deliverables will contain a library of documents and models to guide various industries toward understanding nuclear technologies based on their users’ needs. This paper is a summary of the current project status, and provides insights on suitable pairings for specific industries and reactor technologies

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Chapter 2: Evaluating a Concentrating Solar Power Plantas an Extended-Duration Peaking Resource

We explore the ability of a concentrating solar power (CSP) plant with thermal energy storage (TES) to provide peaking capacity. We focus on future power systems, wherein net load patterns may be significantly different than they are today (e.g., due to higher renewable-energy penetrations). We examine 28 locations in the southwestern United States over an 18-year period. The hourly operation of the CSP plants are simulated to determine their potential to provide energy during an eight-hour peak-load window for each day up to 365 days per year. Our result shows that for the large majority of locations and years, CSP plants with certain configurations (i.e., in terms of solar field and TES sizes) can provide nearly 100% peak-load capacity. We examine also the amount of supplemental energy (e.g.,by using natural gas as a supplemental thermal-energy source) that would be required to ensure that a CSP plant could serve the eight highest-load hours of every day of the year. We find that in most cases, a CSP plant supplemented with natural gas would require less than 5% of the fuel that is used by a natural-gas fired power plant providing the same level of reliable capacity. A series of sensitivity analyses show that these results are robust to the number of peak-load hours and days that are considered and the configuration of the CSP plant.

capacity value↗

Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction

The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO 2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metallic and complex hydride-based electrochemical storage of energy

Abstract The development of efficient storage systems is one of the keys to the success of the energy transition. There are many ways to store energy, but among them, electrochemical storage is particularly valuable because it can store electrons produced by renewable energies with a very good efficiency. However, the solutions currently available on the market remain unsuitable in terms of storage capacity, recharging kinetics, durability, and cost. Technological breakthroughs are therefore expected to meet the growing need for energy storage. Within the framework of the Hydrogen Technology Collaboration Program—H 2 TCP Task-40, IEA’s expert researchers have developed innovative materials based on hydrides (metallic or complex) offering new solutions in the field of solid electrolytes and anodes for alkaline and ionic batteries. This review presents the state of the art of research in this field, from the most fundamental aspects to the applications in battery prototypes.

Cuevas, Fermin (ORCID:0000000290555880)↗

Using Additives to Control the Decomposition Temperature of Sodium Borohydride

Hydrogen (H 2 ) shows great promise as zero-carbon emission fuel, but there are several challenges to overcome in regards to storage and transportation to make it a more universal energy solution. Gaseous hydrogen requires high pressures and large volume tanks while storage of liquid hydrogen requires cryogenic temperatures; neither option is ideal due to cost and the hazards involved. Storage in the solid state presents an attractive alternative, and can meet the U.S. Department of Energy (DOE) constraints to find materials containing > 7 % H 2 (gravimetric weight) with a maximum H 2 release under 125 °C. While there are many candidate hydrogen storage materials, the vast majority are metal hydrides. Of the hydrides, this review focuses solely on sodium borohydride (NaBH 4 ), which is often not covered in other hydride reviews. However, as it contains 10.6% (by weight) H 2 that can release at 133 ± 3 JK -1 mol -1 , this inexpensive material has received renewed attention. NaBH 4 should decompose to H 2 (g), Na(s), and B(s), and could be recycled into its original form. Unfortunately, metal to ligand charge transfer in NaBH 4 induces high thermodynamic stability, creating a high decomposition temperature of 530 °C. In an effort make H 2 more accessible at lower temperatures, researchers have incorporated additives to destabilize the structure. This review highlights metal additives that have successfully reduced the decomposition temperature of NaBH 4 , with temperatures ranging from 522 °C (titanium (IV) fluoride) to 379 °C (niobium (V) fluoride). We describe synthetic methods employed, chemical pathways taken, and the challenges of boron derivative formation on H 2 cycling. Though no trends can be found across all additives, it is our hope that compiling the data here will enable researchers to gain a better understanding of the additives’ influence and to determine how a new system might be designed to make NaBH 4 a more viable H 2 fuel source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance analysis of hybrid power configurations: Impact on primary energy intensity, carbon dioxide emissions, and life cycle costs

In this work, utilization of Natural gas and Hydrogen to support current and future building energy needs to offset the total electric demand while improving the grid resiliency and energy efficiency was investigated. Demand side energy management will play an important role in efficiently managing the available energy resources. Performance assessment of different power generation and energy management configurations is presented in this paper. Development of solutions in addressing grid resiliency by providing the ability to design suitable configurations for meeting individual building energy needs is discussed. Primary movers (PM) such as internal combustion engines (ICE) and fuel cells (FC) along with small scale auxiliary renewable energy source such as photovoltaics (PV) were considered. Key attributes of total carbon foot-print, life cycle costs including capital and operational expenditure, electric grid offset or peak shaving capability, thermal energy availability and its further potential to offset total electric demand, and primary energy intensity are analyzed and discussed in detail.

08 HYDROGEN↗

Turboexpander for Direct Cooling in Hydrogen Vehicle Fueling Infrastructure

Hydrogen fuel cell electric vehicles (FCEVs) have been identified as one of a few options for zero carbon emissions transportation. A major advantage of FCEVs is that they can fuel quickly and follow a familiar fueling behavior to hydrocarbon-fueled vehicles. Whether light duty or heavy duty, the goal for a hydrogen dispenser is to fuel a vehicle in the same amount of time as the fossil fuel equivalent. When hydrogen is dispensed into the vehicle storage system, however, the temperature rises due to the Joule-Thomson effect and the heat of compression. Typically, vehicles store the compressed hydrogen in composite overwrapped pressure vessels that have a polymer liner with an operational temperature limit of 85°C. This temperature limit can be exceeded during fast fueling if hydrogen is not precooled. Precooling allows for a dispenser to fuel a vehicle at a faster flow rate by preventing the storage tank on the vehicle from overheating. Fueling protocols and requirements are presented in SAE J2601 Fueling Protocols for Light Duty Gaseous Hydrogen Surface Vehicles [1]. A heavy-duty equivalent is under development with similar requirements for precooling. Currently, conventional precooling for light-duty vehicle refueling uses a heat exchanger and chiller to cool the hydrogen gas to -40°C before entering the vehicle. The precooling system represents a significant part of the station capital and operating costs, so if the cost of the precooling system can be reduced by improving its efficiency, the overall station capital and operating cost can be reduced. In this project, National Renewable Energy Laboratory (NREL) and Sandia National Laboratories (SNL) researchers teamed up to investigate the turboexpander precooling application. A turboexpander is a device that places a turbine in a flow path where a pressure differential can be attained. This expansion device will extract work and lower the temperature of the fluid as the pressure reduces. While initial calculations based on established principles showed potential for a turboexpander to generate cooled gas, much work needs to be done to prove the concept. Turboexpanders typically work best under steady state conditions, while the dispenser is a very dynamic flow system. Dynamic turboexpander systems have been proven, such as a turbocharger on a gasoline vehicle. The inlet pressure at a dispenser is also much higher than any other known turboexpander system but should behave similarly to higher density fluids at lower pressures. Having both performed initial calculations, NREL and SNL researchers teamed up to investigate the turboexpander precooling application further. A project was soon built around the idea with SNL performing system modeling using previously proven capabilities and NREL performing hardware characterization with established station capabilities. Creare LLC was contracted as the turbomachinery expert to design and build the concept device. Part way through the project, however, contracting issues with the funding partner caused the project to terminate early before building and characterizing the concept device. While the project could not continue, many key findings were already learned. This paper is a summary of those findings.

08 HYDROGEN↗

Striving to translate shale physics across ten orders of magnitude: What have we learned?

Shales will play an important role in the successful transition of energy from fossil-based resources to renewables in the coming decades. Aside from being a significant source of low-carbon intensity fuels, like natural gas, they also serve as geologic seals of subsurface formations that may be used to isolate nuclear waste, sequester CO 2 , or store intermittent energy (e.g., solar hydrogen). Despite their importance, shales pose significant engineering and environmental challenges due to their nanoporous structure and extreme heterogeneity that spans at least ~10 orders of magnitude in spatial scale. Two challenges inhibit a system-level understanding: (1) the physics of fluid flow and phase behavior in shales are poorly understood due to the dominant molecular interactions between minerals and fluids under confinement, and (2) the apparent lack of scale separation that prevents a reliable (closed) description of the physics at any single scale of observation. In this review, we focus on the latter issue and discuss scale translation, which in its broadest sense is transforming data or simulations from one spatiotemporal scale to another. While effective scale translation is not exclusive to shales, but all geologic porous media, the need for it is especially acute in shales given their high degree of heterogeneity. Classical theories like homogenization, while indispensable, fail when scales are not separated. Other methods, like numerical upscaling, scale-translate in only one direction: small to large, but not the reverse, called downscaling. However, the confluence of advances in three areas are bringing challenging problems such as shales within reach: increased computational power and scalable algorithms; high-resolution imaging and multi-modal data acquisition; and machine learning to process massive amounts of data. While these advances equip geoscientists with a wide array of experimental and computational tools, no individual tool can probe the entire gamut of heterogeneity in shales. Their effective use, therefore, requires an ability to bridge between various data types obtained at different scales. The aim of this review is to present a coherent account of computational and experimental methods that may be used to achieve just that, i.e., to perform scale translation. We provide a broader definition of scale translation, one that transcends classical homogenization and upscaling methods, but is consistent with them and accommodates notions like downscaling and data translation. After a brief introduction to homogenization, we review hybrid methods, numerical upscaling and its recent extensions, multiscale computing, high-resolution imaging, and machine learning. We place particular emphasis on multiscale computing and propose an algorithmic framework to bridge between the pore (micro) and Darcy (macro) scales. Throughout the paper, we draw comparisons between the various methods and highlight their (often hidden) similarities, differences, benefits, and pitfalls. We finally conclude with two case studies on shales that exemplify some of the methods presented.

58 GEOSCIENCES↗

A [FeFe] Hydrogenase–Rubrerythrin Chimeric Enzyme Functions to Couple H 2 Oxidation to Reduction of H 2 O 2 in the Foodborne Pathogen Clostridium perfringens

[FeFe] hydrogenases are a diverse class of H 2 -activating enzymes with a wide range of utilities in nature. As H 2 is a promising renewable energy carrier, exploration of the increasingly realized functional diversity of [FeFe] hydrogenases is instrumental for understanding how these remarkable enzymes can benefit society and inspire new technologies. In this work, we uncover the properties of a highly unusual natural chimera composed of a [FeFe] hydrogenase and rubrerythrin as a single polypeptide. The unique combination of [FeFe] hydrogenase with rubrerythrin, an enzyme that functions in H 2 O 2 detoxification, raises the question of whether catalytic reactions, such as H 2 oxidation and H 2 O 2 reduction, are functionally linked. Herein, we express and purify a representative chimera from Clostridium perfringens (termed Cper HydR) and apply various electrochemical and spectroscopic approaches to determine its activity and confirm the presence of each of the proposed metallocofactors. The cumulative data demonstrate that the enzyme contains a surprising array of metallocofactors: the catalytic site of [FeFe] hydrogenase termed the H-cluster, two [4Fe-4S] clusters, two rubredoxin Fe(Cys) 4 centers, and a hemerythrin-like diiron site. The absence of an H 2 -evolution current in protein film voltammetry highlights an exceptional bias of this enzyme toward H 2 oxidation to the greatest extent that has been observed for a [FeFe] hydrogenase. Here, we demonstrate that Cper HydR uses H 2 , catalytically split by the hydrogenase domain, to reduce H 2 O 2 by the diiron site. Structural modeling suggests a homodimeric nature of the protein. Overall, this study demonstrates that Cper HydR is an H 2 -dependent H 2 O 2 reductase. Equipped with this information, we discuss the possible role of this enzyme as a part of the oxygen-stress response system, proposing that Cper HydR constitutes a new pathway for H 2 O 2 mitigation.

08 HYDROGEN↗

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO 2 , H 2 O, and O 2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. Here, the emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoinduced hydrogen dissociation in thymine predicted by coupled cluster theory

The fate of thymine upon excitation by ultraviolet radiation has been the subject of intense debate. Today, it is widely believed that its ultrafast excited state gas phase decay stems from a radiationless transition from the bright ππ* state to a dark nπ* state. However, conflicting theoretical predictions have made the experimental data difficult to interpret. Here we simulate the early gas phase ultrafast dynamics in thymine at the highest level of theory to date. This is made possible by performing wavepacket dynamics with a recently developed coupled cluster method. Our simulation confirms an ultrafast ππ* to nπ* transition (τ = 41 ± 14 fs). Furthermore, the predicted oxygen-edge X-ray absorption spectra agree quantitatively with experiment. We also predict an as-yet uncharacterized πσ* channel that leads to hydrogen dissociation at one of the two N-H bonds. Similar behavior has been identified in other heteroaromatic compounds, including adenine, and several authors have speculated that a similar pathway may exist in thymine. However, this was never confirmed theoretically or experimentally. This prediction calls for renewed efforts to experimentally identify or exclude the presence of this channel.

Kjønstad, Eirik F.↗