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Bioinspired and biomolecular catalysts for energy conversion and storage

Metalloenzymes are remarkable for facilitating challenging redox transformations with high efficiency and selectivity. In the area of alternative energy, scientists aim to capture these properties in bioinspired and engineered biomolecular catalysts for the efficient and fast production of fuels from low-energy feedstocks such as water and carbon dioxide. In this short review, efforts to mimic biological catalysts for proton reduction and carbon dioxide reduction are highlighted. Two important recurring themes are the importance of the microenvironment of the catalyst active site and the key role of proton delivery to the active site in achieving desired reactivity. As a result, perspectives on ongoing and future challenges are also provided.

14 SOLAR ENERGY↗

Lab-scaled performance evaluation of novel water-lean solvents for post combustion CO 2 capture

Here, this work focuses on demonstrating the energetic performance and operational reliability in a continuous system of RTI's water-lean solvents for post-combustion CO 2 capture applications. RTI's Non-Aqueous Solvent, NAS-1A was subjected to 100 h of continuous, CO 2 capture and regeneration operation using a Lab-scale Gas Absorption System (LsGAS) while the CO 2 capture efficiency, mass balance, and total energy inputs were monitored. Throughout the test period, NAS-1A demonstrated stable operation with 90% CO 2 capture while requiring about 15% lower total energy input for solvent regeneration compared to 30 wt% monoethanolamine (MEA) solution. The use of a slipstream of CO 2 -rich solvent from the absorber sump reduced the regenerated CO 2 temperature before the gas was further cooled by the overhead condenser at the top of the desorber. The rich-split setup combined with a wash section may be an effective approach to remove water and solvent vapor from the regenerated CO 2 as well as to recover heat at the top of the desorber. NAS-1B was later developed and included a modifier component that lowers the heat of CO 2 absorption and reduces the vapor pressure of the amine component. The total energy inputs for 90% CO 2 capture with NAS-1B was found to be 25% less than that of the MEA. A gas chromatograph was used to monitor the amine concentration in the gas leaving the absorber wash section. It was found that under similar operating conditions, the presence of the modifier in NAS-1B reduces the amine in the absorber off-gas from 143 ppm in NAS-1A to 20 ppm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subtask 1.3 – Integrated Carbon Capture and Storage for North Dakota Ethanol Production

The Energy & Environmental Research Center (EERC), in partnership with Red Trail Energy, LLC (RTE), a North Dakota ethanol producer; the North Dakota Industrial Commission (NDIC) Renewable Energy Program (REP); and the U.S. Department of Energy (DOE), conducted a feasibility and implementation study for a commercial carbon capture and storage (CCS) effort. This subtask provided technical support and developed recommended practices of how small-scale industrial CO2 emitters (<1,000,000 tonnes of CO2 emitted annually) may economically deploy CCS. The 64-million-gallon dry mill RTE ethanol facility, emitting an average 180,000 tonnes of CO2 annually, was the subject of the case study. The positive outcome of this research, which shows technical and economic potential for ethanol–CCS in North Dakota, has resulted in RTE acquiring an approved Permit to Drill on December 2, 2019, for a stratigraphic test well in early 2020, a necessary step toward a North Dakota CO2 Storage Facility Permit (SFP) for the RTE CCS effort. Outcomes include 1) validating the Broom Creek Formation as a regional target for CCS, 2) determining the full carbon life cycle of an industrial fuel production facility with CCS, 3) developing a field implementation plan (FIP) for small-scale CCS, and 4) determining the validity and pathway for using CCS to meet low-carbon fuel (LCF) standards. The technical team included the EERC, RTE, Trimeric Corporation, Schlumberger Carbon Services, and Computer Modelling Group (CMG). Findings from activities conducted November 2016 – May 2020 are summarized as follows. Several key steps have been accomplished toward validating the Broom Creek Formation as a CO2 injection and storage target at the RTE CCS site, including verification of the presence and structure of sandstone layers that may comprise the potential CO2 storage reservoir and the several thousand feet of overlying confining zone. Work included site characterization using existing data, interpretation of seismic data within the study area, and geologic modeling simulation of CO2 injection. Interpreted results estimate 3000 feet of confining zone between the Broom Creek Formation (storage target) and the lowermost underground source of drinking water (e.g., the Fox Hills Formation). The thickness of the Broom Creek injection target varies 230–420 ft within the survey area. Results were used to inform the location of a stratigraphic test well and associated characterization test program. No impediments were identified within the targeted CO2 storage complex that would prevent the project from moving forward. A stratigraphic test well is the next step to validate these results and to acquire remaining data necessary to develop a North Dakota CO2 SFP application. The EERC generated full carbon life cycle estimates for CCS integration with the RTE ethanol facility. Results indicated that an average 40% reduction in CO2 emissions is possible through CCS implementation. Approximately half of the carbon in the overall life cycle for a dry mill ethanol plant is generated through the fermentation process and emitted to the atmosphere; this is the CO2 stream targeted for CCS. The remaining carbon is attributed to corn feedstock farming (diesel, fertilizer), energy for fuel processing (natural gas, electricity), and transportation (diesel) of the fuel product. Life cycle carbon estimates are also affected by the anticipated energy consumption of a potential capture facility, which depend on the type of CO2 product generated. For example, a 30%–40% net CO2 emission reduction is estimated if a liquefied CO2 facility were incorporated compared to a 40%–50% net CO2 reduction if a supercritical “injection-grade” CO2 product is generated; i.e., more energy is required to further refine the CO2 stream, affecting the full carbon life cycle estimates. A CCS FIP was developed and initiated at the RTE CCS site, resulting in the development of several guidance documents: a CO2 Capture Process Design Package, a North Dakota CO2 geologic Storage Permits Template, and a Public Outreach Package for CCS in North Dakota. General FIP components include CO2 capture system, pipeline and well designs; monitoring, verification, and accounting (MVA) plans; geologic characterization and testing programs; and permitting and outreach plans. Vendor bids were also acquired for the CO2 liquefaction facility. Near-surface characterization (groundwater and soil gas sampling) and geologic characterization (seismic survey) were initiated to inform development of a UIC Class VI-compliant MVA plan compliant with a North Dakota CO2 SFP. Designs (well and geologic testing) were completed for a stratigraphic test well compliant with a North Dakota CO2 SFP. In addition, the outreach plan was executed, including community open houses, meetings with city/county/state officials, and development of public materials. Although other entities continued to mature incentive programs in 2019–2020, California and the Internal Revenue Service (IRS) currently provide the most advanced economic opportunities for CCS integrated with fuel production. The California Low-Carbon Fuel Standard (LCFS) adopted a CCS Protocol in January 2019, allowing submittal of a design-based pathway (DBP) application for an approved temporary (not certified) carbon intensity value for a fully engineered facility. An ethanol–CCS DBP application to the California LCFS Program (officially approved February 28, 2020) was developed to show that the RTE CCS effort meets LCFS requirements. The approved DBP provides confidence to advance the project and supports potential investments. Other entities continue to mature incentive programs. The IRS issued guidance in February 2020 that addresses the definition of beginning of construction and revenue procedure on partnerships for the Enhancement of Carbon Dioxide Sequestration Credit (a.k.a. Section 45Q) CCS tax credit program; the IRS anticipates issuing further guidance on issues such as secure geologic storage, utilization qualifications, and recapture of claimed credits. Maturing incentive programs coupled with workable permitting regulations provide confidence to advance CCS projects in North Dakota and support financial investment to proceed with designing, constructing, and implementing CCS projects at small-scale fuel production facilities. The largest hurdles for CCS implementation at small-scale industrial systems are often business/economic-related (i.e., not technical). Market uncertainty already exists for agriculture-based alternative fuels such as corn ethanol, for which production has increased by ~33%, and prices have correspondingly lowered since 2015. Passing the Section 45Q tax credit program improves economic feasibility for CCS but may require external investors for a small business to achieve maximum benefits. Public–private partnerships with NDIC and DOE have resulted in foundational technical and regulatory knowledge, growing stakeholder confidence, and a pathway to implementation that enables similar industrial CCS projects in the region to advance. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by NDIC and RTE. The authors would also like to thank CMG, ESRI, IHS, Neuralog, and Schlumberger for allowing the use of their software packages in support of this work.

42 ENGINEERING↗

Energy-enhanced dimension eight SMEFT effects in VBF Higgs production

We study Higgs boson production via vector boson fusion at the LHC, focusing on the process pp → H + jj and capturing the leading energy-enhanced contributions within the Standard Model Effective Field Theory (SMEFT) up to order 1/Λ$^{4}$. Employing energy-scaling arguments, we predict the magnitude of each higher-dimensional operator’s contribution. Utilizing the geometric formulation of SMEFT, our analysis incorporates dimension-eight operators not previously considered. We find that the kinematics of vector boson fusion — characterized by two highly forward jets — tend to suppress contributions from higher-dimensional operators, requiring a lower scale Λ for SMEFT effects to become observable. This suggests that the SMEFT remains valid for lower Λ than expected. Combined with the fact that LEP constrains the dimension-six operators with the most considerable impact on vector boson fusion, a regime exists where dimension-eight operators can have significant effects. In many cases, these dimension-eight operators also influence associated production processes like pp → HV(jj), though differences in analysis cuts and kinematics mean this is not always the case. Our findings provide insights that could refine the search for SMEFT signals in collider experiments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ripening of Rh Nanoparticle Catalysts in Reverse Water–Gas Shift via a Data-Driven Model Combining Physics, Theory, and Experiment

Degradation via sintering is an ongoing challenge that impedes the broad commercial success of supported metallic nanoparticle catalysts. To mitigate degradation via informed catalyst design and process operations, here we aim to disambiguate the underlying mechanisms of sintering by combining theory and experiment in a quantitative framework. While mechanistic sintering models exist, they only model a single sintering pathway, even though multiple sintering mechanisms can occur simultaneously or dominate at different stages of the process. Data-driven machine learning models have emerged as a means to represent complex processes through data regression. However, machine learning models have very large data needs and lack mechanistic insights due to their black-box encoding. To develop an interpretive model of catalyst degradation via sintering, we constructed a hybrid model combining mechanistic “physics-based” models and data-driven methods to obtain both reliable predictions and mechanistic insights regarding experimentally observed sintering phenomena. Focusing on nanoparticle sintering in the Rh–TiO 2 catalyst for the reverse water–gas shift (RWGS) reaction, the hybrid model couples a mechanistic term for Ostwald ripening with energy values calculated via density functional theory (DFT) with a parametric, data-driven discrepancy function term for unmodeled mechanisms. The hybrid model is trained using Bayesian inference with data collected from small-angle X-ray scattering (SAXS) in situ experiments wherein average nanoparticle diameter versus time was measured at three relevant operating temperatures. The calibrated hybrid model results show that an Ostwald ripening-only model parameterized with fixed DFT energies does not fully capture the time and temperature dependence of the SAXS-observed sintering kinetics, and that an additional functional contribution, or DFT energy calibration, is required to reconcile simulation and experiment. Analysis of the hybrid-model error confirms that the hybrid model outperforms both the purely mechanistic and purely data-driven alternatives in terms of expected predictive accuracy for time-evolving average particle sizes. Furthermore, the results support the hypothesis that the Ostwald ripening mechanism is less important for explaining the sintering phenomena as operating temperature increases under an assumed fixed DFT parameterization. This could be explained in one of two ways: either latent, unmodeled sintering mechanisms dominate at higher temperatures, or the DFT uncertainty increases with temperature. The proposed modeling approach directly links theory to experiments and simulations via a statistical hybrid modeling framework and can be extended to other catalytic systems to improve predictive models and mechanistic understanding.

Bayesian hybrid modeling↗

Dynamically plausible hypotheses of lunar origin

The implausibility of the capture hypothesis of lunar origin is pointed out. The reason for this implausibility is the extreme weakness of the only known energy sink for pure capture, tidal friction. A mechanism proposed by Alfven and Arrhenius (1972) is the locking of the moon in synchronization with a longitudinal variation in the earth's gravitational field. It is shown that collision with preexisting satellite matter is the most effective means of capturing a moon.

Kaula, W. M.↗

Methods of Fabricating Scintillators with Radioisotopes for Beta Battery Applications

Technology has been developed for a class of self-contained, long-duration power sources called beta batteries, which harvest the energy contained in the radioactive emissions from beta decay isotopes. The new battery is a significant improvement over the conventional phosphor/solar cell concept for converting this energy in three ways. First, the thin phosphor is replaced with a thick scintillator that is transparent to its own emissions. By using a scintillator sufficiently thick to completely stop all the beta particles, efficiency is greatly improved. Second, since the energy of the beta particles is absorbed in the scintillator, the semiconductor photodetector is shielded from radiation damage that presently limits the performance and lifetime of traditional phosphor converters. Finally, instead of a thin film of beta-emitting material, the isotopes are incorporated into the entire volume of the thick scintillator crystal allowing more activity to be included in the converter without self-absorption. There is no chemical difference between radioactive and stable strontium beta emitters such as Sr-90, so the beta emitter can be uniformly distributed throughout a strontium based scintillator crystal. When beta emitter material is applied as a foil or thin film to the surface of a solar cell or even to the surface of a scintillator, much of the radiation escapes due to the geometry, and some is absorbed within the layer itself, leading to inefficient harvesting of the energy. In contrast, if the emitting atoms are incorporated within the scintillator, the geometry allows for the capture and efficient conversion of the energy of particles emitted in any direction. Any gamma rays associated with secondary decays or Bremsstrahlung photons may also be absorbed within the scintillator, and converted to lower energy photons, which will in turn be captured by the photocell or photodiode. Some energy will be lost in this two-stage conversion process (high-energy particle to low-energy photons to electric current). The geometric advantage partially offsets this as well, since the absorption depth of high-energy beta radiation is much larger than the depth of a p-n junction. Thus, in a p-n junction device, much of the radiation is absorbed far away from the junction, and the electron- hole pairs are not all effectively collected. In contrast, with a transparent scintillator the radiation can be converted to light in a larger volume, and all of the light can be collected in the active region of the photodiode. Finally, the new device is more practical because it can be used at much higher power levels without unduly shortening its lifetime. While the crystal structure of scintillators is also subject to radiation damage, their performance is far more tolerant of defects than that of semiconductor junctions. This allows the scintillator- based approach to use both higher energy isotopes and larger quantities of the isotopes. It is projected that this technology has the potential to produce a radioisotope battery with up to twice the efficiency of presently used systems.

Rensing, Noa M.↗

Water foraging with dynamic roots in E3SM; The role of roots in terrestrial ecosystem memory on intermediate timescales (Final Technical Report)

Terrestrial ecosystems can show sustained responses to stress events that may last for years after the initial perturbation. This phenomenon is referred to as legacy or memory and it emerges from a set of ecosystem processes that are poorly captured by Earth System and Land Surface Models. Consequently, these models struggle to predict the impact that extreme climate events have on surface energy, carbon and hydrological exchange once a stressor such as drought has relaxed or in response to repeated exposure to stress. In this project, we set out to test how the addition of dynamic root profiles in land surface models impact the capacity for Earth System Models, such as the Department of Energy’s E3SM, to capture realistic legacy effects. Observations have shown that vegetation shifts their root profiles during stress events to forage for water and these altered root profiles may take years to relax back to the initial state. We hypothesized that the alteration of the belowground root structures may be a source of terrestrial ecosystem legacy that is missing from models. To test this idea we undertook three core activities. (1) We developed a global-scale analysis of the impact of dynamic roots on ecosystem legacy building from a recently developed dynamic root module. (2) We developed new root dynamics in the DOE’s Energy Land Model (ELM) that allowed not only root profiles to shift their profile but also simultaneously alter carbon allocation to fine root pools. We then tested the impact of these new dynamics with intensive sensitivity analysis at four long-term AmeriFlux sites. (3) We undertook detailed isotopic analysis of tree rings from these AmeriFlux sites to assess ecophysiological and ecohydrological legacy to stress events that can be used to benchmark the sensitivity experiments with ELM. From these core activities, we report the following key findings. Firstly, on a global scale, the addition of dynamic roots led to chronically water-stressed ecosystems recovering faster to climate stress while wetter ecosystem showed enhanced legacy. This is because across ecosystems, stress events were almost universally associated with water shortages that led to the development of deeper root profiles. These deeper root profiles proved beneficial for recovery from drought stress. While the root dynamics did not universally improve the modeled representation of legacy it showed complex transient dynamics that emerge from the addition of dynamic roots. Secondly, the sensitivity analysis illustrated long term shifts in rooting depths away from the prescribed default profile suggesting that initializing of root profiles could benefit from spin-up simulations that converge on locally optimized root profiles. In addition, by enabling dynamic allocation some of the sites predicted unrealistically low allocation to roots (and high allocation to leaves). While these changes did not dramatically alter modeled gross primary productivity, they illustrated that without more sophisticated root processes in models, there is little penalty to dramatically disinvest in roots. Thirdly, the isotopic analysis of tree rings showed highly distinct legacy responses across species and sites. For example, T. canadensis showed reduced transpiration the year after stress events illustrated by sustained elevated $\delta^{18}$O. In contrast, A saccharum displayed elevated $\delta^{13}$C associated with reduced stomatal conductance in response to the previous years’ stress event. These geochemical signatures of legacy were present despite tree growth returning to normal the year after the stress. The results show the importance of species-level dynamics in legacy that are absent in modeling that assumes common traits within plant functional types. In summary, the work here established new avenues to explore root dynamics in models while illustrating how additional root processes are needed before dynamic carbon allocation can be implemented. Lastly, this project provided mentorship to a postdoctoral fellow, training for an early career scientist and multiple undergraduate students recruited from a minority serving institution.

54 ENVIRONMENTAL SCIENCES↗

A fully light-driven approach to separate carbon dioxide from emission streams

Carbon capture from industrial point sources is an essential component of the global effort to mitigate climate risks. However, traditional approaches require significant energy input—often provided, counterproductively, by fossil fuel combustion. Using sunlight directly as the energy source would significantly improve the energy efficiency of carbon capture processes. Herein, we report the first fully visible-light-driven CO 2 separation system, in which carbon capture is achieved via the photoenolization/addition reaction of inexpensive 2-methylbenzophenone with CO 2 , and CO 2 release is realized through an intramolecular photodecarboxylation reaction. Finally, this system operates isothermally, works with natural sunlight, and facilitates CO 2 removal from natural gas flue emissions, providing a blueprint for other non-thermal chemical separations.

Ahmad, Bayu I. Z. [Cornell Univ., Ithaca, NY (Unit↗

Novel thermal energy storage component: Development, performance, and phase transition diagnosis

Thermal energy storage (TES) using phase change materials (PCMs) is a promising technology for capturing and storing excess thermal energy for later use. However, challenges such as poor heat transfer efficiency and a lack of modular, scalable designs have limited widespread adoption of TES in real-world applications. This study developed and evaluated modular brick-type and blade-type TES prototypes featuring an aluminum housing, an embedded serpentine coil for active or passive thermal exchange, and a cost-effective metal mesh to enhance PCM thermal conductivity. The blade-type TES achieved notable geometric efficiency, with a thickness-to-length ratio of 0.03 and a thickness-to-width ratio of 0.08, enabling highly compact and modular thermal storage suitable for space-constrained applications. The paper presents a detailed evaluation of the TES prototypes’ performance. The comparative analysis indicated that the TES prototypes provide a highly cost-effective, thermally optimized alternative for compact energy storage and load shifting. A novel diagnostic technique was also introduced: using a portable endoscope to capture real-time visualizations of PCM phase transitions inside the TES. This method provides critical insights into internal heat transfer mechanisms, identifies potential issues, and offers valuable support for optimizing the TES design and developing the control algorithm. Overall, the modular brick-type and blade-type TES designs demonstrated in this work provide a scalable, efficient, and economically viable solution for advancing TES across residential, commercial, and industrial sectors. The designs’ compact structure, enhanced thermal performance, and integrated diagnostic capabilities make them strong candidates for future deployment in energy-efficient systems.

Gao, Zhiming [ORNL] (ORCID:0000000271397995)↗

Assessing synergies and trade-offs of diverging Paris-compliant mitigation strategies with long-term SDG objectives

The Sustainable Development Goals (SDGs) and the Paris Agreement are the two transformative agendas, which set the benchmarks for nations to address urgent social, economic and environmental challenges. Aside from setting long-term goals, the pathways followed by nations will involve a series of synergies and trade-offs both between and within these agendas. Since it will not be possible to optimise across the 17 SDGs while simultaneously transitioning to low-carbon societies, it will be necessary to implement policies to address the most critical aspects of the agendas and understand the implications for the other dimensions. Here, we rely on a modelling exercise to analyse the long-term implications of a variety of Paris-compliant mitigation strategies suggested in the recent scientific literature on multiple dimensions of the SDG Agenda. The strategies included rely on technological solutions such as renewable energy deployment or carbon capture and storage, nature-based solutions such as afforestation and behavioural changes in the demand side. Results for a selection of energy-environment SDGs suggest that some mitigation pathways could have negative implications on food and water prices, forest cover and increase pressure on water resources depending on the strategy followed, while renewable energy shares, household energy costs, ambient air pollution and yield impacts could be improved simultaneously while reducing greenhouse gas emissions. Overall, results indicate that promoting changes in the demand side could be beneficial to limit potential trade-offs.

54 ENVIRONMENTAL SCIENCES↗

Predicting industrial building energy consumption with statistical and machine-learning models informed by physical system parameters

The industrial sector consumes about one-third of global energy, making them a frequent target for energy use reduction. Variation in energy usage is observed with weather conditions, as space conditioning needs to change seasonally, and with production, energy-using equipment is directly tied to production rate. Previous models were based on engineering analyses of equipment and relied on site-specific details. Others consisted of single-variable regressors that did not capture all contributions to energy consumption. Further, new modeling techniques could be applied to rectify these weaknesses. Applying data from 45 different manufacturing plants obtained from industrial energy audits, a supervised machine-learning model is developed to create a general predictor for industrial building energy consumption. The model uses features of air enthalpy, solar radiation, and wind speed to predict weather-dependency; motor, steam, and compressed air system parameters to capture support equipment contributions; and operating schedule, production rate, number of employees, and floor area to determine production-dependency. Results showed that a model that used a linear regressor over a transformed feature space could outperform a support vector machine and utilize features more representative of physical systems. Using informed parameters to build a reliable predictor will more accurately characterize a manufacturing facility's energy savings opportunities.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Hybrid-energy approach enabled by heat storage and oxy-combustion to generate electricity with near-zero or negative CO 2 emissions

We assess a hybrid-energy approach that modifies a steam-turbine power plant to use renewable energy sources (electricity, plus options for geothermal and solar heat), plus fossil fuel (natural gas and coal) and/or waste biomass (e.g., Douglas fir woodchips). Heat storage allows heat to be created during periods of excess energy supply and for that heat to be converted to electricity when demanded. Excess electricity, such as from variable renewable energy (VRE), is used to generate oxygen for oxy-combustion furnaces that create very-hot, high-purity CO 2 that heats granular rock beds in insulated vessels. Cool CO 2 leaving the beds is dried, sent to compressors powered by excess VRE electricity, before being sent by pipeline to geologic CO 2 storage. Very-hot CO 2 transfers high-grade heat from storage to the power plant in a closed loop that returns medium-grade heat back to storage, allowing low- and medium-grade renewable-heat sources to be stacked beneath combustion heat, with all heat sources being converted to electricity at the same (high) thermal efficiency. Reliable, on-demand power may be generated with near-zero CO 2 emissions with fossil fuel and with negative CO 2 emissions with waste biomass. Our analyses show that with fossil fuel, up to 35% of gross power can be derived from renewable sources, while for waste biomass, it can be entirely derived from renewable sources. Because our approach has the potential to ensure that grids have a continuous supply of clean energy and because electricity is only generated once, when demanded, it could serve as an efficient alternative to bulk energy storage.

30 DIRECT ENERGY CONVERSION↗

Sorbent Mediated Electrocatalytic Reduction of Dilute CO 2 to Methane

Efficient CO 2 utilization is a critical component of closing the anthropogenic carbon cycle. Most studies have focused on the use of pure streams of CO 2 . However, CO 2 is generally available only in dilute streams, which requires capture by sorbents followed by energy-intensive regeneration to release concentrated CO 2 . Direct utilization of sorbed-CO 2 avoids the costly regeneration step, and the sorbent-CO 2 interaction can kinetically activate CO 2 to tune its reactivity toward products that could otherwise be inaccessible with direct CO 2 reduction. We demonstrate that an N-heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (DPIy), quantitatively reacts with CO 2 from dilute streams (0.04 and 10%) to form the sorbent-CO 2 substrate 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (DPICx). Electrocatalyst iron tetraphenylporphyrin chloride (Fe(TPP)Cl) typically reduces CO 2 to CO; however, with DPICx as the substrate, the eight-electron reduced product methane (CH 4 ) is produced with a high Faradaic efficiency (>85%) and regeneration of the sorbent DPIy. In addition to the overall energy and capital advantages of integrated CO 2 capture and conversion, this result illustrates how sorbents can serve a dual purpose for both CO 2 capture and chemical auxiliary purposes to access unique products. CO 2 has a spectrum of reactivity with different types of sorbents; thus, these studies demonstrate how sorbent-CO 2 interactions can be leveraged for integrated capture and utilization platforms to access a wider range of CO 2 -derived products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Erosion Experimentation in Solar Power Systems

An alternate and sustainable form of energy is concentrated solar power (CSP) systems, which capture and store the sun’s energy in the form of heat. To increase the efficiency and overall cost of the plant, particles were used as a heat transfer medium. As particles flow through this system, the movement of particles creates erosion, in the forms of abrasion and attrition. Experiments were tested at room temperature and 800 degrees Celsius for both abrasion wear and attrition erosion. In abrasion wear, specimens were placed inside a container, particles were added, and the specimen rotated in and out of the particles. In attrition erosion, a steel disk rotated amongst particles which resulted in particles rubbing against each other. Abrasion wear increased when temperature increased while attrition showed that the particles broke down as the amount of time increased. For attrition at 800 degrees Celsius, oxide was increased and mixed with the particles. Durability models will be created to predict attrition and abrasion based on the particle and specimen mechanical properties. This discovery shows that this method of utilizing particles for CSP plants would improve efficiency and decrease overall costs.

14 SOLAR ENERGY↗

Applications of Strain-Coupled Magnetoelectric Composites

This article deals with research, development and future directions of magnetoelectric composites for practical devices applications. In the past 20 years there has been a surge of research in the area of multiferroics (MF) and magnetoelectrics (ME) due to their potential to replace existing technologies based only on ferroelectric or ferromagnetic materials. Some of the magnetoelectric composites show exceptionally high potential in the area of magnetic field sensors, however, work remains before commercialization can be realized. The cross coupling among various ferroic parameters in magnetoelectric composites is several orders higher than single phase magetoelectrics, which make its favorable for low detection (nT or pT) magnetic field sensors. Advances in both layered structures or controlled three-dimensional matrix composites for applications as magnetoelectric nonvolatile memory elements are both required. Robust cross-coupling among various parameters with more than four logic states and its compatibility with complementary-symmetry metal–oxide–semiconductor (CMOS) technology are the main requirements for heterostructure magnetoelectric thin films. The major hurdles in the area of magnetoelectric nonvolatile memory elements are poor interfacial properties and weak magnetoelectric coupling for high density fast read and write processes. Another potential area is strained coupled magneto-electric composites where magnetostriction mediated dimensional change in the magnetic layer effectively modulate the change in the dimension of piezoelectric layers via piezostriction, which leads to a strong ME coupling where their coupling magnitude is sufficient for magnetic field sensors. Energy harvesters based on magnetoelectric composites are also intriguing concepts to capture various types of waste energy, in the form mechanical vibration, pressure, wind energy, hydrothermal and waste temperature.

36 MATERIALS SCIENCE↗

Exobiochemistry

Exobiochemistry is the putative biochemistry of extraterrestrial life. It suggests the possible energy and material bases of extraterrestrial life and could help detect it. The diverse biochemistry of Earth indicates that a wide range of exobiochemistry is possible on other planets. An exobiochemistry will probably use the same energy sources as Earths ecology, light, biological organic material, and more rarely abiotic chemicals. Extraterrestrial life will be based on familiar chemical principles and probably capture, store, and release energy using oxidation-reduction reactions. Extraterrestrial life will give chemical indications of its existence. Key elements will be concentrated, stored, and recycled, altering their availability and isotopic composition. Any significant departure from chemical equilibrium would be good evidence for exobiochemistry, but an integrated system of departures from the expected equilibrium would be better. Exobiochemistry can be expected to include closed biogeochemical cycles of the major life supporting elements and may well show the complex dynamic close-coupled interactions that characterize the terrestrial biosphere. Terrestrial biochemistry provides a basis for generalization and extrapolation but it does not set bounds on exobiochemistry. In exobiochemistry we can expect: 1. closed chemical cycles that recycle materials, nutrients, and catalysts, 2. organisms with complementary metabolisms that cooperate to close the chemical cycles, 3. a high probability of a carbon and water chemistry, but some possibility of a non-carbon or non-water chemistry in extreme environments, and, 4. life similar to bacteria more prevalent than higher plants and animals.

Jones, Harry↗

Early scattering by Jupiter and its collision effects in the terrestrial zone

When Jupiter was on the order of three to ten earth masses in size, there undoubtedly was a considerably larger mass of condensed matter in its zone, since Jupiter would have perturbed most of it to other parts of the solar system. Monte Carlo studies indicate a significant portion would have crossed the earth's orbit. If the earth and moon had not yet fully formed, the probability of earth-zone planetesimals being hit by this Jupiter-scattered material was high. Further Monte Carlo models of these collisions and their products indicate a significant portion of matter was heated to melting, even if less than 5% of the relative kinetic energy went into heat. The models include capture probabilities by an embryo earth and a protolunar swarm. Because heat energy is correlated with comminution energy, and because the capture probability of the swarm is mass-dependent while embryo's is not, the protolunar material suffered much higher heating on the average than did the proto-earth material.

Kaula, W. M.↗