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800 records · Page 45

Center for Frontiers of Subsurface Energy Security (Final Report)

For the past two decades a slowly growing consensus has been that rising temperature is being caused by increases in carbon dioxide (CO 2 ) in the Earth’s atmosphere. What is less consensual is what to do about it. Solutions range from reducing emissions to various ways to capture CO 2 (from effluents of power plants, as plants, etc.) and store it away from the atmosphere. The problem is of such magnitude that it is likely that we will need many methods. Also some methods would cause draconian harm to global economies. This work is about the storage part of the reducing of CO 2 in the atmosphere. There have been many methods proposed for storing CO 2 : in vegetation, at the bottom of oceans, in land farms, and in subsurface formations. The latter is particularly prominent given the large estimated volume in porous formation in the Earth, and the 50-year old experience in injecting CO 2 for enhanced oil recovery. This report is about the science behind subsurface storage, called here geological carbon storage or GCS. Effective GCS requires that billions of metric tons of CO 2 be injected into storage reservoirs annually. GCS feasibility requires balancing the opposing impacts of large emplacement (injection) rates without compromising caprock seal integrity during injection. Once injected, the challenge is to assure the injected CO 2 remains permanently stored. Under most conditions, CO 2 is in a supercritical state, or scCO 2 . scCO 2 is immiscible with the subsurface brine and has a factor of ten smaller viscosity, leading to the development of two-phase fluid flow and scCO 2 bypassing. After the injection of large volumes of scCO 2 , the pore pressure, state of stress, chemical, thermal, and biological steady-state or equilibrium conditions in the subsurface are disrupted, which may lead to unpredictable behavior because the responses to these changes are often non-linear. Current challenges for efficient and reliable scCO 2 storage are: (1) sustaining large injection rates; (2) using available pore space efficiently, and (3) controlling undesired or unexpected behavior, such as scCO 2 leakage. Various aspects of these challenges are addressed by collaborative projects within Center for Frontiers in Subsurface Energy Security (CFSES). Challenge 1 – Sustaining large storage rates. To offset the annual CO 2 emissions of in the United States, ~7 billion metric tons of CO 2 must be injected into the storage reservoirs annually. Injected CO 2 forms a plume that starts spreading, displacing originally resident brine, though inefficiently so. Because of its low viscosity, and buoyant forces, a CO 2 plume rises to the reservoir rock-caprock interface. Injecting large volumes of scCO 2 at sufficiently high rates into subsurface storage formations leads to increases in pore pressures, potential expansion of the reservoir rock, and may result in fracturing of the reservoir rock and/or caprock. CFSES research uses existing and new experimental and modeling approaches to identify chemical-physical controls on the permeability and pore pressure dynamics, anticipating geomechanical (fracturing) events, predicting multi-phase flow patterns and trapping of CO 2 . Challenge 2 – Using pore space with unprecedented efficiency. Since large volumes of scCO 2 are to be stored, the volume available in storage reservoirs must be used efficiently. Storage efficiency is defined as a fraction of pore space occupied by carbon dioxide. Current estimates are that less than 5 percent of available pore volume is available for storage because scCO 2 , having a smaller density and viscosity than reservoir brine, tends to form viscous fingers, and bypass available pore space. This flow regime results in a CO 2 plume spreading over large areas in subsurface. The research goal in Challenge 2 is to advance the fundamental understanding of two-phase flow through porous media, including molecular-to meter- scale experimental and modeling approaches. This work leads to novel strategies to ensure that injected CO 2 occupies more than 5% of the pore space, ideally up to 50%. Challenge 3 – Controlling undesired or unexpected behavior. Following the injection of scCO 2 , the subsurface reservoir re-equilibrates to different physical and chemical states. This re-equilibration in space and time could lead to unexpected and/or undesired behavior: fracturing of reservoir rock and/or caprock, development of preferential flow paths, CO 2 leakage (to the surface or overlaying fresh water reservoirs), induced seismicity, and activation of faults. One of the main research goals of CFSES was to advance the fundamental understanding of how individual chemical and physical processes are coupled. We particularly focused on the chemical-mechanical coupling, and flow-mechanical coupling. We collected experimental and modeling data to determine the temporal and spatial scales of the coupled processes, which may lead to pore collapse caused by creep, activation of fractures and faults, chemically-induced fracture propagation, and self-focusing of scCO 2 flow.

54 ENVIRONMENTAL SCIENCES↗

Local Structural Coherence and Interfacial Charge Transfer in Cu 2 ⁢S/Mo⁢S 2 Heterostructure

Precise control over electronic coupling at nanoscale interfaces is critical for designing materials with tunable charge-transfer behavior and catalytic function. Heterostructures with locally coherent interfaces provide a platform for interrogating interfacial charge redistribution in coupled material systems. Here, we report Cu 2 ⁢S/Mo⁢S 2 heterostructures exhibiting nanoscale crystallographic alignment, which are synthesized through a rapid thermal transformation pathway. We employed electrochemical reduction reactions to probe interfacial charge transfer, revealing shifts in product distribution attributable to modified interfacial energetics, even in the absence of optimized catalytic performance. The observed formate Faradaic efficiency suggests that interfacial electronic modulation in the heterostructure shifts product selectivity towards formate, highlighting how interface-driven electronic modulation can direct reaction pathways and influence product selectivity. Optimizing catalyst loading, architecture, and reactor configuration will be critical for future improvement. Structural and compositional integrity were confirmed through powder x-ray diffraction, x-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Electron transfer between Cu 2 ⁢S and Mo⁢S 2 domains was further evaluated by electrochemical impedance spectroscopy, while selected-area electron diffraction revealed local crystallographic alignment consistent with a local epitaxial relationship at the Cu 2 S/Mo⁢S 2 heterointerface. To illustrate the broader applicability of this approach, a Zn⁢S/Mo⁢S 2 heterostructure was also synthesized using the same microwave strategy, confirming the generalizability of interfacial engineering principles across metal sulfide-Mo⁢S 2 systems. Collectively, these findings demonstrate that controlled local epitaxial alignment serves as an effective design principle for tuning interfacial energetics and catalytic reactivity in complex heterostructure materials.

carbon capture & utilization↗

Free Energy and Flexibility Analysis of Autoinhibited Human BRAF

The RAF serine/threonine protein kinases function as direct effectors of RAS in the intracellular transmission of extracellular growth signals, and they are key targets for drug discovery, given the high incidence of oncogenic mutations in RAF and other components of this signaling pathway. In its inactive state, RAF is held in an autoinhibited conformation in the cytosol through a combination of intramolecular interactions and binding to a regulatory 14−3−3 protein dimer. Activation of RAF is initiated by its interaction with membrane-localized GTP-bound RAS, which induces conformational changes that release RAF from its autoinhibited state. However, the molecular mechanisms governing RAF activation remain incomplete, largely due to the challenges in experimentally capturing the intermediate conformational states in this process. To address this gap, we developed a comprehensive all-atom model of BRAF based on existing cryo-EM structures. Using this model, we performed extensive molecular dynamics simulations to evaluate the stability and free energy landscape of autoinhibited BRAF in solution. Our analysis reveals conformational flexibility within the autoinhibited complex, suggesting that this dynamic behavior may play a role in facilitating BRAF activation upon engagement with the membrane-bound RAS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The structure of graphene on graphene/C60/Cu interfaces: a molecular dynamics study

Two experimental studies reported the spontaneous formation of amorphous and crystalline structures of C 60 molecules intercalated between graphene and a surface. The findings observed included interesting phenomena ranging from reaction between fullerene C60s ('C 60 s' stands for plural of C 60 ) under graphene to graphene sheets sagging between C 60 s and control of strain in these sheets. Motivated by this work, we performed fully atomistic reactive molecular dynamics simulations to investigate the formation and thermal stability of graphene sheet wrinkles as well as graphene attachment to and detachment from a surface when the sheet is laid over a previously distributed array of C 60 molecules on a copper surface at different temperatures. As graphene compresses the C 60 s against the surface, and graphene attachment to the surface in between C 60 s depends on the height of the wrinkles in the graphene sheet, configurations with both frozen and non-frozen fullerenes were investigated in the simulations in order to examine the experimental result of stable, sagged graphene sheets when the distance between C 60 s is about 4 nm and the height of the wrinkles in the sheet is about 0.8 nm. Below a distance of 4 nm between fullerenes, the graphene is predicted to become locally suspended and less strained. The simulations predict that this happens when the fullerenes can deform under the compressive action of the graphene sheet. If the fullerenes are kept frozen, spontaneous 'blanketing' of graphene is predicted only when the distance between neighbouring C 60 s is equal to or great than about 7 nm. These predictions agree with a mechanical model relating the rigidity of a graphene sheet to the energy of graphene-surface adhesion. This work further reveals the structure of intercalated molecules and the role of stability and sheet wrinkling on the preferred configuration of graphene. This study thus might assist in the development of two-dimensional confined nanoreactors for chemical reactions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Quantifying the Impact of Metal Population Distribution in MFI-Supported Mo Catalysts for Methane Dehydroaromatization

Precise evaluation of intrinsic kinetic behavior in Mo/MFI catalysts for methane dehydroaromatization (MDA) is confounded by variations in Mo dispersion and speciation, which are influenced by metal loading and zeolite acidity. This work advances the utility of H 2 -temperature programmed reduction (H 2 -TPR) for characterizing Mo/MFI catalysts by enabling quantitative comparison of MoO x populations distinguished by reduction behavior and linked to initial catalytic performance. A comprehensive H 2 reduction pathway is established through systematic H 2 - TPR studies varying catalyst composition (1–10 wt % Mo, Si/Al = 15, 40, ∞), supplemented by UV-Raman spectroscopy, X-ray powder diffraction, N 2 physisorption, NH 3 -TPD, and advanced spectroscopic analysis (in situ XAS with principal component analysis/multivariate curve resolution—alternating least squares). Two low-temperature H 2 -TPR regions capture distinct Mo populations undergoing initial Mo(VI)→Mo(IV) reduction: a lower-temperature population (Mo-RI) associated primarily with highly dispersed, anchored MoO x species expected to predominantly reside within MFI channels, and a higher-temperature population (Mo-RII) corresponding to a broader set of MoO x species that becomes increasingly bulk-like/extrazeolitic at higher Mo loading. Quantification of these populations provides practical, kinetically relevant descriptors for comparing initial MDA rates across catalysts with varying Mo loading, Si/Al ratio, and MoO x heterogeneity. Application of lower-temperature Mo-RI estimates to kinetic measurements reveals a minimum threshold of ∼0.12 × 10 –3 mol Mo-RI/g cat , above which initial forward benzene rates normalized to this population converge despite differences in metal loading and zeolite Brønsted acidity. This threshold coincides with a transition toward a common C 2 -mediated benzene-forming regime, as indicated by approach-to-equilibrium analysis of methane-to-ethane, ethane-to-ethylene, and ethylene-to-benzene reaction steps. Above this threshold, normalized initial benzene rates are nearly invariant with increasing Mo-RII/Mo-RI population ratio, indicating that excess Mo-RII populations, including bulk-like/extrazeolitic MoO x domains present at higher loading, do not measurably suppress benzene formation associated with anchored and mostly channel-confined Mo population under the initial-rate conditions examined.

Mo/MFI↗

Ba +2 ion trapping using organic submonolayer for ultra-low background neutrinoless double beta detector

If neutrinos are their own antiparticles the otherwise-forbidden nuclear reaction known as neutrinoless double beta decay can occur. The very long lifetime expected for these exceptional events makes its detection a daunting task. In order to conduct an almost background-free experiment, the NEXT collaboration is investigating novel synthetic molecular sensors that may capture the Ba dication produced in the decay of certain Xe isotopes in a high-pressure gas experiment. The use of such molecular detectors immobilized on surfaces must be explored in the ultra-dry environment of a xenon gas chamber. Here, using a combination of highly sensitive surface science techniques in ultra-high vacuum, we demonstrate the possibility of employing the so-called Fluorescent Bicolor Indicator as the molecular component of the sensor. We unravel the ion capture process for these molecular indicators immobilized on a surface and explain the origin of the emission fluorescence shift associated to the ion trapping.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Hydrogen Storage for Flexible Fossil Fuel Power Generation: Integration of Underground Hydrogen Storage with Gas Turbine (Final Report)

As the nation continues to encourage, through market structures and financial incentives, the proliferation of intermittent renewable electricity, how to optimize the ever-changing electric grid and identify means to retain and improve resilience, while ensuring continued reductions in GHG emissions, will be critical. According to Bloomberg, wind & solar generated 10.5% of US electricity in 2020 and that percentage continues to grow. In support of expanding renewable energy use, and to address its intermittent nature, this project will develop the Hydrogen Storage for Flexible Fossil Fuel Power Generation platform that is dispatchable, reliable, repeatable and have the ability to produce zero or negative carbon power while interfacing with geology capable of CO2 and hydrogen storage. GTI Energy (GTIE) and team members Illinois State Geological Survey (ISGS), Mitsubishi Heavy Industries America (MHIA), Ameren Illinois, Hexagon Purus, and the Low Carbon Resources Initiative (LCRI) completed a Phase I Conceptual Study under contract DE-FE0032012 for Hydrogen Storage for Flexible Fossil Fuel Power Generation: Integration of Underground Hydrogen Storage with Gas Turbine. The Hydrogen Storage for Flexible Fossil Fuel Power Generation platform addresses the intermittent nature of the expanding use of Variable Renewable Energy (VRE) generation. The low cost of the electricity (COE) generated results in greater dispatch and more operation at higher power levels (higher efficiency), fewer short intervals, and fewer start/stop cycles. The reliable, resilient system can produce zero carbon power and store hydrogen. It will demonstrate hydrogen storage in geologic formations like those used in natural gas underground storage thus enabling large scale storage of hydrogen in sedimentary strata across the United States rather than in geographically restricted salt caverns. The Phase I study confirmed the system is feasible and generates power at lower cost than other low carbon approaches. The demonstration defines the pathway for broad commercial application and will accelerate the development of larger systems suitable for centralized utility scale electricity production. The study advanced the maturity of the H 2 storage-based system with flexible power generation by completing a Pre-FEED study (Phase II). The Pre-FEED focused on the selected Energy Farm on the University of Illinois Urbana-Champaign (UIUC) site that includes above ground and underground hydrogen storage, low-carbon hydrogen production (GTI’s Compact Hydrogen Generator, CHG) with underground CO2 sequestration, and a 40-MW class gas turbine. The Pre-FEED addressed the entire system and its interconnection to the natural gas and electric grid and mitigation of key risks, such as storage behavior, load-following, and system operation. During Phase 1 of the project, the team completed key tasks, which moved the entire demonstration project, specific components and approaches closer to commercialization. These Phase I Accomplishments include: Completing System Requirements Review; Completing System Layout and Modeling - Heat & Mass Balance and Process Flow Diagram; Completing modelling of 9 turbine performance cases; Evaluating rock strata for underground storage of hydrogen and sequestration of carbon dioxide; Completing initial modelling of underground storage of hydrogen and withdrawal with evaluation of loss and water production; Identifying roadable storage for above ground hydrogen storage; Identifying existing electrical infrastructure for receiving/delivering electricity; Identifying existing gas supply infrastructure for receiving natural gas; Document concept design/development plans in required reports. Conclusions: The 12-month Feasibility study in Phase I study was completed and confirmed the system is feasible and generates power at lower cost than other low carbon approaches and even lower cost than the reference NGCC plant without carbon capture when taking advantage of 45Q carbon credits. The study enabled the fidelity of the concept to be improved and allowed identification of the requirements for the system. Defining the individual system and component requirements was performed via the system requirements review with the whole team. These requirements were then incorporated into and iterated with our Heat & Mass Balance process model and process flow diagrams were generated to reflect the overall system. This information was then used to complete the TEA and show economic feasibility. Large scale non-salt geologic storage of hydrogen is an enabling technology for a hydrogen-fired turbine that can be retrofitted into large-scale electric generating units (EGU). Our demonstration will include 428 MWh or ~4 hours full load of hydrogen storage (above and underground). Carbon capture inherent to the CHG process can capture 90% CO 2 (with upgrades to >98%). This system provides a COE of 23% savings relative to an NGCC with a post combustion amine system. Our proposed storage system decouples carbon capture and hydrogen production from power production; therefore, we expect our proposed system’s efficiency and variable COE to be superior resulting in overall higher dispatch and reduced deep cycling. Our demonstration will be full to multi-day hydrogen storage and has the potential for longer (seasonal) duration commercially. The demonstration defines the pathway for broad commercial application and will accelerate the development of larger systems suitable for centralized utility scale electricity production.

03 NATURAL GAS↗

Gerischer Electrochemistry Today

Semiconductor photoelectrochemistry is a dynamic and interdisciplinary field at the forefront of research in solar fuels, energy conversion, and catalysis. Here, this Perspective captures the collective insights from the second Gerischer Electrochemistry Today Symposium, held at Colorado State University in Fort Collins, CO, in August 2024, which convened leading researchers, early-career scientists, and industry partners to define the critical next steps for the field. Through interactive sessions, technical talks, panel discussions, and training initiatives─including a Semiconductor Electrochemistry Bootcamp─the symposium emphasized three pillars of advancement: (i) facilitating the exchange of new ideas in semiconductor electrochemistry and charge separation; (ii) fostering the development of future researchers, research topics, and participation in the semiconductor workforce; and (iii) building community. This Energy Focus distills key themes from the meeting and identifies major knowledge gaps in the following areas: mechanisms of charge separation and recombination, role of defects and disorder, dynamic and operando characterization methods, interfacial chemistry and surface passivation, theoretical and modeling limitations, and standardization and benchmarking. The inclusive and collaborative structure of the symposium enabled the generation of this comprehensive report that will serve as a roadmap for fundamental and applied research in the rapidly evolving field of semiconductor electrochemistry over the next decade.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗