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At least 523 records · Page 29

Experimental Studies on Enhanced Ignition for Improved Pre-Chamber Combustion in Gas Engines

Global efforts to reduce greenhouse gas emissions and mitigate climate change have intensified the demand for cleaner and more efficient combustion technologies. Heavyduty engines, which remain essential for transportation and power generation, must operate with significantly lower emissions while maintaining high efficiency and fuel flexibility. Lean combustion and exhaust gas recirculation (EGR) offer promising pathways to reduce emissions and improve thermal efficiency; however, these strategies impose severe challenges for engine operation, especially for low reactivity gaseous fuels like natural gas and ammonia. Pre-chamber combustion has emerged as a viable approach that uses turbulent jets to accelerate main chamber ignition, but its performance can degrade under high dilution or with hard-to-ignite fuels. These limitations motivate the central focus of this dissertation: understanding passive pre-chambers and improving their performance under challenging conditions.

Dhotre, Akash [Univ. of Minnesota, Minneapolis, MN↗

Opportunities for Industry to Provide Flexibility While Increasing Profitability

Supply and demand flexibility will both be needed to ensure the electricity system functions properly as the share from variable renewable generation continues to grow. Industrial manufacturing currently consumes about a third of primary energy worldwide, and electricity is projected to supply an increasing share of this demand as the global economy decarbonizes. Therefore, the ability for industry to flex demand poses an enticing opportunity to enable grid flexibility. However, large capital outlays prevent industry from voluntarily altering demand. Here we show that as battery costs continue to fall, industry will soon be able to profitably alter demand in accordance with electricity price variations. Focusing on two established industries– chlor-alkali and electric arc furnaces – and two industries with large future potential – methane pyrolysis and atmospheric CO 2 capture, we use a linear program (LP) optimization to assess the technoeconomic feasibility of flexible industrial demand across both historical and future-looking wholesale day-ahead marginal prices for the Electricity Reliability Council of Texas (ERCOT). We find positive net present values (NPV) from $\$$400K to $\$$50M using projected 2050 battery prices for industrial purchase of behind-the-meter batteries, using only arbitrage as a source of value. These results indicate that, with projected battery prices, profit-seeking industrial players could voluntarily play a future role in stabilizing a high-renewables grid where electricity prices act as accurate signals of grid needs.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Load Margin Constrained Moving Target Defense against False Data Injection Attacks

Cyber physical security of power systems with high penetration of renewable generation has attracted attention from researchers. One critical issue is that cyber-physical attacks, disguised as uncertain renewable generation, can target conventional power system state estimation (SE). Moving target defense (MTD) is a promising defense strategy to detect stealthy false data injection (FDI) attacks against SE. However, all existing studies myopically perturb the reactance of transmission lines equipped with distributed flexible AC transmission system (D-FACTS) devices without adequately considering the system voltage stability. Exacerbated by the renewable generation uncertainty, existing MTD may cause voltage instability when the power grid is under stress. To address this issue, we propose a novel MTD framework that explicitly considers system voltage stability by using continuation power flow. We utilize the sensitivity matrix of power injection to line impedance, on which an optimization problem for maximizing load margin is formulated. This framework is validated on the IEEE 14-bus system and the IEEE 118-bus system, in which net load redistribution attacks are launched by sophisticated attackers. Steady-state simulations and dynamic simulations on PSS/E show the effectiveness of the proposed framework in circumventing the voltage instability while maintaining the detection effectiveness of MTD. The impact of the proposed method on attack detection effectiveness is also revealed.

Zhang, Hang↗

Insights into Methodologies and Operational Details of Resource Adequacy Assessment: A Case Study with Application to a Broader Flexibility Framework

Assessing and maintaining resource adequacy (RA) is a core pillar of power systems. However, recent changes in the physical makeup of these systems and the conditions under which these systems must operate have yielded a renewed interest in the methods, metrics, and assumptions that underpin RA assessments. In this paper, we systematically explore a wide range of RA modeling dimensions, including: the objective function and level of operational detail in the underlying model formulation; the quantity (look-ahead) and quality (accuracy) of data that is available for making operational decisions within those models; and the physical configuration of solar photovoltaics (PV) with battery storage hybrid resources. We apply a set of probabilistic RA tools and production cost modeling tools to a realistic test system based loosely on a future Electric Reliability Council of Texas power system dominated by solar PV resources. Under the assumptions of our system and models, we find that multi-stage probabilistic assessments may provide a more robust evaluation of RA by capturing a wider range of operational and system interactions, but this comes at a computational cost of 1-2 orders of magnitude longer run time depending on the specific configuration. In addition, the information on thermal generator availability impacts RA performance by an order of magnitude more than solar resource forecasts, which is driven by the comparatively larger magnitude of thermal outages than solar forecast errors within our test system. Lastly, the flexibility provided by hybrid and other resources can help reduce system load-shedding event frequencies and enable the system to be more robust to inaccurate forecast information, and alternative hybrid inverter sizes can impact RA levels by 1-2 orders of magnitude. Our results point to the importance of a broader flexibility framework to describe the interaction between (1) flexibility "supply" from both physical resource capabilities and operational constraints considered in the modeling, and (2) flexibility "demand" from forecast errors, thermal generator outages, and other sources of uncertainty, as well as their RA impacts. Results are likely sensitive to the system buildout explored; future work could consider additional system configurations and conditions.

ENERGY PLANNING, POLICY, AND ECONOMY,POWER TRANSMI↗

Concrete Thermal Energy Storage Enabling Flexible Operation without Coal Plant Cycling

The work described in this report is responsive to the Office of Fossil Energy program “Energy Storage for Fossil Power Generation.” The pilot plant built as a result of this project demonstrated the feasibility and performance of a concrete thermal energy storage (CTES) system integrated with a supercritical coal power plant. The 10 MWh electrical (>25 MWh thermal) CTES unit, developed by Storworks Power, was designed to enable flexible operation of coal plants without cycling damage. The project's key technical achievements showcase a significant advancement in energy storage technology. A modular CTES system using 42 “Bolderblocs” units was successfully designed and constructed at Alabama Power’s Plant Gaston Unit 5, with each block containing embedded stainless-steel coils in specialized, cost-effective high-temperature concrete. The system interfaced seamlessly with the plant's 3500 psig (241 barg), 1000°F (538°C) supercritical steam, demonstrating operational flexibility. Over 86 full cycles, the CTES exhibited rapid charging and discharging capabilities, effectively mimicking steam turbine feed conditions and handling varying load profiles and storage durations. Performance validation confirmed the system's ability to consistently meet design target steam conditions of 75 bar-a and ~400°C for nominal baseline discharge. The concrete material withstood repeated thermal cycling without degradation, validating earlier lab-scale tests. Integration of balance of plant components, including a condensate management system with storage tank and air-cooled condenser, minimized plant interfaces and water consumption. A robust control scheme ensured safe, automated operation across various scenarios. Key learnings from the project were invaluable: 1. Initial concrete drying and commissioning procedures were refined for future deployments, enhancing efficiency in subsequent installations. 2. System flexibility exceeded expectations, with rapid response to changing conditions. 3. Design improvements were identified including optimized insulation and piping that will enhance overall system efficiency in future deployments 4. Full cycle thermal roundtrip efficiencies exceeded 88%. While the roundtrip electrical efficiency was somewhat limited by known challenges using input steam, such constraints may be mitigated by swapping steam for hot air as thermal input. 5. A summary of key performance parameters for the pilot test and predicted performance of a full scale commercial system with specified improvements determined from the pilot are shown in Section 8. The project faced challenges, including COVID-19 delays and host plant availability constraints. However, these were overcome through adaptive planning and execution. The successful management of these obstacles demonstrated the resilience and adaptability of the project team and the robustness of the CTES technology. This successful pilot demonstrates the potential for CTES to enhance coal plant flexibility, supporting grid stability as renewable penetration increases. The validated design and operational data provide a solid foundation for scaling up to utility-scale implementations, potentially transforming how thermal plants operate in evolving energy landscapes. The system's ability to rapidly respond to changing grid conditions while maintaining high efficiency makes it a promising solution for balancing intermittent renewable energy sources. Furthermore, the project highlighted the potential for even greater efficiencies in future iterations. The use of air as an input medium could potentially eliminate the limitations observed with steam input, opening new possibilities for energy storage applications beyond coal plant integration. In conclusion, this pilot project not only achieved its primary goals but also uncovered additional benefits and potential applications of the CTES technology. It represents a significant step forward in addressing the challenges of grid stability and flexibility in an increasingly renewable-driven energy landscape.

01 COAL, LIGNITE, AND PEAT↗

Decarbonizing the grid: Utilizing demand-side flexibility for carbon emission reduction through locational marginal emissions in distribution networks

Decarbonization of the electric grid has become an important world-wide priority and is actively happening in many ways by introducing innovations and new technologies from the generation sectors to the demand sectors. In particular, one promising pathway toward such net-zero carbon emissions is to utilize the demand-side flexibility with the increasing number of flexible loads in distribution networks. In this paper, we explore a load shifting strategy with the emerging concept of location marginal emissions (LMEs) to reduce carbon emissions. LMEs measure the impact of carbon emissions including the locational aspect in more granular way and thus provide a novel mechanism for the system operator and load aggregators to design the LME-based load shifting strategy, which can efficiently guide consumers and thus adjust their consumption behaviors. Simulation case studies on the IEEE test networks are performed to validate the capability of the proposed load shifting method to reduce carbon emissions. We also compare this with other relevant strategies to discuss multiple scenarios and corresponding results. Finally, while each provides a different level of flexibility, all the explored strategies tested have led to solutions that have lower carbon emissions, indicating the great potential of demand-side flexibility in reducing carbon emissions for future distribution networks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Rethinking the Price Formation Problem–Part 1: Participant Incentives under Uncertainty

Operators of organized wholesale electricity markets attempt to form prices in such a way that the private incentives of market participants are consistent with a socially optimal commitment and dispatch schedule. In the U.S. context, several competing price formation schemes have been proposed to address the non-convex production cost functions characteristic of most generation technologies. Here, this paper considers how the design and analysis of price formation policies for non-convex markets are affected by the uncertainty inherent in electricity demand and supply. We argue that by excluding uncertainty, the analytical framework underlying existing policies mischaracterizes the incentives of market participants, leading to inefficient price formation and poor incentives for flexibility. We establish favorable theoretical properties of a new construct, ex ante convex hull pricing , and demonstrate the difference between this idealized benchmark and existing methods on a large-scale test system. Given increased operational uncertainty with a transition to wind and solar generation, distortions caused by poor incentives for flexibility are likely to grow without improved price formation in organized wholesale markets.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Sensitivity analysis of design parameters in RowWise borehole layout for ground heat exchangers

Ground source heat pump systems offer a promising pathway toward energy-efficient building heating and cooling. The performance and cost-effectiveness of these systems heavily depend on the design of the ground heat exchanger (GHE), particularly the spatial placement of boreholes used in large commercial buildings. Among various borefield layout strategies, the RowWise approach generates and optimizes borehole configurations within irregular polygonal land boundaries, providing land-use efficiency and installation flexibility. While multiple geometric design parameters constrain the RowWise layout, their influence on the system thermal performance and total drilling requirements remains unclear. Thus, this study presents a sensitivity analysis of key design parameters influencing the RowWise layout of vertical borehole GHEs, including the perimeter spacing ratio, borehole spacing, borehole field rotation angle, and borehole length. GHEDesigner and Ray Tune are employed to generate and assess different RowWise configurations. A series of parametric simulations was conducted to quantify the impact of each parameter on geometric distribution, economic cost, and computational speed. The results provide critical insights into the sensitivity and relative importance of different design parameters of RowWise method, offering practical guidance for designers aiming to optimize GHE layouts by balancing thermal efficiency, land constraints, and economic feasibility.

Xu, Dikai [Purdue University]↗

Demonstration of NREL Modeling Capability to Design the Next Generation of Floating Offshore Wind Turbines with Stiesdal and Magellan Wind (Cooperative Research and Development Final Report)

This Technology Commercialization Fund (TCF) CRADA involved demonstration of NREL modeling capability using OpenFAST (formerly known as FAST) to design the next generation of floating offshore wind turbines (FOTW) with Stiesdal’s TetraSpar design. The objective of the project was to enable the design and optimization of next generation FOWT that show promise to make FOWT cost-competitive with other energy technologies by upgrading, verifying, and validating improvements to OpenFAST. This objective was achieved by (1) upgrading OpenFAST to compute floating substructure flexibility and member-level loads, which is critical to enable the design of floating substructures—especially newer designs that are streamlined, flexible, and cost-effective; (2) verifying the new OpenFAST capabilities through model-to-model comparisons and validating the capabilities through comparisons to empirical data generated with wave-tank testing, using TetraSpar data provided by Stiesdal; and (3) making available the upgraded OpenFAST tool to the wind energy community to enable next-generation floating wind designs.

17 WIND ENERGY↗

Grid-Forming PV Inverter: Technology Development and Microgrid Applications

Presently, excluding residential backup power applications, grid-forming (GFM) inverters are commercially available for battery energy storage system (BESS) and some PV plus battery systems but not yet for stand-alone PV. This tech update investigates the control design for GFM PV inverter, especially the control required to provide active power reserve and to stabilize the dc link voltage. Subsequently, the use cases of GFM PV plants in utility-level microgrids are discussed considering fully inverter-based microgrids (i.e., with PV and BESS) as well as mixed-source microgrids (i.e., with PV and diesel generator). Scenarios where active power up-reserve from GFM PV plants is beneficial are illustrated. Moreover, requirements and specifications for GFM PV plant, especially for its active power reserve function are developed. In addition, stability of an example utility-level microgrid with two GFM PV plants and a diesel generator is analyzed to shed light on the potential unstable interaction between multiple GFM resources and the countermeasures. This research aims to advance GFM PV technology to offer more flexibility in microgrid design. With GFM PV available, depending on the level of reliability required, cost-benefit analysis, etc., the GFM BESS or diesel generator may be sized smaller while leveraging the full potential of PV generation inside the microgrid.

14 SOLAR ENERGY↗

In situ visualisation of zeolite anisotropic framework flexibility during catalysis

Zeolites exhibit framework flexibility driving their chemical and catalytic properties. Since the zeolitic pores are extremely small, a slight strain generated in the crystal induces compelling changes in shape, connectivity, accessibility, and the framework chemical properties. These modifications affected the adsorption and desorption of reactants/products and the diffusion within the channels during reaction. Using in situ 3D Bragg coherent X-ray diffraction imaging, we unveil the dynamics of the zeolite structure during catalysis, contraction and/or expansion of its framework also known as zeolite framework flexibility. Here, we imaged three-dimensionally a single faujasite zeolite crystal during the ethanol dehydration reaction revealing anisotropic lattice dynamics simultaneously to guest molecules formation. Understanding zeolite flexibility could permit to tune zeolites properties towards potentially higher adsorption and selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large-Scale Simulation of Regional Demand Flexibility Implementation and Customer Economic Impact

The Distribution System Operator with Transactive (DSO+T) study conducted a large-scale simulation of over 60,000 customers in a region the size of Texas to demonstrate the effective coordination of distributed energy resources (DERs) in commercial and residential buildings. The integrated simulation included both the bulk (wholesale generation and transmission) and distribution systems. The DERs (including batteries, electric vehicles, air conditioning, and water heaters) participated in a transactive energy retail market that was integrated into an existing competitive wholesale market. The engineering and economic performance of the resulting demand flexibility was evaluated over annual simulations for both moderate and high renewable generation scenarios. A detailed parametric cost model was developed to enable detailed economic analysis of key stakeholders. In addition, fixed and dynamic customer tariffs were designed and applied to the customer population. This allowed the impact on annual customer bills to be analyzed for various building types (residential versus commercial; single- versus multi-family). This paper presents results showing the relative flexibility of batteries, electric vehicles, and building loads throughout the year and under different renewable scenarios. This feeds a detailed breakdown of the impact this flexibility has on the operating costs of the grid and the resulting net economic benefit. Finally, the study showed that practically all customer classes (including non-participating customers) save money under the proposed demand flexibility scheme. The study found overall net annual economic savings of $3.3-5.0B for a region the size of Texas equating to average customer bill savings of 10-16%.

Reeve, Hayden M.↗

Attosecond pulse shaping using a seeded free-electron laser

Attosecond pulses are central to the investigation of valence- and core-electron dynamics on their natural timescales. The reproducible generation and characterization of attosecond waveforms has been demonstrated so far only through the process of high-order harmonic generation. Several methods for shaping attosecond waveforms have been proposed, including the use of metallic filters, multilayer mirrors and manipulation of the driving field. However, none of these approaches allows the flexible manipulation of the temporal characteristics of the attosecond waveforms, and they suffer from the low conversion efficiency of the high-order harmonic generation process. Free-electron lasers, by contrast, deliver femtosecond, extreme-ultraviolet and X-ray pulses with energies ranging from tens of microjoules to a few millijoules. Recent experiments have shown that they can generate subfemtosecond spikes, but with temporal characteristics that change shot-to-shot. In this paper we report reproducible generation of high-energy (microjoule level) attosecond waveforms using a seeded free-electron laser. We demonstrate amplitude and phase manipulation of the harmonic components of an attosecond pulse train in combination with an approach for its temporal reconstruction. The results presented here open the way to performing attosecond time-resolved experiments with free-electron lasers.

47 OTHER INSTRUMENTATION↗

Flexible polyurethanes, renewable fuels, and flavorings from a microalgae oil waste stream

Renewable polymers have become an important focus in next-generation materials, and algae biomass offers an environmentally low-impact feedstock that can serve multiple uses. This study aims to develop a scalable methodology for production of microalgae-based polyols for polyurethane synthesis from waste oils derived from algae biomass. Following separation of omega-3 fatty acids from algae oil, residual oils can offer valuable building blocks for petrochemical replacements. However, unlike vegetable oils, algae oils contain organic contaminants, including photosynthetic pigments and hydrophobic cofactors that can complicate preparative methodologies. Here we convert and purify waste streams from omega-3 depleted Nannochloropsis salina algae oil, with major components consisting of palmitic and palmitoleic acid, into azelaic acid (AA) as a building block for flexible polyurethanes, with a simultaneous production of heptanoic acid (HA) as a flavor and fragrance precursor. Conversion of free fatty acid mixtures into a soft soap allows extraction of organic contaminants, and urea complexation provides isolated palmitoleic acid, which is subsequently ozonolyzed to produce AA and HA. Bio-based polyester diols are prepared from AA via esterification to provide a polyol monomer for flexible polyurethane foam preparation. The HA co-product is modified to produce the flavoring agent methyl heptanoate and also decarboxylated to produce hexane as a renewable solvent. This scalable process can be performed on oils from multiple algal species, offering valuable monomers from a highly sustainable source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

IDAES GTEP 0.1 Release

The Institute for the Design of Advanced Energy Systems (IDAES) Generation and Transmission Expansion Planning (GTEP) package provides a Pyomo-based implementation of a modular, flexible, Generalized Disjunctive Programming (GDP) formulation for power infrastructure planning problems. This package is designed with the following goals in mind: - Abstract GTEP modeling away from any particular case study or fixed modeling assumptions (e.g., technologies, temporal resolution, spatial resolution, policy implications, etc.) - Admit flexible decision sets and heterogeneous parameterization - Allow high-level modeling options to be understood easily, chosen modularly, and changed rapidly

AS↗

Porogen‐Integrated Rapid Oxidation Enables Structured Mesoporous Metal Oxide Films

Structured metal oxide films have promise in optoelectronics, sensing, energy storage, and catalysis but their uptake is predominately limited due to their long and high‐temperature syntheses. Here, in this study, a self‐assembling polymer is used which can act as a chelating fuel source in a solution combustion reaction to generate highly structured mesoporous aluminum oxide films at <250 °C in a matter of minutes through a process termed porogen‐integrated rapid oxidation (PiRO). The resulting films with thicknesses up to 500 nm show an open‐cell, face‐centered cubic structure of spheroidal pores. Further, an additional ligand can be included to control the self‐assembly step to yield both through‐film ordering or tunable disordering for increased pore volume as confirmed by both grazing incidence small angle X‐ray scattering and ellipsometry. Finally, roll‐to‐roll manufacturing with PiRO is demonstrated on flexible polymeric substrates. The method offers a tunable, scalable, low‐temperature, and lower‐cost method to generate large‐area structured mesoporous metal oxide films.

36 MATERIALS SCIENCE↗

Robust Combined Heat and Hybrid Power (CHHP) for High Electrical Efficiency Cogeneration

Georgia Tech (Prime Recipient), the University of Texas at El Paso (UTEP) and the National Energy Technology Laboratory (NETL) investigated a hybrid fuel cell/ gas turbine system concept as a combined heat and hybrid power (CHHP) system for both robust and high power-to-process heat ratio cogeneration. The novelty of the proposed system entailed the distinct, elevated electrical efficiencies it maintains while simultaneously supporting a broad span of heating needs (e.g., supply temperatures) demanded across variable heat loads. The scope included: 1) leveraging a pioneering national lab facility configured for dynamic system operability development of hybrid fuel cell/gas turbine cycles; 2) enabling technology development to adjust and modulate the quality and quantity of thermal supply to bottoming heat loads via novel extreme temperature gas bypass valves. Hybrid fuel cell/gas turbine systems have primarily been reduced-to-practice in a constrained (e.g., initial proof-of-concept) manner and have still demonstrated considerable electrical efficiencies. However, these pre-pilot systems have focused upon electrical efficiencies and electrical power generation as the exclusive energy demand. Such hybrid systems had not been extensively researched or developed for flexible and variable operation consisting of both power and heat demands; however, these variable combined power and heat demands are characteristic of many types of manufacturers such as animal/poultry processing, bakeries and milk/flour/pastry manufacturing, textile mills, and electrochemical processing. Commercially, developing the system into a working combined heat and power system benefits these types of manufacturers by allowing them to meet their power and heat demands at a lower cost, higher efficiency, and/or through onsite generation. Therefore, the technical scope of this project was largely to study and facilitate these hybrid systems as combined heat and hybrid power (CHHP) systems that include dynamic operability for variable heat and power loads and/or grid dynamics for various types of manufacturers. Simulation results were used to predict the performance of the CHHP system and conceptually develop it to achieve desired dynamic operability. Experimentally, the primary goal was to design, manufacture, and experiment upon a high-temperature bypass valve. Experimental data included air mass flow rates through the valve orifice when the valve was changed to variable extent between fully closed and fully open. The experimental data was then used to create a semi-empirical computational model of the bypass valve. Concluded simulation goals for the research included developing computational heat exchanger models for the hybrid system inclusive of the bottoming heat exchanger and the recuperative heat exchanger, and then combining the computational recuperator model with the computational valve model. Afterwards, the computational models were then integrated to predict the dynamic operation of hybrid fuel cell/gas turbine cycles throughout a design space and reporting such. The scope stated in the preceding paragraph was packaged into five specific goals: 1) enabling the simulation of dynamic combined heat and power through the creation of computational, modular heat exchanger models; 2) simulation and exploration of the CHHP system’s performance by integrating the heat exchanger models with the national lab’s pre-existing hybrid system (computational) simulation, but without the recuperator bypass valve concept in order to initially determine how the (baseline) system behaves and can be controlled in order to meet variable heat and power demands; 3) development and initial deployment of the high-temperature recuperator bypass valve technology in order to confirm and characterize the approach; 4) usage of the experimental data for the valve to create a semi-empirical computational model for the bypass valve which could then be combined with the heat exchanger computational models; 5) repeat of the second task of simulating and exploring the system’s performance, but this time including the bypass valve to resolve its efficacy. Tasks were successfully completed, and the general notion of flexibly operating, high electrical efficiency CHHP was further corroborated. Supportive details are provided in the report.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Effect of Flexibility in Molecular Simulations of Carbon Dioxide Adsorption and Diffusion in a Cuprous Triazolate Framework

Using fixed atom force fields to model gas adsorption in flexible metal organic frameworks (MOFs) is known to pose difficulties in accurately reproducing and predicting experimental results. This paper studies the difference in accuracy between flexible and fixed atom force fields in reproducing CO 2 adsorption measurements in MAF-2 ([Cu(etz)]∞ (MAF-2, Hetz) 3,5-diethyl-1,2,4-triazole), an NbO-type triazolate scaffold with a bcu cavity system and attached ethyl groups. The flexible force field used to run the hybrid molecular dynamics and grand canonical Monte Carlo calculations were generated using the QuickFF software incorporating van der Waals parameters from the Universal Force Field (UFF) and density derived electrostatic and chemical (DDEC) charges. The fixed atom force field used was composed of UFF van der Waals parameters together with DDEC charges. The calculations were run at 298 K and at pressures of 0.1, 0.3, 0.5, 0.8, and 1 bar. It was observed that for this MOF the rigid force field overpredicted gas adsorption, whereas the flexible force field values closely matched experimental data. In the flexible structure, the freely moving ethyl groups of MAF-2 hindered adsorption, reducing the interaction energy between CO 2 and the N atoms of the triazolate framework as well as reducing the size of the largest cavity diameter. Here, the combination of these factors led to improved prediction of adsorption values with the flexible forcefield as compared to the rigid forcefield, demonstrating the need for modeling MOFs in a way more indicative of their behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗