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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,513 records · Page 84
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Occupant Preference-Aware Load Scheduling for Resilient Communities

The load scheduling of resilient communities in the islanded mode is subject to many uncertainties such as weather forecast errors and occupant behavior stochasticity. To date, it remains unclear how occupant preferences affect the effectiveness of the load scheduling of resilient communities. This paper proposes an occupant thermal preference-aware load scheduler for resilient communities operating in the islanded mode. First, key resilience indicators are selected to quantify its impacts on the load scheduling of a resilient community. A deterministic model predictive control-based load scheduling framework is adopted as the baseline. Then, a chance-constrained controller is proposed to address the occupant-induced uncertainty in room temperature setpoints. Finally, the chance-constrained controller is compared with the deterministic controller on a virtual community testbed based on a real-world net-zero energy community in Florida, U.S. Results have shown that the proposed chance-constrained controller performs better in terms of serving occupants’ thermal preference and the required battery sizes compared to the deterministic controller with the presence of the assumed stochastic occupant behavior. This work indicates that it is necessary to consider the stochasticity of the occupant behavior when designing optimal load schedulers for resilient communities.

Wang, Jing↗
DOE OSTI2019

Preliminary experimental comparison and feasibility analysis of CO2/R134a mixture in Organic Rankine Cycle for waste heat recovery from diesel engines

This paper presents results of a preliminary experimental study of the Organic Rankine Cycle (ORC) using CO2/R134a mixture based on an expansion valve. The goal of the research was to examine the feasibility and effectiveness of using CO 2 mixtures to improve system performance and expand the range of condensation temperature for ORC system. The mixture of CO 2 /R134a (0.6/0.4) on a mass basis was selected for comparison with pure CO 2 in both the preheating ORC (P-ORC) and the preheating regenerative ORC (PR-ORC). Then, the feasibility and application potential of CO 2 /R134a (0.6/0.4) mixture for waste heat recovery from engines was tested under ambient cooling conditions. Preliminary experimental results using an expansion valve indicate that CO 2 /R134a (0.6/0.4) mixture exhibits better system performance than pure CO 2 . For PR-ORC using CO 2 /R134a (0.6/0.4) mixture, assuming a turbine isentropic efficiency of 0.7, the net power output estimation, thermal efficiency and exergy efficiency reached up to 5.30 kW, 10.14% and 24.34%, respectively. For the fitting value at an expansion inlet pressure of 10 MPa, the net power output estimation, thermal efficiency and exergy efficiency using CO2/R134a (0.6/0.4) mixture achieved increases of 23.3%, 16.4% and 23.7%, respectively, versus results using pure CO2 as the working fluid. Finally, experiments showed that the ORC system using CO2/R134a (0.6/0.4) mixture is capable of operating stably under ambient cooling conditions (25.2-31.5 °C), demonstrating that CO 2 /R134a mixture can expand the range of condensation temperature and alleviate the low-temperature condensation issue encountered with CO 2 . Under the ambient cooling source, it is expected that ORC using CO 2 /R134a (0.6/0.4) mixture will improve the thermal efficiency of a diesel engine by 1.9%.

42 ENGINEERING↗
DOE OSTI2018

Effects of long-term climate change on global building energy expenditures

This paper explores potential future implications of climate change on building energy expenditures around the globe. Increasing expenditures result from increased electricity use for cooling, and are offset to varying degrees, depending on the region, by decreased energy consumption for heating. The analysis is conducted using a model of the global buildings sector within the GCAM integrated assessment model. The integrated assessment framework is valuable because it represents socioeconomic and energy system changes that will be important for understanding building energy expenditures in the future. Results indicate that changes in net expenditures are not uniform across the globe. Net expenditures decrease in some regions, such as Canada and Russia, where heating demands currently dominate, and increase the most in areas with less demand for space heating and greater demand for space cooling. We explain these results in terms of the basic drivers that link building energy expenditures to regional climate.

Climate change impacts↗
DOE OSTI2012

Decarbonizing the Electric Sector: Combining Renewable and Nuclear Energy using Thermal Storage

Both renewable and nuclear energy can provide significant contributions to decarbonizing the electric sector. However, a grid employing large amounts of wind and solar energy requires the balance of the system to be highly flexible to respond to the increased variability of the net load. This makes deployment of conventional nuclear power challenging both due to the technical challenges of plant cycling and economic limits of reduced capacity factor. In the United States nuclear power plants generally provide constant, base load power and are most economic when operated at constant power levels. Operating nuclear power plants in load-following modes decreases the plants' annual energy output and increases the levelized cost of energy, decreasing economic competitiveness. One possible solution is to couple thermal energy storage to nuclear power plants. This would enable the reactor to remain at nearly constant output, while cycling the electrical generator in response to the variability of the net load. This paper conceptually explores combinations of wind, solar, and nuclear that can provide a large fraction of a system's electricity, assuming the use of thermal energy storage that would allow nuclear power to provide load following and cycling duty while operating at a constant reactor power output.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2013

A Dynamic Simulation of the Indirect Land Use Implications of Recent Biofuel Production and Use in the United States.

The global indirect land use change (ILUC) implications of biofuel use in the United States of America (USA) from 2001 to 2010 are evaluated with a dynamic general equilibrium model. The effects of biofuels production on agricultural land area vary by year; from a net expansion of 0.17 ha per 1000 gallons produced (2002) to a net contraction of -0.13 ha per 1000 gallons (2018) in Case 1 of our simulation. In accordance with the general narrative about the implications of biofuel policy, agricultural land area increased in many regions of the world. However, oil-export dependent economies experienced agricultural land contraction because of reductions in their revenues. Reducing crude oil imports is a major goal of biofuel policy, but the land use change implications have received little attention in the literature. Simulations evaluating the effects of doubling supply elasticities for land and fossil resources show that these parameters can significantly influence the land use change estimates. Therefore, research that provides empirically-based and spatially-detailed agricultural land-supply curves and capability to project future fossil energy prices is critical for improving estimates of the effects of biofuel policy on land use.

Oladosu, Gbadebo A.↗
DOE OSTI2018

An updated assessment of oil market disruption risks

The probability of the size and duration of another oil disruption is critical to estimating the value of any policies for reducing the economic damages from a sudden oil supply disruption. The Energy Modeling Forum at Stanford University developed a risk assessment framework and evaluated the likelihood of one or more foreign oil disruptions over the next ten years. Leading geopolitical, military and oil-market experts provided their expertise on the probability of different events occurring, and their corresponding link to major disruptions in key oil market regions. The study evaluated 5 primary regions of production: Saudi Arabia, Other Persian Gulf, Africa, Latin America, and Russian / Caspian States. Disruptions are defined as being net of offsets (e.g., OPEC spare capacity), with the notable exception that the SPR is not included as a source of offsets. Furthermore, at least once during the 10-year time frame (2016–2025), there exists approximately an 80% probability of a net (of offsets) disruption of 2 MMBD (million barrels per day) or more lasting at least 1 month.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2017

Quantification and mapping of urban fluxes under climate change: Application of WRF-SUEWS model to Greater Porto area (Portugal)

Climate change and the growth of urban populations are two of the main challenges facing Europe today. These issues are linked as climate change results in serious challenges for cities. Recent attention has focused on how urban surface-atmosphere exchanges of heat and water will be affected by climate change and the implications for urban planning and sustainability. In this study energy fluxes for Greater Porto area, Portugal, were estimated and the influence of the projected climate change evaluated. To accomplish this, the Weather Research and Forecasting Model (WRF) and the Surface Urban Energy and Water Balance Scheme (SUEWS) were applied for two climatological scenarios: a present (or reference, 1986–2005) scenario and a future scenario (2046–2065), in this case the Representative Concentration Pathway RCP8.5, which reflects the worst set of expectations (with the most onerous impacts). The results show that for the future climate conditions, the incoming shortwave radiation will increase by around 10%, the sensible heat flux around 40% and the net storage heat flux around 35%. In contrast, the latent heat flux will decrease about 20%. The changes in the magnitude of the different fluxes result in an increase of the net all-wave radiation by 15%. The implications of the changes of the energy balance on the meteorological variables are discussed, particularly in terms of temperature and precipitation. - Highlights: • Assessment of energy fluxes behaviour under past period and medium-term climate change projection. • Evaluation of climate change at urban scale. • Meteorological variables alters the partitioning of the energy fluxes. • Changes in the partition of the annual energy balance are found between the two analysed periods. • Increase in the magnitude of sensible and storage heat fluxes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2011

Internal hydraulic analysis of impeller rounding in centrifugal pumps as turbines

The use of pumps as turbines in different applications has been gaining importance in the recent years, but the subject of hydraulic optimization still remains an open research problem. One of these optimization techniques that include rounding of the sharp edges at the impeller periphery (or turbine inlet) has shown tendencies of performance enhancement. In order to understand the effect of this hydraulic optimization, the paper introduces an analytical model in the pump as turbine control volume and brings out the functionalities of the internal variables classified under control variables consisting of the system loss coefficient and exit relative flow direction and under dependent variables consisting of net tangential flow velocity, net head and efficiency. The paper studies the effects of impeller rounding on a combination of radial flow and mixed flow pumps as turbines using experimental data. The impeller rounding is seen to have positive impact on the overall efficiency in different operating regions with an improvement in the range of 1-3%. The behaviour of the two control variables have been elaborately studied in which it is found that the system loss coefficient has reduced drastically due to rounding effects, while the extent of changes to the exit relative flow direction seems to be limited in comparison. The reasons for changes to these control variables have been physically interpreted and attributed to the behaviour of the wake zone at the turbine inlet and circulation within the impeller control volume. The larger picture of impeller rounding has been discussed in comparison with performance prediction models in pumps as turbines. The possible limitations of the analytical model as well as the test setup are also presented. The paper concludes that the impeller rounding technique is very important for performance optimization and recommends its application on all pump as turbine projects. It also recommends the standardization of the rounding effects over wide range of pump shapes including axial pumps. (author)

42 ENGINEERING↗
DOE OSTI2020

Optimization of energy requirements for CO 2 post-combustion capture process through advanced thermal integration

The energy optimization modeling work described here was performed to determine efficiency improvements that could be achieved for existing coal-fired power plants to retrofit a partial CO 2 capture from the post-combustion flue gas for carbon sequestration through thermal integration. The work presented includes optimization of the mono-ethanol amine (MEA)-based post-combustion CO 2 capture to reduce energy requirements that could be achieved at existing power plants by thermal integration of the steam turbine cycle, boiler, CO 2 compression train and post-combustion CO 2 capture process to offset efficiency and capacity losses that would be incurred by retrofit or implementation of post-combustion CO 2 capture. Furthermore, partial CO 2 capture, involving treatment of less than 100% of the flue gas leaving the plant and modular design of the CO 2 scrubbing system, was also investigated. Thermal integration of the steam turbine cycle with boiler and CO 2 compression train improved cycle and plant performance and offset, in part, the negative effects of post-combustion CO 2 capture. The best-analyzed integration options improved gross power output by 5% and net unit efficiency by 1.57%, relative to the conventional MEA process. Operating with 40% CO 2 capture increased gross power output by 11.6–14% (depending on the MEA thermal integration option), relative to the conventional MEA integration and 90% CO 2 capture. The improvement in net unit performance is larger compared to the improvement in turbine cycle performance because of the CO 2 compression work, which is also reduced by partial CO 2 capture.

42 ENGINEERING↗
DOE OSTI2015

Analysis of a tungsten sputtering experiment in DIII-D and code/data validation of high redeposition/reduced erosion

We analyze a DIII-D tokamak experiment where two tungsten spots on the removable DiMES divertor probe were exposed to 12 s of attached plasma conditions, with moderate strike point temperature and density (~20 eV, ~4.5 × 10 19 m –3 ), and 3% carbon impurity content. Both very small (1 mm diameter) and small (1 cm diameter) deposited samples were used for assessing gross and net tungsten sputtering erosion. The analysis uses a 3-D erosion/redeposition code package (REDEP/WBC), with input from a diagnostic-calibrated near-surface plasma code (OEDGE), and with focus on charge state resolved impinging carbon ion flux and energy. The tungsten surfaces are primarily sputtered by the carbon, in charge states +1 to +4. We predict high redeposition (~75%) of sputtered tungsten on the 1 cm spot—with consequent reduced net erosion—and this agrees well with post-exposure DiMES probe RBS analysis data. As a result, this study and recent related work is encouraging for erosion lifetime and non-contamination performance of tokamak reactor high-Z plasma facing components.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2 (UO 2 ) 6 O 4 (OH) 6 ·8H 2 O and Na 2 (UO 2 ) 6 O 4 (OH) 6 ·8H 2 O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmol L -1 ). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.

58 GEOSCIENCES↗
DOE OSTI2022

New insights into Mn 2+ and Mg 2+ inhibition of calcite growth

Impurity ion and isotope partitioning into carbonate minerals provide a window into the molecular processes occurring at the fluid-mineral interface during crystal growth. Here, we employ calcium isotope fractionation together with process-based modeling to elucidate the mechanisms by which two divalent cations with starkly contrasting compatibility, magnesium and manganese, inhibit calcite growth and incorporate into the mineral lattice. Calcite growth inhibition by Mg 2+ is log-linear and K Mg is on the order of 0.02–0.03 throughout the range of {Mg 2+ }/{Ca 2+ } studied here (0.01–2.6). Mn 2+ exhibits much stronger log-linear growth rate inhibition at low Mn 2+ concentrations (fluid {Mn 2+ }/{Ca 2+ } = 0.001–0.02). Mn 2+ is readily incorporated into the calcite lattice to form a calcite-rhodochrosite solid solution, with large partition coefficients (K Mn 4.6–15.6) inversely correlated to growth rate. For both Mn 2+ and Mg 2+ , calcium isotope fractionation is found to be invariant with {Me 2+ }/{Ca 2+ } despite more than an order of magnitude decline in growth rate. This invariant Δ 44/40 Ca suggests that the presence of Mn 2 + or Mg 2+ does not significantly change the relative rates of Ca 2+ attachment and detachment at kink sites during growth, indicative of a dominantly kink blocking inhibition mechanism. Because the partitioning behavior dictates that Mn 2+ must attach to the surface significantly faster than Ca 2+ , attachment of Mn 2+ is likely to be as a non-monomer species such as an ion pair or possibly a larger polynuclear cluster. We propose that calcite growth rate inhibition by Mn is determined by the kinetics of carbonate attachment at Mn-occupied kink sites, potentially due to slow re-orientation kinetics of carbonate ions that have formed an inner-sphere complex with Mn 2+ at the surface but must reorient to incorporate into the lattice. We demonstrate that patterns in Mg 2+ partitioning and inhibition behavior are broadly consistent with growth inhibition driven by slow Mg 2+ -aquo complex dehydration relative to Ca 2+ but argue that this mechanism likely represents one endmember scenario, seen in Mg-calcite growth at low supersaturations and net precipitation rates. During growth at faster net precipitation rates, some portion of Mg 2+ is likely incorporated as a partially hydrated or otherwise complexed species, but calcite growth remains significantly inhibited by the kinetics of CO 3 2- attachment at Mg 2+ kink sites. These findings suggest a hybrid classical/nonclassical growth mechanism whereby Ca 2+ incorporates largely as a free ion at kink sites while Mn 2+ and some portion of Mg 2+ are incorporated via non-monomer attachment. This pattern may be generalizable; trace constituent cations with aquo-complex desolvation rates significantly slower than the mineral growth rate preferentially incorporate as a non-monomer species during otherwise classical crystal growth.

58 GEOSCIENCES↗
DOE OSTI2015

Economic evaluation on CO₂-EOR of onshore oil fields in China

Carbon dioxide enhanced oil recovery (CO₂-EOR) and sequestration in depleted oil reservoirs is a plausible option for utilizing anthropogenic CO₂ to increase oil production while storing CO₂ underground. Evaluation of the storage resources and cost of potential CO₂-EOR projects is an essential step before the commencement of large-scale deployment of such activities. In this paper, a hybrid techno-economic evaluation method, including a performance model and cost model for onshore CO₂-EOR projects, has been developed based on previous studies. Total 296 onshore oil fields, accounting for about 70% of total mature onshore oil fields in China, were evaluated by the techno-economic method. The key findings of this study are summarized as follows: (1) deterministic analysis shows there are approximately 1.1 billion tons (7.7 billion barrels) of incremental crude oil and 2.2 billion tons CO₂ storage resource for onshore CO₂-EOR at net positive revenue within the Chinese oil fields reviewed under the given operating strategy and economic assumptions. (2) Sensitivity study highlights that the cumulative oil production and cumulative CO₂ storage resource are very sensitive to crude oil price, CO₂ cost, project lifetime, discount rate and tax policy. High oil price, short project lifetime, low discount rate, low CO₂ cost, and low tax policy can greatly increase the net income of the oil enterprise, incremental oil recovery and CO₂ storage resource. (3) From this techno-economic evaluation, the major barriers to large-scale deployment of CO₂-EOR include complex geological conditions, low API of crude oil, high tax policy, and lack of incentives for the CO₂-EOR project.

02 PETROLEUM↗
DOE OSTI2021

Energy use of piperazine with the advanced stripper from pilot plant testing

Here, piperazine with the Advanced Stripper (PZAS™) was tested at the National Carbon Capture Center (NCCC) at coal and NGCC conditions. Energy performance was measured with accounting for heat loss. The net heat duty was found to be identical at 2.45 GJ/tonne for both 4 and 12% CO 2 at 90% CO 2 removal. The average measured heat loss was 0.38 GJ/tonne and represented 30% of the gross heat rate. For PZAS, the warm rich piping before the control valve is the largest in surface area. Heat loss at this location increased heat duty by 80% of the heat loss value. Therefore, the total heat duty was decreased by 80% of the heat loss. The Independence™ model was validated using 112 steady-state pilot plant runs and predicted average net heat duty with an error of 9% and lean loading with an error of 10%. The model was used to simulate process impacts of heat loss for the PZAS and simple stripper configurations. For both strippers, heat loss was found to impact heat duty at locations other than just the steam heater. While heat loss in the steam heater was the most important for PZAS, heat loss in the column was the most important for the simple stripper due to a large top-side pinch and CO 2 reabsorption at the same location. CO 2 reabsorption in PZAS occurred only at high heat loss values (~0.14 GJ/hr), compared to low heat loss values (~ 0.03 GJ/hr) in the PZ-simple stripper. Excessive packing in the PZ-simple stripper caused a large top-side pinch at 0.23 mol/mol lean loading, making the column very sensitive to heat loss. Heat loss in the PZ-simple stripper increased heat duty by 120–150% at typical heat loss values and lean loading of 0.23 mol/mol. Heat loss in the MEA-simple stripper only increased heat duty by 1–13% in a typical lean loading range of 0.1–0.2 mol/mol. A large bottom side pinch at low lean loading for 7 m MEA made the effect of heat loss less pronounced.

42 ENGINEERING↗
DOE OSTI2014

Proton Therapy Expansion Under Current United States Reimbursement Models

Purpose: To determine whether all the existing and planned proton beam therapy (PBT) centers in the United States can survive on a local patient mix that is dictated by insurers, not by number of patients. Methods and Materials: We determined current and projected cancer rates for 10 major US metropolitan areas. Using published utilization rates, we calculated patient percentages who are candidates for PBT. Then, on the basis of current published insurer coverage policies, we applied our experience of what would be covered to determine the net number of patients for whom reimbursement is expected. Having determined the net number of covered patients, we applied our average beam delivery times to determine the total number of minutes needed to treat that patient over the course of their treatment. We then calculated our expected annual patient capacity per treatment room to determine the appropriate number of treatment rooms for the area. Results: The population of patients who will be both PBT candidates and will have treatments reimbursed by insurance is significantly smaller than the population who should receive PBT. Coverage decisions made by insurers reduce the number of PBT rooms that are economically viable. Conclusions: The expansion of PBT centers in the US is not sustainable under the current reimbursement model. Viability of new centers will be limited to those operating in larger regional metropolitan areas, and few metropolitan areas in the US can support multiple centers. In general, 1-room centers require captive (non–PBT-served) populations of approximately 1,000,000 lives to be economically viable, and a large center will require a population of >4,000,000 lives. In areas with smaller populations or where or a PBT center already exists, new centers require subsidy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2020

Thermodynamically consistent forward and reverse degrees of rate control in reversible reactions

The net rate of a composite reaction is the difference between the forward and reverse reaction rates, which are kinetically distinct despite sharing elementary reaction steps and therefore have different rate-controlling transition states and species. Thus, degrees of rate control defined to identify rate-controlling transition states and species for the net rate confound contributions from the forward and reverse reactions. Herein, the forward and reverse degrees of rate control are defined to independently quantify the extent that species and transition states control the forward and reverse rates in reversible reactions. These degrees of rate control are defined as the relative change in the forward and reverse reaction rates per k B T decrease in the standard-state molecular free energies of transition states and species, and they are related to experimentally measurable quantities such as steady-state fractional coverages, reaction orders, and energies and entropies of activation of the forward and reverse reaction rates. The forward/reverse degrees of rate control represent stoichiometric coefficients for species and transition states in an equilibrium between the apparent initial states and the apparent transition states of the apparent rate-controlling steps of forward and reverse overall reactions. At equilibrium, the apparent transition states for the forward reaction and reverse reaction converge, and thus the forward and reverse rate-controlling steps combine to form a single apparent rate-controlling step at equilibrium. Here, this apparent rate-controlling step is comprised of an apparent initial state, transition state, and final state, where the apparent final state of the forward reaction is the apparent initial state of the reverse reaction. The apparent rate-controlling step behaves identically to an elementary step reaction at equilibrium with a pseudo-mass-action rate function given by the transition-state-theory (TST) form rate function (Foley and Bhan, 2020) with a stoichiometric number equal to the affinity-averaged stoichiometric number, $\bar{σ}$ The ratio of the forward and reverse TST-form rate functions is identical to the overall thermodynamic equilibrium relation, consistent with the principles of microscopic reversibility and detailed balance at equilibrium.

42 ENGINEERING↗
DOE OSTI2024

Catalytic resonance theory: Circumfluence of programmable catalytic loops

Chemical reactions on heterogeneous catalyst surfaces exhibit complex networks of elementary reactions with multiple pathways to fluid phase products, sometimes leading to surface reaction loops consisting of a closed cycle reaction pathway. While conventional catalysts at steady state exhibit zero net flux in either direction around a catalytic loop, the loop turnover frequency of three-species surface loops was evaluated in this work via microkinetic modeling to assess the reaction loop behavior resulting from a catalytic surface oscillating between two or more surface energy states. For dynamic heterogeneous catalysts undergoing applied oscillations of surface energy (i.e., programs), surface reaction loops of three species were shown to exhibit non-zero net flow of molecules around the loop, with the extent of loop turnover frequency varying with the applied frequency and amplitude of a sinusoidal or square wave oscillation. Alternatively, some dynamic surface reactions exhibited oscillations only between two surface species or resulted in surfaces covered by a single species at all times. Here, more complex behavior was observed for dynamic surface programs of three distinct electronic states, with the temporal order of applied states controlling the direction of flow of molecules within a three-molecule surface loop. Catalytic loops have the potential to limit overall catalytic reaction rates and use energy in programmable catalysts, while some applications could purposely impose non-zero loop turnover frequency for improved surface reaction control.

Catalysis↗