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At least 253 records · Page 14

Probing reaction channels via reinforcement learning

Abstract Chemical reactions are dynamical processes involving the correlated reorganization of atomic configurations, driving the conversion of an initial reactant into a result product. By virtue of the metastability of both the reactants and products, chemical reactions are rare events, proceeding fleetingly. Reaction pathways can be modelled probabilistically by using the notion of reactive density in the phase space of the molecular system. Such density is related to a function known as the committor function, which describes the likelihood of a configuration evolving to one of the nearby metastable regions. In theory, the committor function can be obtained by solving the backward Kolmogorov equation (BKE), which is a partial differential equation (PDE) defined in the full dimensional phase space. However, using traditional methods to solve this problem is not practical for high dimensional systems. In this work, we propose a reinforcement learning based method to identify important configurations that connect reactant and product states along chemical reaction paths. By shooting multiple trajectories from these configurations, we can generate an ensemble of states that concentrate on the transition path ensemble. This configuration ensemble can be effectively employed in a neural network-based PDE solver to obtain an approximation solution of a restricted BKE, even when the dimension of the problem is very high. The resulting solution provides an approximation for the committor function that encodes mechanistic information for the reaction, paving a new way for understanding of complex chemical reactions and evaluation of reaction rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

[Challenges and Opportunities in] Process Modeling of Intensified Chemical Processes

Before the benefits of process intensification can be fully realized, a multitude of advances in process modeling will be necessary. Process intensification (PI) has the potential to speed development of chemical engineering innovations. Among its many benefits, PI can increase the driving forces (physical and/or chemical) for transport phenomena, separations, and/or reactions in chemical processes, and inspire novel process configurations with major technical and economic benefits. Examples of PI applications include integrated process units such as heat exchange networks, sorption- or membrane-enhanced reactors, and dividing-wall distillation columns, among others [AIChE(2017)].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Temperature Ceramic-Carbonate Dual-Phase Membrane Reactor for Pre-combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Arizona State University, in collaboration with University of South Carolina, worked on a project aimed at development of a new high temperature, high pressure CO 2 perm-selective membrane reactor for water-gas-shift reaction (WGS) with simulated gasifier syngas to produce a high concentration H 2 stream with CO 2 capture. The membrane reactor is made of a CO 2 semi-permeable ceramic-carbonate dual-phase (CCDP) membrane with high CO 2 perm-selectivity/permeance and thermal/mechanical stability for application in WGS reaction. The objectives of this project were to (1) synthesize the chemically/thermally stable tubular CCDP membranes with CO 2 permeance and selectivity (with respect to H 2 , CO or H 2 O) larger than 6.5×10-7 mol/m2·s·Pa and 500, respectively; (2) establish CCDP membrane reactor setup and study high pressure CO 2 permeation and WGS reaction with CO 2 capture using the setup; and (3) identify conditions for WGS in the CCDP membrane reactor that produce CO 2 and H 2 streams with purity of >99% and >90% respectively at CO conversion >95% and overall carbon capture >90%. The work in this project included both membrane development and membrane reactor process study. The membrane development efforts were focused on investigating a H 2 S resistant and highly oxygen-ionic conducting metal oxide material and membrane for CO 2 separation, fabrication of tubular samaria-doped-ceria/molten-carbonate CCDP membrane with high mechanical strength, and experimental and modeling study of high-pressure CO 2 permeation of the CCDP membranes. Mathematical models were developed to describe WGS in the CCDP membrane reactor without a catalyst or packed with a commercial high temperature WGS catalyst. Experiments on WGS in the CCDP membrane reactor with the commercial WGS catalyst, guided by the model analysis, were performed to identify optimum conditions for achieving the CO conversion, carbon capture, and the purity of the H 2 and CO 2 streams mentioned above. At 30 atm feed pressure, 750°C operation temperature, space velocity of 250 h-1, and with steam sweep, a single-stage CCDP membrane reactor with average CO 2 permeation flux of 0.5 cm3(STP)/min.cm2 can achieve CO 2 conversion of 95% and overall carbon capture of 94%, and produce CO 2 and H 2 streams with dry-based purity of >99% and 92% respectively. The project also included process design and techno-economic analysis (TEA) for a CCDP membrane reactor process for WGS reaction with CO 2 capture for a 550 MW coal-fired IGCC power plant, and its comparison with the conventional fixed-bed reactor system for WGS with follow-up CO 2 capture by an amine absorption process. The target performance for the reactor for WGS with CO 2 capture includes CO conversion >95%, hydrogen stream purity >90%, CO 2 stream purity >95%, and total carbon capture >90%. The CCDP membrane developed in this project can achieve the performance target, without subsequent CO 2 capture process at the optimum conditions identified in this project. The outcome of the process design and TEA analysis shows that the membrane reactor for WGS with in-situ CO 2 capture has an operating cost about 40% lower than that for the conventional fixed-bed reactor with a separate amine absorption process for CO 2 capture. However, the capital cost of the membrane reactor process is about twice that of the conventional process because of the higher cost of the CCDP membrane. Modeling analysis shows that a membrane reactor using a CCDP membrane with higher CO 2 permeance (about three times the current value) can deliver the targeted performance for WGS reaction with CO 2 capture at a much higher space velocity and lower membrane surface area to catalyst volume ratio, leading to a smaller catalyst amount and/or membrane area and hence significantly reduced membrane reactor capital costs.

20 FOSSIL-FUELED POWER PLANTS↗

Cell-free bioelectrocatalytic platform for carbon dioxide reduction (Final Technical Report)

The University of Minnesota (UMN) EcoSynBio Team aimed to develop a cell-free, enzyme-based platform for the electro- biocatalytic conversion of CO2 into formate as a platform chemical for further upgrading. This type of bio electrocatalytic process delivers a clean product stream without the need for extensive separation from the electrolyte as in electrochemical synthesis and microbial processes. The reduction reaction is catalyzed by metal-dependent formate dehydrogenases (mFDHs) that are capable of efficient electrocatalytic CO2 reduction without the need of costly co-factors. The development of an efficient, scalable electrobiocatalytic process with high total turnover numbers and viable space time yields, however, was not without its challenges. The UM team has developed a protein-based scaffolding system that facilitates enzyme stabilization and attachment to electrodes along with electron transfer. Yet, although FDHs are highly promising enzymes for cell-free, electrobiochemical CO2 reduction, they are also greatly understudied and especially for applications in electrocatalysis. The UM team used the best described mFDH from Clostridium as its benchmark system and spent significant time and effort in attempting to replicate published data and finally, redesigned a recombinant production system for proper metal co-factor incorporation. The UM team has also identified a small set of new enzyme homologs from extreme microorganisms with superior stabilities that have yielded initial structural data for further engineering. In addition, a new bioelectrocatalytic reactor system has been developed that can be 3D printed and used for enzyme attachment to electrodes. In summary the project has generated critical basic information for the further development of this class of enzymes for the electricity driven reduction of CO2 into formate as platform chemical for upgrading into various other chemicals, including fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

6Li as a three-body system in the (p, 3He) reaction at astrophysical energies

Several astrophysical processes are governed by the occurrence of nuclear reactions involving light nuclei at energies below the Coulomb barrier. Among other effects, their understanding is challenged by the appearance of clustered structures in the ground-state configuration of some of these nuclei, which may have a significant impact on the reaction cross section. In this contribution, we focus on the Li 6 (p, He 3 ) He 4 reaction, to probe the role of clustered configurations of Li 6 . In particular, we consider a three-body ab-initio calculation, based on the hyperspherical harmonics (HH) method, of the Li 6 wave function (WF), together with a more phenomenological three-body model. We observe that the HH WF entails a degree of clustering much larger than obtained from the phenomenological WFs. However, the corresponding reaction cross section, evaluated as a direct two-nucleon transfer in distorted-wave Born approximation, still follows the scaling with the clustering strength already pointed out in a previous work [1] and exhibits an energy trend very similar to that obtained with realistic phenomenological WFs. This opens up interesting perspectives towards constraining

Perrotta, S.↗

Thermal Process Intensification: Transforming the Way Industry Uses Thermal Process Energy (Workshop Report)

The US Department of Energy’s (DOE’s) Advanced Manufacturing Office held the virtual workshop entitled “Thermal Process Intensification: Transforming the Way Industry Uses Thermal Process Energy” in November and December 2020. The workshop brought together participants from universities/laboratories, industries, equipment manufacturers, technology vendors, nongovernmental organizations, and subject-matter experts to discuss transformative technologies and strategies to substantially improve the performance (e.g., energy productivity, thermal efficiency, reduced greenhouse gas [GHG] emissions, reduced number of process steps) of thermal processing systems in the industrial sector. The US industrial sector accounts for 32% of the nation’s primary energy use (including feedstocks), and refining, chemicals, pulp and paper, iron and steel, and food products represent the top energy-consuming sectors. Thermal processing or process heating represents the largest energy use category; it accounts for 63% of all energy use in manufacturing. Additionally, thermal processing is the largest contributor of carbon dioxide (CO2) generation, resulting from combustion of fuels and process related chemical reactions, such as in the case of cement and lime production. The challenge of achieving net-zero industrial GHG emissions is colossal considering the established industrial base that depends mainly on carbon-based processes and energy sources; the time frame and cost to replace carbon-based energy sources and feedstocks; and the long-term outlook for development with large-scale adaptation of alternative non carbon–based technologies. The goals of the DOE Advanced Manufacturing Office Thermal Process Intensification Workshop were as follows: (1) Identify R&D gaps and opportunities to facilitate transformative improvement in industrial thermal processes beyond current technologies and allow for entirely new methods for processing materials; (2) Gain insight into new and innovative approaches to thermally intensify processes, reduce heat demand, harness waste heat, and use fuels and hydrocarbon feedstocks more efficiently; (3) Identify the R&D pathways to thermal process intensification (TPI) with the highest potential for impact and adoption by the industrial sector; (4) Define areas of research, development, and demonstration (RD&D) activities to accelerate development and application of emerging and transformative technologies to intensify thermal processes in industry. The scope and focus of the workshop were defined to meet these goals. Based on the available data for energy use and GHG emissions, the industries that collectively use more than 80% of the total process heating energy consumption were selected as primary focus areas. The chosen industries were combined into the following four groups based on similarities in their thermal processes: high-temperature metal processing (iron and steel industry, alumina-aluminum industry); high-temperature nonmetal and mineral processing (cement and glass industry); medium- to low-temperature thermal processing (food processing and pulp and paper industry as part of forest products sector); and hydrocarbon processing (petroleum refining and chemical industry). Furthermore, all potential TPI technologies associated with the processes defined were considered as part of the workshop. Different types of TPI technologies possible in industrial in the document.

42 ENGINEERING↗

Non-equilibrium plasma co-upcycling of waste plastics and CO 2 for carbon-negative oleochemicals

Mechanical recycling and chemical upcycling by thermochemical reactions have been the major approaches for recycling end-of-life plastics. Herein, we report an electrified approach to upcycle waste plastics into carbon-negative commodity chemicals using greenhouse gas CO 2 as the oxidant and additional carbon source. In this non-equilibrium plasma process, waste polyolefins were oxidatively depolymerized by plasma-activated CO 2 to produce oleochemicals and hydrocarbon chemicals in a single-step process at high reaction rates. In addition, a mixture of CO 2 and a small amount of O 2 was employed as plasma gases to selectively produce fatty alcohols from polyolefins. Based on this atmospheric pressure, non-solvent, and non-catalyst process, up to 97.6% of fatty alcohols could be produced within minutes. In this article, the co-conversion approach was demonstrated using common polyolefins and real-world mixed waste plastics to obtain comparable results. The techno-economic analysis estimates the internal rate of return to be 42.2% and 43.5% for the plasma-based conversion of waste plastics, depending on the plasma gas composition. Lifecycle assessment indicates the global warming potential is between −3.33 and −3.07 kg CO 2e per kg of plastic.

42 ENGINEERING↗

From thermal catalysis to plasma catalysis: a review of surface processes and their characterizations

The use of atmospheric pressure plasma to enhance catalytic chemical reactions involves complex surface processes induced by the interactions of plasma-generated fluxes with catalyst surfaces. Industrial implementation of plasma catalysis necessitates optimizing the design and realization of plasma catalytic reactors that enable chemical reactions that are superior to conventional thermal catalysis approaches. This requires the fundamental understanding of essential plasma-surface interaction mechanisms of plasma catalysis from the aspect of experimental investigation and theoretical analysis or computational modeling. In addition, experimental results are essential to validate the relative theoretical models and hypotheses of plasma catalysis that was rarely understood so far, compared to conventional thermal catalysis. This overview focuses on two important application areas, nitrogen fixation and methane reforming, and presents a comparison of important aspects of the state of knowledge of these applications when performed using either plasma-catalysis or conventional thermal catalysis. We discuss the potential advantage of plasma catalysis over thermal catalysis from the aspects of plasma induced synergistic effect and in situ catalyst regeneration. In-situ/operando surface characterization of catalysts in plasma catalytic reactors is a significant challenge since the high pressure of realistic plasma catalysis systems preclude the application of many standard surface characterization techniques that operate in a low-pressure environment. Here, we present a review of the status of experimental approaches to probe gas-surface interaction mechanisms of plasma catalysis, including an appraisal of demonstrated approaches for integrating surface diagnostic tools into plasma catalytic reactors.

54 ENVIRONMENTAL SCIENCES↗

Recent progress in atomic-scale controlled plasma processing

Atomic-scale control in plasma processing is becoming increasingly critical for fabricating of advanced semiconductor devices, particularly as the industry shifts toward three-dimensional (3D) architectures and high-aspect-ratio (HAR) structures. This review presents a comprehensive overview of recent developments in atomic-scale controlled plasma processes, organized along two key directions: the hierarchical structure of plasma–surface interactions and the generational evolution of atomic layer processing (ALP) technologies. We examined the gas phase, where molecular design enables selective generation of ions and radicals; the boundary layer, where transport phenomena govern species delivery into nanoscale features, and the surface, where temperature-dependent reactions and cyclic processing determine etching selectivity and precision. Building on this foundation, we outline five generations of ALP—from thermal atomic layer deposition to transport-aware, temporally and structurally decoupled processes—highlighting the increasing sophistication of process control. The review further explores the transition from empirical recipe development to science-based, data-driven methodologies. By integrating quantum-chemical modeling, advanced diagnostics, and machine learning, we demonstrated how predictive models can link plasma species composition to process outcomes, enabling autonomous and adaptive control strategies. Finally, this review discusses the broader societal implications of plasma process innovation through the E4 quartet: energy and resource efficiency, environmental sustainability, evolutionary advancement, and educational promotion. These principles guide the development of sustainable and intelligent atomic-scale manufacturing technologies that are not only technically advanced but also socially responsible.

Ishikawa, Kenji [Nagoya Univ. (Japan)] (ORCID:0000↗

Cross sections for the formation of Rb84m,g, Rb83, and Rb82m in Sr86(d,x) reactions up to deuteron energies of 49 MeV: Competition between α-particle and multinucleon emission processes

Cross sections of Sr86(d,x) reactions leading to the products Rb84m,g, Rb83, and Rb82m were measured by the stacked-sample activation technique up to deuteron energies of 49 MeV. Nuclear model calculations were performed using the codes talys and empire, which combine the statistical, precompound, and direct interaction components. In all cases, the empire results were much higher than the talys calculation. Fairly good agreement was obtained between measured data and the talys calculation after some optimization of the input model parameters. Insight into competition between α-particle and multinucleon emission in the Y88 compound-nucleus system was also gained.

59 ≤ A ≤ 89↗

Thermodynamic and Kinetic Barriers Limiting Solid-State Reactions Resolved through In Situ Synchrotron Studies of Lithium Halide Salts

Although halide salts such as LiCl and LiBr are routinely used as a source of Li ions during ion exchange reactions, a detailed understanding of the processes controlling the rates of these reactions is presently lacking. Recently, it has been discovered that the rate limiting barriers for ion exchange are commonly associated with these salts rather than the ceramic target of ion exchange, making it important to quantitatively understand of salt processes. Here it is demonstrated that in situ synchrotron studies of ion exchange reactions can be used to precisely quantify the thermodynamic activation energies associated with these solid state reactions in a manner that can be directly compared with predictions from density functional theory (DFT). While the temperature dependence of the LiCl reaction rate is found to be set by a barrier associated with ion hopping, it was discovered that for LiBr it is also affected by the defect formation energy – an energy found to be substantially lower than predicted by DFT. Furthermore, it is shown that when reaction rates for different relative amounts of reactants are varied, it is possible to identify the rate-limiting reagent and to elucidate an overall scaling relationship that controls the concentration-dependence of the reaction rate. Also, it is demonstrated that global fits across doped and undoped salts can be used to probe both intrinsic and extrinsic vacancy concentrations. This improved understanding of ion exchange mechanisms can be used to accelerate ion exchange reaction rates by orders of magnitude. In conclusion, the techniques demonstrated here can be broadly applied to probe the kinetics and thermodynamics of solid state reactions.

36 MATERIALS SCIENCE↗

Experimental Determination of 𝛼 Widths of 21 Ne Levels in the Region of Astrophysical Interest: New 17 O +𝛼 Reaction Rates and Impact on the Weak 𝑠 Process

The efficiency of the weak 𝑠 process in low-metallicity rotating massive stars depends strongly on the rates of the competing 17 O ⁡(𝛼,𝑛)⁢ 20 Ne and 17 O ⁡(𝛼,𝛾)⁢ 21 Ne reactions that determine the potency of the 16 O neutron poison. Their reaction rates are poorly known in the astrophysical energy range of interest for core helium burning in massive stars because of the lack of spectroscopic information (partial widths, spin parities) for the relevant states in the compound nucleus 21 Ne . In this Letter, we report on the first experimental determination of the 𝛼-particle spectroscopic factors and partial widths of these states using the 17 O ⁡( 7 Li, 𝑡)⁢ 21 Ne 𝛼-transfer reaction. With these the 17 O ⁡(𝛼, 𝑛)⁢ 20 Ne and 17 O ⁡(𝛼, 𝛾)⁢ 21 Ne reaction rates were evaluated with uncertainties reduced by a factor more than 3 with respect to previous evaluations and the present 17 O ⁡(𝛼, 𝑛)⁢ 20 Ne reaction rate is more than 20 times larger. Finally, the present (𝛼, 𝑛)/(𝛼, 𝛾) rate ratio favors neutron recycling and suggests an enhancement of the weak 𝑠 process in the Zr-Nd region by more than 1.5 dex in metal-poor rotating massive stars.

direct reactions↗

CFD Simulation of the Dosing Behavior within the Atomic Layer Deposition Feeding System

The effective operation of atomic layer deposition (ALD) feeding system is the premise of realizing specific ALD processes. In the present work, a detailed computational fluid dynamics (CFD) model of the feeding system has been developed and validated, which accounts for the roles of ALD valves and manifolds. A numerical simulation of the compressible fluid flow and heat/mass transfer within the feeding system was conducted. The dosing amounts and the spatiotemporal distributions of the precursors can be accurately predicted using the CFD model, as validated by experimental results. Different precursors, operating conditions, and structures of the feeding system were simulated and analyzed to examine the operating flexibility of the feeding system. The simulation results can be adopted as the upstream boundary conditions for simulations of the ALD process in the reaction chamber. The substrate-scale simulation indicates that the effect of the feeding system on the film deposition is highly related to the surface kinetics of ALD. The present work can serve as a guide for the development and optimization of different ALD-based processes via proper operation and even the design of the feeding system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimentally Constrained (\(n,\gamma \)) Reaction Rates Relevant to r- and i-Process Nucleosynthesis

The element distribution that we observe in the Universe today, tells a fascinating story of nucleosynthesis events that have taken place throughout the 13.7-billion-years-long history starting with the Big Bang. It is known for a long time that radiative neutron-capture reactions play a major role in synthesizing elements heavier than iron. However, many questions remain when it comes to our understanding of neutron-capture processes in extreme stellar environments. In particular, the intermediate and rapid neutron-capture processes are very challenging to describe, as there exist little or no data on the much-needed neutron-capture rates. In this work we discuss possibilities to obtain indirect, experimental constrains on these rates by means of the Oslo and the β-Oslo methods.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Successful νp -process in neutrino-driven outflows in core-collapse supernovae

The origin of the solar system abundances of several proton-rich isotopes, especially 92,94 Mo and 96,98 Ru, has been an enduring mystery in nuclear astrophysics. An attractive proposal to solve this problem is the νp-process, which can operate in neutrino-driven outflows in a core-collapse supernova after the shock is launched. Years of detailed studies, however, have cast doubt over the ability of this process to generate sufficiently high absolute and relative amounts of various p-nuclei. The νp-process is also thought to be excluded by arguments based on the long-lived radionuclide 92 Nb. Here, we present explicit calculations, in which both the abundance ratios and the absolute yields of the p-nuclei up to A ≲ 105 are successfully reproduced, even when using the modern (medium enhanced) triple-α reaction rates. The process is also shown to produce the necessary amounts of 92 Nb. The models are characterized by subsonic outflows and by the protoneutron star masses in the ≳ 1.7 M ⊙ range. In conclusion, this suggests that the Mo and Ru p-nuclides observed in the Solar System were made in CCSN explosions characterized by an extended accretion stage.

79 ASTRONOMY AND ASTROPHYSICS↗

Radiation-Induced Catalysis of Chemical Reactions

Nuclear energy is a process which achieves zero-carbon energy and heat generation that can provide a consistent electricity load to supply the grid when renewables are not available. However, on a cost per kilowatt-hour comparison, nuclear energy is more expensive than many of the renewable energy generation technologies such as wind and solar. In order to increase the economic viability of next generation nuclear reactors for energy production, generation of a secondary product such as a chemical feedstock would increase the economic viability of nuclear energy, particularly for new installations of next-generation nuclear reactors for power production. Currently, commercial nuclear reactors are primarily used for their heat to generate steam for electricity production. There is a large amount of unused energy in the form of photon and neutron radiation that could be exploited to drive chemical processes to produce feedstock materials as a secondary product of a nuclear plant. Chemical processing with radiation is not a new concept. In fact, gamma radiation is an excellent source of high energy photons to drive photochemical reactions. Dow chemical produced commercial quantities of ethyl bromide using gamma irradiation from a 60 Co source in the 1960s and 1970s because it was the most cost-effective means of production to meet the demand.5, 6 Due to the potential economic advantages, there is a new emphasis on studying feedstock production which can be enhanced by excess gamma and neutron radiation, particularly if the reaction could be monitored in real-time which is advantageous for process optimization. A model system of lignocellulose degradation under γ- radiation was chosen for this study while following the degradation products with Raman spectroscopy in real-time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Continuous Production of Carbon-Supported and Surfactant-Free Pt-M (M=Fe, Co, Ni, and Cu) Nanocrystals for Catalyzing Oxygen Reduction

Scalable production of carbon-supported Pt-M (M=Co, Ni, and Fe) alloy nanocrystals is of great importance for their practical application as catalysts towards the oxygen reduction reaction (ORR), a process key to the operation of proton-exchange membrane fuel cells. Here we report the use of a fluidic device for the in situ nucleation and growth of Pt-M nanocrystals on a commercial carbon support in a continuous and scalable fashion. The use of dimethylformamide not only enables well dispersion of the carbon powders for the creation of a homogeneous reaction mixture but also helps reduce metal precursors for the heterogeneous nucleation and growth of nanocrystals on the carbon surface. The size, shape, and composition of the nanocrystals can all be tuned by changing the metal precursors added into the reaction mixture, resulting in Pt-M nanocrystals uniformly distributed across the surface of the carbon support. Among the nanocrystals, the carbon-supported Pt-Co nanocrystals show the highest ORR specific and mass activities at 0.9 V, demonstrating 11.4- and 8.8-fold enhancements over the state-of-the-art commercial Pt/C catalyst.

Electrochemistry↗