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At least 1,063 records · Page 59

Automatic building energy model development and debugging using large language models agentic workflow

Building energy modeling (BEM) is a complex process that demands significant time and expertise, limiting its broader application in building design and operations. While Large Language Models (LLMs) agentic workflow have facilitated complex engineering processes, their application in BEM has not been specifically explored. This paper investigates the feasibility of automating BEM using LLM agentic workflow. Here, we developed a generic LLM-planning-based workflow that takes a building description as input and generates an error-free EnergyPlus building energy model. Our robust workflow includes four core agents: 1) Building Description Pre-Processing, 2) IDF Object Information Extraction, 3) Single IDF Object Generator Suite, and 4) IDF Debugging Agent. These agents divide the complex tasks into manageable sub-steps, enabling LLMs to generate accurate and reliable results at each stage. The case study demonstrates the successful translation of a building description into an error-free EnergyPlus model for the iUnit modular building at the National Renewable Energy Laboratory. The effectiveness of our workflow surpasses: 1) naive prompt engineering, 2) other LLM-based workflows, and 3) manual modeling, in terms of accuracy, reliability, and time efficiency. The paper concludes with a discussion on the interplay between foundational models and LLM agent planning design, advocating for the use of fine-tuned, specialized models to advance this field.

97 MATHEMATICS AND COMPUTING↗

Aspect-Oriented Programming

Computer science has experienced an evolution in programming languages and systems from the crude assembly and machine codes of the earliest computers through concepts such as formula translation, procedural programming, structured programming, functional programming, logic programming, and programming with abstract data types. Each of these steps in programming technology has advanced our ability to achieve clear separation of concerns at the source code level. Currently, the dominant programming paradigm is object-oriented programming - the idea that one builds a software system by decomposing a problem into objects and then writing the code of those objects. Such objects abstract together behavior and data into a single conceptual and physical entity. Object-orientation is reflected in the entire spectrum of current software development methodologies and tools - we have OO methodologies, analysis and design tools, and OO programming languages. Writing complex applications such as graphical user interfaces, operating systems, and distributed applications while maintaining comprehensible source code has been made possible with OOP. Success at developing simpler systems leads to aspirations for greater complexity. Object orientation is a clever idea, but has certain limitations. We are now seeing that many requirements do not decompose neatly into behavior centered on a single locus. Object technology has difficulty localizing concerns invoking global constraints and pandemic behaviors, appropriately segregating concerns, and applying domain-specific knowledge. Post-object programming (POP) mechanisms that look to increase the expressiveness of the OO paradigm are a fertile arena for current research. Examples of POP technologies include domain-specific languages, generative programming, generic programming, constraint languages, reflection and metaprogramming, feature-oriented development, views/viewpoints, and asynchronous message brokering. (Czarneclu and Eisenecker s book includes a good survey of many of these technologies).

Elrad, Tzilla↗

Techno-economic evaluation of industrial heat pump applications in US pulp and paper, textile, and automotive industries

Industrial process heat decarbonization through electrification could contribute significantly to climate change mitigation efforts. In the US industry, thermal processes accounted for more than two-thirds of the total final energy demand in 2021. Cross-cutting electrification technologies like industrial heat pumps are suitable for the process heat supply to several industrial unit operations in a sustainable way while also improving overall energy efficiency. This study employs a bottom-up approach to investigate the techno-enviro-economic potentials of deploying high-temperature and steam-generating heat pumps in US textile, pulp and paper, and automotive sectors in different timeframes. The results show that the annual technical potential energy and CO 2 savings by electrifying heat supply are 310 PJ (or 36% of the projected energy demand) and 28 MtCO 2 (or 71% of the projected CO 2 emissions) in 2050 respectively, however, these incur additional costs in each sector (ranging between 5 and 18 $\$$/GJ). The required heating capacity of industrial heat pumps is estimated at 15 GW, which translates roughly into a market of over 6000 heat pump units and an investment volume of $\$$7 billion in the studied processes. Although there may be individual cost-effective opportunities for electrifying heat supply in specific industrial sites, the overall costs are estimated to be high in the three industrial sectors due to the large disparity between electricity and natural gas prices and low heat source temperatures. To overcome the identified techno-economic barriers, comprehensive action plans for different stakeholders are also given. This study provides novel insights that should inform policymakers’ and executives’ decisions about the electrification of the current and future US industrial heat supply in relevant industrial sectors.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Helicopter Flight Simulation Motion Platform Requirements

To determine motion fidelity requirements, a series of piloted simulations was performed. Several key results were found. First, lateral and vertical translational platform cues had significant effects on fidelity. Their presence improved performance and reduced pilot workload. Second, yaw and roll rotational platform cues were not as important as the translational platform cues. In particular, the yaw rotational motion platform cue did not appear at all useful in improving performance or reducing workload. Third, when the lateral translational platform cue was combined with visual yaw rotational cues, pilots believed the platform was rotating when it was not. Thus, simulator systems can be made more efficient by proper combination of platform and visual cues. Fourth, motion fidelity specifications were revised that now provide simulator users with a better prediction of motion fidelity based upon the frequency responses of their motion control laws. Fifth, vertical platform motion affected pilot estimates of steady-state altitude during altitude repositioning. Finally, the combined results led to a general method for configuring helicopter motion systems and for developing simulator tasks that more likely represent actual flight. The overall results can serve as a guide to future simulator designers and to today's operators.

Schroeder, Jeffery Allyn↗

Towards an IPv6-only WLCG: More successes in reducing IPv4

The Worldwide Large Hadron Collider Computing Grid (WLCG) community’s deployment of dual-stack IPv6/IPv4 on its worldwide storage infrastructure has been very successful. Dual-stack is not, however, a viable longterm solution; the HEPiX IPv6 Working Group has focused on studying where and why IPv4 is still being used, and how to flip such traffic to IPv6. The agreed end goal is to turn IPv4 off and run IPv6-only over the wide-area network to simplify both operations and security management.This paper reports our work since the CHEP2023 conference. Firstly, we present our campaign to deploy IPv6 on CPU services and Worker Nodes, with a deadline of end of June 2024. Then, the WLCG Data Challenge (DC24) performed in February 2024 was an excellent opportunity to observe the percentage of data transfers carried by IPv6. We observed the predominance of IPv6 in data transfers during DC24 and were able to understand yet more reasons for the use of IPv4 and areas for remedial action.The paper ends with the working group’s plans for moving WLCG to “IPv6- only”. One aspect of this is the possible automated use of IPv6-only clients configured with a customer-side translator, or CLAT, together with a deployment of NAT64 using what is often known as “IPv6-Mostly”, enabling IPv6-only sites to connect to non-WLCG IPv4-only services.

Attebury, Garhan [U. Nebraska, Lincoln]↗

Preadaptation to the stimulus rearrangement of weightlessness: Preliminary studies and concepts for trainer designs

An effort to develop preflight adaptation training (PAT) apparatus and procedures to adapt astronauts to the stimulus rearrangement of weightless spaceflight is being pursued. Based on the otolith tilt-translation reinterpretation model of sensory adaptation to weightlessness, two prototype preflight adaptation trainers (PAT) have been developed. These trainers couple pitch movement of the subject with translation of the visual surround. Subjects were exposed to this stimulus rearrangement for periods of 30 m. The hypothesis is that exposure to the rearrangement would attenuate vertical eye movements was supported by two experiments using the Miami University Seesaw (MUS) PAT prototype. The Dynamic Environment Simulator (DES) prototype failed to support this hypothesis; this result is attributed to a pecularity of the DES apparatus. A final experiment demonstrated that changes in vertical eye movements were not a consequence of fixation on an external target during exposure to a control condition. Together these experiments support the view that preflight adaptation training can alter eye movements in a manner consistent with adaptation to weightlessness. Following these initial studies, concepts for development of operational preflight trainers were proposed. The trainers are intended to: demonstrate the stimulus rearrangement of weightlessness; allow astronauts to train in altered sensory environment; modify sensory motor reflexes; and reduce/eliminate space motion sickness symptoms.

Parker, D. E.↗

Quantitative computer representation of propellant processing

With the technology currently available for the manufacture of propellants, it is possible to control the variance of the total specific impulse obtained from the rocket boosters to within approximately five percent. Though at first inspection this may appear to be a reasonable amount of control, when it is considered that any uncertainty in the total kinetic energy delivered to the spacecraft translates into a design with less total usable payload, even this degree of uncertainty becomes unacceptable. There is strong motivation to control the variance in the specific impulse of the shuttle's solid boosters. Any small gains in the predictability and reliability of the booster would lead to a very substantial payoff in earth-to-orbit payload. The purpose of this study is to examine one aspect of the manufacture of solid propellants, namely, the mixing process. The traditional approach of computational fluid mechanics is notoriously complex and time consuming. Certain simplifications are made, yet certain fundamental aspects of the mixing process are investigated as a whole. It is possible to consider a mixing process in a mathematical sense as an operator, F, which maps a domain back upon itself. An operator which demonstrates good mixing should be able to spread any subset of the domain completely and evenly throughout the whole domain by successive applications of the mixing operator, F. Two and three dimensional models are developed and graphical visualization two and three dimensional mixing processes are presented.

Hicks, M. D.↗

Model Checking JAVA Programs Using Java Pathfinder

This paper describes a translator called JAVA PATHFINDER from JAVA to PROMELA, the "programming language" of the SPIN model checker. The purpose is to establish a framework for verification and debugging of JAVA programs based on model checking. This work should be seen in a broader attempt to make formal methods applicable "in the loop" of programming within NASA's areas such as space, aviation, and robotics. Our main goal is to create automated formal methods such that programmers themselves can apply these in their daily work (in the loop) without the need for specialists to manually reformulate a program into a different notation in order to analyze the program. This work is a continuation of an effort to formally verify, using SPIN, a multi-threaded operating system programmed in Lisp for the Deep-Space 1 spacecraft, and of previous work in applying existing model checkers and theorem provers to real applications.

Havelund, Klaus↗

Development of an Effective Finite-rate Oxidation Model for NuSil-coated Charred Carbon Preform Ablators

Recently, a detailed effective finite-rate surface chemistry model was developed for the oxidation of FiberForm [1] using the molecular beam experimental data of Poovathingal et al., [2]. FiberForm is the major building block of the thermal protection system (TPS) material Phenolic Impregnated Carbon Ablator (PICA), commonly used by NASA. The surface chemistry model consists of detailed surface reaction mechanisms such as adsorption, desorption, and several types of Langmuir-Hinshelwood (LH) reactions to characterize the oxygen-carbon interactions at the surface. This model provides excellent agreement with the experimental data for oxidation product compositions and corresponding translational energy distributions. Further, an effective oxidation model was constructed that captures the equivalent interaction of oxygen inside the microstructure (including multiple surface collisions) via a modified reactivity for a smooth wall boundary condition. This enables the use of this model directly into Computational Fluid Dynamics (CFD) codes and Material Response (MR) codes to accurately simulate the gas–surface interactions within FiberForm without using the detailed micro-structure. However, this effective model is valid only for the virgin FiberForm. As the TPS material undergoes ablation, the preform carbon burns and turns into char. In addition, PICA is also coated with a protective silicon coating called NuSil for the purpose of mitigating the spread of phenolic dust, and limit contamination during clean room operations. Fig. 1 shows a X-ray microtomography image of a charred NuSil-coated PICA. The NuSil layer introduces species containing silicon into the product mixture. Further, the reactivity of the carbon within the char layer is different from the virgin FiberForm as shown in Fig. 2. Recently a new set of molecular beam experiments were performed on this NuSil-coated TPS material [3] with the same type of oxygen beam used in the previous experiments. Using the latest experimental data, the previously developed effective model will be extended to account for the charred carbon as well as the NuSil coating. Finally, this new effective model with three phases – preform carbon, char, and NuSil; will be compared and validated against the experimental product compositions.

K Swaminathan Gopalan↗

High-sensitivity in vivo contrast for ultra-low field magnetic resonance imaging using superparamagnetic iron oxide nanoparticles

Magnetic resonance imaging (MRI) scanners operating at ultra-low magnetic fields (ULF; <10 mT) are uniquely positioned to reduce the cost and expand the clinical accessibility of MRI. A fundamental challenge for ULF MRI is obtaining high-contrast images without compromising acquisition sensitivity to the point that scan times become clinically unacceptable. Here, we demonstrate that the high magnetization of superparamagnetic iron oxide nanoparticles (SPIONs) at ULF makes possible relaxivity- and susceptibility-based effects unachievable with conventional contrast agents (CAs). We leverage these effects to acquire high-contrast images of SPIONs in a rat model with ULF MRI using short scan times. This work overcomes a key limitation of ULF MRI by enabling in vivo imaging of biocompatible CAs. These results open a new clinical translation pathway for ULF MRI and have broader implications for disease detection with low-field portable MRI scanners.

42 ENGINEERING↗

Automating an orbiter approach to Space Station Freedom to minimize plume impingement

The Space shuttle orbiter Reaction Control System's (RCS) plume impingement during proximity operations with Space Station Freedom (SSF) is a structural design driver for the SSF solar panels and radiators. A study underway at JSC is investigating whether the use of an automated approach controller could result in the reduction of plume impingement induced loads during orbiter approach to SSF. Ongoing real time person-in-the-loop (PIL) simulations of an orbiter approaching the SSF show that orbiter trajectory control can vary significantly from one pilot to the next. This variation is a cause for concern since current analyses predict that plume impingement loads resulting from PIL orbiter approaches may exceed the solar panel and radiator load limits. The use of an automated approach controller is expected to reduce peak loads by both minimizing orbiter translational jet firings in certain directions and controlling the frequency at which they occur during various phases of the approach.

Spehar, Peter T.↗

Velocimeter LIDAR Based Bulk Velocity Estimation for Terrain Relative Navigation Applications

A novel batch state estimation approach to estimate the translational and angular velocity states of a vehicle using a state-of-the-art velocimeter Light Detection and Ranging (LIDAR) sensor for use in Terrain and Hazard Relative Navigation (TRN/HRN) applications is presented in this paper. The velocimeter LIDAR is capable of measuring three dimensional position and line-of-sight (LOS) velocity associated with every pixel in the field-of-view (FOV). This new batch state estimation methodology is shown to provide accurate and statistically consistent velocity estimates with no a priori information. In contrast to traditional computer vision approaches for TRN, the proposed technique is not dependent on image features. This feature alleviates the need for accurate feature detection and correspondence to a predefined map making it suitable for unknown operating environments. Following a detailed development of the mathematical details associated with the batch state estimation methodology, the efficacy and utility of the proposed algorithms are evaluated through emulation robotics experiments performed at Texas A&M’s Land, Air, and Space Robotics (LASR) laboratory.

Skulsky, Eli↗

Vision System Measures Motions of Robot and External Objects

A prototype of an advanced robotic vision system both (1) measures its own motion with respect to a stationary background and (2) detects other moving objects and estimates their motions, all by use of visual cues. Like some prior robotic and other optoelectronic vision systems, this system is based partly on concepts of optical flow and visual odometry. Whereas prior optoelectronic visual-odometry systems have been limited to frame rates of no more than 1 Hz, a visual-odometry subsystem that is part of this system operates at a frame rate of 60 to 200 Hz, given optical-flow estimates. The overall system operates at an effective frame rate of 12 Hz. Moreover, unlike prior machine-vision systems for detecting motions of external objects, this system need not remain stationary: it can detect such motions while it is moving (even vibrating). The system includes a stereoscopic pair of cameras mounted on a moving robot. The outputs of the cameras are digitized, then processed to extract positions and velocities. The initial image-data-processing functions of this system are the same as those of some prior systems: Stereoscopy is used to compute three-dimensional (3D) positions for all pixels in the camera images. For each pixel of each image, optical flow between successive image frames is used to compute the two-dimensional (2D) apparent relative translational motion of the point transverse to the line of sight of the camera. The challenge in designing this system was to provide for utilization of the 3D information from stereoscopy in conjunction with the 2D information from optical flow to distinguish between motion of the camera pair and motions of external objects, compute the motion of the camera pair in all six degrees of translational and rotational freedom, and robustly estimate the motions of external objects, all in real time. To meet this challenge, the system is designed to perform the following image-data-processing functions: The visual-odometry subsystem (the subsystem that estimates the motion of the camera pair relative to the stationary background) utilizes the 3D information from stereoscopy and the 2D information from optical flow. It computes the relationship between the 3D and 2D motions and uses a least-mean-squares technique to estimate motion parameters. The least-mean-squares technique is suitable for real-time implementation when the number of external-moving-object pixels is smaller than the number of stationary-background pixels.

Talukder, Ashit↗

Low thrust chemical rocket technology

An on-going technology program to improve the performance of low thrust chemical rockets for spacecraft on-board propulsion applications is reviewed. Improved performance and lifetime is sought by the development of new predictive tools to understand the combustion and flow physics, introduction of high temperature materials and improved component designs to optimize performance, and use of higher performance propellants. Improved predictive technology is sought through the comparison of both local and global predictions with experimental data. Predictions are based on both the RPLUS Navier-Stokes code with finite rate kinetics and the JANNAF methodology. Data were obtained with laser-based diagnostics along with global performance measurements. Results indicate that the modeling of the injector and the combustion process needs improvement in these codes and flow visualization with a technique such as 2-D laser induced fluorescence (LIF) would aid in resolving issues of flow symmetry and shear layer combustion processes. High temperature material fabrication processes are under development and small rockets are being designed, fabricated, and tested using these new materials. Rhenium coated with iridium for oxidation protection was produced by the Chemical Vapor Deposition (CVD) process and enabled an 800 K increase in rocket operating temperature. Performance gains with this material in rockets using Earth storable propellants (nitrogen tetroxide and monomethylhydrazine or hydrazine) were obtained through component redesign to eliminate fuel film cooling and its associated combustion inefficiency while managing head end thermal soakback. Material interdiffusion and oxidation characteristics indicated that the requisite lifetimes of tens of hours were available for thruster applications. Rockets were designed, fabricated, and tested with thrusts of 22, 62, 440 and 550 N. Performance improvements of 10 to 20 seconds specific impulse were demonstrated. Higher performance propellants were evaluated: Space storable propellants, including liquid oxygen (LOX) as the oxidizer with nitrogen hydrides or hydrocarbon as fuels. Specifically, a LOX/hydrazine engine was designed, fabricated, and shown to have a 95 pct theoretical c-star which translates into a projected vacuum specific impulse of 345 seconds at an area ratio of 204:1. Further performance improvment can be obtained by the use of LOX/hydrogen propellants, especially for manned spacecraft applications, and specific designs must be developed and advanced through flight qualification.

Schneider, Steven J.↗

Nozzle flow with vibrational nonequilibrium

This research concerns the modeling and numerical solutions of the coupled system of compressible Navier-Stokes equations in cylindrical coordinates under conditions of equilibrium and nonequilibrium thermodynamics. The problem considered was the modeling of a high temperature diatomic gas N2 flowing through a converging-diverging high expansion nozzle. The problem was modeled in two ways. The first model uses a single temperature with variable specific heats as functions of this temperature. For the second model we assume that the various degrees of freedom all have a Boltzmann distribution and that there is a continuous redistribution of energy among the various degrees of freedom as the gas passes through the nozzle. Each degree of freedom is assumed to have its own temperature and, consequently, each system state can be characterized by these temperatures. This suggests that formulation of a second model with a vibrational degree of freedom along with a rotational-translation degree of freedom, each degree of freedom having its own temperature. Initially the vibrational degree of freedom is excited by heating the gas to a high temperature. As the high temperature gas passes through the nozzle throat there is a sudden drop in temperature along with a relaxation time for the vibrational degree of freedom to achieve equilibrium with the rotational-translation degree of freedom. That is, we assume that the temperature change upon passing through the throat is so great that the changes in the vibrational degree of freedom occur at a much slower pace and consequently lags behind the rotational-translational energy changes. This lag results in a finite relaxation time. In this context the term nonequilibrium is used to denote the fact that the energy content of the various degrees of freedom are characterized by two temperatures. We neglect any chemical reactions which could also add nonequilibrium effects. We develop the energy equations for the nonequilibrium model from first principles. The resulting equations, which model the nozzle flow, can be expressed in various forms. In most forms the resulting equations are coupled systems of nonlinear partial differential equations subject to certain boundary conditions. To solve the resulting coupled system of nonlinear partial differential equations, several numerical techniques were investigated: (1) the explicit MacCormack method, (2) the explicit-implicit MacCormack method, (3) the method of operator splitting, (4) factorization schemes, and (5) the Steger-Warming scheme.

Heinbockel, J. H.↗

Agentic framework for programmatic crystal structure generation using a fine-tuned worker–supervisor large language model

Platinum group metals (PGMs) underpin many catalytic technologies but face severe supply constraints, motivating the search for alternative materials and computational methods to accelerate discovery. While atomistic simulation tools such as Pymatgen and ASE have streamlined structure manipulation, they require detailed inputs, limiting accessibility for experimentalists and slowing early-stage exploration. Here, in this study, we present an AI-driven agentic framework that orchestrates worker–supervisor large language models (LLMs). The worker translates natural-language prompts of varying abstraction into valid crystallographic structures using a compact LLM fine-tuned with low-rank adaptation on a curated text–code–CIF dataset, emphasizing energy-efficient training. Benchmarking against the baseline CodeGen-350M-mono model shows that fine-tuning reduces hallucination rates from 100% to as low as 5% and improves structural match accuracy to up to 82% for fully specified inputs. Accuracy declines with decreasing prompt detail but remains nontrivial even when only stoichiometry and space group are provided, underscoring the LLM’s capacity for crystallographic inference. The supervisor Claude LLM evaluates the outputs and triggers iterative refinement through the worker’s built-in structure manipulation capabilities (e.g., supercell scaling, strain, vacancy, and substitution operations). We further demonstrate use cases for technologically relevant catalysts, including IrO 2 , pyrochlore Pb 2 Ir 2 O 7 , Ni 2 FeO 4 , and Ni 3 Mo, where the framework generates physically consistent structures that can be refined via geometry optimization. This work introduces a low-energy, language-driven pathway for integrating human and machine intelligence in materials design, paving the way for AI-assisted synthesis planning and high-throughput screening of complex oxides.

AI agent↗

Incorporating Speech Recognition into a Natural User Interface

The Augmented/ Virtual Reality (AVR) Lab has been working to study the applicability of recent virtual and augmented reality hardware and software to KSC operations. This includes the Oculus Rift, HTC Vive, Microsoft HoloLens, and Unity game engine. My project in this lab is to integrate voice recognition and voice commands into an easy to modify system that can be added to an existing portion of a Natural User Interface (NUI). A NUI is an intuitive and simple to use interface incorporating visual, touch, and speech recognition. The inclusion of speech recognition capability will allow users to perform actions or make inquiries using only their voice. The simplicity of needing only to speak to control an on-screen object or enact some digital action means that any user can quickly become accustomed to using this system. Multiple programs were tested for use in a speech command and recognition system. Sphinx4 translates speech to text using a Hidden Markov Model (HMM) based Language Model, an Acoustic Model, and a word Dictionary running on Java. PocketSphinx had similar functionality to Sphinx4 but instead ran on C. However, neither of these programs were ideal as building a Java or C wrapper slowed performance. The most ideal speech recognition system tested was the Unity Engine Grammar Recognizer. A Context Free Grammar (CFG) structure is written in an XML file to specify the structure of phrases and words that will be recognized by Unity Grammar Recognizer. Using Speech Recognition Grammar Specification (SRGS) 1.0 makes modifying the recognized combinations of words and phrases very simple and quick to do. With SRGS 1.0, semantic information can also be added to the XML file, which allows for even more control over how spoken words and phrases are interpreted by Unity. Additionally, using a CFG with SRGS 1.0 produces a Finite State Machine (FSM) functionality limiting the potential for incorrectly heard words or phrases. The purpose of my project was to investigate options for a Speech Recognition System. To that end I attempted to integrate Sphinx4 into a user interface. Sphinx4 had great accuracy and is the only free program able to perform offline speech dictation. However it had a limited dictionary of words that could be recognized, single syllable words were almost impossible for it to hear, and since it ran on Java it could not be integrated into the Unity based NUI. PocketSphinx ran much faster than Sphinx4 which would've made it ideal as a plugin to the Unity NUI, unfortunately creating a C# wrapper for the C code made the program unusable with Unity due to the wrapper slowing code execution and class files becoming unreachable. Unity Grammar Recognizer is the ideal speech recognition interface, it is flexible in recognizing multiple variations of the same command. It is also the most accurate program in recognizing speech due to using an XML grammar to specify speech structure instead of relying solely on a Dictionary and Language model. The Unity Grammar Recognizer will be used with the NUI for these reasons as well as being written in C# which further simplifies the incorporation.

Chapa, Nicholas↗

Electrochemical Conversion of CO 2 to Methyl Formate in a Flow Electrolyzer with Mixed Propylene Carbonate/Methanol Catholyte

Despite the promise of electrochemical carbon dioxide reduction as a technology for the production of clean fuels and decarbonization of the chemical industry, research has mostly focused on aqueous systems with a relatively limited set of products that have been achieved via electrosynthesis. Increasingly, CO 2 electroreduction in nonaqueous solvents is being pursued to develop new avenues for expanding the suite of products that can be made with high selectivity. CO 2 reduction in alcohols coupled with in situ esterification to produce esters is one such route that utilizes nonaqueous electrolyte. To be practical, such electrochemical syntheses need to be translated to a high-performance reactor such as a flow electrolyzer. However, many organic solvents, such as alcohols, wet and flood porous electrodes, thus impeding reactor performance. In this work, methanol was mixed with propylene carbonate as a catholyte for a gas-fed CO 2 flow electrolyzer that avoided cathode flooding. Simultaneously, a dual aqueous anolyte was used for water oxidation as a scalable and sustainable anodic half-reaction. The performance effect of methanol concentration, catholyte acidity, CO 2 flow rate, and dilute water in the catholyte were investigated. With 10 vol % methanol in 90 vol % propylene carbonate, 63% faradaic efficiency for methyl formate ester product was sustained without cathode flooding. However, improvements are still needed to lower the cell resistance and further increase the operating current density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗