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Kryptonate Hydrogen Detection System (Final Report)

A prototype model of a multipurpose instrument which demonstrates the applicability of the Kryptonate® technique for detecting hydrogen gas was developed. This report describes the construction of the instrument and presents a laboratory evaluation of its performance. Performance was excellent. The instrument was designed to detect hydrogen in air at concentrations of 0-3% by volume, and to detect hydrogen in nitrogen or other inert gas at concentrations of 0-10% by volume. Other detection levels (both higher and lower) could be set if required. Ultimate response times can be made of the order of 0.5 seconds. The instrument is an all solid state device operating from 120V 60 Hz power source. The instrument has been designed to enable modifications to be made with a minimum amount of difficulty.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND

Hybrid Plasmonic Coupled‐Mode Metasurface Design for Shot‐Noise Limited Ppb‐Level Hydrogen Detection

Plasmonic hydrogen sensors have enabled hydrogen detection below parts-per-million (ppm) range by boosting the sensitivity using localized surface plasmonic resonant (LSPR) structures. However, the intrinsic optical losses of Palladium (Pd), the primary plasmonic metal used for hydrogen detection, result in a low quality (Q) factor LSPR, which fundamentally hinders further improvement. In this work, a hybrid plasmonic metasurface is proposed that couples Pd-based LSPR structure with an Au film supporting surface plasmon polariton mode (Au-SPP). The coupled near-perfect absorber resonance yields a spectrally narrow, high Q response that retains strong sensitivity to hydrogen while improving resonance localization. Numerical analysis shows that, under shot-noise-limited conditions, the limit of detection (LoD) can be improved by over threefold compared to the state-of-the-art designs. Furthermore, this hybrid plasmonic coupled-mode metasurface thus presents a promising pathway to achieve parts-per-billion-level (ppb-level) hydrogen detection with enhanced spectral precision and robustness.

coupled modes

Hydrogen Detection via a Low-Cost Prototype Fiber-Optic Sensing System

The developed low-cost prototype sensing system successfully detects hydrogen concentrations across a wide range, demonstrating immediate feasibility for commercial deployment. Utilizing fiber-optic technology, the system delivers stable, reproducible performance from parts-per-million levels up to 100% pure H2 environments. Environmental and chemical cross-sensitivity evaluations confirm robust selectivity against methane and temperature changes, establishing its readiness for near-term commercialization.

fiber-optic H2 sensor

Limitations of Hydrogen Detection After 150 Years of Research on Hydrogen Embrittlement

Hydrogen's significance in contemporary society lies in its remarkable energy density, yet its integration into the worldwide energy grid presents a substantial challenge. Exposing materials to hydrogen environments leads to degradation of mechanical properties, damage, and failure. While the current approach for assessing hydrogen's impact on materials involves mainly multiscale modeling and mechanical testing, there exists a significant deficiency in detecting the intricate interactions between hydrogen and materials at the nanoatomic scales and under in situ conditions. This perspective review highlights the experimental endeavors aimed at bridging this gap, pointing toward the imminent need for new experimental techniques that can detect and map hydrogen in materials’ microstructures and their site‐specific dependencies.

Tunes, Matheus A.

BOS Gas Detection Pipeline (Integrated System for Optical Hydrogen Detection Using Background Oriented Schlieren and Machine Learning) [SWR-26-007]

This software is the world's first integrated background oriented schlieren and machine learning-based leak detection system. The system provides real time visualization of gas leaks and machine learning interpenetration of leak severity. The software is supplemented by SWR-25-177, "gpu_piv (Graphics Processing Unit Accelerated Background Oriented Schlieren Algorithm", also developed by the National Laboratory of the Rockies. SEE DOECODE ID 182832.

Palin, Ian [National Laboratory of the Rockies (NL

Hydrogen Detection Strategies to Support H2@SCALE - The NREL Sensor Laboratory

Hydrogen represents a major pathway to decarbonize and stabilize the national and international energy industry and select manufacturing markets. To facilitate the development of hydrogen markets, the US Department of Energy initiated H2@Scale to bring together stakeholders to advance affordable hydrogen production, transport, storage, and utilization to increase revenue opportunities in multiple energy sectors. One major impediment to hydrogen implementation is cost. To expedite the use of hydrogen in energy and other markets, the United States announced in 2021 the Hydrogen Shot, which seeks to reduce the cost of clean hydrogen by 80% to $1 per 1 kilogram in 1 decade ("1 1 1"). As the cost of hydrogen drops, new applications will emerge that will require unique configurations of existing equipment and infrastructure, and eventually lead to advances in the generation and utilization of hydrogen. As the hydrogen economy expands, sensors and detection methods will need to adapt to changing infrastructure demands to address the primary targets of health & safety, emissions monitoring, and process control. The NREL Sensor Laboratory is playing a pivotal role in advancing the use of hydrogen sensors and detection methodologies in each of these categories to support DOE's mission for safe and efficient utilization in emerging markets. Health & safety monitors are required to ensure that operators and facilities can react to unintended hydrogen releases, either as GH2, LH2, or as a constituent of blends (e.g., natural gas or ammonia). Current detection methodologies focus on safety applications to detect near its lower flammable limit (4 vol %), and typically include point sensors in applications such as fixed or mobile detectors (e.g., personal gas monitors). Methodologies amenable for area detection include acoustic, emerging optical imaging methods, and flame detectors. Comparable detection strategies can be utilized for emissions monitoring and quantization, however few methods can simultaneously cover both low (emissions) and high (health & safety) levels. Deployment of emission level detectors will be required to 1) reduce product loss through small but potentially significant leaks from an environmental or cost perspective, 2) reduce downtime of high demand systems by early identification of eminent system failures (leaks through pump or compressor seals indicative of impending failure), and 3) address potential emission monitoring requirements that may be set by regulating bodies. The first two points should be adopted by industry to reduce the cost-of-goods-sold. The third main category for hydrogen detection relates to process control and may be advantageous for many existing applications. Two main applications are emerging. For example, the purity requirements for hydrogen that is dispensed from refueling systems for hydrogen fuel cell electric vehicles (FCEV) is rigorously regulated by the Standard SAE J2719, which prescribes maximum allowable levels of multiple impurities in the hydrogen fuel and must be verified by a regulatory body. Hydrogen contaminant detectors (HCD) integrated to the fueling station can assure this compliance. HCDs must be able operate in 100% H2 backgrounds and be able to distinguish between multiple contaminants at low ppm to low ppb levels. Secondly, as a strategy to decarbonize the natural gas grid, there are proposals to blend hydrogen with natural gas. This blending will affect transport applications (pipeline infrastructure), stationary combustion systems (turbines), and consumer and commercial appliances. In the short-term, hydrogen levels up to 20% are proposed. Variations in the hydrogen level can have dramatic impact on the combustion process and on the potential response of safety sensors. These mixtures may be regulated so that the concentration at a delivery point must be monitored with high precision. However, routine maintenance may introduce background gases such as ambient air (with water) or maintenance gases (introduced with welding processes or adhesive outgassing.) Therefore, the detection methodology must be robust enough to recover or respond to various contaminants. Several reviews can be found in literature addressing sensing and detection technologies, including their limitations and applications. However, for most applications, limitations can be alleviated by combining various detection techniques either through system integration or implementation of machine learning methods (artificial intelligence). In this presentation, we will discuss several applications, highlight their current approach for hydrogen detection, and suggest detection strategies to supplement their limitations.

ENERGY STORAGE,HYDROGEN

The NREL Sensor Laboratory Detection of Hydrogen Emissions

The development of a functional hydrogen detection system is a multifaceted process that integrates hardware, deployments strategies, and analytics which can be supported by the NREL Sensor Laboratory: 1. Support of the design, validation and optimization of sensing prototypes; 2. Guide optimized sensing element development, including control electronics; 3. Laboratory testing to validate/optimize metrological performance (measurement range, detection limit, etc.); 4. Provide test sites for field deployments representative of real-world scenarios with controlled hydrogen releases; 5. Develop sensor placement and operation guidance; 6. Provide guidance on electronics to accommodate facility integration; 7. Electrical safety designs to allow for operation within restricted zones; 8. Integration into facility monitoring and control systems; 9. Guide incorporation of cyber security elements to protect facilities from malicious attacks; 10. Modeling and application of advanced analytics to detect and quantify emissions; 11. Higher Order dispersion models to guide sensor placement for reliable detection; 12. Advanced analytics for improved metrological performances, and to inform inverse modeling; 13. Market support and commercialization (national and international markets); 14. Commercial deployments in H2@SCALE markets (e.g., HUBs and other large-scale hydrogen markets); and 15. Leverage off international collaborations/partnerships (e.g., NREL is on the advisory board for the European initiative "pre-Normative Research on Hydrogen Releases Assessment"-NHyRA).

08 HYDROGEN

The NREL Sensor Laboratory: Hydrogen Leak Detection for Large Scale Deployments: Preprint

The NREL Hydrogen Sensor Laboratory was commissioned in 2010 as a resource for sensor developers, end-users, and regulatory agencies within the national and international hydrogen community. The Laboratory continues to provide as its core capability the unbiased verification of hydrogen sensor performance to assure sensor availability and their proper use. However, the mission and strategy of the NREL Sensor Laboratory has evolved to meet the needs of the growing hydrogen market. The Sensor Laboratory program has expanded to support research in conventional and alternative detection methods as hydrogen use expands to large-scale markets as envisioned by the DOE National Clean Hydrogen Strategy and Roadmap. Current research encompasses advanced methods of hydrogen leak detection including stand-off and wide area monitoring approaches for large scale and distributed applications. In addition to safety applications, low-level detection strategies to support the potential environmental impacts of hydrogen and hydrogen product losses along the value chain are being explored. Many of these applications utilize detection strategies that supplement and may supplant the use of traditional point sensors. The latest results of the hydrogen detection strategy research at NREL will be presented.

detection

Detection and Quantitation of Hydrogen Emissions Role and Status of Detection Technology

Hydrogen is a critical strategy to decarbonize energy and manufacturing industries. Hydrogen is nontoxic and can be handled safely, but potential for secondary greenhouse impacts. Hydrogen releases arise from a variety of mechanisms (process, design features, "leaks") that contribute to total hydrogen releases. Detection methodologies will be critical to detect and quantify hydrogen emissions. Detection is to be integrated with advanced analytics (AI) and behavior modelling to effectively identify, quantify, and source locate hydrogen releases. Modelling of emissions will contribute to facility safety and reliability. DOE is committed to develop the tools to model and mitigate the impact of hydrogen releases which include: Support modeling to elucidate released hydrogen degradation; Support the development of tools for emissions quantitation; and Support engineering advancements to minimize hydrogen losses along the value chain (including process, design features, and leaks).

detection

Real-Time Detection of Hydrogen and Ammonia Isotopologues for Impurity Removal and Recovery of Tritium

To accommodate gas measurements for impurity removal and recovery of tritium, a silver-coated optical or waveguide is employed for collecting Raman scattered signals to determine relative hydrogen and ammonia isotopologue populations in real time. The data and results presented here demonstrate an analytical methodology for the analysis of four ammonia and three hydrogen isotopologues in a hydrogen–deuterium exchange reaction by gas phase Raman spectroscopy. Standard chemometric modeling techniques effectively unravel the signatures of the isotopologues involved observed here; however, a sophisticated quantum chemical approach supports the spectral assignments. An interpretation of the data presented here can emphasize the practicality and reliability of the gaseous monitoring system in complex chemical environments for the hydrogen fuel economy as well as the more distant energy source from a facility that handles tritium. There are still considerable concerns about the measurement of tritium in isotope separation and radiological impurities from gas processing. A common impurity in gas processing is ammonia, which can form readily in the presence of nitrogen and tritium. Substituted ammonia (NQ 3 ), where Q = H, D, or T, is traditionally removed through getters or diffusers along with other non-hydrogen contaminants. A preferable analytical approach is noninvasive and can be deployed for real-time process evaluation in radiological environments.

Ammonia

Solid-State Mixed-Potential Electrochemical Sensors for Natural Gas Leak Detection and Quality Control (Final Technical Report)

Mitigation of methane emissions are a critical factor to limiting the impact of the natural gas industry on global climate change. Throughout the period of 2020-2024, the University of New Mexico and its commercialization partner and subcontractor, SensorComm Technologies, Inc. (SCT), have worked together to develop a low-cost Artificial Intelligence (AI)-driven Internet of Things (IoT)-based multi-gas sensor platform for methane emissions detection. In the final year of the project, we extended this work to include hydrogen detection in support of a transition to a hydrogen economy where hydrogen could be transported through existing natural gas infrastructure. Mixed potential electrochemical sensors were first prototyped by ceramic additive manufacturing and then transitioned to conventional ceramic manufacturing tape casting and screen-printing technologies in preparation for mass production. Demonstrated limits of detection of 5 ppm of methane in natural gas and 1 ppm of hydrogen were measured. These limits of detection are among the lowest of solid-state electrochemical sensors that have been reported in the literature or available in the industry. Machine learning algorithms were developed to identify natural gas mixtures with > 98% accuracy level and quantify methane concentrations at 97% accuracy. The presence of hydrogen could also be identified, and its concentration quantified at these accuracy levels. These algorithms were optimized for running on portable computing hardware which enabled > 1 Hz processing rates. A portable packaged IoT system was integrated with the electrochemical sensor in collaboration with SCT. The package consists of readout electronics with < 1 mV resolution, sensor temperature control, and data transmission over cellular wireless and/or Wi-Fi networks. Field testing was performed in two rounds at Colorado State University’s Methane Emissions Technology Evaluation Center (CSU METEC). The first round of testing demonstrated successful measurements of methane from an underground natural gas leak of 20 standard liters per minute (SLPM), which agreed with previously published literature using more sophisticated and expensive analytical equipment. The second round of testing showed that an above ground leak of 2 SLPM of hydrogen could be detected at 32 ft. This project has resulted in six published peer reviewed journal articles, over ten presentations at professional conferences, and one full patent application filed in 2023. Future work on this project includes increased sensitivity, higher production yields, and applications in the hydrogen safety and flare emissions monitoring spaces.

03 NATURAL GAS

Proton Conducting Neuromorphic Materials and Devices

Neuromorphic computing and artificial intelligence hardware generally aims to emulate features found in biological neural circuit components and to enable the development of energy-efficient machines. In the biological brain, ionic currents and temporal concentration gradients control information flow and storage. It is therefore of interest to examine materials and devices for neuromorphic computing wherein ionic and electronic currents can propagate. Protons being mobile under an external electric field offers a compelling avenue for facilitating biological functionalities in artificial synapses and neurons. In this review, we first highlight the interesting biological analog of protons as neurotransmitters in various animals. We then discuss the experimental approaches and mechanisms of proton doping in various classes of inorganic and organic proton-conducting materials for the advancement of neuromorphic architectures. Since hydrogen is among the lightest of elements, characterization in a solid matrix requires advanced techniques. We review powerful synchrotron-based spectroscopic techniques for characterizing hydrogen doping in various materials as well as complementary scattering techniques to detect hydrogen. First-principles calculations are then discussed as they help provide an understanding of proton migration and electronic structure modification. Outstanding scientific challenges to further our understanding of proton doping and its use in emerging neuromorphic electronics are pointed out.

36 MATERIALS SCIENCE

Analysis of Off-Gas Streams from Small- and Large-Scale Sparging Salt Vessels using Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is being developed as an analytical monitoring tool for molten salt reactor (MSR) systems. A mobile LIBS platform was configured on a small-scale salt vessel (~100 g of salt) and then transported 0.6 km to successfully monitor an engineering-scale pumped salt loop (~100 kg of salt). Several studies on monitoring salt aerosols, hydrogen isotopes, and noble gases were performed on the small-scale system. All these studies were then implemented for monitoring various tests on the engineering-scale loop. Aerosolized salts from both the storage tank and pump bowl were monitored using LIBS to assess bulk salt analyte ratios (Mg, Na, K) and evaluate impurities (H, O, Ca). In addition to monitoring salt aerosols, LIBS was used in tandem with a residual gas analyzer (RGA) and a Raman spectroscopy system to detect hydrogen isotopes as they were sparged through and subsequently depleted from the loop storage tank. Lastly, a similar test with noble gases (100 ppm Kr, 1000 ppm Xe) was performed, in which LIBS demonstrated a faster response than the RGA used in-line. The tests and results are summarized in this report with detailed publications to follow. Key takeaways are listed in the conclusion of the report.

22 GENERAL STUDIES OF NUCLEAR REACTORS

Femtosecond two-photon-resonant parametric four-wave mixing detection of atomic hydrogen

Here, we demonstrate an ultrafast parametric four-wave mixing method for the collisional-quenching-free detection of atomic hydrogen. Two photons of 243 nm light resonantly excite the n = 1 to n = 2 transition of atomic hydrogen, and a third probe photon scatters from the electronic coherence to generate the parametric emission of a degenerate signal photon. Laser-induced photofragmentation fluorescence from water, also excited with the same 243 nm pulses, is used as a convenient method to visualize beam overlap in space and time. The femtosecond time resolution enables the suppression of unwanted nonresonant contributions to the signal and separation from resonant mixing in water molecules because of the significantly different coherence lifetimes. A folded BOXCARS phase-matching configuration yields a spatially isolated, laser-like, signal beam, amenable to measurements in highly luminous backgrounds. Measurements in an H 2 /CH 4 /air flame demonstrate quantitative agreement with simulated H-atom concentration profiles. A coherence decay time constant of 42 ps is recorded in the atmospheric pressure flame.

Kliewer, Christopher Jesse [Sandia National Labora

Hydrogen Leak Modeling for Development of Smart Distributed Monitoring Under Unintended Releases

Hydrogen is a versatile and clean energy carrier that can be produced from various renewable sources such as wind, solar, and hydropower. Hydrogen has the potential to play a crucial role in decarbonizing industrial processes that are currently reliant on fossil fuels and provide long-duration and/or seasonal energy storage to enable electricity decarbonization. Hydrogen can also be used as a fuel for fuel cell vehicles, providing a zero-emission alternative to traditional internal combustion engines. DOE launched the Hydrogen Energy Earthshot (Hydrogen Shot) in June 2021 to reduce the cost of clean hydrogen by 80% to $1 per 1 kilogram in 1 decade ("1 1 1"). While promising, Hydrogen is highly-flammable, and in the presence of oxygen, it can form explosive mixtures. . Therefore, understanding leak scenarios is essential to evaluate and mitigate the safety risks associated with potential hydrogen leaks. An increased understanding of leak behavior, and having tools to model leaks, can help assess how hydrogen would disperse in different environments, influencing emergency response plans and safety measures, and identify potential issues with materials and design systems that can withstand the challenges posed by hydrogen. Recently, researchers have attempted to study hydrogen leaks for development of risk management strategies. However, the focus has been on closed or semi-closed spaces like storage rooms, vehicles, garages, and fueling stations - all promising locations for future hydrogen infrastructure. In this presentation, the modeling environment extends the span of research further by modeling hydrogen leak in an outdoor, open space. We will present the key challenges with modeling hydrogen leaks in an uncontrollable environment, how they were handled, and how modeling results informed sensor selection and placement. A Hydrogen research facility at the National Renewable Energy Laboratory (NREL) was used as a case study to model hydrogen leaks. In the future, Hydrogen wide area detection methodologies will be developed and tested at this site to monitor for unintended and operational hydrogen releases. The data generated from modeling will be used to develop a predictive model to detect hydrogen leak location based on concentration measured by sensors in this open space. Furthermore, the facility was also chosen because controlled hydrogen releases can be performed. A computational fluid dynamics (CFD) based modeling approach was taken to model hydrogen leak. The full-scale hydrogen facility was modeled with a large ambient domain. The electrolyzer at the facility can produce a controlled release rate of 27 kg-H2/hr. Site-specific atmospheric and weather condition data such as wind direction, wind speed at various altitudes, and temperature were used as inputs to the model. To capture the variability of weather conditions, a subset of the weather conditions experienced during daytime hours without precipitation over the course of three months was generated; using established data clustering techniques, a total of 100 condition sets were chosen. The results show statistical distributions and ranges of hydrogen concentrations at locations throughout the domain. These distributions are compared to experimental data from a constant mass flow, controlled hydrogen release at the facility. The stochastic wind conditions of the release make direct validation difficult, therefore, statistical comparison approaches were used. Wind conditions are found to significantly impact the release behavior, including direction and concentration. Sensor selection and placement is proposed for the facility and is now based on release behavior predicted for the facility given its weather patterns; this is much more informed than without the modeling results. The methodology and analysis procedure can be translated to other facilities using modified geometries and site-specific weather conditions. Hydrogen holds great promise as a renewable energy fuel, but ensuring safety in its production, storage, and use is paramount. Studying potential leak scenarios in an open space will help develop sensors to detect hydrogen on a large spectrum of concentration and eventually build a smart distributed monitoring system.

CFD

Hydrogen Analysis by Gas Chromatography–Mass Spectrometry

The detection of hydrogen in complex gas mixtures is essential for many applications. Conventional approaches such as gas chromatography (GC) with thermal conductivity detection (TCD) and residual gas analyzers (RGAs) face significant limitations: TCD exhibits poor response when helium is used as a carrier gas, whereas RGAs lack chromatographic separation, preventing reliable quantification of hydrogen because of interference from other species. Traditional GC methods rely on dual-column configurations with packed or molecular-sieve porous layer open tubular (PLOT) columns to separate hydrogen from O2, N2, CO, CO2, CH4, and other hydrocarbons, increasing system complexity and limiting compatibility with mass spectrometry (MS) detection. In this work, we developed and validated a robust GC–MS method capable of directly detecting and quantifying hydrogen using electron ionization (EI) without dopants, reagent gases, or ion–molecule reaction schemes. By integrating a modified EI source and a cryogenically cooled single capillary column configuration, we achieved baseline separation of hydrogen from all major permanent gases and hydrocarbons in a refinery gas mixture using helium as the carrier gas. The method demonstrated excellent linearity, high sensitivity, and exceptional reproducibility. Adjustable sample-loop volumes and split ratios enabled optimization of peak shape and signal-to-noise performance for trace-level and percent-level hydrogen concentrations. Beyond hydrogen quantitation, the method provides simultaneous compositional profiling of other gases in a mixture in a single run, making it valuable for a wide range of tasks.

Lobodin, Vlad [ORNL]