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At least 325 records · Page 18

Plasma-Assisted Pre-Chamber Ignition System for Highly Dilute Stoichiometric Heavy-Duty Natural Gas Engines (Final Technical Report)

This project explored advanced ignition technologies to significantly enhance efficiency and reduce operating costs for heavy-duty natural gas engines operating at stoichiometric conditions, while meeting ultra-low NOx emission standards. The main goal was to develop and validate a plasma-assisted pre-chamber ignition system that could deliver at least a 2% increase in brake thermal efficiency (BTE) and a 4% decrease in total cost of ownership (TCO) compared to a typical multi-cylinder engine with three-way catalyst aftertreatment, ensuring compatibility with the expected 2027 EPA/CARB regulations. In the first half of the project, the research team concentrated on developing and testing plasma-assisted pre-chamber ignition using nanosecond pulsed discharges. Extensive experiments were conducted in an optically accessible rapid-compression and expansion machine, a constant-volume chamber, and an optical single-cylinder engine. Experiments were coupled with CFD simulations. The work produced unique insights into pre-chamber flame formation, jet ignition, dilution effects, and flame quenching at pressures, temperatures, and dilution levels relevant to engines. Although plasma-assisted ignition showed promise in controlled lab settings, the research also identified fundamental and practical challenges when applying this technology to real engine conditions. Midway through the project, a crucial pivot was made, guided by three key findings. First, the power electronics required for nanosecond plasma discharges were found to be too costly for commercial use, undermining the project’s cost-of-ownership goals. Second, nanosecond plasma ignition was highly sensitive to turbulent flow in the pre-chamber, resulting in lower ignition reliability than traditional spark under engine-like conditions. Third, achieving a truly diffuse low-temperature plasma at high pressures near top dead center was not possible, reducing the anticipated chemical enhancement benefits. These results collectively suggested that continuing with plasma-assisted ignition was unlikely to meet both efficiency and cost objectives. In response, the project shifted focus to a more realistic approach: enhancing traditional spark-based pre-chamber ignition with significantly less spark energy. Using insights gained earlier in the project, the team redesigned the pre-chamber to maintain high dilution tolerance and quick combustion, even with lower ignition energy. Testing confirmed that with optimized pre-chamber design and combustion timing, a lower-energy spark could reliably ignite highly diluted stoichiometric mixtures, reduce burn time, and boost thermal efficiency. Final engine testing and techno-economic analysis verified that this revised approach successfully achieved the project goals. The optimized pre-chamber ignition system provided over a 2% increase in calculated brake thermal efficiency compared to the baseline engine. Notably, the lower ignition energy and simplified hardware reduced component stress, extended maintenance intervals, and lowered the total cost of ownership. When used with stoichiometric operation and traditional three-way aftertreatment, the system remained compatible with near-zero NOx emissions targets without increasing cost or complexity in the emissions control system. In summary, although the project deviated from its initial plasma-assisted ignition idea, the work produced a more practical and commercially viable solution. The results show that precisely optimized, low-energy pre-chamber spark ignition can significantly improve efficiency and reduce overall ownership costs for heavy-duty natural gas engines. This directly aligns with DOE goals for cleaner, more efficient, and cost-effective transportation technologies.

03 NATURAL GAS↗

Evaluating Class 6 Delivery Truck Fuel Economy and Emissions Using Vehicle System Simulations for Conventional and Hybrid Powertrains and Co-Optima Fuel Blends

The US Department of Energy’s Co-Optimization of Engine and Fuels Initiative (Co-Optima) investigated how unique properties of bio-blendstocks considered within Co-Optima help address emissions challenges with mixing controlled compression ignition (i.e., conventional diesel combustion) and enable advanced compression ignition modes suitable for implementation in a diesel engine. Additionally, the potential synergies of these Co-Optima technologies in hybrid vehicle applications in the medium- and heavy-duty sector was also investigated. In this work, vehicles system were simulated using the Autonomie software tool for quantifying the benefits of Co-Optima engine technologies for medium-duty trucks. A Class 6 delivery truck with a 6.7 L diesel engine was used for simulations over representative real-world and certification drive cycles with four different powertrains to investigate fuel economy, criteria emissions, and performance. Comparisons were made between ultralow-sulfur diesel and a blend of 25% hexyl hexanoate with diesel. Model validation data were informed by 2019 model year Cummins ISB 6.7 L diesel engine maps and transient validation data in a pre-production hybrid configuration and a direct dyno coupled configuration with diesel fuel and a blend of 25% hexyl hexanoate with diesel.

33 ADVANCED PROPULSION SYSTEMS↗

Theoretical Analysis of Resonant Tunneling Enhanced Field Emission

In this paper, we develop an exact analytical quantum theory for field emission from surfaces with a nearby quantum well, by solving the one-dimensional time-independent Schrödinger equation. The quantum well, which may be introduced by ions, atoms, nanoparticles, etc., is simplified as a square potential well with depth H, width d, and distance to the surface L. The theory is used to analyze the effects of the quantum well (d, H, and L), the cathode properties (work function W and Fermi energy E F ), and dc field F. It is found that the quantum well can lead to resonant tunneling enhanced field emission up to several orders of magnitude larger than that from bare cathode surfaces. In the meantime, the electron-emission-energy spectrum is significantly narrowed. The strong enhancement region is bounded by the conditions eFL + H ≥ W + C and eFL ≤ W, with e being the elementary charge (positive) and C a constant dependent on dc field F. It is also found that the linear shift of resonance peaks in the electron-emission-energy spectrum with dc field F follows ε p =ε p⁢0 –e⁢FL, with ε p⁢0 being approximately the eigenenergies for electrons confined in a square potential well without a dc field. Finally, the theory provides insights for the design of high-efficiency field emitters, which can produce a high current and highly collimated electron beams.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Fluorescence Enhancement in the Solid State by Isolating Perylene Fluorophores in Metal–Organic Frameworks

Polycyclic aromatic hydrocarbons such as perylene, pyrene, and their derivatives are highly emissive fluorophores in solution. Furthermore, the practical applications of these materials in the field of molecular electronic and light emitting devices are often hindered by self-quenching effects due to the formation of non-fluorescent aggregates in concentrated solutions or in the solid state. Herein, we demonstrate that aggregation caused quenching of perylenes can be minimalized by molecular incorporation into metalorganic frameworks (MOFs). This study utilized a stable Zr 6 cluster-based MOF, UiO-67, as a matrix. Linear linkers containing the photo-responsive moieties were designed and incorporated into the parent UiO-67 scaffold through the partially replacement of the non-fluorescent linkers of a similar length, forming mixed-linker MOFs. Here, the average distance between perylene moieties was tuned by changing the linker ratios, thus controlling the fluorescence intensity, emission wavelength, and quantum yield. Molecular modeling was further adopted to correlate the number of isolated perylene linkers within the framework to the ratio between the two linkers, therefore rationalizing the change in the observed fluorescent properties. Taking advantage of the tunable fluorescence, inherent porosity, and high chemical stability of this MOF platform, it was applied as a fluorescent sensor for oxygen detection in the gas phase, a model reaction, showing fast response and good recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Global Building Decarbonization Trends and Strategies

It is evident from extreme weather patterns that climate change is impacting the whole world. The consequences in the form of unpredicted severe weather conditions, hurricanes, floods, and wildfires have been disrupting national economies and affecting lives across the globe. As the global economy is recovering from the COVID-19 pandemic, the temporary drop in greenhouse gas (GHG) emissions mainly caused due to travel bans and economic slowdowns is no longer the case and, moving forward, controlling the increase in GHG emissions has emerged as a global challenge. The impact of climate change has enabled an acknowledgement of the challenge and this coincided with the rapid development of clean energy technologies for buildings, transportation, and industrial sectors, while ensuring a significant reduction in costs for their wide implementation.

54 ENVIRONMENTAL SCIENCES↗

Investigating realistic anode off-gas combustion in SOFC/ICE hybrid systems: mini review and experimental evaluation

Solid oxide fuel cells (SOFCs) have been deployed in hybrid decentralized energy systems, in which they are directly coupled to internal combustion engines (ICEs). Prior research indicated that the anode tailgas exiting the SOFC stack should be additionally exploited due to its high energy value, with typical ICE operation favoring hybridization due to matching thermodynamic conditions during operation. Consequently, extensive research has been performed, in which engines are positioned downstream the SOFC subsystem, operating in several modes of combustion, with the most prevalent being homogeneous compression ignition (HCCI) and spark ignition (SI). Experiments were performed in a 3-cylinder ICE operating in the latter modus operandi, where the anode tailgas was assimilated by mixing syngas (H 2 : 33.9%, CO: 15.6%, CO 2 : 50.5%) with three different water vapor flowrates in the engine’s intake. While increased vapor content significantly undermined engine performance, brake thermal efficiency (BTE) surpassed 34% in the best case scenario, which outperformed the majority of engines operating under similar operating conditions, as determined from the conducted literature review. Nevertheless, the best performing application was identified operating under HCCI, in which diesel reformates assimilating SOFC anode tailgas, fueled a heavy duty ICE (17:1), and gross indicated thermal efficiency ([Formula: see text]) of 48.8% was achieved, with the same engine exhibiting identical performance when operating in reactivity-controlled compression ignition (RCCI). Overall, emissions in terms of NO x and CO were minimal, especially in SI engines, while unburned hydrocarbons (UHC) were non-existent due to the absence of hydrocarbons in the assessed reformates.

Engineering↗

Strategy for Ultranarrow Light Down-Conversion for Displays Based on Bicolor-Emitting 2D Colloidal Heterostructures

The demand for ultranarrow spectral emission below 10 nm is critical for next-generation displays. Although current colloidal nanocrystals are successful in light down-conversion applications, they fall short in matching the stringent color purity requirements set by standards like Rec. 2020. Achieving such narrow linewidths through material engineering alone remains elusive, necessitating innovative light management strategies that avoid optical losses and maintain device efficiency. Here, in this work, we present a novel 2D colloidal heterostructure design, combining a CdSe core nanoplatelet, a CdS crown, and a CdZnS shell, to achieve bright bicolor emission in the solid state (green/red) emission with tunable intensity ratios controlled by excitation power (either optical or electrical). Integration of these nanoplatelets into a dielectric cavity further narrows the emission linewidth to sub-2 nm while enhancing the photoluminescence intensity by up to 200 times, meeting the Rec. 2020 color purity targets. This approach paves the way for a strategy avoiding complex laser-based solutions.

2D nanocrystals↗

Enhancing and Extinguishing the Different Emission Features of 2D (EA(1-)(x)FA(x))(4)Pb3Br10 Perovskite Films

2D hybrid perovskites are attractive for optoelectronic devices. In thin films, the color of optical emission and the texture of crystalline domains are often difficult to control. Here, a method for extinguishing or enhancing different emission features is demonstrated for the family of 2D Ruddlesden-Popper perovskites (EA(1-)(x)FA(x))(4)Pb3Br10 (EA = ethylammonium, FA = formamidinium). When grown from aqueous hydrobromic acid, crystals of (EA(1-)(x)FA(x))(4)Pb3Br10 retain all the emission features of their parent compound, (EA)(4)Pb3Br10. Surprisingly, when grown from dimethylformamide (DMF), an emission feature, likely self-trapped exciton (STE), near 2.7 eV is missing. Extinction of this feature is correlated with DMF being incorporated between the 2D Pb-Br sheets, forming (EA(1-)(x)FA(x))(4)Pb3Br10 center dot(DMF)(y). Without FA, films grown from DMF form (EA)(4)Pb3Br10, retain little solvent, and have strong emission near 2.7 eV. Slowing the kinetics of film growth strengthens a different emission feature, likely a different type of STE, which is much broader and present in all compositions. Films of (EA(1-)(x)FA(x))(4)Pb3Br10 center dot(DMF)(y) have large, micron-sized domains and homogeneous orientation of the semiconducting sheets, resulting in low electronic disorder near the absorption edge. The ability to selectively strengthen or extinguish different emission features in films of (EA(1-)(x)FA(x))(4)Pb3Br10 center dot(DMF)(y) reveals a pathway to tune the emission color in these compounds.

2D halide perovskites↗

Pathways to Carbon Neutrality 2050 in Malaysia and Kuala Lumpur

Malaysia has recently set an ambitious target of achieving carbon neutrality as early as 2050. To accomplish this, the country will need to strategically reduce its emissions across all sectors. In 2020, Malaysia emitted approximately 368 MtCO2e, with the largest sources of emissions including electricity (36% of total emissions), transportation (17%), and industry (15%)1. We find that the greatest reductions in emissions can therefore come from decarbonizing power generation and electrifying end-use sectors. Digitalization, smart technologies, and improved energy efficiency will significantly reduce economy-wide energy consumption. By leveraging efficient technologies, both Malaysia and Kuala Lumpur can address the challenges posed by rapid urbanization and climate change. Digitalization is a broad category that includes a variety of measures; for example, the wide adoption of high-efficiency appliances and lighting or improved building energy codes in the buildings sector. Similarly, technological improvements can advance industrial energy efficiency, and for transportation, smart technologies cover a shift from private to public transportation and the greater use of electric vehicles. While renewable energy (RE) will play a crucial role in decarbonization, achieving carbon neutrality in certain sectors will be difficult without emerging technologies like carbon capture and storage (CCS) and innovative fuel sources such as hydrogen. In order for Malaysia to rely on CCS as a mitigation option, early investment and incentives to the private sector will be critical. This holds for the use of hydrogen as well: investing in the necessary technology, infrastructure, and human capital will allow Malaysia to position itself as an innovator in the region and leverage these advanced technologies as a key part of its climate strategy. Another possible carbon removal option other than CCS would be a land-use sink; however, given that Malaysia is still developing and may deforest in the near-term, this report does not focus on the mitigation potential of land-use change. With its innovative and bold climate plans, Kuala Lumpur is primed to be a leader in regional climate change efforts. Kuala Lumpur is also engaged in several international collaborations to ensure sustainable city development such as the C40 network and the ASEAN Smart Cities Partnership. As such, the city will play a critical role in contributing to Malaysia’s overall climate goals and as a policy trendsetter through ambitious, scalable plans. One key factor in these emissions reductions is that Kuala Lumpur has full control over its building guidelines, allowing for ambitious policies resulting in significant emissions reductions. However, in other sectors, Kuala Lumpur has less direct control over regulations; for example, power generation and integration of RE are largely in the hands of the Malaysian government. With limited and primarily light industry, Kuala Lumpur’s contributions to emissions reductions here are curbed. And, while Kuala Lumpur has control over local transportation policies like increasing access to and quality of public transportation, broad shifts in transportation will stem from national-level policies. As such, multi-level governance is an integral component of Malaysia’s climate strategy and coordination between local and national governments will be essential in reducing emissions and achieving other climate goals. This report addresses these and other key challenges and opportunities Malaysia faces on the road to carbon neutrality.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Is infrared-collinear safe information all you need for jet classification?

Machine learning-based jet classifiers are able to achieve impressive tagging performance in a variety of applications in high-energy and nuclear physics. However, it remains unclear in many cases which aspects of jets give rise to this discriminating power, and whether jet observables that are tractable in perturbative QCD such as those obeying infrared-collinear (IRC) safety serve as sufficient inputs. In this article, we introduce a new classifier, Jet Flow Networks (JFNs), in an effort to address the question of whether IRC unsafe information provides additional discriminating power in jet classification. JFNs are permutation-invariant neural networks (deep sets) that take as input the kinematic information of reconstructed subjets. The subjet radius and a cut on the subjet’s transverse momenta serve as tunable hyperparameters enabling a controllable sensitivity to soft emissions and nonperturbative effects. We demonstrate the performance of JFNs for quark vs. gluon and Z vs. QCD jet tagging. For small subjet radii and transverse momentum cuts, the performance of JFNs is equivalent to the IRC-unsafe Particle Flow Networks (PFNs), demonstrating that infrared-collinear unsafe information is not necessary to achieve strong discrimination for both cases. As the subjet radius is increased, the performance of the JFNs remains essentially unchanged until physical thresholds that we identify are crossed. For relatively large subjet radii, we show that the JFNs may offer an increased model independence with a modest tradeoff in performance compared to classifiers that use the full particle information of the jet. These results shed new light on how machines learn patterns in high-energy physics data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Effect of nitric oxide and exhaust gases on gasoline surrogate autoignition: iso-octane experiments and modeling

Exhaust gas recirculation (EGR) is widely used in advanced internal combustion engines to reduce engine emissions as well as control combustion phasing. Among various species present in EGR gases, CO 2 and H 2 O are two major components that can thermally and chemically affect fuel autoignition. It is of fundamental interest to isolate the thermal and chemical effects of CO 2 and H 2 O on fuel autoignition, especially as such an effort has not been reported in the literature. Moreover, nitric oxide (NO) is known to exhibit strong chemical effects on fuel autoignition, which in turn affects engine combustion phasing. The effects of ultra-low NO addition (< 100 ppm) on fuel autoignition at low temperatures are also not well understood. Recognizing these problems, autoignition experiments of iso-octane (a major gasoline surrogate component) in air are performed in this study using a rapid compression machine at varying compressed pressures, equivalence ratios, dilution levels with an EGR gas analogue (consisting of CO 2 , H 2 O, O 2 , and N 2 ) and N 2 only, and varying amounts of NO addition. Furthermore, the thermal and chemical effects of the EGR gas analogue are isolated and evaluated by comparing the ignition delay time datasets of EGR and N2-only diluted cases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transient simulation of biomass combustion in a circulating fluidized bed riser

Interest in circulating fluidized bed (CFB) boilers as a power generation technology has sky-rocketed in recent years because of several advantages this technology offers over conventional boilers, such as increased gas-solid mixing, which results in higher combustion efficiency and the ability to use lower rank fuels. CFB combustors are operated at lower temperatures than conventional thermal power generation combustors, thus reducing NO x emissions, while SO 2 emissions can be conveniently controlled through the addition of Ca-based sulfur sorbents within the combustor. Herin this paper summarizes the modeling effort on a 50 kW th CFB combustor designed, built, and operated at CanmetENERGY in Ottawa, Canada. The numerical model employs the multiphase particle-in-cell (PIC) approach in the open-source Multiphase Flow with Interphase eXchanges (MFiX) Software Suite. The MFiX-PIC model parameters for the simulation are tuned against cold-flow experiments from CanmetENERGY using olivine sand as the inert bed material. It is shown that for the relatively coarse fluid meshes and large parcel sizes necessitated by the scale of the simulation, filter size dependent corrections to the drag law must be incorporated to ensure accuracy of the simulation results. The validated cold flow model is extended to simulate reacting flow with torrefied hardwood as the feedstock and to validate the combustion reaction scheme. The species concentrations at the riser outlet are compared against CanmetENERGY’s experiments and show satisfactory agreement. The simulations demonstrate the ability of MFiX-PIC to accurately capture both the physics and chemistry of a CFB combustor at bench scales, which can be further extended to pilot- and industrial-scale systems.

09 BIOMASS FUELS↗

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

A novel metal–organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE–Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV–Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal X-ray diffraction (SCXRD), scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Finally, Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.

36 MATERIALS SCIENCE↗

Programmable Photoluminescence via Intrinsic and DNA-Fluorophore Association in a Mixed Cluster Heterometallic MOF

In this report a rapid and facile design strategy to create a highly complex optical tag with programmable, multimodal photoluminescent properties is described. This was achieved via intrinsic and DNA-fluorophore hidden signatures. As a first covert feature of the tag, an intricate novel heterometallic near-infrared (NIR)-emitting mesoporous metal–organic framework (MOF) was designed and synthesized. The material is constructed from two chemically distinct, homometallic hexanuclear clusters based on Nd and Yb. Uniquely, the Nd-based cluster is observed here for the first time in a MOF and consists of two staggered Nd μ3-oxo trimers. To generate controlled, multimodal, and tailorable emission with difficult to counterfeit features, the NIR-emissive MOF was post-synthetically modified via a fluorescent DNA oligo labeling design strategy. The surface attachment of several distinct fluorophores, including the simultaneous attachment of up to three distinct fluorescently labeled oligos was achieved, with excitation and emission properties across the visible spectrum (480-800 nm). The DNA inclusion as a secondary covert element in the tag was demonstrated via the detection of SYBR Gold dye association. Importantly, the approach implemented here serves as a rapid and tailorable way to encrypt distinct information in a facile and modular fashion and provides an innovative technology in the quest toward complex optical tags.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydroporphyrin-Doped Near-Infrared-Emitting Polymer Dots for Cellular Fluorescence Imaging

We report Near-infrared (NIR) fluorescent semiconductor polymer dots (Pdots) have shown great potential for fluorescence imaging due to their exceptional chemical and photophysical properties. This paper describes the synthesis of NIR emitting Pdots with great control and tunability of emission peak wavelength. The Pdots were prepared by doping poly [(9,9-dioctylfluorenyl-2,7-diyl)-altco-(1,4-benzo-(2,1’,3)-thiadiazole)] (PFBT), a semiconducting polymer commonly used as a host polymer in luminescent Pdots, with a series of chlorins and bacteriochlorins with varying functional groups. Chlorins and bacteriochlorins are ideal dopants due to their high hydrophobicity, which precludes their use as molecular probes in aqueous biological media but on the other hand prevents their leakage when doped into Pdots. Additionally, chlorins and bacteriochlorins have narrow deep-red to NIR emission bands and the wide array of synthetic modifications available for modifying their molecular structure enables tuning their emission predictably and systematically. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements show the chlorin and bacteriochlorin-doped Pdots to be nearly spherical with an average diameter of 46±12 nm. Efficient energy transfer between PFBT and the doped chlorins or bacteriochlorins decreases the PFBT donor emission to near baseline level and increases the emission of the doped dyes that serve as acceptors. The chlorin and bacteriochlorindoped Pdots show narrow emission bands ranging from 640 nm to 820 nm depending on the doped dye. The paper demonstrates the utility of the systematic chlorin and bacteriochlorin synthesis approach by preparing Pdots of varying emission peak wavelength, utilizing them to visualize multiple targets using wide field fluorescence microscopy, binding them to secondary antibodies, and determining the binding of secondary antibody-conjugated Pdots to primary antibody-labeled receptors in plant cells. Additionally, the chlorin and bacteriochlorin doped Pdots show a blinking behavior that could enable their use in super resolution imaging methods like STORM.

13C-NMR↗

Molecular Insights into Geochemical Reactions of Iron-Bearing Minerals: Implications for Hydrogen Geo-Storage

Here, this study investigates the reaction of hydrogen (H 2 ) with pyrite (FeS 2 ), focusing on how temperature and the presence of water influence the reaction pathways and kinetics. Utilizing computational molecular simulations and kinetic analyses, we explore the impact of these factors on the formation of hydrogen sulfide (H 2 S) and related species. First, grand canonical Monte Carlo/molecular dynamics (GCMC/MD) simulations reveal that physical H 2 adsorption occurs in distinct layers on the pyrite surface. In addition, increased temperatures reduce the absolute adsorption capacities. Reactive MD simulations demonstrate that H 2 interacts differently with pyrite under varying conditions. At 298 K, H 2 reacts with pyrite to form HS – , leading to the formation of HS – through covalent bonding with sulfur of pyrite. However, no H 2 S is produced at this temperature, suggesting that a kinetic barrier (i.e., activation energy) may prevent this reaction. At higher temperatures, H 2 S production significantly increases. The presence of water introduces additional complexity to the reaction mechanism. Unlike dry conditions, water enhances H 2 S generation, even at low temperatures. Water also facilitates the formation of additional products, such as SOH, indicating a more intricate chemical environment on the pyrite surface. Our findings identify the association of HS – ions to form H 2 S as the rate-limiting step, with temperature influencing this process. This finding suggests that while the presence of water can create a more dynamic reaction environment, the overall mechanisms leading to H 2 S formation remain consistent. These outcomes suggest the need for developing targeted strategies to manage and control H 2 S emissions within the context of underground hydrogen storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning colour centres at a twisted hexagonal boron nitride interface

The colour centre platform holds promise for quantum technologies, and hexagonal boron nitride has attracted attention due to the high brightness and stability, optically addressable spin states and wide wavelength coverage discovered in its emitters. However, its application is hindered by the typically random defect distribution and complex mesoscopic environment. In this study, employing cathodoluminescence, we demonstrate on-demand activation and control of colour centre emission at the twisted interface of two hexagonal boron nitride flakes. Further, we show that colour centre emission brightness can be enhanced by two orders of magnitude by tuning the twist angle. Additionally, by applying an external voltage, nearly 100% brightness modulation is achieved. Our ab initio GW and GW plus Bethe–Salpeter equation calculations suggest that the emission is correlated to nitrogen vacancies and that a twist-induced moiré potential facilitates electron–hole recombination. This mechanism is further exploited to draw nanoscale colour centre patterns using electron beams.

36 MATERIALS SCIENCE↗

Modulating charge transport via 2 MeV He + irradiation in VO 2

Vanadium dioxide (VO 2 ) is of interest for adaptive electronic applications such as neuromorphic neuristor devices and variable emissivity or tunable thermal control materials, thanks to its key property—a metal–insulator transition (MIT) at 68 °C that is accompanied by a dramatic change in electrical and optical properties. To improve performance in these roles, it is critical to develop approaches to engineer transport properties and the MIT behavior. While many documented techniques exist to modulate the MIT and film resistivities via lattice strain and chemical doping, less is known about the effects of ion irradiation on the intrinsic properties of VO 2 , despite the ability to control the spatial distribution of irradiation beams and the prevalence of high energy ion implantation in the semiconductor industry. The impact of irradiation of different acceleration energies on the responses of VO 2 is of specific interest, as charged particle energy generally impacts both the resulting defect profile and corresponding transport behavior. Here, we demonstrate that 2 MeV He ions at equivalent calculated displacements per atom, in two different types of films, can create remarkable changes to the nature of charge transport in VO 2 , especially in the low-temperature insulating phase. Simulation of resulting changes in electrical conductivity reveals that He ion irradiation offers a strategy to increase both oscillation frequency and the signal transmission. These results provide insights into the intentional design of defect populations to modulate transport for neuromorphic VO 2 devices.

Gurrola, Rebeca M. [Texas A & M Univ., College Sta↗