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At least 487 records · Page 27

Numerical Investigation of Susceptor-Catalyst Design for Ethylene Generation in Radio Frequency Based Reactors

Ethylene is the most widely produced petrochemical component in the world. Whether reactors are heated directly or indirectly via steam, manufacturers use economies of scale to overcome inherent thermodynamic inefficiencies when burning fossil fuels. While allowing large-scale operations to use alternative sources of energy and raw materials, new methods of supplying energy to chemical reactor systems can reduce the energy waste produced by conventional processes. One viable method for effectively supplying energy to reactor systems is electromagnetic (EM) induction heating. Using the properties of radio frequency (RF) waves, heterogeneous catalysts can be precisely targeted for heating inside reactors. Site-selective heating can greatly lower the energy requirements of the process by supplying heat to reaction sites while reducing needless heat transfer elsewhere. In this study, a microscale model was used to help create guidelines for susceptors and catalysts to improve ethylene production. The oxidative dehydrogenation of ethane is investigated by utilizing several catalysts and potential catalyst/susceptor combinations, with heat provided by an EM susceptor. Having the susceptors and catalyst function separately results in higher gradients in both heat and mass transfer, which drives transport through the catalyst region, while still providing adequate heating for endothermic reactions. However, using a susceptive core with a catalyst covering produces the maximum ethylene concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Dynamics Simulations of Supercritical Carbon Dioxide and Water using TraPPE and SWM4-NDP Force Fields

The increased levels of carbon dioxide (CO 2 ) emissions due to the combustion of fossil fuels and the consequential impact on global climate change have made CO 2 capture, storage, and utilization a significant area of focus for current research. In most electrochemical CO 2 applications, water is used as a proton donor due to its high availability and mobility and use as a polar solvent. Additionally, supercritical CO 2 is a promising avenue for electrochemical applications due to its unique chemical and physical properties. Consequently, understanding the interactions between water and supercritical CO 2 is of great importance for future electrochemical applications. Molecular dynamics (MD) simulation is a powerful tool that enables atomistic-resolution dynamics of molecular systems, which can complement and guide future experimental investigations. This study employed atomistic MD to study the cosolubilities, codiffusivities, and structure of supercritical CO 2 and water systems, with a polarizable water model (SWM4-NDP) and a nonpolarizable CO 2 model (TraPPE). Additionally, ab initio MD simulations were used to better understand how atomistic polarizable/nonpolarizable models compare to explicit modeling of electron densities. The polarizable water model exhibited substantial improvement in water-associated properties. In conclusion, we anticipate the development of a compatible polarizable CO 2 model to yield similar improvement, providing a pathway for realizing novel high-pressure electrochemical systems.

25 ENERGY STORAGE↗

The Role of Interface Band Alignment in Epitaxial SrTiO 3 /GaAs Heterojunctions

Recent concerns surrounding climate change and the contribution of fossil fuels to greenhouse gas (GHG) emissions have sparked interest and advancements in renewable energy sources including wind, solar, and hydroelectricity. These energy sources, often referred to as “clean energy”, generate no operational onsite GHG emissions. They also offer the potential for clean hydrogen production through water electrolysis, presenting a viable solution to create an environmentally friendly alternative energy carrier with the potential to decarbonize industrial processes reliant on hydrogen. To conduct a full life cycle analysis, it is crucial to account for the embodied emissions associated with renewable and nuclear power generation plants as they can significantly impact the GHG emissions linked to hydrogen production and its derived products. In this work, we conducted a comprehensive analysis of the embodied emissions associated with solar photovoltaic (PV), wind, hydro, and nuclear electricity. We investigated the implications of including plant-embodied emissions in the overall emission estimates of electrolysis hydrogen production and subsequently on the production of synthetic ammonia, methanol, and Fischer– Tropsch (FT) fuels. Results show that average embodied GHG emissions of solar PV, wind, hydro, and nuclear electricity generation in the United States (U.S.) were estimated to be 37, 9.8, 7.2, and 0.3 g CO 2 e/kWh, respectively. Life cycle GHG emissions of electrolytic hydrogen produced from solar PV, wind, and hydroelectricity were estimated as 2.1, 0.6, and 0.4 kg of CO 2 e/kg of H 2 , respectively, in contrast to the zero-emissions often used when the embodied emissions in their construction were excluded. Average life cycle emission estimates (CO 2 e/kg) of synthetic ammonia, methanol, and FT-fuel from solar PV electricity are increased by 5.5, 16, and 49 times, respectively, compared to the case when embodied emissions are excluded. This change also depends on the local irradiance for solar power, which can result in a further increase of GHG emissions by 35–41% in areas of low irradiance or reduce GHG emissions by 21–25% in areas with higher irradiance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and Durability of Pure-Water-Fed Anion Exchange Membrane Electrolyzers Using Baseline Materials and Operation

Water electrolysis powered by renewable electricity produces green hydrogen and oxygen gas, which can be used for energy, fertilizer, and industrial applications and thus displace fossil fuels. Pure-water anion-exchange-membrane (AEM) electrolyzers in principle offer the advantages of commercialized proton-exchange-membrane systems (high current density, low cross over, output gas compression, etc.) while enabling the use of less-expensive steel components and nonprecious metal catalysts. AEM electrolyzer research and development, however, has been limited by the lack of broadly accessible materials that provide consistent cell performance, making it difficult to compare results across studies. Further, even when the same materials are used, different pretreatments and electrochemical analysis techniques can produce different results. Here, we report an AEM electrolyzer comprising commercially available catalysts, membrane, ionomer, and gas-diffusion layers operating near 1.9 V at 1 A cm –2 in pure water. After the initial break in, the performance degraded by 0.67 mV h –1 at 0.5 A cm –2 at 55 °C. We detail the key preparation, assembly, and operation techniques employed and show further performance improvements using advanced materials as a proof-of-concept for future AEM-electrolyzer development. Here, the data thus provide an easily reproducible and comparatively high-performance baseline that can be used by other laboratories to calibrate the performance of improved cell components, nonprecious metal oxygen evolution, and hydrogen evolution catalysts and learn how to mitigate degradation pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable Gas Diffusion Electrode Fabrication for Electrochemical CO 2 Reduction Using Physical Vapor Deposition Methods

Electrochemical CO 2 reduction (ECR) promises the replacement of fossil fuels as the source of feedstock chemicals and seasonal storage of renewable energy. While much progress has been made in catalyst development and electrochemical reactor design, few studies have addressed the effect of catalyst integration on device performance. Using a microfluidic gas diffusion electrolyzer, we systematically studied the effect of thickness and the morphology of electron beam (EB) and magnetron-sputtered (MS) Cu catalyst coatings on ECR performance. We observed that EB-Cu outperforms MS-Cu in current density, selectivity, and energy efficiency, with 400 nm thick catalyst coatings performing the best. Additionally, the superior performance of EB-Cu catalysts is assigned to their faceted surface morphology and sharper Cu/gas diffusion layer interface, which increases their hydrophobicity. Tests in a large-scale zero-gap electrolyzer yielded similar product selectivity distributions with an ethylene Faradaic efficiency of 39% at 200 mA/cm 2 , demonstrating the scalability for industrial ECR applications.

36 MATERIALS SCIENCE↗

Chemical Feedback in the Self-Assembly and Function of Air–Liquid Interfaces: Insight into the Bottlenecks of CO 2 Direct Air Capture

As fossil fuels remain a major source of energy throughout the world, developing efficient negative emission technologies, such as direct air capture (DAC), which remove carbon dioxide (CO 2 ) from the air, becomes critical for mitigating climate change. Although all DAC processes involve CO 2 transport from air into a sorbent/solvent, through an air–solid or air–liquid interface, the fundamental roles the interfaces play in DAC remain poorly understood. In this work, we study the interfacial behavior of amino acid (AA) solvents used in DAC through a combination of vibrational sum frequency generation spectroscopy and molecular dynamics simulations. This study revealed that the absorption of atmospheric CO 2 has antagonistic effects on subsequent capture events that are driven by changes in bulk pH and specific ion effects that feedback on surface organization and interactions. Among the three AAs (leucine, valine, and phenylalanine) studied, we identify and separate behaviors from CO 2 loading, chemical changes, variations in pH, and specific ion effects that tune structural and chemical degrees of freedom at the air–aqueous interface. The fundamental mechanistic findings described here are anticipated to enable new approaches to DAC based on exploiting interfaces as a tool to address climate change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel Structural Motif To Promote Mg-Ion Mobility: Investigating ABO 4 Zircons as Magnesium Intercalation Cathodes

There is an increasing need for sustainable energy storage solutions as fossil fuels are replaced by renewable energy sources. Multivalent batteries, specifically Mg batteries, are one energy storage technology that researchers continue to develop with hopes to surpass the performance of Li-ion batteries. However, the limited energy density and transport properties of Mg cathodes remain critical challenges preventing the realization of high-performance multivalent batteries. In this work, ABO 4 zircon materials (A = Y, Eu and B = V, Cr) are computationally and experimentally evaluated as Mg intercalation cathodes. Remarkably good Mg-ion transport properties were predicted and Mg-ion intercalation was experimentally verified in sol-gel synthesized zircon YVO 4 , EuVO 4 , and EuCrO 4 . Among them, EuVO 4 exhibited the best electrochemical performance and demonstrated repeated reversible cycling. While we believe that the one-dimensional diffusion channels and redox-active species tetragonal coordination limit the value of many zircons as high-performance cathodes, their unique structural motif of overlapping polyhedra along the diffusion pathway appears instrumental for promoting good Mg-ion mobility. The motif results in a favorable "6-5-4" change in coordination that avoids unfavorable sites with lower coordination along the diffusion pathway and a structural design metric for future Mg cathode development.

25 ENERGY STORAGE↗

Effects of the Hydrophobic Block Length Ratio of Poly(vinylbenzyl N -methylpiperidinium carbonate)- b -polyethylene- b -poly(vinylbenzyl N -methylpiperidinium carbonate) Block Copolymers for Anion Exchange Membrane Electrolysis

Electrolysis of water to produce hydrogen from renewable electricity is an extremely attractive strategy to reduce energy dependence on fossil fuels. Development of membrane and ionomer materials that maintain high performance with long lifetimes is needed. We developed and investigated the performance and durability of a series of polyethylene-based ABA triblock copolymer anion exchange ionomer and membrane (AEI, AEM) materials for anion exchange membrane water electrolysis. Poly(vinylbenzyl N-methylpiperidinium carbonate)-b-polyethylene-b-poly(vinylbenzyl N-methylpiperidinium carbonate) was synthesized with different hydrophobic/hydrophilic block ratios (1.02:1, 2.58:1, and 4.46:1) resulting in a range of ion exchange capacities (1.1–1.8 meq g –1 ) and water swelling (23–154%) characteristics. All AEMs showed full anionic dissociation, as evidenced by linear Arrhenius correlations, and excellent carbonate conductivity of 8–94 mS cm –1 at 50 °C. Hydrophilic phase separation may offer superior chemical durability by only wetting the ion-conducting region of the polymer and avoiding attack at the nonwetted backbone. We evaluated the performance and durability of these AEMs as a function of hydrophobic polyethylene (PE) content. The AEM containing the least amount of PE displayed the highest performance of 1 A cm –2 at 2.3 V but degraded at 40 mV h –1 before catastrophically failing after <3 h at 0.5 A cm –2 . With greater PE-containing AEMs, the degradation rate was reduced by 3 orders of magnitude with only a 0.2 V increase in voltage. Constant current electrolysis for 50 h resulted in a voltage change of 0.3 mV h –1 in a single-cell water electrolyzer and 1 M potassium carbonate. In a 600 h test, the voltage change in the final 200 h was impressively low for an experimental film, 58 μV h –1 . Postmortem analysis indicated that the membrane did not thin and that water becomes more tightly hydrogen-bound in the polymer after electrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of PLA/PHB Blend Ratio and Wood Flour Loading on the Melt Rheology and Thermomechanical Properties of Biobased Polymer Composites

The development of sustainable, biobased polymer composites is crucial for reducing supply chain dependence on fossil fuels. A major challenge lies in understanding and predicting the processability of these sustainable material alternatives, which directly impacts large-scale manufacturing. Here, this study systematically investigates the effect of poly(lactic acid) (PLA)/polyhydroxybutyrate (PHB) blend ratios and wood flour (WF) loadings on the thermal, rheological, and mechanical properties of the composites. Composites were prepared via melt compounding and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), oscillatory shear melt rheology, tensile testing, and scanning electron microscopy. Results showed that increasing the PHB content lowered the glass transition temperature, while higher PHB and WF loadings decreased thermal stability. Complex viscosity decreased with increasing PHB in 0 and 10% WF, whereas it increased in 20% and 30% WF for PHB-rich blends (80/20 and 70/30 PLA/PHB) due to stronger filler interactions with flexible PHB chains. At 30% WF, PHB-containing composites also showed elastic dominance with G′ higher than G″. This behavior was confirmed by van Gurp–Palmen plots, where the phase angle decreased with increasing PHB and WF loadings. WF addition also shifted Cole–Cole plots away from semicircular terminal relaxation, while time–temperature superposition validity was maintained, confirming that polymer chain dynamics continue to dominate melt behavior. Young’s modulus increased with WF loading, while tensile strength and toughness decreased due to weaker interfacial adhesion between the matrix and the filler. Interestingly, 10% WF systems containing PHB exhibited the highest toughness among all of the filled systems, indicating synergistic reinforcement from WF fillers and PHB-induced ductility. Overall, melt rheology effectively captured the internal structure and stiffness of the composites as the formulation changed, reinforcing the concept that the PLA/PHB ratio and WF content can be tuned to adjust melt elasticity and balance mechanical property trade-offs for targeted applications.

melt rheology↗

(Photo)Electrocatalytic CO 2 Reduction at the Defective Anatase TiO 2 (101) Surface

Excessive carbon dioxide (CO 2 ) emissions by combustion of fossil fuels are linked to global warming and rapid climate change. One promising route to lowering the concentration of CO 2 in the atmosphere is to reduce it to useful small molecules via photoelectrocatalytic hydrogenation, which would enable solar energy storage with a zero-carbon emission cycle and perform a more efficient separation of the photogenerated electron and hole pair than pure photocatalysis. Indeed, photoelectrocatalytic CO 2 reduction has been an intense focus of research. Using the density functional theory (DFT), we studied the CO 2 reduction reaction on the defective anatase TiO 2 (101) surface, at both the solvent/catalyst and the electrolyte/catalyst interfaces. The analysis of the electronic structure of the surface shows a contrast between the solvent/catalyst and the electrolyte/catalyst interfaces, which results in the two corresponding catalytic cycles being distinct. Furthermore, our study explains at the electronic and mechanistic levels why methanol is the main product in the presence of the electrolyte and why the overpotential is not only controlled by the reaction process but also by the diffusion process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalyst Deactivation and Its Mitigation during Catalytic Conversions of Biomass

Biofuel or biochemical production from biomass, especially lignocellulosic biomass, is the most promising option to replace fossil-based products to achieve sustainability. However, biomass is currently under-utilized because biomass conversion technologies have faced significant challenges to compete with incumbent petroleum technologies. Advancement in catalysis plays a central role in increasing the readiness of biomass conversion technologies. In this respect, improving catalyst stability is one of the well-known grand challenges for biomass conversion catalysis, which impedes the scaling up and commercialization of many biomass conversion techniques. In comparison to conventional processing of fossil fuels (petroleum, coal, and natural gas), biomass conversion is largely challenged by three unique properties of biomass-derived feedstocks—high water and oxygen content, high degree and reactivity of oxygen functionalization, and high contamination by minerals and heteroatoms—which all cause greater catalyst deactivation in different ways. Therefore, research on catalyst deactivation mitigation and catalyst regeneration is extremely important for the development of biomass conversion technologies. This review aims to highlight studies on catalyst deactivation and mitigation for catalytic processes in biomass conversion, with emphasis on the deactivation caused by the three unique characteristics of biomass-derived feedstocks. Further, this work will provide information on correlating the characteristics of biomass-derived streams, their potential impact on catalyst lifetime, and a potential mitigation approach, which could guide a more rational design of a robust catalyst and processes for biomass conversion.

09 BIOMASS FUELS↗

Enhanced Electrocatalytic and Selective CO 2 -to-CO Reduction by a Rhenium(I) Complex Bearing 6,6′-Substituted 2,2′-Bipyridines

The electrochemical reduction of CO 2 (CO 2 RR) into value-added chemicals offers a promising route toward a circular carbon economy and reduced reliance on fossil fuels. A detailed understanding of the structural and electronic factors governing the performance of molecular CO 2 RR electrocatalysts is essential for the design of efficient, tunable systems. Here, in this study, we report a series of rhenium(I) complexes, fac-[Re I (6,6′-(R) 2 -bpy)(CO) 3 Cl] (bpy = 2,2′-bipyridine; R = mesityl (mes), 2,4,6-triisopropylphenyl (trip), or isophthalic acid (phth)) and evaluate their electrocatalytic activity. Among these, fac-[Re I (6,6′-(mes) 2 -bpy)(CO) 3 Cl] exhibited the highest performance, enabling selective CO 2 -to-CO conversion for 1 hour with Faradaic efficiency (FE) > 97%, representing an unprecedented activity level for a Re-bpy catalysts. Single-crystal X-ray diffraction and density functional theory (DFT) calculations indicated that favorable CO 2 binding could be promoted by the tilting of the 6,6′-(mes)2-bpy ligand (from the Re-CO coordination plane), providing mechanistic insight into the observed enhancement. The study consequently demonstrates a rational correlation between the CO 2 electrocatalytic performance of Re-bpy catalysts and their structural variations, as derived from X-ray data and corroborated by computational modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double-Site Substitution of Ce into (Ba, Sr)MnO 3 Perovskites for Solar Thermochemical Hydrogen Production

Solar thermochemical hydrogen production (STCH) is a renewable alternative to hydrogen production using fossil fuels. While serial bulk experimental methods can accurately measure STCH performance, screening chemically complex materials systems for new promising candidates is more challenging. Here we identify double-site Ce-substituted (Ba,Sr)MnO 3 oxide perovskites as promising STCH candidates using a combination of bulk synthesis and high-throughput thin-film experiments. The Ce substitution on the B-site in 10H-BaMnO 3 and on the A-site in -SrMnO 3 leads to 2–3 times higher hydrogen production compared to CeO 2 , but these bulk single-site substituted perovskites suffer from incomplete reoxidation. Double-site Ce substitution on both A- and B-sites in (Ba,Sr)MnO 3 thin films increases Ce solubility and extends the stability of 10H and 3C structures, which is promising for their thermochemical reversibility. This study demonstrates a high-throughput experimental method for screening complex oxide materials for STCH applications.

08 HYDROGEN↗

Incorporation of Ion Transport Chains into Multivariate MOF for Improved Water Oxidation

The climate crisis demands clean energy technologies to cut CO 2 emissions from fossil fuels. Hydrogen fuel cells and solar-driven CO 2 reduction are promising, but both rely on efficient water oxidation. Polypyridyl ruthenium complexes are active catalysts for water oxidation; however, they exhibit poor stability and recyclability. Our group improved performance by embedding these complexes into metal−organic frameworks (MOFs). As water oxidation is pH-dependent, proton management further enhances reactivity. To address the issue, we introduced proton transfer pathways into the MOF structure. Specifically, we incorporated −SO 3 H groups onto the biphenyl linkers of UiO-67 loaded with [Ru(tpy)(dcbpy)OH 2 ]PF 6 catalyst (where tpy = 2,2′:6′,2″-terpyridine; dcbpy = 5,5-dicarboxy-2,2′- bipyridine). The sulfonated MOF exhibited a 2.5-fold increase in oxygen evolution compared to the nonsulfonated analogue. After 1 h of electrolysis, the sulfonated MOF exhibited a turnover number of 25 for oxygen evolution reaction compared to 10 for the native MOF, demonstrating the benefits of built-in proton management.

Catalysts↗

Direct Observation of Phase Change Accommodating Hydrogen Uptake in Bimetallic Nanoparticles

Hydrogen holds great promise as a cleaner alternative to fossil fuels, but its efficient and affordable storage remains a significant challenge. Bimetallic systems, such as Pd and Ni, present a promising option for storing hydrogen. In this study, using the combination of different cutting-edge X-ray and electron techniques, we observed the transformations of Pd–Ni nanoparticles, which initially consist of a NiO-rich shell surrounding a Pd-rich core but undergo a major transformation when they interact with hydrogen. During hydrogen exposure, the Pd core breaks into smaller pockets, dramatically increasing its surface area and enhancing the hydrogen storage capacity, especially in nanoparticles with lower Pd content. The findings provide a deep understanding of the morphological changes at the atomic level during hydrogen storage and contribute to designing cost-effective hydrogen storage using multimetallic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

p -Coumaroylated Lignins Are Natively Produced in Three Rosales Families

Carbon-rich plant cell walls contain biopolymers that, with some processing, could replace fossil fuels as a major component of the current petrochemical production. To realize this, biorefineries need to be paired with biomass that during the deconstruction and fractionation processes transforms into the desired products. One component of interest is p-coumarate that, in some species, can account for up to 1% of the biomass’ dry weight. When p-coumarate is present in eudicot cell walls, it is mostly part of the suberin (bark and root), acylates the γ-hydroxy group of the lignin, in part of the tannins, or is a metabolite. The current understanding of eudicot plant cell wall composition is that the lignin is sometimes acylated with acetate and rarely with hydroxycinnamates (p-coumarate or ferulate). This study identified a clear division in the Rosales in which three families produce p-coumaroylated lignins whereas the other six families showed no evidence of the trait.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Microstructured BaTiO 3 -Embedded PVDF–HFP/PEO Film for Enhanced Triboelectric Interface in Self-Sufficient Energy Generation and Sensing

The global reliance on fossil fuels and natural gas has largely dominated the energy production field, but due to finite resource depletion and escalating greenhouse gas emissions, the immediate exploration of sustainable energy alternatives to mitigate climate change and ensure resource security has been a major concern. There has been extensive research into other more renewable methods of energy production, such as wind and hydropower. Of these current energy generation types, there are many areas of untapped potential from the mechanical movements generated ambiently not only in the large scale of power generation but also on a smaller scale. The piezoelectric and triboelectric effects are phenomena where these ambient mechanical movements can generate electrical energy. Developing a hybrid system that leverages both mechanical stress and surface charges presents an ideal opportunity to exploit these untapped energy sources. Producing a hybrid PVDF–HFP/PEO film with perovskite BaTiO 3 (BTO) enables ambient power harvesting from both mechanical movement and surface charge. The optimized cell produced a potential of up to 15 V and a current of 200 nA with a 68 kΩ resistor, a substantial increase from a base system with an average of 2.1 V and 40 nA. These hybrid TENGs offer significant potential for energy harvesting in small-scale applications, such as health monitoring devices and indicators in electric circuits.

Ybarra, Rigobert [University of Texas Rio Grande V↗

Room-Temperature Optical Detection of 14 CO 2 below the Natural Abundance with Two-Color Cavity Ring-Down Spectroscopy

Radiocarbon’s natural production, radiative decay, and isotopic rarity make it a unique tool to probe carbonaceous systems in the life and earth sciences. However, the difficulty of current radiocarbon ( 14 C) detection methods limits scientific adoption. Here, two-color cavity ring-down spectroscopy detects 14 CO 2 in room-temperature samples with an accuracy of one-tenth the natural abundance in 3 min. The intracavity pump–probe measurement uses two cavity-enhanced lasers to cancel out cavity ring-down rate fluctuations and strong one-photon absorption interference (>10 000 1/s) from hot-band transitions of CO 2 isotopologues. Selective, room-temperature detection of small 14 CO 2 absorption signals (<1 1/s) reduces the technical and operational burdens for cavity-enhanced measurements of radiocarbon, which can benefit a wide range of applications like biomedical research and field-detection of combusted fossil fuels.

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