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The Role of Quantum Science Concepts in Enhancing Sensing and Imaging Technologies: Applications for Biology: Proceedings of a Workshop

Quantum concepts hold the potential to enable significant advances in sensing and imaging technologies that could be vital to the study of biological systems. The workshop Quantum Science Concepts in Enhancing Sensing and Imaging Technologies: Applications for Biology, held online March 8–10, 2021, was organized to examine the research and development needs to advance biological applications of quantum technology. Hosted by the National Academies of Sciences, Engineering, and Medicine, the event brought together experts working on state-of-the-art, quantum-enabled technologies and scientists who are interested in applying these technologies to biological systems. Through talks, panels, and discussions, the workshop facilitated a better understanding of the current and future biological applications of quantum-enabled technologies in fields such as microbiology, molecular biology, cell biology, plant science, mycology, and many others. The workshop was organized around three main themes. The first, quantum in biology, examined quantum concepts that are hypothesized to be important for life processes and that researchers are working to observe through biological imaging and sensing. The second, quantum for biology, addressed ways to use quantum concepts to enhance technologies for biological imaging and sensing. The third, biology for quantum, offered a wider discussion of how the frontiers of biological imaging and sensing could enable future study using quantum concepts, tools, or technologies. Throughout the workshop, participants identified a wide range of emerging approaches and opportunities at the intersection of quantum physics and biological sensing and imaging. During the workshop, there were some differences in how each speaker defined the term quantum. During one of the panels, Prem Kumar offered thoughts on what phenomena are classical versus quantum, explaining that techniques get progressively more quantum as you move from just having superposition to having superposition with measurement and entanglement. Another explanation from Clarice Aiello delineates the definition into several levels. This includes a base level of “quantum-ness,” which reflects that all matter is made of atoms, and when these particles are isolated they behave based on quantum mechanical principles. A second level is related to quantum coherence, where a single quantum object might be found in a coherent superposition state. A final level, which she described as the quantum-entangled level, involves multiple quantum systems which are entangled among themselves. Overall, the workshop touched on concepts such as superposition, entanglement, and squeezing and their potential implications for communication, computing, and simulation, in addition to the workshop’s main focal area, biological sensing and imaging. At the opening of the workshop, Thorsten Ritz of the University of California, Irvine, identified two questions at the heart of quantum biology: Is the machinery of life quantum mechanical, and can quantum mechanics be used to study the machinery of life in new ways? Participants highlighted systems in which researchers have explored these questions, from the vast array of molecular interactions involved in biological processes such as photosynthesis, to the mechanics involved in cellular functions such as differentiation and aggregation, to the role of oscillating magnetic fields in flight orientation among birds. Sensing and imaging technologies are crucial to biological research; these technologies could both enhance the study of quantum effects and be enhanced by quantum concepts. A critical challenge in biological research is to develop imaging and sensing tools that do not damage or interfere with the often fragile and fleeting systems being studied. Attendees discussed a variety of established and emerging technologies that could enhance noninvasive biological imaging, including single- and two-photon spectroscopy, single-molecule spectroscopy, quantum illumination, ghost imaging, and cryo-electron microscopy. One example came from Marlan Scully who gave a keynote address on the first day of the workshop. Scully emphasized the use of different laser technologies, which exhibit coherence and other quantum properties, in moving toward real-world biological applications, such as the detection of SARS-CoV-2. Both tools and theory will play an important role in advancing quantum biology research and applications. Several participants suggested theorists and experimentalists should work in tandem to understand and model biological processes. While physics often reduces systems to their simplest forms for fundamental insights, participants also noted the value of observing and understanding biological systems in all their “messiness,” capturing both the inner workings of biological systems and the complex interactions that occur within and between organisms. In discussions among participants, several attendees stressed the need to match emerging tools with the right scientific questions. Rather than developing quantum technologies as “a hammer looking for a nail,” participants emphasized a focus on exploring the problems these technologies are best suited to address. For example, it is important to consider the size of the phenomenon being studied, the timescales that are important in answering the scientific question, and other relevant considerations. Every tool along the spectrum from classical to quantum involves its own set of trade-offs. For example, Ted Laurence of the Lawrence Livermore National Laboratory said that quantum measurements, such as single photon counting, fluorescence transitions, and lasers, can take longer to produce the same results as classical measurements. These quantum measurements, however, do not require calibration and can enable new research questions to be answered. Prem Kumar, Northwestern University, noted that, despite their promise, quantum approaches should not be used simply for the sake of using quantum, especially in situations where classical approaches better meet the needs of the researcher. Understanding and applying quantum concepts could enable advances in a wide range of application areas including energy, synthetic biology, medicine, and sustainability. For example, Michelle O’Malley, University of California, Santa Barbara, described how improved noninvasive imaging approaches could help capture the complex interactions and functions involved in the breakdown of organic matter by microbial communities and lead to new technologies for capturing valuable products from plant waste. Several other participants discussed needs in tracking the movement of metabolites and molecules in microbial communities for insights into nutrient cycling in environments such as soil. Margaret Ahmad, Sorbonne University, discussed potential opportunities to leverage the magnetic properties of cryptochromes to advance new treatment approaches for diseases such as COVID-19 and cancer. Looking toward the future development of the field, participants discussed challenges to advancing quantum biology that arise from disciplinary disconnects between physicists and biologists. The siloing of academic research disciplines represents a significant barrier to progress. Disconnects in terminology, motivations and priorities, and structural barriers to collaborative work underscore the need for concerted efforts to bridge these divides. Attendees and speakers offered suggestions for resolving these divergences, establishing a shared language, moving the field forward, and fostering meaningful feedback between disciplines. Overall, participants stressed a need for balance, open communication, collaboration, unity, and clear dialogue on trade-offs between quantum and classical approaches. Keiko Torii, The University of Texas at Austin, said that the best collaborations happen when the project provides mutual advantages that can show off everyone’s talents, each team finds the work interesting, and partners develop a camaraderie to pursue new knowledge. To enable near- and long-term opportunities in this space, participants suggested that exploratory, high-risk funding could improve existing instrumentation to explore quantum enhancement collaboratively. They also emphasized the need for collaboration between quantum physicists and sensing/imaging scientists, which could be advanced through a dedicated quantum biology investigator program. People, even more than technology, will be crucial to the future of quantum biology. Participants explored training, education, and workforce needs to further develop this burgeoning field and cultivate the next generation of scientists. While many programs are still in their nascent stages, participants highlighted examples of approaches and programs being developed at various types of institutions to engage students and professional scientists in quantum biology research. Several participants stressed the need for an inclusive approach, spanning disciplines as well as communities to foster a diverse field fueled by the intellectual contributions of a wide range of people, including historically under-resourced schools and students. To increase awareness and excitement about quantum physics and related areas of biology, attendees suggested capitalizing on the “buzz” around quantum. Several participants emphasized the need to start early, introducing students to quantum concepts and their appealing “weirdness” in K–12 education. Engaging students early—before they become entrenched in traditional disciplinary siloes as typically happens in graduate school—could help to galvanize interest in the area and foster a generation of scientists with the interdisciplinary mindset and skills needed to advance this interdisciplinary field. While these efforts could be advanced at many levels and across multiple sectors, several participants suggested a national quantum biology center could be a valuable hub to coordinate and support quantum biology education and workforce development across academia, industry, and government.

59 BASIC BIOLOGICAL SCIENCES↗

Advances in Carbon Electrode Integration for Stable and Efficient Perovskite Solar Cells and Modules

Carbon-electrode-based perovskite solar cells (C-PSCs) have emerged as a cost-effective and scalable alternative to noble-metal-based PSCs, addressing critical challenges related to device stability, fabrication complexity, and commercialization potential. This review explores the recent progress in C-PSC development, focusing on the benefits of carbon electrodes (CEs), including their hydrophobicity, chemical inertness to halide corrosion, and compatibility with low-temperature cost-effective solution-based deposition methods. Despite relatively lower power conversion efficiencies (PCEs) than their metal (e.g., Au/Ag) counterparts, recent advances in carbon paste formulation, interfacial contact engineering, and work function modification have elevated C-PSC efficiencies above 22%. This review further examines strategies to enhance electrode conductivity, interfacial properties, and charge selectivity to further increase C-PSC performance. Progress in carbon-electrode-based perovskite solar modules (C-PSMs), particularly within mesoporous and planar architectures, is also analyzed, revealing significant developments in active area scaling and long-term stability. Notably, the limited research in inverted (PIN) C-PSCs is also highlighted as a compelling opportunity for innovation, given the architecture's inherent advantages in flexibility, tandem integration, and low-temperature processing. Collectively, these insights affirm the potential of C-PSCs and C-PSMs to deliver affordable, stable, and high-performance photovoltaics suitable for scalable deployment.

Carbon Electrodes↗

Full-Time, Eye-Safe Cloud and Aerosol Lidar Observation at Atmospheric Radiation Measurement Program Sites: Instruments and Data Analysis

Atmospheric radiative forcing, surface radiation budget, and top of the atmosphere radiance interpretation involves a knowledge of the vertical height structure of overlying cloud and aerosol layers. During the last decade, the U.S. Department of Energy through I the Atmospheric Radiation Measurement (ARM) program has constructed four long- term atmospheric observing sites in strategic climate regimes (north central Oklahoma, In Barrow. Alaska, and Nauru and Manus Islands in the tropical western Pacific). Micro Pulse Lidar (MPL) systems provide continuous, autonomous observation of all significant atmospheric cloud and aerosol at each of the central ARM facilities. Systems are compact and transmitted pulses are eye-safe. Eye-safety is achieved by expanding relatively low-powered outgoing Pulse energy through a shared, coaxial transmit/receive telescope. ARM NIPL system specifications, and specific unit optical designs are discussed. Data normalization and calibration techniques are presented. A multiple cloud boundary detection algorithm is also described. These techniques in tandem represent an operational value added processing package used to produce normalized data products for Cloud and aerosol research and the historical ARM data archive.

Campbell, James R.↗

Thermal Vacuum Chamber Repressurization with Instrument Purging

At the end of James Webb Space Telescope (JWST) OTIS (Optical Telescope Element-OTE-Integrated Science Instrument Module-ISIM) cryogenic vacuum testing in NASA Johnson Space Centers (JSCs) thermal vacuum (TV) Chamber A, contamination control (CC) engineers are mooting the idea that chamber particulate material stirred up by the repressurization process may be kept from falling into the ISIM interior to some degree by activating instrument purge flows over some initial period before opening the chamber valves. This memo describes development of a series of models designed to describe this process. These are strung together in tandem to estimate overpressure evolution from which net outflow velocity behavior may be obtained. Creeping flow assumptions are then used to determine the maximum particle size that may be kept suspended above the ISIM aperture, keeping smaller particles from settling within the instrument module.

Venting↗

Thermal Vacuum Chamber Repressurization with Instrument Purging

At the end of James Webb Space Telescope (JWST) OTIS (Optical Telescope Element-OTE-Integrated Science Instrument Module-ISIM) cryogenic vacuum testing in NASA Johnson Space Centers (JSCs) thermal vacuum (TV) Chamber A, contamination control (CC) engineers are mooting the idea that chamber particulate material stirred up by the repressurization process may be kept from falling into the ISIM interior to some degree by activating instrument purge flows over some initial period before opening the chamber valves. This memo describes development of a series of models designed to describe this process. These are strung together in tandem to estimate overpressure evolution from which net outflow velocity behavior may be obtained. Creeping flow assumptions are then used to determine the maximum particle size that may be kept suspended above the ISIM aperture, keeping smaller particles from settling within the instrument module.

Repressurization↗

Anion exchange and extraction chromatography tandem column isolation of zirconium-89 ( 89 Zr) from cyclotron bombarded targets using an automated fluidic platform

The long-lived positron emitter 89 Zr is a highly promising nuclide employed in diagnostic Positron Emission Tomography (PET) imaging. Methods of radiochemical processing to obtain 89 Zr for clinical use are traditionally performed with a single hydroxamate resin column. In this work, we present a tandem column purification method for the preparation of high-purity 89 Zr from cyclotron bombarded Y metal foils. The primary column is a macroporous, strongly basic anion exchange resin on styrene divinylbenzene co-polymer. The secondary microcolumn, with an internal volume of 33 µL, is packed with an extraction chromatography resin (ExCR) loaded with HDEHP. A condition of “inverted selectivity” is presented, wherein the 89 Zr elution from the primary column is synonymous with the load condition on the secondary column. The ability to transfer 89 Zr from one column to the next allows two sequential column clean-up methods to be performed prior to the final elution of the 89 Zr product. This approach assures delivery of very high purity 89 Zr . The tandem column purification process has been implemented into a prototype automated fluidic system. Optimization of the method is presented, followed by evaluation of the process using seven cyclotron bombarded Y metal foil targets. Once optimized, we found that 93.7±2.3% of the 89 Zr present in the foils was recovered in the secondary column elution fraction (0.8 M oxalic acid). Radiochromatograms of the product elution peaks enabled determination of full width at half-maximum (FWHM) and 89 Zr collection yields as a function of volume. Because of the small size of the secondary microcolumn, a 89 Zr product volume of ~0.28 mL is reported, which provides a substantially increased nuclide concentration over traditional methods. Finally, we evaluated the transchelation of the resulting 89 Zr oxalate product to deferoxamine mesylate (DFOM) salt. We observed effective specific activities (ESA) and bindable metals concentrations ([M B ]) that exceed those reported by the traditional single hydroxamate column method.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Structure of native four-repeat satellite III sequence with non-canonical base interactions

Abstract Tandem-repetitive DNA (where two or more DNA bases are repeated numerous times) can adopt non-canonical secondary structures. Many of these structures are implicated in important biological processes. Human Satellite III (HSat3) is enriched for tandem repeats of the sequence ATGGA and is located in pericentromeric heterochromatin in many human chromosomes. Here, we investigate the secondary structure of the four-repeat HSat3 sequence 5′-ATGGA ATGGA ATGGA ATGGA-3′ using X-ray crystallography, NMR, and biophysical methods. Circular dichroism spectroscopy, thermal stability, native PAGE, and analytical ultracentrifugation indicate that this sequence folds into a monomolecular hairpin with non-canonical base pairing and B-DNA characteristics at concentrations below 0.9 mM. NMR studies at 0.05–0.5 mM indicate that the hairpin is likely folded-over into a compact structure with high dynamics. Crystallographic studies at 2.5 mM reveal an antiparallel self-complementary duplex with the same base pairing as in the hairpin, extended into an infinite polymer. The non-canonical base pairing includes a G–G intercalation sandwiched by sheared A–G base pairs, leading to a cross-strand four guanine stack, so called guanine zipper. The guanine zippers are spaced throughout the structure by A–T/T–A base pairs. Our findings lend further insight into recurring structural motifs associated with the HSat3 and their potential biological functions.

59 BASIC BIOLOGICAL SCIENCES↗

Monolithic Two-Terminal All-Perovskite Tandem Solar Cells with Power Conversion Efficiency Exceeding 21%

Monolithic two-terminal (2-T) all-perovskite tandem solar cells are a promising candidate for the next generation solar cells with ultrahigh efficiency and low fabrication cost. Here, we report on the fabrication of 2-T all-perovskite tandem solar cells consisting of solution-processed wide-bandgap and low-bandgap perovskite subcells connected by a vacuum processed interconnection layer. We employed a bulk-passivation strategy to enlarge the grain size, increase carrier mobilities, reduce electronic disorder, and suppress trap-assisted recombination in the low bandgap mixed Sn-Pb perovskite films, which leads to improved performance of low bandgap perovskite solar cells with an absorber thickness over 750 nm. This advance in high-quality low-bandgap perovskite layers enables the fabrication of efficient 2-T all-perovskite solar cells with power conversion efficiencies of more than 21% and decent stability. Our approach provides a suitable pathway to realize ultra-high efficiency 2-T all-perovskite tandem solar cells.

14 SOLAR ENERGY↗

Best Practices in PEC Water Splitting: How to Reliably Measure Solar-to-Hydrogen Efficiency of Photoelectrodes

Photoelectrochemical (PEC) water splitting, which utilizes sunlight and water to produce hydrogen fuel, is potentially one of the most sustainable routes to clean energy. One challenge to success is that, to date, similar materials and devices measured in different labs or by different operators lead to quantitatively different results, due to the lack of accepted standard operating procedures and established protocols for PEC efficiency testing. With the aim of disseminating good practices within the PEC community, we provide a vetted protocol that describes how to prepare integrated components and accurately measure their solar-to-hydrogen (STH) efficiency (η STH ). This protocol provides details on electrode fabrication, η STH test device assembly, light source calibration, hydrogen evolution measurement, and initial material qualification by photocurrent measurements under monochromatic and broadband illumination. Common pitfalls in translating experimental results from any lab to an accurate STH efficiency under an AM1.5G reference spectrum are discussed. A III–V tandem photocathode is used to exemplify the process, though with small modifications, the protocol can be applied to photoanodes as well. Dissemination of PEC best practices will help those approaching the field and provide guidance for comparing the results obtained at different lab sites by different groups.

08 HYDROGEN↗

Thermal Vacuum Chamber Repressurization with Instrument Purging

At the conclusion of cryogenic vacuum testing of the James Webb Space Telescope Optical Telescope Element Integrated Science Instrument Module (JWST-OTIS) in NASA Johnson Space Center’s (JSCs) thermal vacuum (TV) Chamber A, contamination control (CC) engineers are postulating that chamber particulate material stirred up by the repressurization process may be kept from falling into the Integrated Science Instrument Module (ISIM) interior to some degree by activating instrument purge flows over some initial period before opening the chamber valves. This manuscript describes development of a series of models designed to describe this process. The models are strung together in tandem with a fictitious set of conditions to estimate overpressure evolution from which net outflow velocity behavior may be obtained. Creeping flow assumptions are then used to determine the maximum particle size that may be kept suspended above the ISIM aperture, keeping smaller particles from settling within the instrument module.

Repressurization↗

Compositional analysis of organosolv poplar lignin by using high-performance liquid chromatography/high-resolution multi-stage tandem mass spectrometry

Organosolv treatment is an efficient and environmentally friendly process to degrade lignin into small compounds. The capability of characterizing the individual compounds in the complex mixtures formed upon organosolv treatment is essential for the optimization of the further lignin conversion processes and for the rational genetic engineering of plants used to produce lignin in order to improve lignin properties. In this study, an organosolv poplar lignin sample was initially analyzed by high-resolution mass spectrometry coupled with negative-ion mode electrospray ionization ((-)ESI HRMS). Lignin monomers and dimers were found to constitute the majority of the compounds in the organosolv lignin sample. Larger lignin oligomers, such as trimers and tetramers, and some not lignin-related compounds, were also detected. A high-performance liquid chromatograph/linear quadrupole ion trap/orbitrap mass spectrometer capable of multi-stage high-resolution tandem mass spectrometry experiments (HRMS n ), equipped with an (-)ESI source (HPLC/(-)ESI HRMS n ), was employed to separate the unknown compounds in the organosolv mixture and to obtain structural information for the deprotonated compounds via collision-activated dissociation (CAD) HRMS n experiments. To improve the understanding of the CAD behavior of deprotonated lignin-related compounds, 16 deprotonated model compounds with different functionalities and linkage types were examined. This approach enabled the assignment of likely structures for several lignin monomers, dimers, trimers, and tetramers, and some not lignin-related compounds, most likely fatty acids. Based on the proposed structures, compounds in the organosolv lignin sample contain β-O-4, 5–5, β-5, and possibly also 4-O-5 linkages. Most compounds contain G- and S-monomeric units although a small amount of H-units were also detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical Studies of Phase Transition Phenomena in Microgravity

This work was aimed at developing and applying a new methodology for the efficient and accurate computation of problems involving several phases of matter. In particular, solidification processes typically involve melt/solid and sometimes melt//gas interfaces, whose location and shape is unknown a priori. This class of problems is called the free or moving boundary problem, and the numerical approaches for its solution to date are inaccurate, inefficient, and can not be readily extended to multi-dimensions or to time dependent phenomenon. Ongoing research on crystal growth at NASA and other institutions falls into the category of free boundary problems. It is exactly the accurate determination of the process dynamics and the shape and location of the interface between the phases which is responsible for the ultimate chemical segregation and the mechanical properties in the solid. This work developed the Triad Field Formalism approach for the computation of general multi-dimensional and time dependent free boundary problems. The particular subject addressed is solidification phenomena. All the relevant boundary conditions on the developing interface were exactly resolved. Several computer programs were developed during the course of this research, enabling us to determine for the first time the interplay among the various fields operating in tandem to produce the phenomena observed during solidification processes in weld pools and during crystal growth.

Source record↗

A study of the relationship between the performance and dependability of a fault-tolerant computer

This thesis studies the relationship by creating a tool (FTAPE) that integrates a high stress workload generator with fault injection and by using the tool to evaluate system performance under error conditions. The workloads are comprised of processes which are formed from atomic components that represent CPU, memory, and I/O activity. The fault injector is software-implemented and is capable of injecting any memory addressable location, including special registers and caches. This tool has been used to study a Tandem Integrity S2 Computer. Workloads with varying numbers of processes and varying compositions of CPU, memory, and I/O activity are first characterized in terms of performance. Then faults are injected into these workloads. The results show that as the number of concurrent processes increases, the mean fault latency initially increases due to increased contention for the CPU. However, for even higher numbers of processes (less than 3 processes), the mean latency decreases because long latency faults are paged out before they can be activated.

Goswami, Kumar K.↗

Nature of contaminants introduced in silicon wafers during molecular beam epitaxy chamber annealing

Epitaxial monolithic III–V/Si tandem solar cells are one of the most promising technologies to be adopted by the industry after the efficiency of the current market dominating single junction silicon solar cell saturates at its fundamental limit. One of the key limitations of this technology is the degradation of silicon wafers during in situ annealing in the molecular beam epitaxy chamber. Determining the nature of contaminants in this process is key to improve the efficiency of epitaxial tandem solar cells. However, to date, the nature of contaminants from molecular beam epitaxy chambers remains unknown. In this work, we use photoluminescence imaging, lifetime spectroscopy, and deep level transient spectroscopy to measure the electronic properties of extrinsic impurities incorporated during annealing in the molecular beam epitaxy chamber. Photoluminescence images reveal that at least two impurities diffuse into silicon wafers during molecular beam epitaxy annealing. One is highly localized, while the other one is distributed uniformly across the whole wafer. Phosphorus diffusion is found to confine the localized impurity within the diffused layer but is ineffective at preventing the indiffusion of other impurities. Lifetime spectroscopy shows that metastable impurities with characteristic similar to Cr and CrB in our molecular beam epitaxy annealed silicon wafers. No evidence of Fe or FeB was observed. The emission rates and concentrations of the electrically active defects were measured with deep-level transient spectroscopy: The emission rates of detected defects do not match that of known Cr-related defects.

36 MATERIALS SCIENCE↗

DEIMoS GUI: An Open-Source User Interface for a High-Dimensional Mass Spectrometry Data Processing Tool

In this paper, we report the creation of a graphical user interface (GUI) for the Data Extraction for Integrated Multidimensional Spectrometry (DEIMoS) tool. DEIMoS is a Python package to process data from high-dimensional mass spectrometry measurements. It is divided into several modules, each representing a data processing step, such as peak detection, alignment, and tandem mass spectra extraction and deconvolution. The inputs for and outputs from DEIMoS can include millions of N-dimensional data points, which can be challenging to visualize in a way that is interactive, informative, and responsive. Here, we used the HoloViz Python data stack, including DataShader and Param, to create an interactive visualization of mass spectrometry data. We believe the GUI will increase the accessibility of DEIMoS, and the visualization methods could be useful for other open-source mass spectrometry tools.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inverted organic tandem solar cells with a charge recombination stack employing spatially confined p-type electrical doping

We report on the application of solution-based p-type electrical doping using 12-molybdophosphoric acid hydrate (PMA) to the fabrication of organic tandem solar cells. Such a doping approach leads to a spatially confined vertical doping profile down to a limited depth from the surface of polymer films, thus allowing the hole-collecting component of the charge recombination stack to be embedded in the photoactive layer of the bottom sub-cell. This simplifies the device architecture by removing the need for an extra dedicated hole-collecting layer. It is shown that this novel charge recombination stack comprising a PMA-doped bottom photoactive layer and a trilayer of Ag/AZO/PEIE is compatible with a solution-processed top photoactive layer. Here, the fabricated inverted organic tandem solar cells exhibit an open-circuit voltage that is close to the sum of the open-circuit voltages of the individual sub-cells, and a fill factor that is close to the better fill factor of the two sub-cells.

14 SOLAR ENERGY↗

Resolving Graphite‐Electrolyte Interphase of Lithium‐Ion Batteries using Air‐Tight Ambient Mass Spectrometry

Abstract The formation of a stable solid electrolyte interphase (SEI) at graphite electrode is necessary for lithium‐ion batteries (LIB) to prevent excessive degradation of electrolytes. Until now, the exact organic composition of SEI has not been decisively determined with lithium ethylene mono‐carbonate (LEMC) being one of the debated components. An air‐tight ambient mass spectrometry (MS) platform is developed to directly characterize the air‐sensitive organic components present in SEI. Ionization occurs via a solvent‐free field‐induced process at atmospheric pressure. Our experimental data, based on tandem MS analysis, revealed LEMC to be the major organic component in SEI. This result resolves a long‐standing mystery surrounding the composition of native SEI in LIB, where no trace of the other debated compound, lithium ethylene dicarbonate, was detected. The energetics of fragmentation of LEMC and the corresponding stabilities of various ionic species detected during the air‐tight ambient MS analysis were calculated using density functional theory (DFT). Our findings confirmed favorable protonation energies and suggested the molecular structures for many of the detected species. Solvent (i. e., ethylene carbonate)‐induced stabilization effects observed during the ionization process were also confirmed by DFT. The reported study encourages the routine use of ambient mass spectrometry to characterize both anodic and cathodic electrodes of all battery types as well as to study other air‐sensitive materials in their native state.

25 ENERGY STORAGE↗

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Abstract Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl 3 - tert -butyl chloride (TBC) adducts, which are formed by the dissociation of Al 2 Cl 7 − in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ 1 H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗