Ion-Sensing Systems Based on Mesoporous Carbon: from Bulk Electrodes to Paper-Based Ion Sensors

University of Minnesota Ph.D. dissertation. August 2017. Major: Chemistry. Advisors: Andreas Stein, Philippe Buhlmann. 1 computer file (PDF); xxvii, 206 pages.Potentiometric sensors, comprising ion-selective electrodes (ISEs) and reference electrodes, are a large subgroup of electrochemical ion sensors. In view of affordable and portable analytical devices, all-solid-state ISEs and reference electrodes, in which a solid contact is used as an ion-to-electron transducer, are highly desirable. Compared with conventional ISEs, all-solid-state ISEs offer comparable electrochemical performance with the distinct advantages of simple maintenance and miniaturization. This dissertation focuses on the development of robust all-solid-state potentiometric ion-sensing systems. It starts with the investigation of colloid-imprinted mesoporous (CIM) carbon as a novel solid contact material. CIM carbon exhibits desirable properties as a solid contact material, including a low content of redox-active impurities and a high double layer capacitance. Therefore, sensors based on CIM carbon can be constructed with superior electrochemical performance, including excellent ionic response, reproducibility, signal stability, and resistance to common interfering agents. These outstanding characteristics make CIM carbon-based potentiometric sensors promising candidates for the next generation of commercial ion sensors. To develop low-cost and simple ion sensors for point-of-care applications, this dissertation also involves the development of disposable ion-sensing platforms based on paper. The use of ISEs can be significantly simplified by embedding a conventional potentiometric cell into paper. Paper-based Cl– and K+ sensors are fabricated with highly reproducible and linear responses towards different concentrations of analyte ions in aqueous and biological samples. To further simplify the use of these paper-based ion sensors, CIM carbon-based ISEs and reference electrodes can be integrated into the paper substrate, thus constructing all-solid-state paper-based ion-sensing platforms. Finally, the dissertation explores the possibility of constructing robust calibration-free ion sensors by covalently attaching a redox buffer to CIM carbon. Click chemistry and amide coupling reactions are evaluated for the attachment, and the cobalt-based redox buffer can be attached to CIM carbon. It is found that the open circuit potential of modified CIM carbon films can be affected by the oxidation states of the redox buffer, but a higher redox buffer loading is required to achieve high electrode-to-electrode reproducibility. Possible approaches to achieving such high redox buffer loading are discussed at the end of this dissertation

Norbornene-Based Polymer Electrolytes for Lithium Cells

Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements

New understandings of the June 24th 2017 Xinmo Landslide, Maoxian, Sichuan, China

On June 24, 2017 (21:39 UTC, June 23rd), a catastrophic landslide occurred at Xinmo village of Mao County, Sichuan Province, China. Soon after the event, some research teams carried out field investigations in order to both support the emergency operations and to understand the failure mechanism and possible evolutionary scenarios. Based on further in-depth interpretation of high-resolution remote-sensing images and detailed field surveys, it is newly found that there are at least six old rockfall deposits in the source area that prove the historic activity of the landslide scarp. Seismic data of the event and morphological evidences along the slope indicate that the landslide was preceded by a significant rockfall. Mechanical calculations show that the surface force due to pore water was far less than the impact force due to the rockfall. It means that the subsequent major rock avalanche was more likely due to the impact of the rockfall on the rock slope below, which broke the rock bridges and caused drop of shear resistance along the fractures. According to these new understandings, a different triggering mechanism for the landslide is proposed

Towards Domain-Independent and Real-Time Gesture Recognition Using mmWave Signal

Human gesture recognition using millimeter wave (mmWave) signals provides attractive applications including smart home and in-car interface. While existing works achieve promising performance under controlled settings, practical applications are still limited due to the need of intensive data collection, extra training efforts when adapting to new domains (i.e. environments, persons and locations) and poor performance for real-time recognition. In this paper, we propose DI-Gesture, a domain-independent and real-time mmWave gesture recognition system. Specifically, we first derive the signal variation corresponding to human gestures with spatial-temporal processing. To enhance the robustness of the system and reduce data collecting efforts, we design a data augmentation framework based on the correlation between signal patterns and gesture variations. Furthermore, we propose a dynamic window mechanism to perform gesture segmentation automatically and accurately, thus enable real-time recognition. Finally, we build a lightweight neural network to extract spatial-temporal information from the data for gesture classification. Extensive experimental results show DI-Gesture achieves an average accuracy of 97.92%, 99.18% and 98.76% for new users, environments and locations, respectively. In real-time scenario, the accuracy of DI-Gesutre reaches over 97% with average inference time of 2.87ms, which demonstrates the superior robustness and effectiveness of our system.Comment: The paper is submitted to the journal of IEEE Transactions on Mobile Computing. And it is still under revie

META-SELD: Meta-Learning for Fast Adaptation to the new environment in Sound Event Localization and Detection

For learning-based sound event localization and detection (SELD) methods, different acoustic environments in the training and test sets may result in large performance differences in the validation and evaluation stages. Different environments, such as different sizes of rooms, different reverberation times, and different background noise, may be reasons for a learning-based system to fail. On the other hand, acquiring annotated spatial sound event samples, which include onset and offset time stamps, class types of sound events, and direction-of-arrival (DOA) of sound sources is very expensive. In addition, deploying a SELD system in a new environment often poses challenges due to time-consuming training and fine-tuning processes. To address these issues, we propose Meta-SELD, which applies meta-learning methods to achieve fast adaptation to new environments. More specifically, based on Model Agnostic Meta-Learning (MAML), the proposed Meta-SELD aims to find good meta-initialized parameters to adapt to new environments with only a small number of samples and parameter updating iterations. We can then quickly adapt the meta-trained SELD model to unseen environments. Our experiments compare fine-tuning methods from pre-trained SELD models with our Meta-SELD on the Sony-TAU Realistic Spatial Soundscapes 2023 (STARSSS23) dataset. The evaluation results demonstrate the effectiveness of Meta-SELD when adapting to new environments.Comment: Submitted to DCASE 2023 Worksho

Verification of solitary wave numerical simulation and case study on interaction between solitary wave and semi-submerged structures based on SPH model

Due to significant influence on the safety of marine structures, the interaction between extreme waves and structures is a crucial area of study in marine science. This paper focus on the verification of a solitary wave meshless SPH model and the application of the model on the interaction between solitary waves and semi-submersible structures. A solitary wave propagation model is established based on the SPH method combined with Rayleigh solitary wave theory, quintic kernel function, artificial viscosity, and Symplectic Method. The accuracy of the model is validated by comparing the calculated wave height with the theoretical value. The calculated results with relative particle spacing H0/d0 ≥ 20 are in good agreement with the analytical solution. The simulated solitary wave is also quite stable with a maximum L2 error 0.016. Therefore, the proposed SPH model can accurately simulate the propagation of the solitary waves. A case study on the interaction between solitary waves and semi-submersible platforms is conducted. The results show that the interaction between solitary waves and semi-submersible causes two double peaks with wave heights of 0.398 m and 0.410 m, respectively, induced by overtopping at the center of the platform. The wave transmission coefficient Kt is 0.880 due to that the solitary wave height reduces from 0.498 m to 0.438 m after the solitary wave propagates through the semi-submersible structure. In addition, the solitary wave induces significant vertical wave loads of the structure with a load amplitude of 0.688, while horizontal wave loads are relatively small with a load amplitude of 0.089. The solitary wave arrived the structure induces the upstream and downstream overtopping and forms a hydraulic jump leading to the complex flow field. The maximum velocity at the top and bottom of the structure is 2.2 m/s and 0.8 m/s respectively. Positive or negative vortex are formed at the bottom of the leading edge, top and downstream of the structure with the maximum intensity 28 s-1 and -40 s-1. In a word, the meshless SPH model can conveniently and accurately simulate the propagation of the solitary waves, and be applied to the investigation of the wave height, velocity, vorticity, wave load, and wave breaking of the interaction between solitary waves and structures in ocean engineering

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect