Engineering Commons^™

Minimalistic Peptide-Based Supramolecular Systems Relevant To The Chemical Origin Of Life, Daniela Kroiss

Dissertations, Theses, and Capstone Projects

All forms of life are based on biopolymers, which are made up of a selection of simple building blocks, such as amino acids, nucleotides, fatty acids and sugars. Their individual properties govern their interactions, giving rise to complex supramolecular structures with highly specialized functionality, including ligand recognition, catalysis and compartmentalization. In this thesis, we aim to answer the question whether short peptides could have acted as precursors of modern proteins during prebiotic evolution. Using a combination of experimental and computational techniques, we screened a large molecular search space for peptide sequences that are capable of forming supramolecular complexes with adenosine …

Recent Progress In Copper-Based Catalysts For Electrochemical Co2 Reduction, Wen Lei, Wei-Ping Xiao, De-Li Wang

Journal of Electrochemistry

As the situation of energy crisis and environmental pollution become more and more serious, the electrochemical reduction of carbon dioxide (CO₂) has attracted lots of attention because of its multiple meanings such as environment, resources and economic benefits. In this paper, the state of the art electrochemical reduction of CO₂ in aqueous solution is reviewed, and the latest research progress in Cu-based catalysts with different structures and morphologies is summarized. In the end, the application prospects, opportunities and challenges of Cu-based materials are briefly presented to provide an outlook for future research directions.

Preface To Special Issue Of Electrochemical Reduction Of Carbon Dioxide, Qing Li, Min Liu

Journal of Electrochemistry

No abstract provided.

Statuses, Challenges And Strategies In The Development Of Low-Temperature Carbon Dioxide Electroreduction Technology, Xu-Rui Zhang, Xiao-Lin Shao, Jin Yi, Yu-Yu Liu, Jiu-Jun Zhang

Journal of Electrochemistry

Low-temperature carbon dioxide (CO₂) electrochemical reduction technology is a hotspot for research and development in recent years as a way to reduce the negative impact of CO₂ on the environment and to generate energy storage through converting electricity to low-carbon fuels. Although basic research on catalyst activity, product selectivity, and reaction mechanism has been widely reported, the design and practicality of catalytic stability and corresponding electrochemical reactor systems have not been given sufficient attention and systematic development. In this paper, two important factors affecting the development of CO₂ electrochemical reduction technology in low temperature aqueous solution …

Copper-Based Compounds For Electrochemical Reduction Of Carbon Dioxide, Fan Yang, Pei-Lin Deng, You-Jia Han, Pan Jing, Bao-Yu Xia

Journal of Electrochemistry

The electrochemical reduction of carbon dioxide (CO₂) to useful chemicals and fuels has attracted enormous interest since the deteriorating global warming and energy shortage problems resulted from ever-increasing CO₂ emission. Designing efficient catalysts is of capital significance to realize the efficient and selective conversion of CO₂. Among various catalysts explored, copper-based compounds have promising potentials with acceptable efficiency for hydrocarbon production. Herein, recent advances on copper-based materials are summarized for electrochemical CO₂ conversion. We intend to include the dimensional structure, different forms (alloy, oxide) and molecular catalysts in copper-based catalysts. Moreover, the reaction mechanisms …

Recent Advances In Bismuth-Based Co2 Reduction Electrocatalysts, Rui Zhou, Na Han, Yan-Guang Li

Journal of Electrochemistry

Carbon dioxide (CO₂) is an economical, secure and sustainable carbon resource around us. Its effective capture and recycling have been the focus of our entire society. Using the electrochemical method, CO₂ can be reduced to different value-added chemicals or fuels. This approach not only would mitigate CO₂ accumulation in the atmosphere, but also would help alleviate our dependence on fossil fuel. In this article, the basic principle and process of electrochemical CO₂ reduction are first introduced. The recent development in bismuth-based catalysts for electrocatalytic CO₂ reduction is reviewed with an emphasis on their preparation, …

Electrocatalytic Reduction Of Carbon Dioxide To Carbon Monoxide Using Cobalt Nitride, Chen Ma, Peng-Fei Hou, Peng Kang

Journal of Electrochemistry

Electrocatalytic reduction of carbon dioxide (CO₂) is a promising method to alleviate global warming issues, although it still faces many challenges. Herein, we report cobalt nitride for electrocatalytic reduction of CO₂ to carbon monoxide (CO) in an aqueous electrolyte. A comparison of catalysts with different preparation temperatures and atmospheres suggests that nitrogen doping is critical to improve catalytic activity. For the most active catalyst of 700-Co_5.47N/C, the CO current density reached 9.78 mA·cm^-2 at potential of -0.7 V vs. RHE. In addition, the CO/H₂ ratio could be adjusted from 1:3 to 3:2 by …

Regulation Of Copper Surface Via Redox Reactions For Enhancing Carbon Dioxide Electroreduction, Bao-Hua Hang, Jin-Tao Zhang

Journal of Electrochemistry

A large-scale application of fossil fuels has led to excessive emission of carbon dioxide (CO₂), resulting in serious environmental issues. A promising path to reducing CO₂ emissions is recycling CO₂ into valuable chemicals and fuels through an electrochemical process. Herein, the redox reactions between copper (Cu) and ferric chloride (FeCl₃) have been utilized to regulate the Cu surface composition and structure, aimed to improve the electrocatalytic activity toward CO₂ reduction. Typically, a series of samples (named Cu-1h, Cu-2h, Cu-3h and Cu-4h) were prepared via the redox reactions for various time from 1 to …

Electrochemical Detection Of 4-Nitrophenol Based On Glassy Carbon Electrode Modified By Tio2Nps/Rgo Composite, Lin-Na Jiu, Yong-Qiang Cheng

Journal of Electrochemistry

4-nitrophenol (4-NP) has become factitious pollution, and presented a serious threat to the nature and human health. It is necessary to develop a convenient and fast detection method. In this work, the glassy carbon electrode modified by titanium dioxide nanoparticles (TiO₂NPs)/reduced graphene oxide (RGO) composite as an electrochemical sensor was studied for the trace detection of 4-NP. The morphology of the composite was characterized by scanning electron microscopy (SEM). The homogeneous mixing of titanium dioxide nanoparticles and reduced graphene oxide increased the specific surface area of the composite, and facilitated the electrochemical reaction of 4-NP. The electrochemical characteristics …

Effect Of Morphology Of Fe-N Codoped Carbon Nanomaterial On Electrochemical Reduction Reactions, Er-Ling Li, Fa Yang, Ming-Bo Ruan, Ping Song, Wei-Lin Xu

Journal of Electrochemistry

Graphene nanosheets (GS) and carbon nanotubes have been considered as good catalysts candidates for applications in energy conversion and storage. However, hybrids of GS and carbon nanotubes are always formed in transition metal-based nitrogen-doped system, making the system quite complex for exploring the structure-activity relationship. To prepare the catalysts with desired species controllably, we try to adjust the outcomes with the effect of nitrogen on the growth of carbon nanotubes. In this work, a series of Fe-N co-doped carbon hybrid catalysts containing N-doped GS or hybrids of GS/bamboo carbon nanotubes (BCNTs) or BCNTs were obtained with one-step pyrolyzed method. To …

Preparations And Electrocatalytic Properties Of Cu-Bipy-Btc-Derived Carbon-Based Catalyst For Oxygen Reduction Reaction, Li-Hua Zhang, Jun-Feng Chen, Wan-Tang Huang, Yong-You Hu, Jian-Hua Cheng, Yuan-Cai Chen

Journal of Electrochemistry

Efficient and low-cost oxygen reduction reaction (ORR) electrocatalyst plays a key role for fuel cells. In this paper, ORR active metal organic framework (MOF: Cu-bipy-BTC, bipy = 2,2?-bipyridine, BTC = 1,3,5-tricarboxylate) was prepared using hydrothermal method, and then carbon-based material MOF-800 was obtained from pyrolyzing Cu-bipy-BTC at 800 °C. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), nitrogen sorption isotherm and X-ray photolectron spectroscopy (XPS) were used to characterize the morphologies and structures of the catalysts. Linear sweep voltammetry (LSV) and current-time curve (i-t) were adopted to evaluate the electrocatalytic properties of the catalysts. …

Single-Layer Oxygen Deficiency Δ-Mno2 For Electrochemical Co2 Reduction, Yue-Feng Zhang, Jian-Jun Liu, Zeng-Xi Wei, Xin-Xin Tian, Jian-Min Ma

Journal of Electrochemistry

Manganese dioxide (MnO₂) has been widely used in catalysis. In addition, since the defect engineering can change the electronic properties of the catalyst, here we have systematically studied electrocatalytic carbon dioxide reduction reaction (CO₂RR) on δ-MnO₂ with and without oxygen deficiency, denoted as Ov-MnO₂ and MnO₂, respectively. We calculate the electronic properties and the intermediate of free energy for MnO₂ and Ov-MnO₂ with the help of spin-polarized density functional theory. By analyzing this result, we can find that the introduction of defects change the δ-MnO₂ from semiconducting properties …

Magic Angle Spinning Spheres And Improved Microwave Coupling For Magnetic Resonance, Pin-Hui Chen

Arts & Sciences Electronic Theses and Dissertations

Nuclear magnetic resonance (NMR) is a nondestructive technique used to characterize molecular structure and dynamics with atomic resolution. In solid-state NMR, magic angle spinning (MAS) is commonly implemented to improve spectral resolution by partially averaging anisotropic interactions. To further improve NMR sensitivity, dynamic nuclear polarization (DNP) is utilized to transfer the polarization from electron spins to nuclei of interest using microwaves. Advanced MAS DNP NMR instrumentation, such as spherical rotors for stable and fast spinning, dielectric lenses to effectively couple the microwaves into the sample, and the separation of receiving and transmitting circuits to decrease measurement noise, are developed to …

Wave Function Engineering In Cdse/Pbs Core/Shell Nanocrystal Heterostructures, Brian Matthew Wieliczka

Arts & Sciences Electronic Theses and Dissertations

Colloidal semiconducting nanocrystals hold significant potential for third generation photovoltaics as solution processable materials that can surpass the Shockley-Queisser limit through multiexciton generation. In pursuit of this goal, the synthesis and optical characterization of CdSe/PbS core/shell quantum dots is reported. The spectroscopic behavior of these particles demonstrates their potential for use in optoelectronic devices, taking advantage of wave function engineering of the electron and hole. The rock salt PbS shell grows on all sides of the underlying zinc blende CdSe quantum dot, creating a core/shell structure. With increasing shell thickness, the band edge absorption and photoluminescence transitions decrease in energy …

Erratum: "Imaging The Three‐Dimensional Orientation And Rotational Mobility Of Fluorescent Emitters Using The Tri‐Spot Point Spread Function", Oumeng Zhang, Jin Lu, Tianben Ding, Matthew D. Lew

Electrical & Systems Engineering Publications and Presentations

In the original paper, a calibration error exists in the image-formation model used to analyze experimental images taken by our microscope, causing a bias in the orientation measurements in Figs. 2 and 3. The updated measurements are shown in Fig. E1. We have also updated the supplementary material for the original article to discuss the revised PSF model and estimation algorithms (supplementary material 2) and show the revised model and measurements (Figs. S1, S3, S7, S8, and S10–S13).

Computational Studies Of Thermal Properties And Desalination Performance Of Low-Dimensional Materials, Yang Hong

Department of Chemistry: Dissertations, Theses, and Student Research

During the last 30 years, microelectronic devices have been continuously designed and developed with smaller size and yet more functionalities. Today, hundreds of millions of transistors and complementary metal-oxide-semiconductor cells can be designed and integrated on a single microchip through 3D packaging and chip stacking technology. A large amount of heat will be generated in a limited space during the operation of microchips. Moreover, there is a high possibility of hot spots due to non-uniform integrated circuit design patterns as some core parts of a microchip work harder than other memory parts. This issue becomes acute as stacked microchips get …

A Simple And Effective Way To Overcome Carbon Monoxide Poisoning Of Platinum Surfaces In Direct Formic Acid Fuel Cells, Yaser M. Asal Mr., Islam M. Al-Akraa Dr, Sohair A. Darwish Ms

Chemical Engineering

A glassy carbon (GC) electrode modified with multi-walled carbon nanotubes (MWCNTs) and platinum nanoparticles (PtNPs), Pt/MWCNTs-GC, has been introduced for formic acid electro-oxidation (FAO). A similar loading of PtNPs has been conserved for a proper comparison between the Pt/MWCNTs-GC and the unmodified Pt/GC electrodes. The modification with MWCNTs could enhance the loading of PtNPs onto the GC electrode in a way that minimizes its agglomeration and increases its dispersion in the CNTs network. This not only increases the surface area exposed to the reaction but also interrupts the contiguity of the Pt active sites minimizing the adsorption of the poisoning …

A Promising Modification Of Pt Surfaces With Cnts For Decreasing Poisoning Impact In Direct Methanol Fuel Cells, Yaser M. Asal Mr., Islam M. Al-Akraa Dr, Aya A. Khalifa Ms.

Chemical Engineering

Direct methanol fuel cells (DMFCs) are clean energy sources that have many applications due to the high energy density of methanol as a fuel. However, this type of fuel cells (FCs) has limitations that are preventing it from being commercialized. One such limitation is the adsorption of intermediates such as CO into the surface of the Platinum (Pt) catalyst during methanol oxidation (MO) which deactivates its active sites, where the reaction is taking place, and leads to poisoning of the electrode over the long term. In this study, multi-walled carbon nanotubes (MWCNTs) have been introduced to the Pt-modified glassy carbon …

Recent Advances In Nanofluidic Electrochemistry For Biochemical Analysis, Zhong-Qiu Li, Zeng-Qiang Wu, Xing-Hua Xia

Journal of Electrochemistry

Nanofluidics, as a young research field, has been receiving more and more attentions. It has been successfully applied in various fields including nanoscale separation, biochemical sensing and energy conversion. The development of nanofluidics is closely related to electrochemistry that can provide a driving force for the study of the material transport characteristics in nanopores/nanochannels. On the other hand, nanopores/nanochannels can creat a microenvironment for study of spatially nanoconfined electrochemistry. The combination of nanofluidics and electrochemistry has given rise to many new theories and technologies for single molecule/particle analysis and nanofluid manipulation. Herein, we provide a review of the recent progresses …

A Low Noise Temperature Control System For Nanopore-Based Single Molecule Analysis, Cheng-Yu Yang, Zhen Gu, Zheng-Li Hu, Yi-Lun Ying, Yi-Tao Long

Journal of Electrochemistry

Nanopore employs a single bio-molecule interface, which is a highly sensitive single-molecule detection technology for measuring single biomolecules such as DNA, RNA, protein, and peptide. The interaction between single molecule and nanopore is thermodynamically controlled. Therefore, it is urgent to precisely control the temperature of the nanopore system without introduction of any noise. In this paper, we have developed a low-noise temperature control system for single-molecule detection of nanopores to achieve precise regulation at the ambient temperature during measurements. The system utilizes the thermoelectric effect of the semiconductor refrigerating chip to heat or cool the detection chamber, while adopts electromagnetically …

Recent Progresses Of Enzymes Assembled In Nanochannels For Catalytic Reaction, Shangguan Li, Xu Xuan, Liu Song-Qin

Journal of Electrochemistry

The research of enzymes assembled and catalytic reaction not only is beneficial to exploit the essences of life’s activities, but also is significant in developing the practical application of enzymes in these areas including industrial production, analysis and detection, treatment of disease, etc. The effective immobilization and ordered assembly of enzymes are important methods for maintaining the catalytic activity, catalytic reaction stability and catalytic process controllability of enzymes. Among them, single or multi-enzymes are immobilized orderly in nanochannels that exhibit unique features and advantages, accordingly, the confinement effect of nanochannels can increase the selectivity and catalytic efficiency of enzymes through …

Electrocatalytic Nanomaterials For Reduction Of Hydrogen Peroxide As Potential Radioprotectors, Rui-Hong Jia, Jin-Xuan Zhang, Xiao-Dong Zhang, Mei-Xian Li

Journal of Electrochemistry

Nanomaterials have shown many potential application prospects in the biomedical field, such as medical imaging, drug delivery and biosensing due to their unique physical and chemical properties. In this review we focus on nanomaterials that have shown not only abilities of radiation protection, but also good electrocatalytic activities toward reduction reactions of hydrogen peroxide and oxygen. We discuss the abilities of radiation protection of these nanomaterials that are ascribed to their enzyme-like activities because their catalytic properties provide an effective pathway for scavenging free radicals in vivo via rapid reactions with reactive oxygen species. We also provide insights into electrocatalytic …

Single Particle Impact Electrochemistry: Analyses Of Nanoparticles And Biomolecules, Jian-Hua Zhang, Yi-Ge Zhou

Journal of Electrochemistry

Single particle impact electrochemistry (SPIEC) has grown rapidly in recent years and shown great promise in the analysis of nanoparticle properties as well as the detection of biomolecules including DNA, RNA, protein, enzyme, bacteria, virus, vesicles and others. This minireview summarizes recent advances in electroanalytical applications of SPIEC according to different analytical methods, i.e., direct electrolysis of nanoparticles or labeled nanoparticles, direct electrolysis of soft particles encapsulated redox molecule, indirect electrochemistry of particles, area and diffusion blocking, and changes in current magnitude and collision frequency.

Correlated Optical Imaging And Electrochemical Recording For Studying Single Nanoparticle Collisions, Lin-Lin Sun, Wei Wang, Hong-Yuan Chen

Journal of Electrochemistry

With the development of nano-fabrications in recent years, a novel strategy based on random collisions of single electroactive nanoparticles (NPs) onto an inert ultramicroelectrode (UME) has been emerged in the field of nanoelectrochemistry, and named as single nanoparticles collisions (SNCs). The technique uses a chronoamperometric method to detect transient current generated by random collisions of single NPs onto an UME. By analyzing the current signal, one could study the properties of single NPs. Although this technique can detect electrochemical or electrocatalytic currents of a single NP, the traditional SNCs technology lacks necessary spatial resolution to identify and characterize a specific …

Defect Chemistry And Ion Intercalation During The Growth And Solid-State Transformation Of Metal Halide Nanocrystals, Bo Yin

McKelvey School of Engineering Theses & Dissertations

Abstract of the Dissertation

Defect Chemistry and Ion Intercalation During the Growth and Solid-State Transformation of Metal Halide Nanocrystals

Semiconductor metal halides as light-sensitive materials have applications in multiple areas, such as photographic film, antibacterial agents and photocatalysts. One focus of this dissertation is to achieve novel morphologies of ternary silver bromoiodide (AgBr1-xIx, 0

For the silver halide system, we demonstrate that the anion composition of AgBr1-xIx nanocrystals determines their shape through the introduction of twin defects as the nanocrystals are made more iodide-rich. AgBr1-xIx nanocrystals grow as single-phase, solid solutions with the rock salt crystal structure for anions compositions …

Experimental And Computational Study On Magnetic Nanowires Of Layered Titanates, Caleb Layne Heath

Graduate Theses and Dissertations

The intricate nanostructures of layered titanates are unique among nanomaterials due to their easy and inexpensive syntheses. These nanomaterials have been proven valuable for use in industries as varied as energy, water treatment, and healthcare, and can be produced at industrial scales using already existent equipment. They have complex morphology, and surface structure well suited to chemical modification and doping. However, there is a longstanding debate on their lattice structure after the doping. There is a long-unmet need to understand, using both experimental and simulation methods, how dopants alter the clay-like layered crystal structure and associated physical and chemical properties. …

Engineering Multifunctional And Morphologically Diverse Polymer Brush Surfaces, Cassandra M. Reese

Dissertations

The combination of surface-initiated polymerization (SIP) and post-polymerization (PPM) serves as a powerful approach to fabricate complex, multifunctional polymer films, which can be precisely tuned for desired surface engineering applications. Careful manipulation of PPM parameters such as reaction conditions, the tethered brush parameters, and the physical properties of the unbound post-modifier greatly influence the depth of penetration of the post-modifier and the polymer brush compositional heterogeneity. This dissertation focuses on engineering polymer brush surfaces with multifunctional chemistries and tunable morphologies by investigating the PPM parameters that dictate the distribution of post-modifiers on grafted polymer brush surfaces.

The first chapter of …

Surface-Enhanced Infrared Absorption Spectroscopy- Surface Sensitive In Situ Label-Free Spectroelectrochemistry, Lie Wu, Jian-Long Sun, Xiu-E Jiang

Journal of Electrochemistry

Surface-enhanced infrared absorption spectroscopy (SEIRAS), especially in attenuated total reflectance (ATR) mode, taking advantages of surface-enhancement and near-field optical effect of enhancing substrate, is a ultra-sensitive infrared spectroscopy, which could achieve surface-selected detection at a sub-monolayer level. Since the enhancing substrate could simultaneously serve as a working electrode, ATR-SEIRAS is a readily surface-sensitive in situ label-free spectroelectrochemistry technique. With the advantages of small influence from metal species on enhancement effect, good potential reversibility of spectra, simple surface selection rule and sensitivity to polar molecules, ATR-SEIRAS has been widely applied in the fields of orientation analysis and species identification of interfacial …

In Situ/Operando Visualization Of Electrode Processes In Lithium-Sulfur Batteries: A Review, Shuang-Yan Lang, Xin-Cheng Hu, Rui Wen, Li-Jun Wan

Journal of Electrochemistry

Lithium-sulfur (Li-S) batteries have been regarded as one of the most promising candidates for the next-generation energy storage devices. Fundamental understanding of the structure and evolution processes at electrode-electrolyte interfaces is essential to the further development. In this review, we summarize recent advances in the interfacial observations by means of various in situ/operando visualization techniques, including scanning probe microscopy (SPM), electron microscopy (EM), X-ray microscopy (XRM) and optical microscopy (OM). The real-time investigation provides important evidence for the morphology and component changes including S/Li₂S transformation, polysulfide dissolution on cathodes and Li/solid electrolyte interphase (SEI) evolution on anodes, which …

Recent Progress Of Electrochemiluminescence Sensors Based On Electrically Heated Electrode, Hui-Fang Zhang, Yi-Ting Chen, Fang Luo, Zhen-Yu Lin, Guo-Nan Chen

Journal of Electrochemistry

Electrochemiluminescence (ECL) has broad application in the fields of environmental monitoring and biological analysis due to its intrinsic advantages such as excellent versatility, good detection sensitivity, and high specificity. The intensity of ECL can be influenced by temperature variation in the ECL quantum efficiency and the rate of electrochemical reaction. However, traditional temperature control is commonly realized through bulk solutions heating, which is complicated and unfavorable for detection when the volatile and thermally unstable materials existed. In order to address these problems, electrically heated electrodes are used to adjust the temperature desired. The major character of this technique lies in …