Chemistry Commons^™

Electrochemical Preparations And Applications Of Nano-Catalysts With High-Index Facets, Chi Xiao, Na Tian, Zhi-You Zhou, Shi-Gang Sun

Journal of Electrochemistry

The performance of catalysts highly depends on their surface structure and composition. Nanocrystals bounded by high-index facets usually exhibit high catalytic activity due to their high-density low-coordinated step atoms with high reactivity. In this paper, we have reviewed the preparations of noble metals (e.g., Pt, Pd and Rh) nanocatalysts with high-index facets by electrochemical square-wave potential method developed in our group. The square-wave potential method includes a nucleation procedure to generate nuclei, followed by a square-wave potential procedure for a certain period of time for the growth of nuclei into nanocrystals. The formation mechanism of high-index facets is also discussed. …

In-Situ Raman Spectroscopic Study Of Electrochemical Reactions At Single Crystal Surfaces, Min Su, Jin-Chao Dong, Jian-Feng Li

Journal of Electrochemistry

Since the 1970s, in-situ spectroscopy (Raman, infrared, etc.) has been used to systematically study the electrochemical interfacial reactions which can provide more information about surface reactions and reveal the mechanisms from microscopic view due to its excellent surface sensitivity and energy resolution. With the development of nano-technology, surface-enhanced Raman scattering effect spectroscopy has made rapid progress. Recently, the emergence of SHINERS provides a good in-situ spectroscopic technique for the study of catalytic reactions on single crystal model electrodes with deterministic surface structure. In this paper, we have summarized the application of SHINERS in the study of …

Nanoscale Colocalization Of Fluorogenic Probes Reveals The Role Of Oxygen Vacancies In The Photocatalytic Activity Of Tungsten Oxide Nanowires, Meikun Shen, Tianben Ding, Steven T. Hartman, Fudong Wang, Christina Krucylak, Zheyu Wang, Che Tan, Bo Yin, Rohan Mishra, Matthew D. Lew, Bryce Sadtler

Electrical & Systems Engineering Publications and Presentations

Defect engineering is a strategy that has been widely used to design active semiconductor photocatalysts. However, understanding the role of defects, such as oxygen vacancies, in controlling photocatalytic activity remains a challenge. Here, we report the use of chemically triggered fluorogenic probes to study the spatial distribution of active regions in individual tungsten oxide nanowires using super-resolution fluorescence microscopy. The nanowires show significant heterogeneity along their lengths for the photocatalytic generation of hydroxyl radicals. Through quantitative, coordinate-based colocalization of multiple probe molecules activated by the same nanowires, we demonstrate that the nanoscale regions most active for the photocatalytic generation of …

Towards Machine Learning In Chemical Sensing : Milk Differentiation And Quality Control Through Two-Dimensional Nano-Sensor Array, Yu Sheng Chen

Legacy Theses & Dissertations (2009 - 2024)

Herein, we developed a novel artificial tongue using machine learning and 12 nanoassemblies (2D-NAs) to identify and analyzed different kinds of milk beverages for quality control. This biomimetic sensor array was trained to “taste” different milk types as an “artificial tongue” which is the first time we demonstrated that this sensor array can be implemented to complex systems. Two-dimensional nanoparticles (2D-nps) and nine fluorescently labeled single stranded oligonucleotides (ssDNA) with different length and nucleobases were assembled to create 12 2D-NAs. The artificial tongue was deployed to identify and analyze five milk types. All five milk types were discriminated with 95% …

Development Of Dual Functional Dna/Rna Nanostructures For Drug Delivery, Vibhav Amit Valsangkar

Legacy Theses & Dissertations (2009 - 2024)

In addition to the traditional biochemical functions, DNA and RNA have been increasingly studied as building blocks for the formation of various 2D and 3D nanostructures. DNA has emerged as a versatile building block for programmable self-assembly. DNA-based nanostructures have been widely applied in biosensing, bioimaging, drug delivery, molecular computation and macromolecular scaffolding. A variety of strategies have been developed to functionalize these nanostructures. The major advantage is that DNA is a very stable molecule and its base-pairing properties can be easily utilized to control and program the formation of desired nanostructures. In addition, some of these DNA/RNA nanostructures have …

Synthesis Of Metal Oxide Surface And Interface Arrays By A Combined Solid-Liquid- Vapor/Vapor-Liquid-Solid Approach, Alexandra J. Riddle

Theses and Dissertations--Chemistry

This project was motivated by an in situ heating experiment in the transmission electron microscope (TEM) in which gold (Au) nanoparticles were observed to dissolve tin dioxide (SnO2) nanowires (NWs) under vacuum. The explanation for this observation was that the high-temperature and low-pressure environment of the TEM caused the reverse reaction of the well-known vapor-liquid-solid (VLS) method commonly used to grow NWs. In the VLS process, a metal catalyst absorbs reactant vapor until it becomes supersaturated. The precipitation of the NW occurs at the liquid-solid interface, which ceases when there is no longer reactant vapor, and the diameter of the …

Transient Electrochemical Surface-Enhanced Raman Spectroscopic Study In Electrochemical Reduction Of P-Nitrothiophenol, Yun Ling, Jing Tang, Guo-Kun Liu, Cheng Zong

Journal of Electrochemistry

P-nitrothiophenol (PNTP) is one of the most common probe molecules studied by surface-enhanced Raman spectroscopy (SERS). The research in electrochemical reduction behavior of PNTP will help understanding the mechanism for the nitrobenzene reduction. In this paper, we used transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to study the SERS of PNTP with cyclic voltammetry and chronoamperometry on gold electrodes. The results show that the TEC-SERS provide a time resolution that equals the transient electrochemical methods, and we concluded that the reaction was so quick that we did not observe the spectral information of intermediate species described in the literatures with a …

An Aptasensor Based On Aunps/Pani/Tnts Nanocomposite For Electrochemical Detection Of Tobramycin, Yong-Ling Nong, Ni-Na Qiao, Ying Liang

Journal of Electrochemistry

A novel well-constructed electrochemical aptamer-based sensor for the detection of tobramycin was presented, using differential pulse voltammetry (DPV) as a detection technique and methylene blue(MB) as an electrochemical indicator. A glassy carbon electrode modified with a nanocomposite of Au nanoparticles/polyaniline/titania nanotubes (AuNPs/PANI/TNTs) was constructed as the electrode scaffold. The nanocomposite was characterized by transmission electron microscopy and X-ray photoelectron spectroscopy in detail. The results of cyclic voltammetry and electrochemical impedance measurements demonstrated that the AuNPs/PANI/TNTs nanocomposites can improve greatly the electron transfer on the interface. For the detection of tobramycin, the DPV results showed a linear relationship between the current …

Electrochemical Preparation And Photocatalytic Performance Of Lanio3/Tio2 Nanotube Arrays, Cheng Gong, Ze-Yang Zhang, Si-Wan Xiang, Lan Sun, Chen-Qing Ye, Chang-Jian Lin

Journal of Electrochemistry

The LaNiO₃/TiO₂ nanotube arrays were prepared by pulse electrodeposition combined with high temperature annealing. The LaNiO₃ nanoparticles modified on the TiO₂ nanotube arrays had small particle size (< 10 nm), uniform distribution and controllable loading. Some LaNiO₃ nanoparticles were deposited inside the TiO₂ nanotubes. The UV-visible absorption spectra displayed that the absorption band edge of LaNiO₃/TiO₂ nanotube arrays was obviously red-shifted as compared with that of TiO₂ nanotube arrays, and the visible light absorption was enhanced significantly. The photocatalytic degradation results of rhodamine B (RhB) under visible light showed that the LaNiO₃/TiO₂ nanotube arrays prepared …

Electrochemical Sensor Based On Magnetic Electrode Modified With Magnetic Molecularly Imprinted Nanoparticles Immobilized Hemoglobin For Determination Of Hydrogen Peroxide, Yang Yuan, Jia-Xin Wang, Yu-Hua Cao

Journal of Electrochemistry

In this work, the surface-imprinted technique was used to prepare magnetic hemoglobin (Hb) imprinted nanoparticles, using Fe₃O₄@SiO₂ NPs as the carrier, Hb as the template molecule, and tetraethyl orthosilicate (TEOS) as the imprinted polymer monomer. The nanoparticles had a core-shell structure, with magnetic Fe₃O₄ NPs as the core and Hb imprinted polymers as the shell. Therefore, Hb could be concentrated and fixed on the surface of the magnetic imprinted nanoparticles (MMIPs NPs). Furthermore, MMIPs NPs were immobilized with chitosan (CS) on the surface of a magnetic electrode to constitute Hb enzyme-like biosensor …

Novel Silica Filled Deep Eutectic Solvent Based Nanofluids For Energy Transportation, Changhui Liu, Hui Fang, Xinjian Liu, Ben Xu, Zhonghao Rao

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Liquid range of nanofluids is a crucial parameter as it intensively determines their application temperature scope. Meanwhile, improved thermal conductivity and stability are of great significances and comprise the main fundamental research topics of nanofluids. In this work, 2- butoxy-3,4-dihydropyran (DP), produced from a convenient one-pot three-component reaction in water, was employed as dual lipophilic brusher and metal nanoparticle anchor. It was found that DP was able to enhance the dispersing ability and thermal conductivity of SiO2 nanoparticle filled deep eutectic solvent (DES) based nanofluids simultaneously. The key to the success of this protocol mainly relies on the electrophilic property …

A Facile Route To Synthesize Pt-Wo3 Nanosheets With Enhanced Electrochemical Performance For Her, Peng-Jie Jiang, Yi Lv, Chang-Miao Chen, Hong-Cheng He, Yong Cai, Ming Zhang

Journal of Electrochemistry

Platinum-tungsten trioxide (Pt-WO₃) nanosheets were synthesized on nickel foams (NFs) directly. As great conductive networks, NFs substrates could greatly improve the electrode performance of WO₃. The modified platinum nanoparticles not only enhanced the electron transformation of catalysts, but also increased the active sites for hydrogen evolution reaction (HER). Pt-WO₃/NF revealed a better catalytic activity than WO₃/NFs with a smaller Tafel slope (80 mV·dec^-1) and a lower overpotential of 72 mV at the current density of 10 mA·cm^-2. In addition, Pt-WO₃/NF showed great durability and stability during …

Preparations And Electrochemical Properties Of Co@Nc Nanocomposites Based On Zif-67, Xiao-Li Tan, Deng-Hong He, Xing-Wang Zhang

Journal of Electrochemistry

It is necessary to develop an inexpensive catalyst for the replacement of precious metal catalysts (such as RuO₂, IrO₂). In this article, the metal organic framework ZIF-67 was synthesized by solvothermal method at room temperature, and then the high temperature carbonization was used to prepare the nitrogen-doped carbon-based composite material Co@NC with the Co nanoparticle inside. The effects of the carbonization temperature on surface morphology, chemcial composition and electrocatalytic property were investigated. Most importantly, the Co@NC catalyst with the best morphology and structure was synthesized, and its catalytic activity and stability toward oxygen evolution reaction (OER) …

Preparation Of Nanostructural Mno-Porous Graphene Hybrid Material By Thermally-Driven Etching Of Mno For Lithium-Air Batteries, Juan Yang, Jun-Wei Lang, Peng Zhang, Bao Liu

Journal of Electrochemistry

In this paper, improving the surface morphology of graphene(GNSs) as designed concept. we describe a MnO/porous-graphene(MnO-PGNSs) was synthesized by a simple site-localized Mn²⁺ on GO (Mn-GO) by charge adsorption and then driving by high-temperature calcination, growing MnO nanoparticles and etching GNSs achieved on step. And Then focus on the key factors of influenced the etch hole formation are analyzed, founded the dispersion of Mn-GO; layer number of GO and calcination temperature also affected the formation of holes. In addition, the MnO-PGNSs as lithium-air battery cathode exhibits high reversible capacity compared with GNSs and PGNs and it is able to …

Pd Nanoparticles Supported On The Etched Ni Foams As High-Performance Electrocatalysts For Direct Ethanol Fuel Cells, Chi Zhang, Cheng-Fei Li, Gao-Ren Li

Journal of Electrochemistry

The development of non-Pt anode electrocatalysts with high activity and long-term durability at low cost for fuel cells still remains enormous challenge. Here we report the Pd nanoparticles supported on Ni foams etched by the mixed acids (HNO₃+H₂SO₄+H₃PO₄+CH₃COOH) (Pd/ME-NF) that are designed and fabricated as high-performance electrocatalysts for ethanol oxidation in alkaline media. Because of the advantages of large open space, fast electrolyte penetration/diffusion and rapid electron transfer process, the Pd/ME-NF catalysts exhibited significantly improved electrocatalytic activity and durability compared with the commercial Pd/C catalysts.

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 …

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 …

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 …

Organically Modified Inorganic Nanoparticles For Halochromic Ionophores And Nucleic Acids, William Johnston

Doctoral Dissertations

In this dissertation, four nanoparticle reaction schemes were developed as substrates for halochromic dyes or nucleic acids. The reaction schemes include the use of two substrates: silica nanoparticles and halloysite nanotubes. The protocols can incorporate silica (SiO2) nanoparticles and halloysite aluminosilicate (AlO2SiO2) nanotubes due to the presence of silane groups on the surface of either substrate. The reaction schemes are presented along with detailed protocols which were written to facilitate both reproducibility and to serve as an aid to further study and for easy modification of the protocol to suit a researcher's needs. The data is discussed in the materials …

Potential For On-Site, Prosecutorial Evidence From Drug Residues Collected On Plasmonic Paper: A Pilot Study For Sers-Psi-Ms, Daniel S. Burr

Theses and Dissertations

Given the potential impact of improvements to on-site drug testing, as well as recent, successful displays of paper spray ionization mass spectrometry (PSI-MS) in this regard, this thesis pilots the implementation of Raman spectroscopy as a compliment to MS for field-based confirmatory drug testing. Surface enhanced Raman scattering (SERS) is utilized for applications to trace detection. Two-tiered analysis of individual drug samples is enabled using triangularly-cut plasmonic papers, from which both SERS and PS-MS analysis may be performed. Several drug compounds, representative of traditional and emerging drug types, are examined by these techniques, both separately and as a fully integrated, …

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, Li Shangguan, Xuan Xu, Song-Qin Liu

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 …

Synthesis Of Metal Oxide Surfaces And Interfaces With Crystallographic Control Using Solid-Liquid-Vapor Etching And Vapor-Liquid-Solid Growth, Beth S. Guiton, Lei Yu

Chemistry Faculty Patents

The present invention provides integrated nanostructures comprising a single-crystalline matrix of a material A containing aligned, single-crystalline nanowires of a material B, with well-defined crystallographic interfaces are disclosed. The nanocomposite is fabricated by utilizing metal nanodroplets in two subsequent catalytic steps: solid-liquid-vapor etching, followed by vapor-liquid-solid growth. The first etching step produces pores, or “negative nanowires” within a single-crystalline matrix, which share a unique crystallographic direction, and are therefore aligned with respect to one another. Further, since they are contained within a single, crystalline, matrix, their size and spacing can be controlled by their interacting strain fields, and the array …

Nano Fab Lab 63, Brian K. Deemer, Josh Clemons, Nick Brodine, Delaney Fitzsimmons

Mechanical Engineering

Lawrence Livermore National Laboratories (LLNL) has several steps in the production process for ceramic nanofiber tubes that they would like to improve - electrospinning, cutting, rolling, sealing and heat treating. We undertook the challenge to deliver LLNL with a semi-automated process that efficiently integrates the steps of cutting, rolling, and sealing to save time and improve control over end dimensions. In this document, we discuss the technical background of the manufacturing steps currently followed to create nanofiber tubes, identify which steps are incorporated in our prototype and explain how they will interface with one another, define the design requirements, present …

Triperyleno[3,3,3]Propellane Triimides: Achieving A New Generation Of Quasi-D3h Symmetric Nanostructures In Organic Electronics, Lingling Lv, Josiah Roberts, Chengyi Xiao, Zhenmei Jia, Wei Jiang, Chad Risko, Lei Zhang

Chemistry Faculty Publications

Rigid three-dimensional (3D) polycyclic aromatic hydrocarbons (PAHs), in particular 3D nanographenes, have garnered interest due to their potential use in semiconductor applications and as models to study through-bond and through-space electronic interactions. Herein we report the development of a novel 3D-symmetric rylene imide building block, triperyleno[3,3,3]propellane triimides (6), that possesses three perylene monoimide subunits fused on a propellane. This building block shows several promising characteristics, including high solubility, large π-surfaces, electron-accepting capabilities, and a variety of reactive sites. Further, the building block is compatible with different reactions to readily yield quasi-D_3h symmetric nanostructures (9, …

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

McKelvey School of Engineering Graduate Student 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 …