Physical Chemistry Commons^™

Band Alignments Of Metal/Oxides-Water Interfaces Using Ab Initio Molecular Dynamics, Yong-Bin Zhuang, Jun Cheng

Journal of Electrochemistry

Band alignments of electrode-water interfaces are of crucial importance for understanding electrochemical interfaces. In the scenario of electrocatalysis, applied potentials are equivalent to the Fermi levels of metals in the electrochemical cells; in the scenario of photo(electro)catalysis, semiconducting oxides under illumination have chemical reactivities toward redox reactions if the redox potentials of the reactions straddle the conduction band minimums (CBMs) or valence band maximums (VBMs) of the oxides. Computational band alignments allow us to obtain the Fermi level of metals, as well as the CBM and VBM of semiconducting oxides with respect to reference electrodes. In this tutorial, we describe …

Recent Progress Of Bifunctional Electrocatalysts For Oxygen Electrodes In Unitized Regenerative Fuel Cells, Tian-Long Zheng, Ming-Yu Ou, Song Xu, Xin-Biao Mao, Shi-Yi Wang, Qing-Gang He

Journal of Electrochemistry

Unitized regenerative fuel cells (URFCs), which oxidize hydrogen to water to generate electrical power under thefuel cells (FCs) mode and electrolyze water to hydrogen under the water electrolysis (WE) mode for recycling, areknown as clean and sustainable energy conversion devices. In contrast to the hydrogen oxidation reaction (HOR) andhydrogen evolution reaction (HER) on the hydrogen electrode side, the sluggish kinetics of oxygen reduction reaction(ORR) and oxygen evolution reaction (OER) on the oxygen electrode side requires highly efficient bifunctional oxygencatalysts. Conventional precious metal oxygen catalysts combine Pt and IrO₂ with excellent ORR and OER activities toachieve bifunctional electrocatalysis performance, but …

Electrochemical Scanning Tunneling Microscopy: Taking The Initial Stage Of Cu Electrodeposition On Au(111) As An Example, Zhuo Tan, Kai-Xuan Li, Bing-Wei Mao, Jia-Wei Yan

Journal of Electrochemistry

Electrochemical scanning tunneling microscopy (ECSTM) plays an important role in the field of electrochemistry, which can obtain potential-dependent structural information of electrode surface with high spatial resolution and observe some reaction processes in electrolyte solutions, and provide a powerful way to understand the interfacial structure and electrode processes from the perspective of high spatial resolution. In this article, the study of electrodeposition of Cu on Au (111) by ECSTM is taken as an example to introduce the experimental methods required for ECSTM and share our experience with other electrochemical groups. Firstly, the working principle of STM is introduced so that …

Measuring And Enhancing The Ionic Conductivity Of Chloroaluminate Electrolytes For Al-Ion Batteries, Anthony J Lucio, Iwan Sumarlan, Elena Bulmer, Igor Efimov, Stephen Viles, A Robert Hillman, Christopher J Zaleski, Karl S Ryder

Faculty, Staff and Student Publications

At the core of the aluminum (Al) ion battery is the liquid electrolyte, which governs the underlying chemistry. Optimizing the rheological properties of the electrolyte is critical to advance the state of the art. In the present work, the chloroaluminate electrolyte is made by reacting AlCl3 with a recently reported acetamidinium chloride (Acet-Cl) salt in an effort to make a more performant liquid electrolyte. Using AlCl3:Acet-Cl as a model electrolyte, we build on our previous work, which established a new method for extracting the ionic conductivity from fitting voltammetric data, and in this contribution, we validate the method across a …

High Resolution Intracavity Laser Absorption Spectroscopy Of Transition Metal-Containing Diatomic Molecules, Kristin Bales

Dissertations

Three transition metal-containing diatomic molecules have been studied using intracavity laser spectroscopy. Many of the transitions were recorded using a Fourier-transform spectrometer for detection, allowing collection at Doppler-limited resolution for the gas phase molecules. Several vibrational bands in two electronic transition systems of tantalum fluoride (TaF) have been analyzed, and new molecular constants provided. Transitions involving six electronic states of tungsten sulfide (WS) have been analyzed, with new and updated constants provided, including a deperturbation analysis of three vibrational bands in two of the states. Finally, a fresh perspective on two electronic states of tungsten oxide (WO) included a deperturbation …

Photophysical Properties Of Synthetic Oligomeric Phenylene Ethynylene, Hugh F. Fritz Jr.

Chemistry and Chemical Biology ETDs

Oligomeric Phenylene Ethynylenes (OPEs) are a class of synthetically prepared compounds with the basic structure of phenylene rings connected by triple-bonded carbon atoms, also known as an ethyne link. This structure can be modified by incorporating functional groups onto one or more of the phenylene rings. The addition of functional groups, such as sulfoxide or imidazole, may alter the photophysical properties in detectable ways. The photophysical techniques used in this report include fluorescence, spectroscopy in the ultraviolet and visible light range (UVVIS), and photon-based excitation using a photo chamber.

One attractive function of OPEs is their antimicrobial property. Previously published …

First-Principles Simulations Of Attosecond Transient X-Ray Absorption, Min Chen

LSU Doctoral Dissertations

The first part of this dissertation presents calculations of the extinction spec- tra of gold-silver/silver-gold core-shell nanospheres. The goal of this projectsis to get a deeper understanding of surface plasmonic resonance in metal nanospheres with core-shell geometry. Here, we used the finite-difference time-domain (FDTD) method and total-field/scattered-field (TFSF) framework to compute the extinction spectra of nanoparticles to determine the geometry of gold-silver/silver-gold core-shell nanoparticles. This supported experimental work on monitoring the growth dynamics of colloidal gold- silver/silver-gold core-shell nanoparticles using in situ second harmonic generation (SHG) and extinction spectroscopy.

The second and main project involved simulating attosecond transient spectra for …

Clear As Glass: Novel Antibiotic Glasses Vitrified From Solution, Claire Lamberti

Chemistry Theses and Dissertations

The World Health Organization (W.H.O.) has maintained a list of essential medicines since 1977 (1). This list contains the medications considered to be the most effective and of the utmost importance to the needs of worldwide healthcare systems. If new forms of these drugs can be created, they can be studied for potential stability and transportation purposes, as well as drug delivery mechanisms. There are strategies to try and improve the physicochemical properties including forming polymorphs, salts, cocrystals, and amorphous formulations. There are issues with these techniques, and a large one is that in most cases the crystal structures of …

The Decomposition Of Normal Vibrational Modes In Different Chemistry Problems, Mateus Macedo Quintano

Chemistry Theses and Dissertations

The least action principle yields the Euler-Lagrange equations, which explain molecular vibrations in minimizing action. Subsequently, the Lagrangian gives rise to the equations of motion using the Euler-Lagrange equations. We can then solve the characteristic value problem to obtain normal vibrational modes. Ultimately, the vibrational spectrum of a molecule can be extracted from the characteristic values. Normal coordinates are linear combinations of internal or Cartesian coordinates. However, the delocalization of normal vibrational modes across the molecule restricts the direct use of normal mode frequencies and force constants for measuring bond strength. From the force constant matrix and the normal mode …

Adsorption Performance Of Mg0.33ni0.33co0.33fe2o4 Nanoparticles Doped With Gadolinium And Lanthanum For Lead (Ii) Removal, Mariam Rabaa, Amani Aridi, Ghassan Younes, Ramadan Awad

BAU Journal - Science and Technology

The issue of water pollution has become a major concern in recent times, and the need for effective strategies for treating contaminated water sources has become more urgent. One promising approach that has been gaining attention in the field of wastewater treatment is the use of nano-ferrites. In this regard, novel Mg_0.33Ni_0.33Co_0.33La_xFe_2-xO₄ and Mg_0.33Ni_0.33Co_0.33Gd_xFe_2-xO₄ nanoparticles (NPs), where x = 0.00, 0.01 and 0.08, were synthesized to test their adsorption performance for the removal of Pb (II). The structural …

Modeling Exciton Migration In Two-Dimensional Space, Christian D. Etnyre

DePaul Discoveries

Computational analysis through density matrix quantum mechanics was performed to model exciton migration in two-dimensional space for a zinc-substituted tetraazaphthalocyanine. The model produced resembles a two-dimensional sheet of molecules. Energy transport mechanisms, controlled by point dipole couplings, were evaluated while altering the size of the crystal lattice. It was determined that energy transport was much more significant with a decreasing size of the crystal lattice. Likewise, the result of increasing the size of the crystal lattice had the effect of dampening the rate of energy transport. It was of interest to determine, with varying crystal lattice dimensions, the time that …

Preface To The Special Issue On Interfactial Regulation And Electrochemical Sensors, Jing-Hong Li, Yang Tian, Yuan-Hong Xu, Li-Min Zhang

Journal of Electrochemistry

No abstract provided.

An Aptamer-Based Microelectrode With Tunable Linear Range For Monitoring Of K+ In The Living Mouse Brain, Yuan-Dong Liu, Jia-Run Li, Li-Min Zhang, Yang Tian

Journal of Electrochemistry

Potassium ion (K⁺) is widely involved in several physiopathological processes, and its abnormal changes are closely related to the occurrence of brain diseases of cerebral ischemia. In vivo acquirement of K⁺ variation is significant to understand the roles of K⁺ playing in brain functions. A microelectrode based on single-stranded DNA aptamers was developed for highly selective detection of K⁺ in brain, in which the aptamer probes were designed to contain an aptamer part for specific recognition of K⁺, an alkynyl group used for stable confinement of aptamer probe on the gold surface, and …

Boronate Affinity-Assisted Electrochemically Controlled Atrp For Ultrasensitive Electrochemical Aptasensing Of Carcinoembryonic Antigen, Qiong Hu, Shi-Qi Li, Yi-Yi Liang, Wen-Xing Feng, Yi-Lin Luo, Xiao-Jing Cao, Li Niu

Journal of Electrochemistry

As an acidic glycoprotein, carcinoembryonic antigen (CEA) is of great value as a broad-spectrum tumor marker in the differential diagnosis and surveillance of malignant tumors. In this work, we report an electrochemical aptasensor for the ultrasensitive and highly selective detection of CEA, taking advantage of the dual amplification by the boronate affinity-assisted electrochemically controlled atom transfer radical polymerization (BA-eATRP). Specifically, the BA-eATRP-based electrochemical aptasensing of CEA involves the capture of target antigens by nucleic acid aptamers, the covalent crosslinking of ATRP initiators to CEA antigens via the selective interactions between the phenylboronic acid (PBA) group and the cis-diol group of …

Metal-Organic Frameworks For Electrochemical And Electrochemiluminescent Immunoassay, Xiao-Li Qin, Zi-Ying Zhan, Sara Jahanghiri, Kenneth Chu, Cong-Yang Zhang, Zhi-Feng Ding

Journal of Electrochemistry

Development of ultrasensitive, highly accurate and selective immunosensors is significant for the early diagnosis, screening, and monitoring of diseases. Electrochemical and electrochemiluminescent (ECL) immunoassays have both attracted great attention and become a current research hotspot due to their advantages such as good stability, high sensitivity and selectivity, wide linear range, and good controllability. Metal-organic frameworks (MOFs), as a new class of porous crystalline materials, have been widely applied in electrochemical and ECL immunosensors owing to their large specific surface area, good chemical stability, as well as adjustable pore size and nanoscale framework structures. Various MOF nanomaterials with different properties for …

Colorful "Stars" In The Dark, Chao Jing, Yi-Tao Long

Journal of Electrochemistry

Plasmonic nanoparticles such as Au and Ag with localized surface plasmon resonance (LSPR) property exhibit unique scattering and absorption features. The plasmonic scattering and absorption bands are mainly located at visible light region which can be easily applied in visual detections. By modulating the size, shape, and composition of gold and silver colloid solutions, plenty of colorimetric methods have been constructed for the detection of metal ions, biomolecules, and environmental contaminants, etc. For many years, the LSPR-based measurements are implemented in reagent tubes. Since 2000, the plasmon resonance scattering (PRS) light of metal nanoparticles captured by dark-field microscopy enables the …

Recent Advances In Electrochemical Impedance Spectroscopy-Based Pathogenic Bacteria Sensing, Tao Chen, Yuan-Hong Xu, Jing-Hong Li

Journal of Electrochemistry

Pathogenic bacteria have been throwing great threat on human health for thousands of years. Their real-time monitoring is in urgent need as it could effectively halt the spread of pathogenic bacteria and thus reducing the risk to human health. Up till now, diverse technologies such as electrochemistry, optics, piezoelectricity and calorimetry have been developed for bacteria sensing. Therein, electrochemical impedance spectroscopy (EIS)-based sensors show great potential in point-of-care bacterial analysis because of their low-cost, short read-out time, good reproducibility, and portable equipment construction. In this review, we will primarily summarize the typical applications of electrochemical impedance technology in bacteria sensing …

Scanning Photoelectrochemical Microscopic Study In Photoinduced Electron Transfer Of Supramolecular Sensitizers-Tio2 Thin Films Systems, Sheng-Ya Zhang, Min Yao, Ze Wang, Tian-Jiao Liu, Rong-Fang Zhan, Hui-Qin Ye, Yan-Jun Feng, Xiao-Quan Lu

Journal of Electrochemistry

Crafting charge transfer channels at titanium dioxide (TiO₂) based photoanodes remain a pressing bottleneck in solar-to-chemical conversion technology. Despite the tremendous attempts, TiO₂ as the promising photoanode material still suffers from sluggish charge transport kinetics. Herein, we propose an assembly strategy that involves the axial coordination grafting metalloporphyrin-based photosensitizer molecules (MP) onto the surface-modified TiO₂ nanorods (NRs) photoanode, forming the composite MP/TiO₂ NRs photoelectrode. As expected, the resulted unique MP_B/TiO₂ NRs photoelectrode displays significantly improved photocurrent density as compared to TiO₂ NRs alone and MP_A/TiO₂ NRs photoelectrode. Scanning …

N–((2–Acetylphenyl)Carbamothioyl)Benzamide: Synthesis, Crystal Structure Analysis, And Theoretical Studies, Akin Oztaslar, Hakan Arslan

Karbala International Journal of Modern Science

N–((2–Acetylphenyl)carbamothioyl)benzamide has been synthesized and characterized. The molecular conformation of the investigated compound is stabilized by C16–H16B⋅⋅⋅O2ⁱ (i: 1+x, y, z) intermolecular and C14–H14⋅⋅⋅S1, N2–H2⋅⋅⋅O2, and N2–H2⋅⋅⋅O1 intramolecular H–bonds. All DFT calculations have been implemented at the B3LYP level with the 6–311G(d,p) basis set. The optimized molecular structure parameters have been compared with the experimental one in the solid phase. The energy gap, global chemical reactivity descriptor parameters, MEP, Fukui functions, DoS, NLO, and NBO analysis were also computed and investigated. The intermolecular interactions and their energies are evaluated using Hirshfeld surface and energy framework analyses. To determine …

Methods Of Magneto-Optical Spectroscopy And Analysis For Porphyrins And Polymer Thin-Films, Emigdio E. Turner

Chemistry and Chemical Biology ETDs

This dissertation describes the construction of two high precision magneto-polarimeters for performing Faraday rotation and Magnetic Circular Dichroism (MCD) measurements of polymer thin-films. There is a focus in materials science on the development of thin-film magneto-optically active materials. These materials could allow for the construction of a thin-film optical diode, an important device for next-generation photonic technology. Upon completion of the Faraday rotation spectrometer, two publications were generated from Faraday rotation measurements of novel polymer thin-film materials.

With growing interest by materials scientists in magneto-optically active transition-metal containing materials, an MCD spectrometer was constructed to study these materials. This spectrometer …