Chemistry Commons^™

Ionic Thermoelectric Paper, Fei Jiao, Ali Naderi, Dan Zhao, Joshua Schlueter, Maryam Shahi, Jonas Sundström, Hjalmar Granberg, Jesper Edberg, Ujwala Ail, Joseph W. Brill, Tom Lindström, Magnus Berggren, Xavier Crispin

Physics and Astronomy Faculty Publications

Ionic thermoelectric materials, for example, polyelectrolytes such as polystyrene sulfonate sodium (PSSNa), constitute a new class of materials which are attracting interest because of their large Seebeck coefficient and the possibility that they could be used in ionic thermoelectric SCs (ITESCs) and field effect transistors. However, pure polyelectrolyte membranes are not robust or flexible. In this paper, the preparation of ionic thermoelectric paper using a simple, scalable and cost-effective method is described. After a composite was fabricated with nanofibrillated cellulose (NFC), the resulting NFC–PSSNa paper is flexible and mechanically robust, which is desirable if it is to be used in …

Electrochemical Synthesis Of Homoallylic Alcohols And Homoallylic Amines, Wei-Qiang Zhong, Xiang-Hui Liang, Jing-Mei Huang

Journal of Electrochemistry

Electrochemical technique has been widely applied in the organic synthesis. This review focuses on the electrochemical synthesis of homoallylic alcohols and homoallylic amines from the allylation of carbonyl compounds and imines. This method has been developed impressively, especially in the field of electrochemical allylation in a green solvent of aqueous media. Improvement of the efficiency of the electricity, regio-selectivity and chiral synthesis are expected.

Characteristics And Mechanism For The Simons Electrochemical Fluorination Of Methanesulfonyl Fluoride, Wen-Lin Xu, Bao-Tong Li, Da-Wei Wang, Ya-Qiong Wang

Journal of Electrochemistry

The characteristics and mechanism for the Simons electrochemical fluorination processes were investigated during the electrochemical fluorination of CH₃SO₂F to CF₃SO₂F. The results showed that the reaction mechanism for the electrochemical fluorination of organic compounds to organic fluorides was the same as that of chemical fluorination processes using fluorinating agents such as CoF₃. The electrochemical fluorination in anhydrous HF was a heterogeneous process, and nickel fluorides on the surface of the nickel anode played the role of a mediator in the Simons process to transfer oxidation potential from the anode to …

Ionic Liquid-Supported Tempo/Polymeric Ionic-Liquid/Carbon Black Ternary Composites: Preparations And Applications In Electrochemical Oxidation Of Alcohols, Xin Lin, Cao-Cao Sun, Zhi-Rong Liu, Cheng-Chu Zeng

Journal of Electrochemistry

To effectively recover redox catalyst and supporting electrolyte, a novel ternary composite consisting of ionic liquid-supported TEMPO, polymeric ionic-liquid and carbon black was prepared. The ionic-liquid supported redox catalyst TEMPO-IL-BF₄ was firstly synthesized from 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and followed by the reaction of polydimethyldiallylammonium chloride (PDDA) and bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) to form poly[diallyldimethylammonium bis(trifluoromethanesulfonyl)imide] (PDDA(Tf₂N)). A combination of the above mentioned two synthesized materials and carbon black afforded to obtain the ternary composite, which was used as the recoverable supporting electrolyte and mediator for the electrochemical oxidation of alcohol. The results indicate that various alcohols could be oxidized …

Preparations And Applications Of Irsnox Electrode In Electrochemical Synthesis Of 2,5-Dichlorophenol, Xiang-Yu Ma, Xu-Guo Tu, Rui-Nan He, Ya Chen, Gui-Sheng Zhu, Shou-Yan Shao, Song Chen

Journal of Electrochemistry

The electrodes of titanium based iridium tin oxides (IrSnOx) have been prepared by traditional thermal decomposition method and further applied to the electrosynthsis of 2,5-dichlorophenol in order to explore a green and high efficient synthesis route. The results showed that the electrode surface existed apparent cracks, while the intermediate layer prepared with Sn:Sb=94:6 existed less cracks and longer life time. The main products of the electrolytic reaction were 2,5-dichlorophenol, p-chlorophenol, and 1,2,4-trichlorobenzene. The electrosynthsis yield of 2,5-dichlorophenol reached 57% and the selectivity of 2,5-dichlorophenol was as high as 93% by using the IrSnOx as an anode, which is obviously better …

Electrocatalysis Of Nanotin Dioxide In The Battery Reaction Of Zinc-Nitrobenzene, Xu-Guo Tu, Xiang-Yu Ma, Rui-Nan He, Xiao-Juan Wang, Chen Ling, Yun-Xia Sun, Song Chen

Journal of Electrochemistry

The tin dioxide (SnO₂) nanoparticles were synthesized by using a simple hydrothermal route in the presence of tetrapropyl ammonium bromide (TPAB) as a surfactant. Accordingly, the titanium mesh based SnO₂ catalyst electrode was prepared. The morphologies and structures of SnO₂ nanostructures were characterized by scanning electron microscopy and X-ray diffraction spectrometry. The influences of reactant concentration, reaction temperature and time on the morphology of the products were investigated in detail. The electrocatalytic performance of SnO₂ for the reduction of nitrobenzene with zinc was studied. Possible formation process and growth mechanism for such hierarchical SnO_{2 …}

Selective Direct Electro-Oxidation Of C-H Bond, Yan-Mei Liao, Qian-Qian Wu, An-Lun Zhang, Ying-Hong Zhu, Chun-An Ma

Journal of Electrochemistry

Carbon-hydrogen (C-H) bond is the most basic chemical bond in organic compounds. The activation and direct conversion of C-H bond are the effective methodology for synthesis of different kinds of organic compounds from alkane compounds. The oxidative activation and functionalization of C-H bonds constitute an important and challenging area of investigation. The electro-oxidative activation of C-H bonds to form new C-O, C-C and C-N bonds has proven to be interesting and important in organic chemistry using the clean electron as the oxidant. The target C-O, C-C and C-N compounds could be selectively achieved by choosing the appropriate electrode, supporting electrolyte …

Nanomaterials As Stationary Phases And Supports In Liquid Chromatography: A Review, Sandya Beeram, Elliott Rodriguez, Suresh Doddavenkatanna, Zhao Li, Allegra Pekarek, Darin Peev, Kathryn Goerl, Gianfranco Trovato, Tino Hofmann, David S. Hage

David Hage Publications

The development of various nanomaterials over the last few decades has led to many applications for these materials in liquid chromatography (LC). This review will look at the types of nanomaterials that have been incorporated into LC systems and the applications that have been explored for such systems. A number of carbon-based nanomaterials and inorganic nanomaterials have been considered for use in LC, ranging from carbon nanotubes, fullerenes and nanodiamonds to metal nanoparticles and nanostructures based on silica, alumina, zirconia and titanium dioxide. Many ways have been described for incorporating these nanomaterials into LC systems. These methods have included covalent …

In Situ Electron Microscopy Of Plasmon-Mediated Nanocrystal Synthesis, Peter Sutter, Ying Li, Christos Argyropoulos, Eli A. Sutter

Department of Electrical and Computer Engineering: Faculty Publications

Chemical processes driven by nonthermal energy (e.g., visible light) are attractive for future approaches to energy conversion, synthesis, photocatalysis, and so forth. The growth of anisotropic metal nanostructures mediated by excitation of a localized surface plasmon resonance (LSPR) is a prototype example of such a reaction. Important aspects, notably the growth mechanism and a possible role of plasmonic “hot spots” within the metal nanostructures, remain poorly understood. Here, we use in situ electron microscopy to stimulate and image the plasmon-mediated growth of triangular Ag nanoprisms in solution. The quantification of the time-dependent evolution of the lateral size and thickness of …

Recent Progress In Template-Assisted Synthesis Of Nitrogen-Doped Porous Carbons For Oxygen Electroreduction, Wenhan Niu, Ligui Li, Shaowei Chen

Journal of Electrochemistry

Nitrogen (N)-doped porous carbons are potential alternatives to precious metal catalysts for oxygen reduction reaction (ORR) at the cathodes of proton exchange membrane fuel cells and metal-air batteries. Template-assisted synthesis has been used extensively as a robust and versatile method in the preparation of such carbon catalysts, where the ORR activity has been found to be dependent on various structural parameters, such as the concentrations and molecular configurations of the dopants, and the porosity, surface accessibility and electrical conductivity of the carbon materials. In this review, we summarize recent progress in this area of research focusing on the design, preparation …

Comparative Studies Of Fe, Ni, Co And Their Bimetallic Nanoparticles For Electrochemical Water Oxidation, Maduraiveeran Govindhan, Brennan Mao, Aicheng Chen

Journal of Electrochemistry

The design of efficient, durable, and earth-abundant electrocatalysts via environmentally compatible strategies for the oxygen evolution reaction (OER) is a vital for energy conversion processes. Herein we report a facile approach for the fabrication of low-cost and earth abundant metal catalysts, including iron (Fe), nickel (Ni), cobalt (Co), CoNi, and CoFe nanoparticles (NPs) on titanium (Ti) substrates through a one-step electrochemical deposition. Field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) spectrocopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques were employed to characterize these nanoparticles. Our electrochemical results revealed that among the five synthesized nanomaterials, the …

Impact Of Nafion Loading And Anion Adsorption On The Synthesis Of Pt Monolayer Core-Shell Catalysts, Lijun Yang, Dustin Banham, Elod Gyenge, Siyu Ye

Journal of Electrochemistry

Carbon supported palladium (Pd) nanoparticles were used as a model core material for the synthesis of platinum (Pt) monolayer core-shell catalysts using rotating disk electrode method and a copper (Cu) under potential deposition technique. The impact of Nafion on the synthesis process was revealed by electrochemical testing with various Nafion contents. The existence of Nafion influenced the Cu under potential deposition, galvanic replacement and eventually the oxygen reduction reaction activity of the core-shell catalyst. However, as long as the Nafion content was less than 5 wt% in the test film, adding Nafion could help to bind catalyst onto the surface …

Comparison Of Oxygen Reduction Reaction Activity Of Pt-Alloy Nanocubes, Yongan Tang, Lin Dai, Shouzhong Zou

Journal of Electrochemistry

Alloying Pt with the first row non-noble transition metals has been demonstrated to increase the catalytic activity toward oxygen reduction reaction (ORR), which is the cathode reaction of the proton exchange membrane fuel cells (PEMFCs) and metal-air batteries. However, how much the ORR activity improvement comes from the alloying elements remains controversial. In this paper, the nanocubes of PtMn, PtFe, PtCo, and PtNi with the similar size and composition were prepared and their ORR activities were explored, in order to investigate the effects of alloying elements on the catalytic activity. The use of cubic shape particles minimizes the contribution to …

Novel Composites Between Nano-Structured Nickel Sulfides And Three-Dimensional Graphene For High Performance Supercapacitors, Xiaomin Wang, Huanglin Dou, Zhen Tian, Jiujun Zhang

Journal of Electrochemistry

In this paper, a three-dimensional graphene (3DG) network grown on nickel foam was employed as a template for synthesizing graphene-based composite materials of supercapacitor electrode. The composites (crystal Ni₃S₂ nanorods on the surface of 3DG (abbreviated as Ni₃S₂/3DG)) were obtained through a one-step hydrothermal reaction. The morphological and structural evolution of the Ni₃S₂/3DG composites were investigated by SEM, TEM, XRD and Raman spectroscopy. Detailed electrochemical characterization showed that the Ni₃S₂/3DG-coated electrodes exhibited both a specific capacitance as high as 1825 F·g^-1 at 5 mV·s …

Designing Pt-Skin Of Pt-Based Bimetallic Electrocatalysts For Oxygen Reduction Reaction, Binwei Zhang, Yunxiao Wang, Yanfei Xu, Huakun Liu, Shixue Dou

Journal of Electrochemistry

In the past decade, great advancement has been made in the development of nanocatalysts for energy conversion and storage. Pt-skin of Pt-based bimetallic has shown a great potential in the tuning the electronic structures of electrocatalytically active materials toward oxygen reduction reaction. Here, we offer a brief overview of the recent research on the design and preparation of catalysts. Our focus is paid on the systematic studies of preparation and performance of Pt-skin catalysts towards oxygen reduction reaction.

Electrodeposition Of Ruo2 Layers On Tio2 Nanotube Array Toward Co2 Electroreduction, Bei Jiang, Lina Zhang, Xianxian Qin, Wenbin Cai

Journal of Electrochemistry

RuO₂/TiO₂ composite materials have multitude of electrocatalytic applications including but not limited to CO₂ reduction reaction (CO₂RR). RuO₂/TiO₂ electrodes were previously prepared by repetitive coating and thermal decomposition (TD) of a Ru(III) precursor solution on Ti substrate. In this work, electrochemical potential cycling is applied to deposit amorphous RuO₂ (α-RuO₂) layers onto TiO₂ nanotube array (TNA) (RuO₂^CV/TNA) preformed on Ti foil. SEM, GIXRD, and voltammetry are applied to characterize the structures of the resulting RuO₂^CV/TNA. Ru loading on the RuO_{2 …}

Environmentally Friendly Synthesis Of Transition Metalorganic Hybrid Nanocomposites, Aubrey N. Penn

Masters Theses & Specialist Projects

Research on metal nanoparticles (MNPs) synthesis and their applications for optoelectronic devices has been a recent interest in the fields of nanoscience and nanotechnology Photovoltaics are one of such systems in which MNPs have shown to be quite useful, due to unique physical, optical, magnetic, and electronic properties, including the metal nanoparticles synthesized in this research.

Owing to the challenges with the most common physical and chemical methods of preparing MNPs, including the use of high temperatures, toxic reducing agents, and environmentally hazardous organic solvents, there is a critical need for a benign synthesis procedure for MNPs. In this work, …

Fatty Acid Biomarker Detection For Breast Cancer Using Differential Mobility Spectrometry With Non-Radioactive Ion Source, James Joseph Alberti

USF Tampa Graduate Theses and Dissertations

Differential Mobility Spectrometry (DMS) using a non-radioactive ion source (NRIS) is investigated as a possible medical diagnostic instrument for near real-time detection of breast cancer biomarkers. In previous clinical studies, concentrations of Linoleic, Palmitic and Stearic fatty acids have been observed at different levels in women with carcinoma breast cancer versus women with benign tumors or healthy women showing no signs of breast cancer. Present diagnostic methods require a biopsy of the suspect tissue and a microscopic lab analysis performed to determine its disease state. This process can take hours or days before the patient and doctor are informed of …

The Problem Of The Anode Electrolyte In H-Type Electrolytic Cell For Electrochemical Reduction Of Carbon Dioxide, Rui Zhang, Wei-Xin Lv, Li-Xu Lei

Journal of Electrochemistry

Electrochemical reduction of carbon dioxide (CO₂) was studied in the H-type electrolytic cell. It was found that the voltage between the cathode and the anode would increase during the long time electrolysis process, for this reason the electrolytic process would be unsustainable. After the experimental investigations carried out by constant potential electrolysis, constant current electrolysis, pH test and KHCO₃ concentration analysis of anode electrolyte before and after the electrolysis, the increase in cell voltage might be caused by the following process: H⁺, that was generated from the anodic oxygen evolution reaction, reacted with HCO_{3 …}

Effects Of Flame Retardant On The Rate Capability And Safety Performances Of The Soft-Package 5ah Lithium Ion Battery, Yan-Zhuo Lv, Xiao-He Wang, Yi-Ming Qin, Zhen-Bo Wang, Ke Ke

Journal of Electrochemistry

The 5 Ah soft packed lithium ion batteries with LiNi _0.4Co_0.2Mn_0.4 O₂ as the positive electrode material and the organic electrolytes with different amounts of fire retardants as the electrolyte solution were prepared. The effects of the fire retardant amount (5 %,10 %,20 %) of the fire retardants on the rate performances, short-circuit characteristics and overcharged behaviors of the 5 Ah soft packed lithium ion battery were investigated by electrochemical methods. The results indicated that the best rate performances were obtained by adding 5 vol.% of the fire retardants in the electrolyte solution when the …

Application Of Composite Ionic Liquid In Electro-Oxidation Activation Of A C-H Bond, Zi-Ying Chen, Qian-Qian Wu, Jian-Qing Zhang, Ying-Hong Zhu, Chun-An Ma

Journal of Electrochemistry

In this paper, the ionic liquid/carbon nanotube composite material was prepared through modifying the ionic liquid 1-ethyl-3-methylimidazolium acetate to multi-walled carbon nanotubes. The electro-oxidation properties of p-methoxy toluene (p-MT) were studied using the composite as an electrolyte. The effects of scanning speed, temperature and substrate concentration were studied by cyclic voltammetry and chronoamperometry. The electrochemical kinetics of p-MT in this system was also studied. The results showed that the electrochemical oxidation of p-MT in the composite electrolyte solution was irreversible. The process was mainly controlled by diffusion, and the diffusion coefficient (D) was 7.69×10-10 cm²·s^-1. Increasing …

Electrochemical Nucleation Of Invar Alloy On Glassy Carbon Electrode, Xian-Jie Huang, Hui Yan, Shuai-Shuai Huang, Fang-Zu Yang, Zhong-Qun Tian, Shao-Min Zhou

Journal of Electrochemistry

The linear sweep voltammetry, cyclic voltammetry and potential step methods were used to study the electrodeposition mechanism of Invar nickel-iron alloy (the mass fraction of nickel was 32~36%) on glassy carbon electrode surface in the weak acidic bath. The results demonstrate that the electrodeposition is was a diffusion controlled irreversible electrode process in this system. The Scharifker-Hill (SH) theory theoritic model (SH) were was used employed to fitting the experimental data and the result shows that the codeposition of Invar alloy on glassy carbon electrode surface conformed to the diffusion controlled three-dimensional instantaneous nucleation mechanism. The kinetic parameters were obtained …

Electrochemical Synthesis Of Porous Polyaniline Electrodes Using Hkust-1 As A Template And Their Electrochemical Supercapacitor Property, Qiong Luan, Chun-Feng Xue, Hong-Ye Zhu, Fu-Juan Yang, Xu-Li Ma, Xiao-Gang Hao

Journal of Electrochemistry

Excellent electrode plays vital important role in the performance of supercapacitors. Polyaniline (PANI) with good conductivity is often used to prepare electrode. However, its available surface is limited and results in a poor supercapacitance in many cases. It is desirable to fabricate an electrode containing electroactive PANI with high surface area deriving from its porous structure. Here, the metal-organic framework (MOF) material with high surface area was selected as a hard template for synthesizing porous PANI. Microporous PANI composite electrodes (Micro-PANI/CC) were fabricated by depositing aniline on to carbon cloth (CC) pre-coated with MOF material of HKUST-1 using a unipolar …

Sn-Doped Α-Fe2O3 Photocatalyst Containing Oxygen Vacancy For Water-Splitting, Zu-Hua Wang, Dong-Fang Niu, Hui-Cheng Li, Rong-Bin Du, Heng Xu, Xin-Sheng Zhang

Journal of Electrochemistry

The α-Fe₂O₃ nanoparticles containing oxygen vacancies were synthesized in atmospheric N₂ by dip-dropping method without a high vacuum employed before annealing. The influences of annealing atmosphere and Sn-doping on the photocatalytic performance of α-Fe₂O₃ nanoparticles were studied by annealing the photocatalyst in N₂ or air and adding SnCl₄ to the precursor directly. The results showed that the current density of Sn-doping α-Fe₂O₃ annealed in N₂ at 550 °C and 1.23 V (vs. RHE) was 35 times greater than that of pristine α-Fe₂O₃ annealed in …

Preparation And Electrochemical Properties Of Attapulgite-Supported Nitrogen-Doped Carbon@Nico2O4 Composites For Supercapacitors, Hui Wan, Zong-Rong Ying, Xin-Dong Liu, Jian-Jian Lu, Wen-Wen Zhang

Journal of Electrochemistry

In this work, the attapulgite-supported nitrogen-doped carbon (ANC) was prepared by in-situ chemically polymerizing polyaniline coating upon attapulgite, followed by high temperature heat treatment, and then NiCo₂O₄was reacted onto the surface of ANC by a combination of hydrothermal reaction and calcination to synthesize ANC@NiCo₂O₄ composites. The chemical composition and morphology of the samples were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N₂ adsorption/desorption. The electrochemical properties were evaluated by means of constant current charge discharge (GCD) and cyclic voltammetry (CV). …

An Investigation In The Performance Of Lithium Sulfur Battery With A Tic Coated Separator, Jian-Hua Fang, Yong Cao, Mao-Ping Yang, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

To improve the specific capacity and cycle stability of lithium-sulfur (Li-S) battery, a TiC/Celgard coating separator was developed and its performance in Li-S battery was investigated. The electrochemical test results confirmed that the TiC coating layer could significantly increase the capacity and cycle stability. At a high rate of 2C, it still delivered the capacity of 650 mAh·g^-1. At 0.5C, the specific capacity was maintained at 841.3 mAh·g^-1 after 100 cycles.

Direct Electrochemistry Of Glucose Oxidase Based On Ws2 Quantum Dots And Its Biosensing Application, Chen-Lu Li, Hua-Ping Peng, Zhong-Nan Huang, Yi-Lun Sheng, Pei-Wen Wu, Xin-Hua Lin

Journal of Electrochemistry

In this study, a novel electrochemical glucose biosensor has been developed by immobilizing glucose oxidase (GOx) on tungsten disulfide quantum dots (WS₂ QDs) on the surface of glassy carbon electrode (GCE). Transmission electron microscopy, UV-vis spectroscopy and cyclic voltammetry were employed to characterize the morphology, structure, and electrochemical behaviors of the as-prepared WS₂ QDs and the biofilm modified electrode. The results suggested that the WS₂ QDs could accelerate the electron transfer between the electrode and the immobilized enzyme, which enabled the direct electrochemistry of GOx without any electron mediator. Besides, the immobilized GOx in WS₂ QDsfilm …

Application Of Adamantane Schiff Base Nickel Complexes/Graphene Oxide/Glassy Carbon Modified Electrode In Detection Of Carmine, Peng Guo, Zheng Liu, Hai-Ying Li, Li-Ming Ma

Journal of Electrochemistry

The Schiff base nickel complexes/graphene oxide/glassy carbon electrodes were prepared by embedded method and electrodeposition on which were used to quantitatively detect the contents of carmine. Cyclic voltammetry, chronoamperometry, scanning electron microscopy (SEM) and other methods were employed to characterize properties and morphologies of the modified electrodes. The results show that the adamantane double Schiff base nickel complexes/graphene oxide/glassy carbon electrode had high electric catalytic activity toward carmine oxidation reaction, and might provide an easy and quick way to detect carmine content with good reproducibility.

A Fast Linear Electro-Optical Effect In A Non-Chiral Bent-Core Liquid Crystal, Yuri Panarin, S.P. Sreenilayam, J.K. Vij, A. Lehmann, C. Tschierske

Articles

We report the observation of an electro-optical effect for a linear rotation of the optical axis as function of the electric field in an achiral tilted bent-core liquid crystalline compound, in which 4-cyanoresorcinol bisbenzoate core is symmetrically terminated by long linear alkyl chains (n =16) on both ends. The linear electro-optic effect observed in this material is similar to the deformed helical ferroelectric liquid crystal (DHFLC) effect reported previously in a FLC material except that dimensions of the helical pitch differ by two orders of magnitude. In the chiral systems, the helical pitch usually lies on the scale of sub-optical …

Nuclear Power: Black Sky Liability Or Black Sky Asset?, Sherrell R. Greene

International Journal of Nuclear Security

Ready access to abundant electricity is a key enabler of modern life. During the past decade the vulnerability of Critical Infrastructure sectors in the U.S. to a variety of natural hazards and man-made threats has become increasingly apparent. The electrical infrastructure (the “Grid”) is the foundation for all other critical civil infrastructures upon which our society depends. Therefore, protection of the Grid is an energy security, homeland security, and national security issue of highest importance. Geomagnetic disturbances (GMD) induced by solar coronal mass ejections (CMEs), electromagnetic pulse (EMP) attacks, and cyber attacks are three events having the potential to plunge …