Physical Chemistry Commons^™

Using Two Different Approaches For The Creation Of Poly(3-Hexylthiophene)-Functionalized Siloxane Nanoparticles For Organic-Based Solar Cells, Nicholas A. Wright

Mahurin Honors College Capstone Experience/Thesis Projects

Poly(3-hexylthiophene)-functionalized silsesquioxane nanoparticles were prepared from direct hydrolysis and condensation of P3HT-silane precursor using “grafting from” and “grafting to” methods. The size, shape, and surface morphology of these polymer grafts particles were visualized using transmission electron microscopy and scanning electron microscopy. Their compositions confirmed by FTIR, thermogravimetric analysis and elemental analysis. The XRD analysis revealed the polymer orientation and packing pattern of the nanocomposites, indicating the highly ordered lamella stacks of P3HT polymer chains. The photovoltaic performance of the blends of P3HT-nanohybrid with the C60 derivative PCBM was evaluated upon annealation in different temperatures, ranging from 50°C to 150 °C. …

The Kinetics And Mechanisms Of Some Fundamental Organic Reactions Of Nitro Compounds, Zhao Li

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

In chemistry, kinetics is the study of the rates of chemical reactions. A reaction mechanism describes in detail exactly what takes place at each stage of an overall chemical reaction from reactants to products. The work outlined in this dissertation was carried out in order to find out the true mechanisms of some fundamental organic reactions of nitro compounds by means of a series of novel kinetic techniques and analysis methods.

The target reactions include (1) the proton transfer reactions of nitroalkanes and (2) the aromatic nucleophilic reactions of trinitroarenes, both of which are undeniably among the most elementary and …

Electrochemical Preparation Of Nanostructural Pt-Ni And Pd-Ni Films For Ethanol Electro-Oxidation, Chen-Zhong Yao, Hui-Xuan Ma, Bo-Hui Wei

Journal of Electrochemistry

The Pt-Ni and Pd-Ni films were successfully prepared on Ti substrates by electrodeposition method. The porous Pt-Ni nanoflakes appeared to be uniform with the thickness of the slices about 10 ~ 20 nm. The porous Pd-Ni nanoparticles with a flower shape appeared to be uniform with the diameters of 50 ~ 60 nm. The XRD patterns also indicated that the Pd-Ni and Pt-Ni nanostructures have the poor crystallinity. The onset potentials of ethanol oxidation were negatively shifted to –0.74 V on Pt-Ni electrodes and –0.71 V on Pd-Ni electrodes, respectively. Addition of Ni could enhance catalytic activities and antitoxic properties …

Ethanol Electrooxidation On Pt/Mo2/Cnts Catalysts, Yu-Long Cheng, Jie Sun, Ji-Gang Li, Li-Gong Zhang, Tian Zhou, Geng Chang, Zhong-Chao Dong

Journal of Electrochemistry

The ethanol electrooxidation behaviors on Pt/MO₂/CNTs（M=Sn, Ti, Ce）and Pt/CNTs catalysts in H₂SO₄ solutions were researched by cyclic voltammetry. It has revealed that the catalysts with the addition of metal oxides presented higher electrooxidation activity for ethanol, in particular, the Pt/CeO₂/CNTs catalyst showed the best activity for ethanol electrooxidation intermediate. The Pt/SnO₂/CNTs catalyst demonstrated the best ethanol electrooxidation activity when considering the synthetic effects of such parameters as the onset oxidation potential, peak current densities and total oxidation area.

Electrochemical Study Of Protein Modification, Jing Zhao, Xiao-Li Zhu, Gen-Xi Li

Journal of Electrochemistry

Protein post-translational modification is a key physiological procedure, which has received more and more research interests from the scientists not only in protein science but also in some other fields. The usually employed techniques for the study of protein modification include mass spectrum, affinity chromatography, etc. Considering the complexity of protein modification and the urgent demand of such kind of study, it is highly required to develop new techniques to perform more studies. Electrochemical methods, which have been widely used in chemical study and analysis, are playing an increasingly important role in many fields of biological studies. The modification of …

Preparation And Electrochemical Performance Of Mo-Doped Li3V2(Po4)3/C Cathode Materials, Zhi-Yuan Tang, Wei Yuan, Ji Yan, Wen-Feng Mao, Li Ma

Journal of Electrochemistry

The molybdenum-doped Li₃V_2-xMo_x(PO₄)_3/C (x = 0.01, 0.02 and 0.03) cathode materials were prepared with a sol-gel method by using Li₂CO₃, NH₄H₂PO₄, V₂O₅ and MoO₃ as raw materials, and citric acid as both chelating reagent and carbon source. The X-ray diffraction (XRD) analyses showed that the crystal structure of as-prepared samples is monoclinic with space group P2₁/n. Scanning electron microscopy (SEM) observations indicated the uniform morphology for Li₃Mo_0.02V_1.98(PO₄) …

Synthesis And Electrochemical Properties Of Lifeso4F/Graphene Composite As Cathode Material For Lithium-Ion Batteries, Wei Guo, Ya-Xia Yin, Li-Jun Wan, Yu-Guo Guo

Journal of Electrochemistry

The LiFeSO₄F was successfully synthesized from the reactions of FeSO₄∙xH₂O (x=1, 4, 7) with LiF in tetraethylene glycol media through a facile low temperature method. The structures and microscopic features of the products were characterized by XRD, SEM and TEM. TGA result shows the good thermal stability of the as-prepared LiFeSO₄F. No diffraction peaks of the FeSO₄ are observed in the as-prepared products with the starting material of either FeSO₄∙4H₂O or FeSO₄∙7H₂O, which should be ascribed to delaying the release of H_{2 …}

Catalytic Activities Of Electrochemically Dealloyed Pt(Pd)-Cu Catalysts For Oxygen Reduction Reaction, Rui-Zhi Yang, Strasser Peter, Toney Michael

Journal of Electrochemistry

The electrochemically dealloyed Pt(Pd)-Cu catalysts were prepared by electrochemical dealloying of Cu₃Pt(Pd) and their catalytic activities toward oxygen reduction reaction (ORR) were studied in 0.1 mol·L^-1 HClO₄ . solutions. The structural features of the dealloyed Pt(Pd)-Cu were revealed by synchrotron-based anomalous X-ray diffraction (AXRD) and surface X-ray scattering (SXS) at an atomic scale. We established a relationship between the structure and the catalytic activity by comparing the ORR activity and the structure of dealloyed Cu₃Pt nanoparticles with similarly dealloyed Cu₃Pt thin films and Cu₃Pt(111). The enhancement in the activity of …

Electrocatalytic Oxidation Of Ethanol On Ni-P-Tio2 Composite Coating Electrodes, Guang-Hui Hu, Hai-Xia Zeng, Zhi-Gang Wei, Zhan-Chang Pan, Shu-Guang Xie, Yan-Di Zou

Journal of Electrochemistry

The Ni-P-TiO₂ composite coating electrodes with different contents of TiO₂ particulates were prepared by electroless plating technique from Ni-P plating bath containing TiO₂ powders on brass. Cyclic voltammetry, linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS) were used to test the electrochemical performance of Ni-P-TiO₂/Cu electrodes. It was indicated that the Ni-P-TiO₂/Cu electrodes exhibited very strong electrocatalytic activity toward the oxidation of ethanol in alkaline medium at ambient temperature. The electrocatalytic activity of ethanol oxidation on the Ni-P-TiO₂ electrodes depended on the amounts of TiO₂ in the coatings. The …

NaXMYFe(Cn)6(M=Fe, Co, Ni): A New Class Of Cathode Materials For Sodium Ion Batteries, Jiang-Feng Qian, Min Zhou, Yu-Liang Cao, Han-Xi Yang

Journal of Electrochemistry

Three types of Prussian blue compounds, Na_xM_yFe(CN)₆ (M = Fe, Co, Ni), were prepared simply by solution precipitation method and tested as cathode materials for sodium-ion batteries. X-ray diffraction and SEM measurements demonstrated that the prepared materials, namely, NaFeFe(CN)₆, Na₂CoFe(CN)₆, and Na₂NiFe(CN)₆, exhibited a perfect cubic structure with a particle size of several tens nanometers. Cyclic voltammetric and galvanostatic cycling tests revealed very different electrochemical behaviors of these three materials. The specific capacities of NaFeFe(CN)₆ and Na₂CoFe(CN)₆ could reach 113 mAh·g …

Synthesis Of Lini0.5Co0.2Mn0.3O2 For Lithium Ion Batteries And The Mechanism Of Capacity Fading At High Temperature, Wen Liu, Miao Wang, Ji-Tao Chen, Xin-Xiang Zhang, Heng-Hui Zhou

Journal of Electrochemistry

The Ni-rich cathode materials, LiNi_0.5Co_0.2Mn_0.3O₂, have been synthesized by Co-precipitation and high-temperature solid-phase sintering method. Constant current charge-discharge tests showed high discharge capacity of 179.2 mAh·g^-1 in the 3.0~4.4 V at 0.2C. However, at 55 °C the LiNi_0.5Co_0.2Mn_0.3O₂ experienced the dramatic capacity fading after 100 charge-discharge cycles. Electrochemical Impedance Spectroscopy, X-Ray Photoelectron Spectroscopy, Atomic Emission Spectroscopy have been employed to study the capacity fading mechanism of LiNi_0.5Co_0.2Mn_0.3O₂ cycled at high temperature in range of high-voltage charge and …

Electrochemical Performances Of Carbon-Coated Na2Ti6O13 Nanotubes, Guo-Ran Li, Shuai Sun, Xue-Ping Gao

Journal of Electrochemistry

With rutile TiO₂ and NaOH as starting materials, the Na₂Ti₆O₁₃ nanotubes were prepared by a hydrothermal reaction. The carbon-coated Na₂Ti₆O₁₃ nanotubes were obtained by treating the Na₂Ti₆O₁₃ nanotubes for 4 h in glucose aqueous solutions containing 0.1 mol·L^-1 NaOH. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microcopy (TEM). The results showed that the dimensions of carbon-coated Na₂Ti₆O₁₃ nanotubes were 14 ~ 19 nm of outer diameter, 2 ~ 5 …

Synthesis And Electrochemical Properties Of Yttrium-Doped Lini0.49Mn1.49Y0.02O4, Xian-Wen Zhang, Zheng-Xi Zhang, Li Yang, Shao-Hua Fang, Long Qu

Journal of Electrochemistry

The LiNi_0.49Mn_1.49Y_0.02O₄ cathode material was synthesized using the citric acid-assisted sol-gel method by partial substitutions of Ni and Mn with Y in the LiNi_0.5Mn_1.5O₄ material. The influences of Y doping on the structure and electrochemical properties were investigated by means of X-ray diffraction, cyclic voltammetry, galvanostatic charge/discharge tests and AC impedance spectroscopy. The results showed that the introduction of Y into the LiNi_0.5Mn_1.5O₄ greatly improved the cycle performance and rate capability. When the charge and discharge current was 1 C in the potential …

Template-Free Synthesis Of Porous Nio Hierarchical Structure For High Performance Supercapacitors, Yun Huang, Zhong Wu, Xin-Bo Zhang

Journal of Electrochemistry

A facile and template-free hydrothermal method is proposed to successfully synthesize porous NiO hierarchical structure, which is found to be assembled from ultrathin NiO nanosheets. As for electrochemical pseudocapacitor application, the obtained material exhibits not only high specific capacitances of 435 F·g^-1 at 20 mV·s^-1 and 367 F·g^-1 at 10 A·g^-1, but also holds a good electrochemical stability over 1000 cycles at a current rate of 20 mV·s^-1. These results suggest that the hierarchical structured porous NiO is a promising supercapacitor electrode material.

Intercalation/Deintercalation Reaction Of Olivine-Type Phosphate, Jun Wu, Zhi-Hu Li, Qun Wu, De-Cheng Li, Jun-Wei Zheng, Yan-Hui Xu

Journal of Electrochemistry

In the present work the rate-limited step during Li intercalation/deintercalation processes for olivine-type phosphate has been discussed. It is found that the increase in the carbon content is effective to improve the electrode capacity and the electrochemical activity of the Mn element in the active materials. It is also found that the asymmetric phenomenon exists in the charge-discharging curves, especially when the carbon content is low. During charging the Fe²⁺/Fe³⁺ the plateau capacity is much less than the corresponding theoretical capacity, while the capacity that corresponds to Co²⁺/Co³⁺ couple is more than the theoretical …

Electrochemical Reduction Of Co2 On Sn/Cu Electrodes, Chen-Chen Zhao, Jian-Wei Guo, Li Wang, Xiang-Ming He, Cheng Wang, Zhi-Xiang Liu

Journal of Electrochemistry

The Sn/Cu electrodes were prepared by electroplating method and their morphologies under different galvanization current densities were determined by SEM. In alkali, the effects of Sn/Cu electrodes on the activities towards hydrogen evolution and electrochemical reduction of CO₂ were investigated in alkaline solutions using a three-electrode system. These results indicated that the Sn/Cu electrodes prepared at 10 mA/cm² and 15 mA/cm² showed good activities, while that prepared at 15 mA/cm² was even better in activities. The synergetic structure of the Sn/Cu electrode to be beneficial to electrochemical reduction of CO₂ has been pointed out.

Electrochemical Properties Of The Keggin-Type Lacunary Heteropolysilicate Anion And Its Eectrocatalysis For H2O2 Reduction, Xi-Long Liu, Chun-Yan Wu, Fang Zhou, Hong-Sheng Liu, Ying-Jie Hua, Chong-Tai Wang, Xiao-Yang Liu

Journal of Electrochemistry

Electrochemical properties of the Keggin-type lacunary heteropolysilicate anion SiW₁₁O₃₉^8- (SiW₁₁) and its indirect electrocatalysis for H₂O₂ reduction in the supporting electrolyte containing 0.1 mol·L^-1 NaHSO₄ and Na₂SO₄ solutions were investigated using cyclic voltammetry, square wave voltammetry and alternating current impedance spectroscopy. Experimental results indicated that SiW₁₁ showed two pairs of reversible redox waves on the glassy carbon (GC) electrode in an acidic solution. The electron transfer number corresponding to the two pairs of waves was one, and the proton transfer number involved was two during …

Corrosion Inhibition Of 316l Steel Using Sodium Diethyl Dithiocarbamate Solution In Simulated Crude Oil, Xiao-Guang Ren, Jie Yang

Journal of Electrochemistry

The corrosion inhibition behaviors of 316L steel using the sodium diethyl dithiocarbamate (SDDTC) compound in the crude simulation solution were studied in the absence and presence of zinc sulfate or sodium chromate with different compositions. Experiment resultss showed that in the environments of highly acidic and high concentrations of chloride ions the SDDTC compound could well inhibit the corrosion of 316L steel. The good synergic effects on the corrosion inhibition of 316L steel by additions of either zinc sulfate or sodium chromate into SDDTC compound were indicated in this study, which is of great significance and importance in practical applications.

Synthesis And Theoretical Studies Of Pyridyl Fullerene Derivatives For Supramolecular Applications In Photovoltaic Systems, Robert Vina-Marrufo ^, Danisha M. Rivera-Nazario, Agustin Molina-Ontoria, Luis Echegoyen *

COURI Symposium Abstracts, Spring 2012

No abstract provided.

Proton-Coupled Electron Transfer (Pcet) With Bimetallic Systems, Maripaz A. Calderon ^, Dino Villagran *

COURI Symposium Abstracts, Spring 2012

Electron-transfer (ET) is one of the simplest chemical events, yet, it is a vital process for chemical reactivity. Proton-coupled electron transfer (PCET) is the concerted transfer of protons and electrons which is fundamental in chemical and biological systems and processes in electrochemistry, photosynthesis, and enzymatic activity. Similarly, mixed-valence (MV) systems are pervasive in nature and provide a platform for multiple electron transfers systems in nature. While both fields have been studied extensively, little work has been done on the intersection of the two. This project explores the elegant use of MV bimetallic systems through hydrogen bonded networks. A variety compounds …

Bon-Bons: Cyclic Molecules With A Boron-Oxygen-Nitrogen Backbone. Computational Studies Of Their Thermodynamic Properties, Aloysus K. Lawong, David W. Ball

Chemistry Faculty Publications

Although they were first reported in 1963, molecules with a boron-oxygen-nitrogen dimeric backbone do not seem to have been investigated seriously in terms of thermodynamic properties. Here we report on the calculated structures and properties, including thermodynamics, of several so-called “BON-BON” molecules. With the popularity of nitrogen-containing substituents on new high-energy materials, nitro-substituted BON-BONs were a focus of our investigation. A total of 42 BON-BON molecules were evaluated, and thermochemical analysis shows a decrease in the specific enthalpy of combustion or decomposition with increasing NO₂ content, consistent with other systems.

Towards One Key To One Lock: Catalyst Modified Indium Oxide Nanoparticle Thin Film Sensor Array For Selective Gas Detection, Kun Yao, Daniela Caruntu, Sarah Wozny, Rong Huang, Yumi H. Ikuhara, Baobao Cao, Charles J. O'Connor, Weilie Zhou

Advanced Materials Research Institute (AMRI)

Homogeneous In2O3 nanoparticles (NPs) were self-assembled into thin film sensor arrays on a single chip, with further surface modification by noble metal catalysts. The NP film sensor arrays show clear current responses when exposed to different target gases, and both sensitivity and selectivity were greatly improved. Particularly, the sensors modified with Au, Pd, and Pt nanocatalysts demonstrated higher sensitivity to H2S, H-2 and CO, respectively, making the gas discrimination direct and simple, like "one key to one lock". The particle size dependence of the noble metal modifiers to the sensitivity was further investigated by tuning the sputtering parameters. Three different …

K-Shell X-Ray Spectroscopy Of Atomic Nitrogen, M. M. Sant'anna, Gunnar Ohrwall, Wayne C. Stolte, Alfred S. Schlachter, Dennis W. Lindle, B. M. Mclaughlin

Chemistry and Biochemistry Faculty Research

Absolute K-shell photoionization cross sections for atomic nitrogen have been obtained from both experiment and state-of-the-art theoretical techniques. Because of the difficulty of creating a target of neutral atomic nitrogen, no high-resolution K-edge spectroscopy measurements have been reported for this important atom. Interplay between theory and experiment enabled identification and characterization of the strong 1s → np resonance features throughout the threshold region. An experimental value of 409.64 ± 0.02 eV was determined for the K-shell binding energy.

The Electrocatalytic Study Of Licoo2 In Air Electrode For Lithium-Air, Jun Gao, Wei Wu, Yan-Yan Tian, Yong Yang

Journal of Electrochemistry

The LiCoO₂ has been investigated as a new electrocatalyst for air electrodes using homemade lithium-air battery. The electrochemical performance and structural changes of the LiCoO₂ based composite air electrodes have been studied. The results of CV, XRD and charge-discharge tests show that the composite air electrodes composed of LiCoO₂ can greatly improve the discharge performance of lithium-air batteries. In particular when the composite air electrodes are charged to 4.1 V before further discharging, the obvious catalytic effects of LiCoO₂ are attributed to higher valence state of the Co element in LiCoO₂, esp. at charged …

Electrochemical Characterization Of (Phmgcl)2-Alcl3/Mixed Ether Electrolytes, Fei-Fei Wang, Yong-Sheng Guo, Jun Yang, Li-Yan-Na Nu, Jiu-Lin Wang

Journal of Electrochemistry

The (PhMgCl)₂-AlCl₃ salts were prepared and the electrochemical properties of (PhMgCl)₂-AlCl₃ electrolytes containing dimethoxyethane(DME)+THF, Diglyme(DG)+THF and Tetraglyme(TG)+THF solvents with different proportions on various metal electrodes were studied. Compared with (PhMgCl)₂-AlCl₃/THF, the (PhMgCl)₂-AlCl₃/DG+THF(3:2) solvents showed high ionic conductivity of 1.605×10^-3 S·cm^-1, good reversible Mg deposition behavior and anodic anti-oxidation performance with an electrochemical window wider than 2.8 V. In addition, the DG+THF mixed solvent could greatly lower the saturated vapor pressure by reducing from 23.46 kPa to 9.41 kPa, which suppresses volatilization of the …

Electrocatalytic Study Of Pseudomonas Aeruginosa Bte-1 Strain, Ping Zhou, En-Ren Zhang, Li Zhou, Guo-Wang Diao, Jun-Le Niu

Journal of Electrochemistry

The aim of the present study is to investigate the electrocatalytic activity of electricity-producing Pseudomonas aeruginosa BTE-1 strain under anaerobic conditions. Pseudomonas aeruginosa BTE-1 was inoculated into anaerobic three-electrode electrochemical cells, and the electrocatalytic activity was measured at poised potentials. HPLC and cyclic voltammetry were used to detect potential electron mediators in solutions. Experimental results showed that no detectable pyocyanine was excreted by P. aeruginosa BTE-1 strain in the anaerobic electrochemcial cells, and P. aeruginosa BTE-1 exhibited direct electrocatalytic activity through the formation of biofilm on the electrode surface which was induced by the electron transfer from the cells of …

Cycle Lifetime Investigation Of Nickel Electrode Prepared By Electrochemical Impregnation For Applications In Aerospace Nickel Hydrogen Cells, Hai-Chang Zhang, Li-Xin Tan, Cheng Guo, Wen-Cheng Ming, Xue-Ying Ren

Journal of Electrochemistry

In this paper, the effects of overcharge, charge-discharge C rate and pore size on cycle lifetime of 4.5’ electrochemical impregnated nickel electrode were investigated. In the case of the electrode was overcharged to 170% of nominal capacity, the initial capacity of the electrode could be maintained 2.7 Ah up to 150 cycles without deterioration and a discharge capacity of 1.7 Ah (remaining 63% of 2.7 Ah) could be delivered after 300 cycles. Without overcharge, more than 300 charge-discharge cycles could be realized without loss of capacity and a discharge capacity of electrode could be maintained about 76% of initial capacity …

Electrochemical Behavior Of Imidacloprid, Jie-Qiong Wang, Wang Zhang, Ming Chen, Guo-Wang Diao

Journal of Electrochemistry

The electrochemical behavior of imidacloprid（IDP）on glassy carbon electrode has been investigated by cyclic voltammetry. The result shows that the electrochemical reduction of IDP is irreversible and controlled by diffusion. At 25 ℃, the numbers of the electrons transferred of IDP in the electrochemical reaction are four. The diffusion coefficient of IDP is 2.44×10⁶ cm²·s^-1 and the diffusion activation energy is calculated to be 9.33 kJ·mol^-1.

Dissolved Oxygen Seawater Battery With Electrochemical Capacitance, Hai-Bo Xu, Yong-Hong Lu, Wei Zhang, Yan-Ting Yu, Chuan-Wei Yan, Ya-Ping Sun, Lian Zhong, Jian-Guo Liu, Yi Zheng, Bing Han, Yong-Liang Wang

Journal of Electrochemistry

A new concept of seawater battery with electrochemical capacitance (SWB-EC) has been proposed using carbon fibre brush (CFB) as the cathode material, and three testing prototypes have been made accordingly. The discharge performances of the CFB before- and after-oxidation and Mg alloy sacrifice anode were studied by cyclic voltammetry and constant current discharge tests under steady state conditions. Results show that the oxidized CFB exhibits the pseudo-capacitive characteristic and its activity of oxygen reduction reaction (ORR) in stirred seawater highly increases, comparing with the non-oxidized CFB. The open circuit potential of Mg alloy sacrifice anode is -1.74 V, having the …

Simultaneous Determinations Of Ascorbic Acid, Dopamine And Uric Acid At Ca/Gc Electrode, Ying Zhang, Wang Ren, Min-Jiao Li

Journal of Electrochemistry

The citric acid modified glassy carbon electrode (CA/GC) was constructed by potentiostatic technique and used for simultaneous determinations of ascorbic acid (AA), dopamine (DA) and uric acid (UA) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The CA/GC electrode exhibits excellent electrocatalytic activity towards AA, DA and UA. The oxidation peaks are well separated with the potential differences between AA and DA, DA and UA, and AA and UA being 170, 130 and 300 mV, respectively, which is large enough to determine AA, DA and UA simultaneously. The catalytic peak currents obtained were linearly dependent on the concentrations of …