Chemical Engineering Commons^™

Investigation And Synthesis Of Novel Graphene-Based Nanocomposites For Hydrogen Storage, Anthony Joseph D'Angelo

USF Tampa Graduate Theses and Dissertations

It is of great interest to develop and utilize a high surface area material with optimized hydrogen sorption properties. The need for a renewable energy source to replace automobile gasoline has become more critical in the past decade. Hydrogen is a viable fuel source for automobile usage; however, the question of how hydrogen will be safely and efficiently stored still remains. Critical factors for optimum hydrogen storage include ambient conditions and low activation temperature for adsorption and desorption phenomena. In order for optimum hydrogen adsorption to be achieved, the properties of (1) high surface area, (2) optimum hydrogen adsorption energy, …

Synthesis And Electrochemical Performance Of Xlifepo4·Yli3V2(Po4)3 Composites, Ping-Ping Ma, Zhi-Jian Liu, Jian-Hua Xia, Yu Chen, Pu Hu, Zhi-Chao Lu, Ding-Guo Xia

Journal of Electrochemistry

A series of xLiFePO₄·yLi₃V₂(PO₄)₃ composites were systematically synthesized through solid state reactions by variations in the proportions of LiFePO₄ and Li₃V₂(PO₄)₃. The properties of the prepared compounds were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The capacity of 162.7 mAh/g at 0.2 C rate was obtained with the relatively good cycle stability and good conductivity for 0.95LiFePO₄·0.05Li₃V₂(PO₄)₃ due to more uniformed distributed and smaller particle sizes.

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 …

Progress And Perspective Of Fuel Cell Technology, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Fuel cell, a clean and high-efficiency electrochemical power source, has being paid much attention worldwide recent years. In this paper, the progress and perspective of fuel cell technology are elucidated in detail. Fuel cells have been applied in some special fields such as spacecraft, shuttle and submarines. However, in the areas of transportation, stationary station and portable power source, fuel cells are still under demonstration due to the durability and cost problems. The reliability and surrounding survivability of fuel cells should be enhanced in the special application. Meanwhile, the durability and cost of fuel cells are the main issues to …

Analysis Of The Penney-Ante Game Using Difference Equations: Development Of An Optimal And A Mixed-Strategies Protocol, Carl Barratt, Pauline Schwartz

Chemistry and Chemical Engineering Faculty Publications

Penney-Ante is a well known two-player (Player I and Player II) game based on an information paradox. We present a new approach, using difference-equations, to analyzing the outcome for each player. One strategy yields a winning outcome of 75% for Player II, the player playing second. The approach also permits investigation of non-optimal strategies, and demonstrates how mixing of such strategies can be used to tune the winning edge of either player. We generalize the analysis to accommodate the possibility of a biased coin.

Kinetic Models Of The Prebiotic Replication Of Dsrna Under Thermal Cycling Conditions, Pauline Schwartz, Dante M. Lepore, Carl Barratt

Chemistry and Chemical Engineering Faculty Publications

We present computational models for the replication of double stranded RNA (dsRNA) or related macromolecules under thermal cycling conditions that would reflect prebiotic (i.e. non-enzymatic) environments. Two models of the replication of dsRNA are represented as multi-step chemical systems. The objective of this investigation was to better understand the kinetic features of such chemical systems. It is shown that thermal cycling in a chemical system is advantageous (relative to a fixed temperature) if there are two competing reactions, one favored at high temperature and one favored at low temperature. For the prebiotic replication of dsRNA, a high temperature favors formation …

New Precursors And Chemistry For The Growth Of Transition Metal Films By Atomic Layer Deposition, Thomas Joseph Knisley

Wayne State University Dissertations

The advancing complexity of advanced microelectronic devices is placing rigorous demands on currently used PVD and CVD deposition techniques. The ALD deposition method is proposed to meet the film thickness and conformality constraints needed by the semiconductor industry in future manufacturing processes. Unfortunately, there is a limited number of chemical precursors available that have high thermal stability, reactivity, and vapor pressure suitable for ALD film growth to occur. These properties collectively contribute to the lack of suitable transition metal precursors available for use in ALD. In this thesis, we report the discovery of a series of novel transition metal diazadienate …

Catalytic Effects Of Period Iv Transition Metal In The Oxidation Of Biodiesel, Bradley Clark

Wayne State University Theses

CATALYTIC EFFECTS OF PERIOD IV TRANSITION METALS IN THE OXIDATION OF BIODIESEL

BRADLEY R CLARK

December 2011

Advisors: Dr. Steve Salley, Dr. Simon Ng, Dr. Naiem Henien

Major: Alternative Energy Technology

Degree: Masters of Science

Transition metals have the ability to catalyze free radical autoxidation of unsaturated fatty acid methyl esters (i.e., biodiesel). The catalytic effects of the eight period IV transition metals: V, Cr, Mn, Fe, Co Ni, Cu and Zn in soybean oil and cottonseed oil-based biodiesel are investigated. All metals produced a reduction of the induction period of biodiesel, although there are considerable differences in their catalytic …

Development Of Tailor-Designed Gold-Platinum Nanoparticles Binary Catalysts For Efficient Formic Acid Electrooxidation, Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

The modification of a glassy carbon (GC) electrode with platinum (PtNPs) and gold (AuNPs) nanoparticles is targeted to fabricate efficient anodes for the electrooxidation of formic acid (FA). A proper adjustment of the deposition sequence of PtNPs and AuNPs could eventually enhance the electrocatalytic activity of the electrode in such a way that suppresses the CO poisoning effect during FA oxidation. The highest catalytic activity is obtained at the Au/Pt/GC electrode (with PtNPs firstly deposited on the GC electrode followed by AuNPs). This superb enhancement is quantified by comparing the relative ratio of the direct vs. the indirect oxidation peaks …

Novel Blends Of Sulfur-Tolerant Water-Gas Shift Catalysts For Biofuel Applications, Timothy Michael Roberge

USF Tampa Graduate Theses and Dissertations

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations of approximately 30 to 600 ppm H2S in stream. H2S is a catalyst poison which adversely affects downstream processing of hydrogen for gas to liquid plants. The water-gas shift reaction is an integral part of converting CO and steam to H2 and CO2. Currently, all known water-gas shift catalysts deactivate in sulfur concentrations typical of biomass-derived synthesis gas. Novel catalysts are needed to remain active in the presence of sulfur concentrations in order to boost …

Design Of Colloidal Composite Catalysts For Co2 Photoreduction And For Co Oxidation, Bijith D. Mankidy

USF Tampa Graduate Theses and Dissertations

In this doctoral dissertation, novel colloidal routes were used to synthesize nanomaterials with unique features. We have studied the impact of nanoparticle size of catalyst, role of high surface area of a photocatalyst, and the effect of varying elemental composition of co-catalytic nanoparticles in combination with core-shell plasmonic nanoparticles. We have demonstrated how physical and chemical characteristics of nanomaterials with these unique features play a role in catalytic reactions, specifically the oxidation of CO and the photoreduction of CO2. The first objective of this doctoral dissertation involved the preparation of CoO nanoparticles with discrete nanoparticles sizes (1-14 nm) using a …

Organic Photovoltaics: A Charge Transfer Perspective In The Study Of Donor-Acceptor Pairs, Marco Olguin

Open Access Theses & Dissertations

The present research involves the study of donor-acceptor (D/A) dyad complexes from a charge transfer energy perspective. The aim is to provide insight and predictive understanding into the charge transfer processes of the molecular-level components in donor-acceptor based organic solar cells using computational methods to describe photochemical processes at the quantum mechanical level within the Density Functional Theory (DFT) approximation. Predictive understanding is anchored in reproducing experimental results, wherein the present work a perturbative excited-state DFT method is described in detail and shown to give CT energies in excellent agreement with benchmark experimental data. With an accurate excited state method …

Microemulsion Preparation And Electrochemical Characterization Of Pt/C, Ptir/C Electrocatalysts, Ya-Ping Zeng, Sheng Sui

Journal of Electrochemistry

The Pt/C electrocatalysts were prepared by three different systems and the PtIr/C electrocatalysts were prepared with four different Ir contents. The samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), cyclic voltammetry (CV), potentiostatic and potentiodynamic polarizations measurements. The experimental results confirmed that the electrocatalyst particles prepared by the microemulsion method were well distributed on XC-72R supports with the active particle sizes of 5～10nm and good electrocatalysts activity. The Pt85Ir15/C electrocatalysts showed the highest overall electrochemical activity in unitized regenerative fuel cell.

Preparation And Characterization Of The Lani0.6Fe0.4O3-δ Cathode For Intermediate Temperature Solid Oxide Fuel Cell, Hang Liu, Bo Huang, Xin-Jian Zhu

Journal of Electrochemistry

The LaNi_0.6Fe_0.4O_3-δ as cathode material for intermediate temperature solid oxide fuel cell was prepared using a combustion synthesis technique. The X-ray diffraction (XRD) pattern showed that the single-phase LaNi_0.6Fe_0.4O_3-δ perovskite could be obtained after heat treatment at 600°C. The TEM and SEM images of the synthesized powders revealed that the grains were 50-100nm. According to the electrochemical impedance spectra (EIS), the polarization resistance of the symmetric cell LaNi_0.6Fe_0.4O_3-δ/ScSZ/LaNi_0.6Fe_0.4O_3-δ sintered at 1050°C was the smallest (0.70Ω·cm², 0.27Ω·cm^{2 …}

Dynamic Modeling And Characteristic Analysis Of Proton Exchange Membrane Fuel Cell, Qiu-Hong Jia, Ming Han, Bin Deng, Cai-Zhi Zhang

Journal of Electrochemistry

In this paper, a dynamic model of PEMFC is developed to estimate the dynamic performance of PEMFC by analyzing in detail the influence factors of voltage of PEMFC including various losses. The partial pressure of hydrogen and oxygen is obtained using the differential form of the ideal-gas equation in this model. The steady-state model is obtained by setting reasonable parameter values. The simulation results and experimental results have good consistency, which shows that the simulation model is correct, reasonable and effective. It analyzed the dynamic response characteristics of the output voltage and the partial pressure of hydrogen in condition of …

Preparation And Capacitance Characteristics Of Nickel Oxide Electrode With Mesh-Like Structure, Hui Xu, Zhen-Jun Peng, Dong-Hong Guo, Jun-Ling Li

Journal of Electrochemistry

The mesh-like structure of NiO electrode was obtained by first preparing the precursors via hydrothermal process using nickel sulfate and carbamide as reactants, sodium hexametaphosphate as a surfactant, and followed by calcination of the precursors at 400 ℃. The structure, morphology and capacitance characteristics of NiO electrode were characterized by XRD, SEM and constant current charge-discharge testing techniques. The effects of hydrothermal temperatures on the electrochemical properties of NiO electrode were investigated. The results showed that the better property of nickel oxide was obtained when the mole ratio of nickel to urea was 1:4 and the hydrothermal temperature was 140℃. …

Electrochemical Properties Of Tungstogermanate And Electrocatalysis Of H2O2 On Gew11Co/P-Opd/Gc Electrode, Li-Li Zhu, Jian-Ying Qu, Jue Wang, Hao-Yue Feng

Journal of Electrochemistry

The electrochemical properties of Co-substituted trimeric tungstogermanate containing Keggin fragments were studied. Cyclic voltammograms revealed two couples of reversible redox peaks on glassy carbon (GC) electrode in acid solutions. They corresponded to two-electron reductions accompanying by the additions of four protons and three protons, respectively, both were controlled by adsorption. The differences in the peak potentials of 2-electron-4-proton and 2-electron-3-proton reactions were 31 mV and 35 mV, respectively..Furthermore, the tungstogermanate (GeW11Co) modified GC electrode with functionalization by poly(o-phenylenediamine) (P-oPD) was prepared readily by electropolymerization. The GeW11Co/P-oPD/GC electrode could electrocatalyze the reduction of hydrogen peroxide, which showed good stability and quick …

Indirect Electrochemical Reduction And Cotton Dyeing Process In Fe(Ⅲ)-Oxalate-Calcium Gluconate System, Qing-Zhi Wang, Wei Wang

Journal of Electrochemistry

The electrochemical behavior and possible reaction mechanism in Fe(Ⅲ)-oxalate-calcium gluconate system were studied by cyclic voltammetry. The results showed that Fe(Ⅱ)-gluconate was the final reductant. The reduction time, the working voltage and the cathode area influenced the current efficiency. The high current efficiency of 89% for the indirect electrochemical reduction of Vat Scarlet R could be achieved with reduction time of 10 min, working voltage of 4 V and cathode area of 40 cm² in Fe(Ⅲ)-oxalate-calcium gluconate system.

Computational Studies Of Ion Transport In Polymer Electrolytes, Hui Wu

Doctoral Dissertations

Improving ionic conductivity and lithium mobility in polymer electrolytes is important for their practical use for battery electrolytes. In this study, a combination of molecular dynamics and Monte Carlo simulations was used to bring insight into lithium ion transport in poly(ethylene oxide) (PEO) with plasticizers and also next to alumina solid surface doped with lithium salt. The simulations were performed using a moderately high molecular weight polymer (Mn = 10,000 g/mol) at an EO:Li ratio of 15. For the plasticized system, the PEO with LiN(CF3SO 2)2 (LiTFSI) was mixed with 10 wt% plasticizers that included either cyclic ethylene carbonate …

A Modified Surface On Titanium Deposited By A Blasting Process, Caroline O' Sullivan, Peter O'Hare, Greg Byrne, Liam O'Neill, Katie B. Ryan, Abina M. Crean

Publications

Abstract

: Hydroxyapatite (HA) coating of hard tissue implants is widely employed for its biocompatible and osteoconductive properties as well as its improved mechanical properties. Plasma technology is the principal deposition process for coating HA on bioactive metals for this application. However, thermal decomposition of HA can occur during the plasma deposition process, resulting in coating variability in terms of purity, uniformity and crystallinity, which can lead to implant failure caused by aseptic loosening. In this study, CoBlast™, a novel blasting process has been used to successfully modify a titanium (V) substrate with a HA treatment using a dopant/abrasive regime. …

Electrochemical Performance Of Tin Dioxide/Carbon Xerogel Composites As Anode Materials For Lithium-Ion Batteries, Xiao-Jing Liu, Lin-Lin Qin, Yi-Ning Shi, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

The tin dioxide/carbon xerogel composites were synthesized by using vacuum infiltration method. Structural characterization and morphology of the composites were investigated by using XRD, TEM and SEM techniques. BET test was performed to determine the pore size distributions of carbon xerogels and the composites. The results showed that the nano-sized SnO₂ particles (5~10 nm) were encapsulated in the pores of carbon xerogels. During the electrochemical tests the SnO₂ in the composites exhibited capacity retention of 61.9% after 100 cycles of charge-discharge tests at 100 mA/g.

Synthesis And Electrochemical Behaviors Of Li2Coxmn1-XSio4 As A Cathode Material For Lithium-Ion Batteries, Lin Wang, Dong-Ping Lv, Yong Yang

Journal of Electrochemistry

We have successfully synthesized Li₂Co_xMn_1-xSiO₄/C (x=0, 0.1, 0.3, 0.5, 1)/C composites using hydrothermal assisted sol-gel process and ball-milling method. The results of X-ray diffraction show that the solid solutions of Li₂Co_xMn_1-xSiO₄ can be achieved when x≤0.3. The initial capacities increase from 70 mAh·g^-1 of Li₂MnSiO₄/C to 105 mAh·g^-1 of Li₂Co_0.3Mn_0.7SiO₄/C. Cyclic Voltammetry (CV) curves show that the replacement of Mn with Co can reduce the electrochemical polarization, making the insertion-extraction reaction …

Synthesis Of Limnpo4/C Used As Cathode Material For Lithium Ion Batteries, Xin Yang, Xue-Wu Liu, Gui-Chang Liu, Zhi-Cong Shi, Xin Li, Guo-Hua Chen

Journal of Electrochemistry

The LiMnPO₄/C composites were prepared using a solid-state reaction with addition of the resorcinol formaldehyde resin as the carbon source. The effects of reaction temperature and time on the crystal structure, morphology and electrochemical properties of the LiMnPO₄/C composites were investigated. The results show that the best performance was achieved with the LiMnPO₄/C composites synthesized at 600 ^oC for 12 h which had the particle sizes about 100~200 nm. The initial discharge capacities were 121.6 mAh·g^-1 at 0.02C, 110 mAh·g^-1 at 0.1C and more than 60 mAh·g^-1 at 1C. An …

Effect Of Freshman Chemistry On Student Performance In Sophomore Engineering Courses, Michael A. Collura, Shannon Ciston, Nancy Ortins Savage

Chemistry and Chemical Engineering Faculty Publications

The role of first year chemistry courses in engineering programs varies somewhat across programs and disciplines. Clearly most engineering majors will encounter chemistry topics of a general nature in some of their upper-level course work. The purpose of requiring chemistry in the first year, however, goes well beyond learning chemical concepts. As a quantitative science, chemistry requires the use of math, principally algebra, on a regular basis in solving various problems. Students should gain an appreciation of the importance of units in solving problems should come to understand the difference between implicit and explicit properties and should develop other quantitative …

Preparation And Electrocatalytic Activity Of The Pt/Wc/Tio2 Composites, Chun-An Ma, Bin Yu, Mei-Qin Shi, Xiao-Ling Lang

Journal of Electrochemistry

TiO₂ was used as the support for preparation of Pt/WC/TiO₂ composite catalyst. The composites were characterized by XRD, SEM and TEM methods. The electrocatalytical activity of Pt/WC/TiO₂ composite for oxidation of methanol was investigated by cyclic voltammetry. Pt/WC/TiO₂ exhibited higher activity compared with that of Pt/TiO₂ and Pt/WC composite catalysts. Based on this we discussed the effects of crystal phases of TiO₂ on the electrocatalytical activity of Pt/WC/TiO₂ composite catalyst.

Electrochemical Capacitive Performance Of Mesoporous Carbon Based Co-Ni Oxides, Zhen-Sheng Yang, Ling-Bin Kong, Li Deng, Yong-Chun Luo, Long Kang

Journal of Electrochemistry

By using defects on the surface of CMK-3 served as nucleation center, Co_0.25Ni_0.75 oxide/C composite was successfully prepared through a simple chemical co-precipitation method. Characterization was carried by using X-ray diffraction, BET and scanning electron microscopy. Results showed that a perfect mesoporous network of interconnected nanoflakes was obtained for Co_0.25Ni_0.75 oxide/C composite and, this material has a less crystallization, interconnected nanoflakes network structure and a narrow mesoporous distribution at about 3~4 nm. The highly dispersed and loosely packed Co_0.25Ni_0.75 oxide/C composite possessed good electrochemical accessibility and fast diffusion rate of OH …

Synthesis And Catalytic Property Of Flaked Spindle-Like Cuo Nanocrystals, Jian-Feng Fan, Li-Qing Li, Yu-Feng Huang, Lou-Zhen Fan

Journal of Electrochemistry

A simple and efficient electrochemical route was developed for the synthesis of flaked spindle-like CuO nanocrystals using aqueous electrolyte and Cu sacrificial anode (graphite as the cathode) in an undivided cell at a constant potential mode under room temperature. The morphologies, structure and component of CuO nanocrystals obtained were characterized by SEM, XRD, respectively. Flaked spindle-like CuO nanocrystals were successfully used to modify a GC electrode to detect H₂O₂ with cyclic voltammetry (CV) and amperometric (AC).The results showed that products were pure monoclinic CuO nanocrystals. The linear range for the determination of hydrogen peroxide is from 1.0 …

Study On Direct Electro-Oxidation Of Anisaldehyde, Lin-Lin Wu, Ying-Hong Zhu, Shan-Shan Li, Hong-Yan Zeng, Chun-An Ma

Journal of Electrochemistry

The oxidation of anisole on Pt electrode was investigated by cyclic voltammery and constant potential electrolysis. The influence of scan rates, substrate concentration, supporting electrolytes and solvent were considered . The results show that the electro-oxidation process of anisole was irreversible. In this research the sulfuric acid was the best supporting electrolytes and acetone was the best solvent, and the process was controlled by diffusion . The product of constant potential electrolysis was charactered by GC-MS .The results show that the main products was anisaldehyde, and the selectivity was up to 66.5% when using acetone as solvent.

Dft Study Of Co2 Reduction To Hydrocarbons On Cu Surfaces, Li-Hui Ou, Sheng-Li Chen

Journal of Electrochemistry

CO₂ reduction on Cu(111) single crystal surfaces was studied using DFT calculations on the reaction energies and the minimum energy paths. The results indicated that the possible reaction paths for CO₂ reduction on Cu(111) surface are CO₂(g) + H* → COOH* → (CO +OH)*, (CO + H)* → CHO*, CHO + H → CH₂O* → (CH_2⁺O)*, CH₂* + 2H* → CH₄ or 2CH₂* → C₂H₄. On Cu(111) surface, the reaction rate is controlled by steps of CH₂O* → (CH_{2 …}

Comparison Of Catalytic Performance On Different Materials Supported Pd Catalysts For Formic Acid Oxidation, Su-Dong Yang, Yan-Yu Liang, Zhu-Liang Wen, Qi-Jun Song, Xiao-Gang Zhang

Journal of Electrochemistry

Graphite oxide (GO) was prepared from by Hummers method. Then the graphene nanosheets supporting Pd catalysts were prepared by a single-step chemical reduction method. The electrocatalytic performance for formic acid oxidation of the prepared Pd/graphene composite was studied as an electrode material in comparison with the composite catalysts based on the other carbons (MWCNTs, SWCNTs, and Vulcan XC-72 carbon black). X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements indicated that the Pd nanoparticles were well dispersed on the surface of the graphene nanosheets with a small particle size. The electrocatalytic oxidation of formic acid was studied by electrochemically active …