Chemical Engineering Commons^™

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 …

Formation Of Organized Nanostructures From Unstable Bilayers Of Thin Metallic Liquids, Mikhail Khenner, Sagar Yadavali, Ramki Kalyanaraman

Mathematics Faculty Publications

Dewetting of pulsed-laser irradiated, thin (< 20 nm), optically reflective metallic bilayers on an optically transparent substrate with a reflective support layer is studied within the lubrication equations model. A steady-state bilayer film thickness (h) dependent temperature profile is derived based on the mean substrate temperature estimated from the elaborate thermal model of transient heating and melting/freezing. Large thermocapillary forces are observed along the plane of the liquid-liquid and liquid-gas interfaces due to this h-dependent temperature, which, in turn, is strongly influenced by the h-dependent laser light reflection and absorption. Consequently the dewetting is a result of the competition between thermocapillary and intermolecular forces. A linear analysis of the dewetting length scales established that the non-isothermal calculations better predict the experimental results as compared to the isothermal case within the bounding Hamaker coefficients. Subsequently, a computational non-linear dynamics study of the dewetting pathway was performed for Ag/Co and Co/Ag bilayer systems to predict the morphology evolution. We found that the systems evolve towards formation of different morphologies, including core-shell, embedded, or stacked nanostructure morphologies.

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 …

Plasmonic Nanogels With Robustly Tunable Optical Properties, Tao Cong, Satvik N. Wani, Georo Zhou, Elia Baszczuk, Radhakrishna Sureshkumar

Biomedical and Chemical Engineering - All Scholarship

Low viscosity fluids with tunable optical properties can be processed to manufacture thin film and interfaces for molecular detection, light trapping in photovoltaics and reconfigurable optofluidic devices. In this work, self-assembly in wormlike micelle solutions is used to uniformly distribute various metallic nanoparticles to produce stable suspensions with localized, multiple wavelength or broad-band optical properties. Their spectral response can be robustly modified by varying the species, concentration, size and/or shape of the nanoparticles. Structure, rheology and optical properties of these plasmonic nanogels as well as their potential applications to efficient photovoltaics design are discussed.

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 …

Anode Electrodeposition Of Ti/Mno2 Electrode And Electrocatalytic Oxidization Properties Of Phenol Degradation, Ye Chen, Wen-Li Zhao, Qing Wen

Journal of Electrochemistry

Ti-base manganese dioxide (Ti/MnO₂) electrode was prepared by anodically electrodeposition technology in this paper. The structure of the electrode, the microstructure of the electrode surface and the element composition of the electrode were analyzed by XRD, SEM and EDS. The preparation process parameters of the electrode were studied in detail with the help of the V~logi curve and phenol degradation curve. The Ti/MnO₂ electrode was anodically electrodeposited at current density 4mA•cm^-2, the Mn^{2 +} ions concentration 0.5mol•L^-1 and temperature70℃. The V~logi curve and phenol degradation curve were used to evaluate electrocatalytic oxidization properties …

Self-Assembling Organic Semiconductors With Tunable Electronic Properties Based On Novel Asymmetric Phenazine And Bisphenazine, Kyoungmi Jang

UNLV Theses, Dissertations, Professional Papers, and Capstones

Current demands in the area of organic semiconductors focus on both electronic and self-assembling properties. Particularly, one-dimensionally grown nanostructures of small organic semiconductors have drawn much attention for nanodevice fabrication. Self-assembly through various intermolecular interactions has been widely used to produce one-dimensionally grown nanostructures which can be induced by various methods such as rapid solution dispersion, a phase transfer method, vapor annealing, crystallization, and organogelation in conjunction with proper molecular design. Controlling the morphology of the nanostructures plays an important role in achieving desirable properties in optoelectronic device applications. While significant advancements have been made in developing molecular architectures for …

Predicting Homo And Lumo Energy Gaps For Organic Semi-Conductor: A Theoretical Study, Padtaya Pukpayat

Festival of Communities: UG Symposium (Posters)

This poster presents a theoretical approach for characterizing the electronic properties of novel electron-deficient organic semiconductors containing variety of electron donor substituents. In treating these compounds, the following questions will be addressed: What effects to the bandgap will each substituent have? Will any of the substituents lower the band gap to the desired range for solar cell applications(<2.0eV)? Can we use the current, inexpensive and tractable computational methods as a predictive tool for guiding future experimental design of organic based solar cells, rather than depending solely on experimental procedures?

Optimizing Compressed Air Storage For Energy Efficiency, Brian Abels, J. Kelly Kissock

Mechanical and Aerospace Engineering Faculty Publications

Compressed air storage is an important, but often misunderstood, component of compressed air systems. This paper discusses methods to properly size compressed air storage in load-unload systems to avoid short cycling and reduce system energy use. First, key equations relating storage, pressure, and compressed air flow are derived using fundamental thermodynamic relations. Next, these relations are used to calculate the relation between volume of storage and cycle time in load-unload compressors. It is shown that cycle time is minimized when compressed air demand is 50% of compressor capacity. The effect of pressure drop between compressor system and storage on cycle …

Absorption Of Carbon Dioxide In Methylamino Ethanol., Hawar A. M. Haider

Student Works (2010-2019)

Carbon dioxide (CO2) is one of the most significant greenhouse gases as its emissions are currently responsible for over 70% of the enhanced greenhouse effect. One of the common techniques used to remove CO2 from flue gas streams, is absorption by aqueous alkanolamine solutions. Aqueous monoethanolamine (MEA), and aqueous methyldiethanolamine (MDEA) solutions are the most widely used alkanolamine absorbents. The former is preferred for its low molecular weight, high reactivity, low cost and reasonable thermal stability while the latter is known for its higher loading capacity (mole of CO2/mole of amine), less regeneration energy, and high resistance to thermal and …

Synthesis Of Mesoporous Nickel Oxide For Supercapacitor Application, Xuan-Xuan Chen, Zhen-Zhen Zhao, Deng-Chao Wang, Zhong-Jie Huang, Wen-Bin Ni, Li Yu, Jian-Wei Zhao

Journal of Electrochemistry

Mesoporous nickel oxide has been synthesized by calcining metal-organic coordination precursor.Transmission electron microscopy and BET test showed that the prepared NiO had a regular morphology and displayed a narrow size distribution.Electrochemical tests revealed that such mesoporous NiO had a specific capacity of 72 F·g^-1 at the current of 2.0 A·g^-1.Futhermore,the material showed excellent cycle-life stability.There was no degradation of capacitance after 1000 cycles.

Novel Anion Exchange Membranes Base On Copolymer Of 2-(Diethylamino) Ethyl Methacrylate And Fluoro-Polyacrylate For Alkaline Direct Methanol Fuel Cells, Yan-Mei Zhang, Jun Fang, Ge Yan, Yong-Ze Zhuang

Journal of Electrochemistry

Anion exchange membrane fuel cells,which use anion exchange membranes as polyelectrolytes,have attracted more and more research interests recently.In this work,a series of hydroxyl-conducting anion-exchange membranes based on the copolymer of 2-(Diethylamino)ethyl methacrylate and fluoro-polyacrylate were prepared by radical polymerization,and their potential applications in alkaline fuel cells were assessed.It was shown that the ionic conductivity of the membranes reached 10^-2 S·cm^-1 at room temperature,while the methanol permeability was lower than 10^-7 cm²·s^-1.The maximum power density of fuel cell assembled with this membrane was achieved to be 43.2 mW·cm^-2 at room temperature,indicating possible application …

A Titanium-Supported Nanoporous Pd Electrocatalyst For Methanol Oxidation, Feng-Juan Niu, Qing-Feng Yi

Journal of Electrochemistry

Titanium-supported nanoporous palladium electrode(nanoPd /Ti) was prepared by a hydrothermal process in the presence of the ligand EDTA and using formaldehyde as reducing agent.SEM images showed that the size of Pd particles was about 60 nm and the Pd particles were connected with each other to form a three-dimensional network structure.Cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) were applied to evaluate the electrocatalytic activity of the nanoPd/Ti electrode towards methanol oxidation in alkaline solution.CV results showed that the nanoPd /Ti electrode presented high anodic peak densities and a low onset potential for methanol oxidation.Also nanoPd /Ti electrode showed excellent CO tolerance …