Chemical Engineering Commons^™

Phase Transformations In Calcium Substituted Lanthanum Ferrite, Patrick M. Price

Boise State University Theses and Dissertations

Increasing world energy demands are still heavily dependent on fossil fuels. To meet these demands, crude oil is increasingly being extracted from remote locations where natural gas pipelines do not exist. It is not profitable for oil and gas companies to transport natural gas by ship or truck from these remote locations so it is combusted on site in the form of gas flares. Critics oppose this practice due to the environmental impact from pollution and carbon emissions created during the flaring process. Oil and gas companies are eager to find profitable ways to eliminate natural gas lines in order …

Preparation Of Pt/H-Tio2 Catalyst With Improved Catalytic Performance For Methanol Electrooxidation, Jin Han, Zhi-You Zhou, Qiang Wang, Miao-Qiang Lv, Chi Chen, Shi-Gang Sun

Journal of Electrochemistry

White TiO₂ nanorods were synthesized by hydrothermal method with TiCl₄ as a precursor. As-synthesized TiO₂ nanorods were further subjected to high-temperature (550 ^oC) heat treatment for 2 h under H₂ atmosphere to prepare gray black hydrogen-treated TiO₂ (H-TiO₂) nanorods with oxygen vacancies and Ti³⁺ interstitial atoms. The Pt nanoparticles of 1.9 nm were supported on these two types of TiO₂ nanorods to form Pt/TiO₂ and Pt/H-TiO₂ catalysts. XRD data indicates that the crystal structure of TiO₂ was still reserved as rutile after hydrogen treatment, but the surface …

Electrocatalytic Oxidation Of Glycerol At The Platinum Electrode Modified With An Nd-Fe-Moo42- Cyano-Bridged Mixed Coordination Polymer, Yong-Jun Ma, Yu-Xiu Tian, Jing Liu, Min Zhou, Jing Ding, Zhi-Mei Jin, Xiang-Mei Wang

Journal of Electrochemistry

A platinum electrode decorated with the ordered Nd-Fe-MoO₄^2- cyano-bridged mixed coordination polymer was successfully prepared by electrodeposition in virtue of the lyotropic liquid crystal soft template methods, and electrocatalytic oxidation behavior of glycerol was investigated on the chemically modified electrode by cyclic voltammetry. The influences of experimental factors such as the concentrations of H⁺ and SO₄^2- in electrolytes, glycerol concentration and scan rate on the electrocatalytic activity of glycerol at the modified electrode were also studied. It indicated that the proper amount of SO₄^2- in weakly acidic electrolyte could help to improve the …

Synthesis Of Platinum Nanocrystallites And Possible Electrocatalytic Properties For Methanol, Lei-Lei Lu, Bao-Zhong Du, Sha Sun, Jin-Fen Niu, Jie Zhao

Journal of Electrochemistry

Platinum nanocrystallites were synthesized by the colloidal method using oxamide as the stabilizer. The morphologies and electrocatalytic performances for methanol of platinum nanocrystallites prepared at different pH values and with different reactant ratios of precursor and stabilizer were investigated. It was found that the platinum nanocrystallites synthesized at pH=5 and with the reactant ratio of 1:20 showed the best electrocatalytic activity for methanol. The peak current density reached up to 1709 μA·cm^-2. Furthermore, the electrocatalytic activity of platinum nanocrystallites for methanol reduced significantly although the cyclic voltammograms in the blank solution were not obviously changed after exposing in …

Effect Of Temperature On The Self-Humidifying Open-Cathode Proton Exchange Membrane Fuel Cell, Si-Chen Zhao, Ben Wang, Qiu-Hong Jia, Ming Han, Yu-Hong Xie

Journal of Electrochemistry

Based on the experiments about the output characteristics of a home-made temperature-controlled PEMFC system with atmospheric pressure and no external humidifying condition in different loading voltages and operating temperatures, the optimum operating temperature at different loading voltages can be obtained by tracking the output characteristics of PEMFC operating over a range of temperatures. By analyzing the fitted data the kinetic parameters are evaluated and the effect of different operating temperatures on the PEMFC performance is discussed from a view of electrode kinetics.

Electro-Catalytic Oxidation Of Hydrogen Peroxide On Au/ L-Methionine /Gc Electrode, Jian-Feng Fan, Xue-Mei Luo, Jing Li, Lou-Zhen Fan

Journal of Electrochemistry

The modified electrodes have been fabricated by generation of Au nanoparticle chains, which was produced by reaction between HAuCl4 and sodium citrate without any additional capping agents or surfactants. The self-assembled Au nanoparticles were attached to the surface of glassy carbon electrode (GCE) layer by layer, using L-methionine (L-Met), thiourea (TU), allyl thiourea (ATU) and polyvinylpyrrolidone (PVP) as a crosslinking agent, respectively. The experimental results showed that the electrochemical performance of the different modified electrodes varied in [Fe(CN)₆]^3-/4- solution. The Au/L-Met/GCE exhibited an excellent electrochemical property, which is superior to other modified electrodes. In addition, the catalysis …

Development And Utilization Of A Pair Of Sol-Gel Entrapped Lipases For Biodiesel Production From High Free Fatty Acid Oils, Cory M. Schwartz

Department of Chemical and Biomolecular Engineering: Dissertations, Theses, and Student Research

Biodiesel, which consists of fatty acid alkyl esters, is one of the most widely adopted and successful renewable fuels. Traditional physiochemical biodiesel production methods require high cost refined feedstocks, and so alternative methods of catalysis and feedstocks have been explored. This research investigated the use of polysiloxane entrapped lipases to catalyze the production of biodiesel from low cost feedstocks.

In this work, lipase from Burkholderia cepacia (lipase PS) and lipase B from Candida antarctica (CalB) were separately entrapped using sol-gel chemistry. Optimal reaction conditions for the esterification of free fatty acids by immobilized CalB with methanol were determined. Immobilized CalB …

Influence Of Reduction Promoters On Stability Of Cobalt/Γ-Alumina Fischer-Tropsch Synthesis Catalysts, Gary Jacobs, Wenping Ma, Burtron H. Davis

Center for Applied Energy Research Faculty and Staff Publications

This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co⁰ site densities (e.g., in research catalysts), ultra-small crystallites (e.g., < 2–4.4 nm) formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au) that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration) cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co⁰ (e.g., Cu), or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at …

Phase Transitions Of Perfluorocarbon Nanoemulsion Induced With Ultrasound: A Mathematical Model, William G. Pitt, Ram N. Singh, Krystian X. Perez, Ghaleb A. Husseini, Daniel R. Jack

Faculty Publications

While ultrasound has been used in many medical and industrial applications, only recently has research been done on phase transformations induced by ultrasound. This paper presents a numerical model and the predicted results of the phase transformation of a spherical nanosized droplet of perfluorocarbon in water. Such a model has applications in acoustic droplet vaporization, the generation of gas bubbles for medical imaging, therapeutic delivery and other biomedical applications. The formation of a gas phase and the subsequent bubble dynamics were studied as a function of acoustic parameters, such as frequency and amplitude, and of the physical aspects of the …

Synthesis And Electrochemical Properties Of Lico1-XMgXMno4 And Lico1-XAlXMno4 (X= 0, 0.02, 0.05, 0.1) As Positive Materials For Lithium-Ion Batteries, Mei-Ling You, Qing-Song Tong, Xiu-Hua Li, Min Lin, Xing-Kang Huang, Yong Yang

Journal of Electrochemistry

The Al-doped and Mg-doped LiCoMnO₄ materials were synthesized through solid-state reaction. The effects of doping amounts of Mg and Al on the initial capacities, discharge plateaus, and cycle performances were investigated. The morphologies and structures of the as-prepared materials were studied by scanning electron microscopy and powder X-ray diffraction. The results indicate that the as-prepared samples were composed of uniform, well-crystallized particles. The pristine LiCoMnO₄ possessed an initial capacity of 87.0 mAh·g^-1, while LiCo_0.98Mg_0.02MnO₄ and LiCo_0.98Al_0.02MnO₄ delivered 91.3 and 93.6 mAh·g^-1, respectively. The proper …

Electrochemical Oxidation Of Ammonium Nitrite In Absorption Solution Of Flue Gas, Yong-Hong Lu, Xiao-Bo Dong, Li-Sha Wang, Yan Liu, Chen-Jian Zhu, Hai-Bo Xu

Journal of Electrochemistry

In order to make full uses of ammonium nitrite in absorption solution from flue gas simultaneous desulfurization, denitrification and demercurization processes, here the electrochemical oxidation method was used to transform ammonium nitrite into ammonium nitrate. By using polarization curve, cyclic voltammogram and galvanostatic methods, suitable electrode materials were evaluated and chosen. The influence of electrolyte composition was discussed and the appropriate process parameters were obtained. Finally, the effect of electrochemical oxidation was confirmed by chemical analysis method. In 0.05 mol·L^-1 NaNO₂ + 0.05 mol·L^-1 (NH₄)₂SO₄ simulated absorption solution (5 L, pH = …

Fabrication And Impedance Performance Of Gradient Lani0.6Fe0.4O3-δ-Gd0.2Ce0.8O2 Composite Cathodes For Intermediate Temperature Solid Oxide Fuel Cell, Yang Li, Bo Huang, Meng Yuan, Zhi-Qiu Zhang, Zong-Yao Liu, Xu-Chen Tang, Xin-Jian Zhu

Journal of Electrochemistry

A LNF-GDC composite cathode with a gradual change in the composition between ScSZ electrolyte and LNF cathode was fabricated to reduce the cathode polarization resistance (R_p). The gradual change in composition between ScSZ electrolyte and LNF cathode shows the decreases in the charge transfer resistance (R_ct) and gas phase diffusion resistance (R_d). The results revealed that the Rp value, measuring 0.452 Ω·cm² at 750 °C, was the lowest for LNF-GDC composite cathodes with three layers and gradient changes in composition between ScSZ and LNF (Cathode C),, whereas the Rp value of 70%LNF-30%GDC composite …

Study On Carbon Supported Pd Catalysts Modified By Phosphomolybdic Acid For H2O2 Electrocatalytic Reduction, Li-Mei Sun, Cheng Zhang, Ying-Rong Bao, Hong-Xia Li

Journal of Electrochemistry

The Pd/C catalyst was prepared with the chemical reduction method, and phosphomolybdic acid (PMA) was modified on the Pd/C catalyst using the dipping method. The compositions and structures of the Pd/C and Pd/C modified by phosphomolybdic acid (PMA-Pd/C) catalysts were characterized with X-ray diffraction and Fourier Transform infrared spectroscopy analyses. The electrocatalytic activity and stability of the catalysts for the reduction of hydrogen peroxide (H₂O₂) were studied using cyclic voltammetry and chronoamperometry. The results showed that the phosphomolybdic acid was tightly fixed on the surface of Pd/C catalyst through the chemical interaction. The eletrocatalytic activity of …

Preparation Of Pd/Tio2/C Catalyst And Its Electrocatalytic Performance In Basic Solution For Ethanol Oxidation, Qiao-Xia Li, Yi-Chao Yang, Ming-Shuang Liu, Hong-Min Mao, Qun-Jie Xu

Journal of Electrochemistry

Nanoparticles TiO₂ were prepared by hydrothermal method using precursor tetrabutyl titanate. The Pd/TiO₂/C catalyst was synthesized by liquid phase reducing method supported on nano TiO₂ and Vulcan carbon XC-72. The Pd/TiO₂/C catalyst was characterized by XRD, TEM, cyclic voltammetry, and chronopotentiometry. XRD confirmed the face-centered cubic structure of Pd particles, and TEM indicated that Pd particles (size 3 ~ 4 nm) dispersed uniformly on TiO₂ and carbon XC-72. The results from cyclic voltammogram and chronopotentiogram showed the higher ethanol oxidation activity and stability of Pd/TiO₂/C catalyst (20% Pd) as compared with …

Pulse Electrodeposition Of Pd-Ni Alloy Nanoparticles For Electrocatalytic Oxidation Of Formic Acid, Fang-Zu Yang, Jun-Pei Yue, Zhong-Qun Tian, Shao-Min Zhou

Journal of Electrochemistry

The Pd-Ni alloy nanoparticles with nickel atomic contents of 12.0%, 16.4% and 22.6% were successfully electrodeposited from a Pd-Ni alloy electrolyte by square wave pulse plating. The alloy nanoparticles were in the spherical shape with a diameter of 50 ~ 80 nm. As the growth potential of the alloy was negatively shifted, the nickel content of the alloy was increased, and the size of the nanoparticles was almost the same, whereas the number, the degree of crosslinking and the real active area of the nanoparticles were increased. As the nickel content of the alloy nanoparticles increased, the peak current for …

Enzyme Attached On Polymeric Micelles As A Nanoscale Reactor, Moo-Yeal Lee, Kyung-Jin Hong, Seung Pil Han, Toshio Kajiuchi

Chemical & Biomedical Engineering Faculty Publications

Similar to what lipase does, a surface-active enzyme was developed by attaching peroxidase on combshaped polymaleic anhydride-alt-1-tetradecene (PMA-TD) in a microemulsion system composed of n-butyl acetate and buffer solution, and its catalytic characteristics of polyphenol synthesis were investigated in an aqueous solution. The modified peroxidase with PMA-TD tended to form self-assembled aggregates like micelles in the aqueous solution and could be concentrated at solvent/water interfaces without unfolding of the enzyme. The efficiency of conversion of 2,4-dichlorophenol to phenolic oligomers was approximately 2-fold improved with the modified peroxidase compared to native peroxidase. The K _m and V _max values …

Mixed Surfactant Systems: Thermodynamics And Applications In Metal Oxide Imprinting, Suvid Joshi

Theses and Dissertations--Chemical and Materials Engineering

In this work we study mixtures of cationic surfactant (CTAB) and sugar based surfactant(s) (octyl beta-D-glucopyranoside (C8G1), dodecyl maltoside (C12G2) and octyl beta-D-xylopyranoside (C8X1)) to understand the non-ideal thermodynamic behavior of the mixtures of cationic and non-ionic surfactants in water and synthesis of imprinted materials. The thermodynamics of micellization, mixing and dilution of these systems are studied using Isothermal Titration Calorimetry (ITC) and the experimental data obtained are modeled with a pseudo-phase separation model with non-ideal mixing described by regular solution theory. It is shown that a model accounting for enthalpy of demicellization and enthalpy of dilution based on McMillan-Mayer …

Development Of Nickel Oxide And Manganese Oxide Nanostructured Binary Modified Anodes For Methanol Electro-Oxidation, Ghada El-Nowihy

Chemical Engineering

In this investigation, a nanoparticle-based binary catalyst composed of nickel oxide (nano-NiOx) and manganese oxide (nano-MnOx), both were assembled on a platinum substrate, was developed for the direct methanol electro-oxidation (MO) in an alkaline medium. The morphological investigation was performed using field-emission SEM and revealed the electrodeposition of MnOx in a nanorod structure and NiOx in round-shaped nanospheres. The electrocatalytic activity of the modified electrodes towards MO depended critically on the order of deposition of the two oxides. The optimum electrocatalytic activity was obtained at the MnOx/NiOx/Pt electrode (in which nano-NiOx was directly electrodeposited onto the Pt surface followed by …

Development Of Nickel Oxide And Manganese Oxide Nanostructured Binary Modified Anodes For Methanol Electro-Oxidation, Ghada El-Nowihy

Chemical Engineering

No abstract provided.

A Modified Orthogonal Collocation Method For Reaction Diffusion Problems, Moustafa A. Soliman, Yousef S. Al-Zeghayer, Abdelhamid M. Ajbar

Chemical Engineering

A low-order collocation method is often useful in revealing the main features such as concentration and temperature profiles and the effectiveness factor for porous catalyst particles. Two modifications are introduced in this paper to make the method more efficient. The first modification is to add an extra collocation point at the center of the particle. It is shown that such extra point introduces a single variable non-linear equation to be solved after obtaining the standard collocation method solution. In the second modification, the polynomial solution obtained from the application of the orthogonal collocation method is transformed to a rational function …

Effects Of Sodium Hydroxide Pretreatment On Structural Components Of Biomass, Alicia A. Modenbach, Sue E. Nokes

Biosystems and Agricultural Engineering Faculty Publications

Pretreatment is a unit operation in the conversion of biomass to valuable products that utilizes various combinations of conditions, including chemicals, heat, pressure, and time, to reduce the recalcitrance of lignocellulose. Many such pretreatments have been developed over the years, as the operating conditions can be adapted so that lignocellulose is modified in ways unique to each pretreatment. By tailoring pretreatment conditions to achieve these modifications, the types of final products produced can be controlled. The purpose of this review is to provide a consolidated source of information for sodium hydroxide effects on lignocellulose. The structural characteristics of lignocellulose and …

Self-Healing Catalysts: Co3O4 Nanorods For Fischer-Tropsch Synthesis, Cun Wen, Darrius D. Dunbar, Xin Zhang, Jochen A. Lauterbach, Jason R. Hattrick-Simpers

Faculty Publications

We combine kinetic and spectroscopic data to demonstrate the concept of a self-healing catalyst, which effectively eliminates the need for catalyst regeneration. The observed self-healing is triggered by controlling the crystallographic orientation at the catalyst surface.

One-Step Production Of Long-Chain Hydrocarbons From Waste-Biomass-Derived Chemicals Using Bi-Functional Heterogeneous Catalysts, Cun Wen, Elizabeth A. Barrow, Jason R. Hattrick-Simpers, Jochen A. Lauterbach

Faculty Publications

n this study, we demonstrate the production of long-chain hydrocarbons (C₈₊) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C₈₊ hydrocarbons and the catalytic performance was stable …

Quartz Crystal Microbalance Investigation Of Cellulosome Activity From Clostridium Thermocellum On Model Cellulose Films, Shanshan Zhou

Theses and Dissertations--Chemical and Materials Engineering

The cost of deconstructing cellulose into soluble sugars is a key impediment to the commercial production of lignocellulosic biofuels. The use of the quartz crystal microbalance (QCM) to investigate reaction variables critical to enzymatic cellulose hydrolysis is investigated here, extending previous studies of fungal cellulase activity for the first time to whole cell cellulases. Specifically, the activity of the cellulases of Clostridium thermocellum, which are in the form of cellulosomes, was investigated. To clearly differentiate the activity of free cellulosome and cell-bound cellulosome, the distribution of free cellulosome and cell-bound cellulosome in crude cell broth at different growth stages …

Functionalized Membranes For Environmental Remediation And Selective Separation, Li Xiao

Theses and Dissertations--Chemical and Materials Engineering

Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It’s revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of …

Layer-By-Layer Assemblies For Membrane-Based Enzymatic Catalysis, Andrew R. Tomaino

Theses and Dissertations--Chemical and Materials Engineering

While considerable progress has been made towards understanding the effect that membrane-based layer-by-layer (LbL) immobilizations have on the activity and stability of enzymatic catalysis, detailed work is required in order to fundamentally quantify and optimize the functionalization and operating conditions that define these properties. This work aims to probe deeper into the nature of transport mechanisms by use of pressure-induced, flow-driven enzymatic catalysis of LbL-functionalized hydrophilized poly(vinyldiene) (PVDF)-poly(acrylic acid) (PAA)-poly(allylamine hydrochloride) (PAH)-glucose oxidase (GOx) membranes. These membranes were coupled in a sealed series following cellulose acetate (CA) membranes for the elimination of product accumulation within the feed-side solution during operation. …

Phenol Deoxygenation Over Hydrotreating Catalysts, Madelyn R B Ball

Honors Theses and Capstones

Phenol deoxygenation has been investigated as a model reaction for the deoxygenation of fatty acid methyl esters in biodiesel. Hydrodeoxygenated biodiesel is a drop-in fuel for petroleum diesel, and is a premium diesel with a high cetane number. As the first step in this research, two molybdenum catalysts were prepared, characterized and tested in a small-scale reactor. These catalysts were found to produce small amounts of benzene and cyclohexanol in the product stream, and confirmed the activity of the catalyst. A commercial cobalt molybdenum catalyst (Harshaw HT-400) was also tested and benzene, cyclohexanol, and cyclohexane were identified as products. Future …

Evaluating N-Benzylgalactonoamidines As Putative Transition State Analogs For Β-Galactoside Hydrolysis, Qui-Hua Fan, Susanne Striegler, Rebekah Langston, James Barnett

Chemistry & Biochemistry Faculty Publications and Presentations

Experimental evidence is provided for p-methylbenzyl-D-galactonoamidine to function as a true transition state analog for the enzymatic hydrolysis of aryl-β-D-galactopyranosides by β-galactosidase (A. oryzae). The compound exhibits inhibition constants in the low nanomolar concentration range (12–56 nM) for a selection of substrates. Along these lines, a streamlined synthetic method based on phase-transfer catalysis was optimized to afford the required variety of new aryl-β-D-galactopyranosides. Last, the stability of the galactonoamidines under the assay conditions was confirmed.

Controllable Synthesis Of Dispersed Spherical Fe3O4 Nanoparticles As Lithium-Inserted Materials, Hong-Li Zou, Wei-Shan Li

Journal of Electrochemistry

Dispersed spherical Fe₃O₄ nanoparticles were synthesized by a hydrothermal method. The influences of odecyl trimethyl ammonium bromide (DTAB) concentration on the morphology and particle size of the as-prepared Fe₃O₄ were studied. Electrochemical performance of the as-prepared sample as anode materials of lithium ion battery was investigated. It is found that the as-prepared sample exhibits superior rate performance and cycle performance. The nano-sized materials provide structural stability and favor the transfer of lithium ions.

Synthesis And Electrochemical Performance Of Nano Licopo4 By Polyol Method, Fei Wang, Yang Jun

Journal of Electrochemistry

High potential LiCoPO₄ cathode material was synthesized by polyol method. Carbon layer of ca. 3 nm thick was coated on the LiCoPO₄ surfaces by chemical vapor deposition from methylbenzene. Crystalline structure, morphology and electrochemical performance of the sample were studied by XRD, SEM, TEM, CV and galvanostatic charge/discharge curve. The synthesized material via polyol method showed a pure phase of LiCoPO₄. The LiCoPO₄/C electrode delivered a high discharge capacity of 132 mAh·g^-1 and maintained 78% of the initial capacity after 50 cycles at 0.1C rate. The two-step extraction/insertion behavior of Li⁺ in …