Catalysis and Reaction Engineering Commons^™

Ternary Alloy Electrocatalysts For Oxygen Reduction Reaction, Jin Luo, Lefu Yang, Binghui Chen, Chuanjian Zhong

Journal of Electrochemistry

Proton exchange membrane fuel cell represents an important electrochemical energy conversion device with many attractive features in terms of efficiency of energy conversion and minimization of environmental pollution. However, the large overpotential for oxygen reduction reaction at the cathode and the low activity, poor durability and high cost of platinum-based catalysts in the fuel cells constitute a focal point of major barriers to the commercialization of fuel cells. The development of nanostructured catalysts shows promises to addresses some of the challenging problems. The ability to engineer the composition and nanostructure of nanoalloy catalysts is important for developing active, robust and …

Electrocatalytic Activity Of Palladium Nanocatalysts Supported On Carbon Nanoparticles In Formic Acid Oxidation, Jie Huang, Zhiyou Zhou, Yang Song, Xiongwu Kang, Ke Liu, Wancheng Zhou, Shaowei Chen

Journal of Electrochemistry

Palladium nanostructures were deposited onto carbon nanoparticle surface by a chemical reduction method. Transmission electron microscopic studies showed that whereas the resulting metal-carbon (Pd-CNP) nanocomposites exhibited a diameter of 20 to 30 nm, the metal components actually showed a cauliflower-like surface morphology that consisted of numerous smaller Pd nanoparticles (3 to 8 nm). Electrochemical studies showed that the effective surface area of the Pd-CNP nanoparticles was about 40% less than that of Pd black, possibly because the Pd nanoparticles were coated with a layer of carbon nanoparticles; yet, the Pd-CNP nanocomposites exhibited marked enhancement of the electrocatalytic activity in formic …

Advances And Challenges Of Intermediate Temperature Solid Oxide Fuel Cells: A Concise Review, Sanping Jiang

Journal of Electrochemistry

Fuel cell is an electrochemical energy conversion device to directly convert the chemical energy of fuels to electricity. Among all types of fuel cells, solid oxide fuel cells (SOFCs) operating at intermediate temperatures of 600~800 ^oC offer an attractive option that is much more fuel flexible than low temperature fuel cells such as proton exchange membrane fuel cells, and is suitable for a wide range of applications. However, two main challenges remain towards the commercial viability and acceptance of the SOFC technologies: the cost and durability. Both are critically dependent on the process, fabrication, performance, chemical and microstructural stability …

Electrocatalytic Oxidation Of Formic Acid On Pd/Ni Heterostructured Catalyst, Mingjun Ren, Liangliang Zou, Ju Chen, Ting Yuan, Qinghong Huang, Haifeng Zhang, Hui Yang, Songlin Feng

Journal of Electrochemistry

A Pd/Ni bimetallic nanostructured electrocatalyst was fabricated via a two-step reduction route. Owing to an epitaxial growth of Pd atoms on the surface of Ni nanoparticles, heterostructured Pd/Ni nanocomposites were formed and verified by high resolution transmission electron microscopy combined with energy-dispersion X-ray spectroscopy. X-ray diffraction confirmed that the as-prepared Pd/Ni nanocomposites possessed a single face-centered-cubic (fcc) Pd structure, probably due to a weaker diffraction intensity of metallic Ni and/or overlapping by that of Pd. The intrinsic catalytic activity on the Pd/Ni is higher than that on the Pd. Moreover, the durability of formic acid oxidation on the Pd/Ni was …

Adsorption And Electrooxidation Of Carbon Monoxide On Platinum Surfaces Modified With Sulfur, A. Mattox Mathew, W. Henney Matthew, Johnson Adam, Zou Shouzhong

Journal of Electrochemistry

Adsorbed sulfur is commonly considered as a reaction poison. However, small amounts of sulfur on platinum significantly increase the surface reactivity toward carbon monoxide (CO) electrooxidation. For the solution CO oxidation, the onset potential was shifted up to over 300 mV negative to that on S-free surface, and the extent of the negative potential shift increases with the sulfur coverage (X_s) up to about 0.6. The enhanced CO oxidation also depends on the solution pH. For the adsorbed CO, at low sulfur coverages (X_s < 0.3), the oxidation peak potential is about 40 mV negative to that of the corresponding clean Pt. However, at higher coverages, the peak potential is about 30 mV more positive. Surface-enhanced Raman spectra show that the adsorption of sulfur significantly redshifts the Pt-CO stretching frequency. These observations are explained by the weakening of the Pt-CO bond and the hindrance of CO diffusion by Sads.

Kinetic Study Of Photoelectrochemical Oxidation Of Lignin Model Compounds On Tio2 Nanotubes, Min Tian, Daniel Liba, Aicheng Chen

Journal of Electrochemistry

In this study, TiO₂ nanotubes were prepared via the electrochemical oxidation of titanium substrates in a non-aqueous electrolyte and their morphology and microstructures were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photoelectrochemical oxidation of two lignin model compounds, 1-(3,4-dimethoxyphenoxy)-2-(2-methoxyphenoxy)-1,3-propanediol (DMP) and 3-hydroxy-1-(3,4-dimethoxyphenoxy)-2-(2-methoxyphenoxy)-1,3-propanone (HDM), was investigated. A new band appeared at ~304 nm during the photoelectrochemical oxidation of DMP. The rate of DMP intermediate formation was amplified with the increase of initial concentrations, while it was diminished with increased temperature. Despite the similarity in structure between HDM and DMP, there are only small increases in absorbance …

Photocalytic Degradation Of Malic Acid Under Thin Coated Tio2, Vanessa Silveira Rodgher

Electronic Thesis and Dissertation Repository

Opaque fluids have a limited irradiation transmission. Thus, their decontamination employing near UV irradiation poses significant technical challenges. In the present study, a thin UV-transparent/waterproof glue layer coated with a 1.5 wt% of TiO₂ and a new PhotoReactor Cell were implemented. TiO₂ irradiation in the PhotoReactor Cell was effected on the TiO₂ particle side, not directly in contact with the fluid, allowing the postulation of an “h⁺” site mobility mechanism on photocatalysis.

Photocatalytic degradation experiments with malic and malonic acid in water at 10, 20, 30 and 40 ppm showed the complete degradation of malic …

Lignin Yield Maximization Of Lignocellulosic Biomass By Taguchi Robust Product Design Using Organosolv Fractionation, Anton Friedrich Astner

Masters Theses

Lignin, a byproduct of the organosolv pretreatment process using lignocellulosic biomass from switchgrass (Panicum virgatum) and tulip poplar (Liriodendron tulipifera) is currently being explored for its potential use in the production of value-added chemicals and biobased polymers. Pretreatment is one of the most expensive processing steps in cellulosic biomass conversion. Optimization of the process is one of the major goals of the biomass-toethanol conversion process. Taguchi Robust Product Design (TRPD) provides an effective engineering experimental design method for optimizing a system and designing products that are robust to process variations. Given the results of several preliminary …

Refractive Index Chemical Sensing With Noble Metal Nanoparticles, Phillip Blake

Graduate Theses and Dissertations

Chemical sensing is a key component in modern society, especially in engineering applications. Because of their widespread impact, improvements to chemical sensors are a significant area of research. One class of sensors, plasmonic sensors, is being heavily researched because of their ability to detect low levels of analyte in near real time without destroying the analyte. This work studies a new class of plasmonic sensor that utilizes diffractive coupling to improve sensor performance. Specifically, this work outlines the first study of diffractive coupling sensors with typical nanoparticle shapes. Sensitivity of this new class of sensor is directly compared to typical …

Controlled Synthesis Of Single-Walled Carbon Nanotubes By Methane Decomposition And Their Application As Heterogeneous Partial Oxidation Catalyst, Inusa Abdullahi

Electronic Thesis and Dissertation Repository

Single-walled carbon nanotubes (SWCNTs) are materials with unique electronic and mechanical properties suitable for a large number of applications. Although, since their discovery many strategies for SWCNT synthesis have been explored, most of these are either tremendously energy intensive or require complex SWNCT purification strategies. These issues have resulted in expensive SWCNT production processes which in turn have hampered the development of a large range of SWCNT applications. This study deals with the controlled growth of SWCNTs from methane decomposition over iron and cobalt catalysts supported on MgO and the application of the CCVD grown SWCNTs as a catalyst for …

The Oxidation Of Hydrogen Peroxide On Nanostructured Rhodium Microelectrodes, N. Bartlett Philip, F. Esterle Thomas

Journal of Electrochemistry

Mesoporous Rh films were deposited onto platinum microelectrodes from the H₁ lyotropic liquid crystalline phase of C₁₂EO₈ (octaethyleneglycol monododecyl ether). The electrodes show well defined voltammetry for the oxidation and the reduction of hydrogen peroxide at low concentrations (<10 mmol•L-1) with excellent stability for operation at neutral pH. Based on the hysteresis in the current and the potential dependence the oxidation of hydrogen peroxide occurs through a CEE mechanism involving Rh(OH)₃ on the mesoporous Rh electrode surface. At higher hydrogen peroxide concentrations the current reaches a plateau that is due to either saturation of the binding sites for hydrogen peroxide or limitation of the reaction due to acidification of the solution within the pores. For the thin films (below 200 nm) the hydrogen peroxide calibration curves we …

Electrochemical Synthesis Of Silver-Tetracyanoquinodimethane Nanorods At Agar Supported Water/1,2-Dichloroethane Interface, Li Huang, Yixian Wang, Michael V. Mirkin, Bin Ren, Dongping Zhan

Journal of Electrochemistry

Silver-tetracyanoquinodimethane (AgTCNQ) is an important charge transfer salt due to its high conductivity and other electronic properties. In this communication, we report the synthesis of AgTCNQ at the liquid/liquid interface. Agar was used as a gelling agent to support water/1,2-dichloroethane (DCE) interface. Silver ions were transferred from the hydrogel into DCE phase, where they combined with TCNQ^- to form AgTCNQ nanorods. The developed method can provide a new route for synthesis of functional materials based on the electrochemistry at the liquid/liquid interface.

Optimization Of Biodiesel Production Plants, Nghi T. Nguyen

Department of Chemical and Biomolecular Engineering: Theses and Student Research

A conventional biodiesel plant utilizing two distillation columns to purify unreacted reactants and products is considered in this study. Thermodynamic analyses are used to assess the performance of the existing distillation columns, and reduce the costs of operation by appropriate retrofits in a biodiesel production plant. After the retrofits, the overall exergy loss for the two columns has decreased from 2430.87 kW to 1674.12 kW.

A reactive distillation is developed for esterification of lauric acid with methanol using equilibrium and nonequilibrium models. Equilibrium modeling dominated during last few decades due to their straightforward mathematical modeling. In reality, separation depends on …

Nano Tio2/Graphene Composites For Photovoltaic And Photocatalytic Materials, Nasrin Farhangi

Electronic Thesis and Dissertation Repository

Graphene has been recognized as one of the most exciting carbon based materials of the present decade due to its unique electronic, mechanical and thermal properties. High surface area exfoliated graphene sheets with controllable surface functionality is an attractive two-dimensional surface for attaching different metals and semiconductors for improving the performance of catalysts, sensors, photoelectronic and energy conversion devices. Graphene is an ideal material which can be used for improving various metal oxide properties such as those of titania (TiO₂). TiO₂/graphene composites have shown excellent properties compared to bare TiO₂ in various applications. In high …

Characterization Of Heterogeneous Reaction Systems By Thermal Analysis And Mathematical Modeling, Shreya Adhikari, Chuck Tillie

Undergraduate Research Posters 2012

It is anticipated that this research will lead to scale-up parameters that can be used to model a laboratory-scale deposition furnace, and guide further experimentation to advance technologies for protective and conversion coatings.

Synthesis And Electrochemical Characterization Of Li3V2(Po4)3/C Cathode Material By Ball-Milling Assisted Microwave Method, Zhi-Yuan Tang, Wen-Feng Mao, Ji Yan, Wei Yuan, Xin-He Zhang

Journal of Electrochemistry

The cathode materials of Li₃V₂(PO₄)₃/C were successfully synthesized by ball-milling assisted microwave method and the microwave irradiation time was also optimized. It is found that the Li₃V₂(PO₄)₃/C material obtained at a microwave power of 640 W for 18 min showed the best electrochemical performance with the initial reversible capacity of 101.3 mAh.g^-1 and the remained 100.8 mAh.g^-1 at 5C rate after 300 cycles. This excellent electrochemical capability may be resulted from good crystallinity, smaller and uniform particle size of the material, showing …

Synthesis And Electrochemical Properties Of High-Capacity Cathode Material 0.08lico0.75Al0.25O2-0.92linio2, Ru-Ying Wang, Tian Qiu, Chong Mao, Wen-Sheng Yang

Journal of Electrochemistry

CoAl-LDH or Co(OH)₂ coated spherical Ni(OH)₂ precursors were obtained via a co-precipitation method at a constant pH. The mixtures of the precursors and LiOH.H₂O were annealed at high temperature in O₂ atmosphere, and then the cathode materials of 0.08LiCo_0.75Al_0.25O₂-0.92LiNiO₂, 0.08LiCoO₂-0.92LiNiO₂ and LiNiO₂ were synthesized. Effects of the coating layer were also studied. The results showed that the 0.08LiCo_0.75Al_0.25O₂-0.92LiNiO₂ material possessed the best rate and cycle life performance. The discharging capacities at 0.1C, 0.5C and 3C were …

Electrocatalytic Activities Of Mb/Aunps/Mwnts/Gc Electrode For Hydrogen Peroxide Reduction, Zheng-Juan Huang, Hua-Ping Peng, Dai-Jun Cha, Ai-Lin Liu, Wei Chen, Xin-Hua Lin, Yong-Ji You

Journal of Electrochemistry

A novel matrix, multiwalled carbon nanotubes supported Au nanoparticles composite nanomaterial (AuNPs/MWNTs), for immobilization of protein and biosensing was designed using a simple and effective one-step in situ synthesis route. Using myoglobin (Mb) as a model, the direct electrochemistry of the immobilized proteins on the AuNPs/MWNTs composite was studied. The results showed that the AuNPs/MWNTs composite can maintain the bioactivity and facilitate the direct electrochemistry of Mb in the Mb/AuNPs/MWNTs/GC electrode. Based on the direct electron transfer of the immobilized Mb, the protein electrode exhibited excellent electrocatalytic activity to the reduction of H₂O₂ with a linear range …

Electrochemical Performances Of Layered Polypyrrole/Chemically Reduced Graphene Oxide Nanocomposites As Supercapacitor Electrodes, Si-Zhe Xu, Xue-Jiao Zhou, Kun Wu, Yong-Qiang Yang, Hai-Xia Wu

Journal of Electrochemistry

Nanocomposites of polypyrrole (Ppy) and chemically reduced graphene oxide (CRGO), Ppy/CRGO, have been fabricated through in-situ polymerization of pyrrole on graphene oxide (GO) sheets. The as-synthesized Ppy/CRGO composites were characterized complementarily using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier transformed infrared spectroscopy (FT-IR). By controlling the initial ratio of the GO to pyrrole, the layered composites could be obtained and their thickness could be tuned properly. The Ppy/CRGO electrodes were prepared using a mechanical compressing technique and their electrical conductivity and electrochemical properties were characterized systematically. We demonstrated that as electrodes for supercapacitor, the Ppy/CRGO composites with Ppy …

Water Treatment Using Advanced Oxidation Processes: Application Perspectives, Charles R. Gilmour

Electronic Thesis and Dissertation Repository

Advanced oxidation processes (AOPs) using hydroxyl radicals and other oxidative radical species are being studied extensively for removal of organic compounds from various waste streams. However, large scale applications of these highly effective technologies in water and wastewater treatment are still very limited due to cost and inadequate information about the resultant water quality. This study focuses on the evaluation of the upstream processing and downstream post treatment analysis of selective AOPs. In the first stage of research, the performance of a proprietary catalyst (VN-TiO₂) was compared with the industry standard P25 TiO₂, for the use …

Disinfection Of Low Uv Transmittance Fluids: Fundamentals And Applications, Housyn Mahmoud

Electronic Thesis and Dissertation Repository

Modern consumer demands for tasty, safe and healthier liquid foods and beverages. Chemical preservatives are usually added to foods to extend their shelf life and to protect against food borne pathogens. Application of ultraviolet (UV) light is gaining more attention as an alternative technology to disinfect fluids with low UV transmittance replacing classical chemical or thermal procedures due to growing negative public reaction over chemicals added. UV light irradiation has a positive consumer image as it is a physical non-thermal method efficient against microbial hazards, chemicals free cost effective and energy efficient methods and has been approved by regulatory agencies. …

Numerical Simulation Of Catalytic Ozone Decomposition Reaction In A Gas-Solids Circulating Fluidized Bed Riser, Lei Kong

Electronic Thesis and Dissertation Repository

Computational fluid dynamics (CFD) modeling of catalytic ozone decomposition reaction in a circulating fluidized bed (CFB) riser using iron impregnated FCC particles as catalyst is carried out. The catalytic reaction is defined as a one-step reaction with an empirical coefficient. Eularian-Eularian method with kinetic theory of granular flow is used to solve the gas-solids two-phase flow in the CFB riser. The simulation results are compared with experimental data, with the reaction rate modified using an empirical coefficient to provide better simulation results than the original reaction rate. Moreover, the particle size has great effects on the reaction rate. Studies on …

Solar And Visible Light Driven Photocatalysis For Sacrificial Hydrogen Generation And Water Detoxification With Chemically Modified Ti02, Pankaj Chowdhury

Electronic Thesis and Dissertation Repository

Photocatalysis is a recognized approach where light energy is employed to excite the semiconductor material producing electron/hole pair which eventually involves in the detoxification of pollutants and/or water splitting producing hydrogen. Existing photocatalysts suffer from poor activity or no activity in visible light irradiation which restricts them from solar light utilization. This work is focused on two key applications of photocatalysis (i) sacrificial hydrogen generation, and (ii) phenol degradation in visible and/or solar light. Platinum was loaded on TiO₂ photocatalyst by solar photo-deposition method. Eosin Y dye was used as a sensitizer for sensitization of platinum loaded TiO_{2 …}

The Synthesis And Characterization Of Novel Group 13 Nanostructured Building Block Heterogeneous Silicate Catalysts, Joshua G. Abbott

Doctoral Dissertations

A building block approach and sequential addition methodology were utilized to prepare heterogeneous silicate catalysts containing atomically dispersed group 13 metal (B, Al, Ga) centers. The octa(trimethyltin) silsequioxane, Si8[sub]O12[sub](OSnMe3[sub])8[sub], was used as the building block for the synthesis of these materials. Reaction of the building block with a variety of group 13 metal chlorides led to the formation of cross-linked matrices. All prepared materials were characterized by gravimetric analysis, gas absorption, IR, and NMR. In addition, aluminum and boron samples where characterized by 27[sup]Al and 11[sup]B solid state NMR, and gallium samples were studied using x-ray absorption techniques.

Studies found …

En Route Towards Α-Benzotriazoyl Nitroso Derivatives, Jean-Christophe M. Monbaliu, Lucas K. Beagle, Judit K. Beagle, Matthias Zeller, Christian V. Stevens, Alan R. Katritzky

Chemistry Faculty Publications

A new class of geminally-substituted nitroso compounds, i.e., α-benzotriazoyl nitroso derivatives, is presented. These compounds display a rather different behavior than other related nitroso compounds bearing a geminal electron-withdrawing group. An unexpected and spontaneous oxidation to the nitro analog is observed in solution.

Optimization Of A Dynamic Hot Water Pretreatment Of Switchgrass Using Catalysis By Carbonation To Maximize Carbochemical Yields, Rohit Tanaji Dhamdere

Graduate Theses and Dissertations

A bio-refinery is a facility that converts renewable bio-resources into value-added chemicals and products. In this context of a bio-refinery, the production of the carbochemicals such as HMF, furfural and organic acids illustrate that multiple products can be produced from a renewable source such as lignocellulosic biomass (switchgrass). Traditionally, carbochemicals such as furfural and HMF are produced using inorganic acids such as H2SO4, HCL, and H3PO4. The use of such acids requires the application of high cost materials of construction such as Hastelloy-C, titanium etc.

The objective of this study is to develop a semi-continuous process for the conversion of …

Utility Of 1,2,4-Triazoles As Catalysts For Orr In Fuel Cells, Chinmay Nagesh Dabke

Masters Theses

The Oxygen Reduction Reaction (ORR) taking place at the cathode of a fuel cell is catalyzed by Platinum due to its high activity and good stability in the acidic polymer electrolyte membrane fuel cell (PEMFC) environment. Due to its prohibitive cost and limited reserves, it is not practical to use Pt as the catalyst for mass commercialization. By taking inspiration from nature, we have devised a series of catalysts which will help in replacing Platinum at the cathode in commercial fuel cells. To gauge the activity of various ligands, metal salts and carbon surfaces, adsorbed experiments were carried out and …

Determination Of The Kinetic Parameter In The Photodegradation Of Phenol By A Unified Kinetic Model By Using Least Square Curve Fitting And The Genetic Algorithm., Jesus Moreira Del Rio, Benito Serrano, Hugo De Lasa

Jesus Moreira del Rio

No abstract provided.

Solid Oxide Fuel Cells With Both High Voltage And Power Output By Utilizing Beneficial Interfacial Reaction, Chao Su, Zongping Shao, Ye Lin, Yuzhou Wu, Huanting Wang

Faculty Publications

An intriguing cell concept by applying proton-conducting oxide as the ionic conducting phase in the anode and taking advantage of beneficial interfacial reaction between anode and electrolyte is proposed to successfully achieve both high open circuit voltage (OCV) and power output for SOFCs with thin-film samarium doped ceria (SDC) electrolyte at temperatures higher than 600 °C. The fuel cells were fabricated by conventional route without introducing an additional processing step. A very thin and dense interfacial layer (2–3 μm) with compositional gradient was created by in situ reaction between anode and electrolyte although the anode substrate had high surface roughness …

Synthesis Of Spherical Ni3S4 By Solvothermal Method As Supercapacitor Electrodes, Qing-Na Huan, Li-Fang Jiao, Qing-Hong Wang, Hong-Mei Du, Jia-Qin Yang, Wen-Xiu Peng, Yi-Jing Wang, Hua-Tang Yuan

Journal of Electrochemistry

The Ni₃S₄ microspheres have been synthesized via a facile solvothermal method. The crystal structure and surface morphology are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Microspherical Ni3S4 exhibits good electrochemical capacitance validated by electrochemical measurements. The specific capacities of 1120.6 F.g-1 at 0.5 A.g^-1 and 433.4 F.g^-1 at 4 A.g^-1 with the capacitance retention of 89.37 % and 84.88 % were obtained after 1000 cycles, respectively. The electrochemical reaction is expected due to the transformation of Ni(OH)₂ and NiOOH based on the XRD, XPS and CV analysis results.