Engineering Commons^™

Investigation Of Oxidized Carbon Supported Au Catalysts Synthesized Via Strong Electrostatic Adsorption Of Au(En)2Cl3 For The Hydrochlorination Of Acetylene To Vinyl Chloride Monomer, Sean Reginald Noble

Theses and Dissertations

Over 20 million tons of vinyl chloride monomer (VCM) is produced every year using acetylene hydrochlorination using a supported mercuric chloride catalyst. During this process mercury is reduced and sublimes into the environment harming all living animals and humans, so carbon-supported Au catalysts have been developed in attempts to replace it. Various techniques have been used to make these catalysts including several variations of dry impregnation. In this study we investigate the ability of Strong Electrostatic Adsorption (SEA) of Au(en)₂Cl₃ onto various supports to demonstrate the ability to rationally and consistently synthesize gold catalysts with ultra-small particle …

Hydrodeoxygenation Of Acetic Acid Using Monometallic And Bimetallic Catalysts Supported On Carbon, José Luis Contreras Mora

Theses and Dissertations

Heterogeneous catalytic hydrodeoxygenation (HDO) of biomass-derived feeds is a deoxygenation process that is of highly interest. Carboxylic acids are one of the main components of bio-oils and acetic acid is one of the most abundant of these carboxylic acids. This acid is rich in oxygen, therefore a lot of research to produce fuel and other valuable chemicals such as ethanol is of interest.

This dissertation explores the gas-phase catalytic HDO of AA over catalysts supported on activated carbon (Cp-97). Temperature-dependent conversion and selectivity were studied at 1 atm from 200-400⁰C with an AA concentration of 1.1% and 20% …

Static And Dynamic Strain Monitoring Of Reinforced Concrete Components Through Embedded Carbon Nanotube Cement-Based Sensors, Antonella D’Alessandro, Filippo Ubertini, Enrique García-Macías, Rafael Castro-Triguero, Austin Downey, Simon Laflamme, Andrea Meoni, Annibale Luigi Materazzi

Faculty Publications

The paper presents a study on the use of cement-based sensors doped with carbon nanotubes as embedded smart sensors for static and dynamic strain monitoring of reinforced concrete (RC) elements. Such novel sensors can be used for the monitoring of civil infrastructures. Because they are fabricated from a structural material and are easy to utilize, these sensors can be integrated into structural elements for monitoring of different types of constructions during their service life. Despite the scientific attention that such sensors have received in recent years, further research is needed to understand (i) the repeatability and accuracy of sensors’ behavior …

Size-Controlled Large-Diameter And Few-Walled Carbon Nanotube Catalysts For Oxygen Reduction, Xianliang Wang, Qing Li, Hengyu Pan, Ye Lin, Yujie Ke, Haiyang Sheng, Mark T. Swihart, Gang Wu

Faculty Publications

We demonstrate a new strategy for tuning the size of large-diameter and few-walled nitrogen-doped carbon nanotubes (N-CNTs) from 50 to 150 nm by varying the transition metal (TM = Fe, Co, Ni or Mn) used to catalyze graphitization of dicyandiamide. Fe yielded the largest tubes, followed by Co and Ni, while Mn produced a clot-like carbon morphology. We show that morphology is correlated with electrocatalytic activity for the oxygen reduction reaction (ORR). A clear trend of Fe > Co > Ni > Mn for the ORR catalytic activity was observed, in both alkaline media and more demanding acidic media. The Fe-derived N-CNTs exhibited …

Theoretical Analysis Of Stresses In A Lithium Ion Cell, Sindhuja Renganathan, Godfrey Sikha, Shriram Santhanagopalan, Ralph E. White

Faculty Publications

A mathematical model to simulate the generation of mechanical stress during the discharge process in a dual porous insertion electrode cell sandwich comprised of lithium cobalt oxide and carbon is presented. The model attributes stress buildup within intercalation electrodes to two different aspects: changes in the lattice volume due to intercalation and phase transformation during the charge/discharge process. The model is used to predict the influence of cell design parameters such as thickness, porosity, and particle size of the electrodes on the magnitude of stress generation. The model developed in this study can be used to understand the mechanical degradation …

Analytical Expression For The Impedance Response For A Lithium-Ion Cell, Godfrey Sikha, Ralph E. White

Faculty Publications

An analytical expression to predict the impedance response of a dual insertion electrode cell (insertion electrodes separated by an ionically conducting membrane) is presented. The expression accounts for the reaction kinetics and double-layer adsorption processes at the electrode-electrolyte interface, transport of electroactive species in the electrolyte phase, and insertion of species in the solid phase of the insertion electrodes. The accuracy of the analytical expression is validated by comparing the impedance response predicted by the expression to the corresponding numerical solution. The analytical expression is used to predict the impedance response of a lithium-ion cell consisting of a porous LiCoO …

Development Of Method For Synthesis Of Pt–Co Cathode Catalysts For Pem Fuel Cells, Xuguang Li, Héctor R. Colón-Mercado, Gang Wu, Jong-Won Lee, Branko N. Popov

Faculty Publications

A procedure was developed to synthesize a platinum–cobalt (Pt–Co) alloy electrocatalyst for oxygen reduction using Co/C composite as a support. The Pt–Co/C catalysts were synthesized through: (i) chemical oxidation of carbon black, (ii) Co deposition on the oxidized carbon using a chelation method, (iii) chemical treatment in an acidic medium to remove excess of Co on the carbon surface, (iv) Pt deposition onto the Co/C support, and (v) postheat treatment to form the Pt–Co alloy catalyst. The synthesized Pt–Co/C catalyst showed improved activity and long-term stability in polymer electrolyte membrane …

Mechanics Of Hydrogenated Amorphous Carbon Deposits From Electron-Beam-Induced Deposition Of Paraffin Precursor, W. Ding, D. A. Dikin, X. Chen, R. D. Piner, R. S. Ruoff, E. Zussman, X. Wang, Xiaodong Li

Faculty Publications

Many experiments on the mechanics of nanostructures require the creation of rigid clamps at specific locations. In this work, electron-beam-induced deposition(EBID) has been used to depositcarbonfilms that are similar to those that have recently been used for clamping nanostructures. The film deposition rate was accelerated by placing a paraffin source of hydrocarbon near the area where the EBIDdeposits were made. High-resolution transmission electron microscopy, electron-energy-loss spectroscopy, Raman spectroscopy, secondary-ion-mass spectrometry, and nanoindentation were used to characterize the chemical composition and the mechanics of the carbonaceous deposits. The typical EBIDdeposit was found to be hydrogenated amorphous carbon (a-C:H) having …

Development Of Novel Method For Preparation Of Pemfc Electrodes, Hansung Kim, Branko N. Popov

Faculty Publications

A method based on pulse electrodeposition technique was developed for preparation of membrane electrode assemblies (MEAs). In this approach, platinum is deposited directly on the surface of the carbon electrode. The method ensures most of the platinum to be in close contact with the membrane. Using this method it is possible to increase the Pt/C ratio up to 75 wt % near the surface of the electrode resulting in a 5 µm thick catalyst layer. The MEA prepared by pulse electrodeposition exhibits a current density of 0.33 A/cm² at 0.8 V with platinum loading of 0.25 mg of Pt/cm …

A Mathematical Model Of Oxide/Carbon Composite Electrode For Supercapacitors, Hansung Kim, Branko N. Popov

Faculty Publications

A pseudo two-dimensional model is developed for the general application of supercapacitors consisting of an oxide/carbon composite electrode. The model takes into account the diffusion of protons in the oxide particle by employing the method of superposition. RuO₂/carbon system is modeled as a specific example. From the simulation data, it is found that the oxide particle size and proton diffusion coefficient have an enormous effect on the performance at high discharge rate due to the limitation of proton transport into RuO₂ particles. With increasing carbon ratio, the porosity of electrode increases, which causes the potential drop in …

Nanofatigue Studies Of Ultrathin Hard Carbon Overcoats Used In Magnetic Storage Devices, Xiaodong Li, Bharat Bhushan

Faculty Publications

A technique to perform nanofatigue experiments was developed. This technique utilizes a depth-sensing nanoindenter with harmonic force. The nanofatigue behavior of 20 nm thick amorphous carbon coatings was studied. The contact stiffness was monitored continuously throughout the test. The abrupt decrease in the contact stiffness indicates fatigue damage has occurred. The critical load amplitude, below which no fatigue damage occurs, was identified. It was found that the filtered cathodic arc coating exhibits longer fatigue life than a direct ion beam coating. Failure mechanisms of the coatings during fatigue are also discussed in conjunction with the hardness,elastic modulus, and fracture toughness, …

Modeling The Effects Of Electrode Composition And Pore Structure On The Performance Of Electrochemical Capacitors, Changqing Lin, Branko N. Popov, Harry J. Ploehn

Faculty Publications

This work presents a mathematical model for charge/discharge of electrochemical capacitors that explicitly accounts for particle-packing effects in a composite electrochemical capacitor consisting of hydrous RuO₂ nanoparticles dispersed within porous activated carbon. The model is also used to investigate the effect of nonuniform distributions of salt in the electrolyte phase of the electrode in the context of dilute solution theory. We use the model to compare the performance of capacitors with electrodes made from different activated carbons and to investigate the effects of varying carbon content and discharge current density. Even at low discharge current density, concentration polarization in …

Modeling The Effects Of Electrode Composition And Pore Structure On The Performance Of Electrochemical Capacitors, Changqing Lin, Branko N. Popov, Harry J. Ploehn

Faculty Publications

This work presents a mathematical model for charge/discharge of electrochemical capacitors that explicitly accounts for particle-packing effects in a composite electrochemical capacitor consisting of hydrous RuO₂ nanoparticles dispersed within porous activated carbon. The model is also used to investigate the effect of nonuniform distributions of salt in the electrolyte phase of the electrode in the context of dilute solution theory. We use the model to compare the performance of capacitors with electrodes made from different activated carbons and to investigate the effects of varying carbon content and discharge current density. Even at low discharge current density, concentration polarization in …

Synthesis And Characterization Of Hydrous Ruthenium Oxide-Carbon Supercapacitors, Manikandan Ramani, Bala S. Haran, Ralph E. White, Branko N. Popov

Faculty Publications

It is shown that composite Ru oxide-carbon based supercapacitors possess superior energy and power densities as compared to bare carbon. An electroless deposition process was used to synthesize the ruthenium oxide-carbon composites. Ru is dispersed on the carbon matrix as small particles. The effect of electrochemical oxidation and temperature treatment on the material performance has been studied extensively. Increasing the oxidation temperature reduces the proton transport rate and also increases the degree of crystallinity of the deposits. This adversely affects the performance of the composite. Loading a small amount of Ru oxide (9 wt %) on carbon increases the capacitance …

Modeling Lithium Intercalation In A Porous Carbon Electrode, Gerardine G. Botte, Ralph E. White

Faculty Publications

No abstract provided.