Catalysis and Reaction Engineering Commons^™

Advanced Synthesis And Rational Design Of Support Structures For Nobel Metal Heterogeneous Catalysis: Towards Enhanced Activity And Continuous Processes, Brian R. Clark

Theses and Dissertations

The field of catalysis has a wide-ranging impact. Our group has identified the constant need for improved catalytic activity in high-impact applications such as hydrosilylation and cross-coupling reactions. For these reactions, precious metal catalysts often exhibit markedly better performance than their counterparts, but they can be a significant process cost that decreases overall economic efficiencies. To address this challenge, we explored support structures that can enhance catalytic activity at low metal loadings and improve precious metal recovery through simple filtration. We found that a platinum on graphene nanoplatelet catalyst (PtGNP) synthesized via strong electrostatic adsorption with microwave irradiation (SEA-MW) exhibits …

Development Of Novel Catalysts For Hydrogen Gas Production From Biomass Compounds, Boanerges Bamaca

Department of Agricultural and Biological Systems Engineering: Dissertations, Theses, and Student Research

Hydrothermal biomass gasification technologies (sub- and supercritical water gasification and aqueous-phase reforming) have considerable economic, environmental, and technical advantages over other energy-extensive technologies (e.g. natural gas reforming) for hydrogen gas production. However, lack of economically feasible and highly active catalysts is a main challenge that impedes upscaling of these technologies for hydrogen gas production.

The goal of this study was to develop innovative, economically feasible and active heterogeneous supported metal catalysts for hydrothermal processes for producing hydrogen gas from biomass-derived compounds. Because of its stable structure and chemical inertness, graphene was used as catalyst support. Graphene supported metal catalysts were …

Formulation Optimization Effects On Mechanical And Rheological Properties Of Filled Polysiloxanes, Kevin Mcnay

Electronic Theses & Dissertations

Polysiloxanes are a class of high-performance polymeric materials that are used in a wide variety of applications, including O-rings, gaskets, sealants, coatings, and adhesives. These materials have high temperature resistances as well as flexibility at low temperatures. This is due to the bond between the oxygen and silicon atom, a bond that requires a high dissociation energy to break. However, their elastomers, which can be obtained by crosslinking linear precursors using various crosslinkers, generally exhibit low strength and have poor mechanical properties unless reinforced. Therefore, fillers, additives, UV-stabilizers, and anti-oxidants are often incorporated in order to improve the resulting properties. …

Effect Of Pt Promotion On The Ni-Catalyzed Deoxygenation Of Tristearin To Fuel-Like Hydrocarbons, Ryan Loe, Kelsey Huff, Morgan Walli, Tonya Morgan, Dali Qian, Robert Pace, Yang Song, Mark Isaacs, Eduardo Santillan-Jimenez, Mark Crocker

Center for Applied Energy Research Faculty and Staff Publications

Pt represents an effective promoter of supported Ni catalysts in the transformation of tristearin to green diesel via decarbonylation/decarboxylation (deCO_x), conversion increasing from 2% over 20% Ni/Al₂O₃ to 100% over 20% Ni-0.5% Pt/Al₂O₃ at 260 °C. Catalyst characterization reveals that the superior activity of Ni-Pt relative to Ni-only catalysts is not a result of Ni particle size effects or surface area differences, but rather stems from several other phenomena, including the improved reducibility of NiO when Pt is present. Indeed, the addition of a small amount of Pt to the supported Ni …

A Promising Modification Of Pt Surfaces With Cnts For Decreasing Poisoning Impact In Direct Methanol Fuel Cells, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Aya A. Khalifa Ms.

Chemical Engineering

Direct methanol fuel cells (DMFCs) are clean energy sources that have many applications due to the high energy density of methanol as a fuel. However, this type of fuel cells (FCs) has limitations that are preventing it from being commercialized. One such limitation is the adsorption of intermediates such as CO into the surface of the Platinum (Pt) catalyst during methanol oxidation (MO) which deactivates its active sites, where the reaction is taking place, and leads to poisoning of the electrode over the long term. In this study, multi-walled carbon nanotubes (MWCNTs) have been introduced to the Pt-modified glassy carbon …

Recent Progress In Pt-Based Catalysts For Oxygen Reduction Reaction, Jing Li, Xin Feng, Zi-Dong Wei

Journal of Electrochemistry

One major challenge for a large-scale commercialization of the proton-exchange membrane fuel cells (PEMFCs) technologies that enable a shift to ‘zero-emission’ personal transportation, is the expensive and unstable Pt catalysts, which are mainly used to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) occurred on the air electrode of PEMFCs. Many research works have targets to improve the stability of Pt-based catalysts and to construct Pt/transitional metal alloys with low Pt loading amount. Herein, we provide a minireview for the Pt-based ORR catalysts based on our recent work, which covers a brief background introduction, the stability improvement of …

Platinum-Rhodium Alloy Electrocatalyst Activities In The Methanol Oxidation Reaction, William R. Sandorf

Williams Honors College, Honors Research Projects

This study evaluates the electrochemical activity of several compositions of platinum-rhodium alloys on carbon support to identify potential replacements for the expensive platinum electrocatalysts currently used in direct methanol fuel cells (DMFCs). The electrochemical active surface areas (ECSAs) of each sample were determined using cyclic voltammetry (CV) in a 0.5 M H₂SO₄ solution to normalize CV currents generated in the methanol oxidation reaction (MOR). The activity of five compositions was tested; Pt₃Rh, Pt₂Rh, PtRh, Pt₂Rh, and Pt₃Rh. 100 mg of each catalyst was synthesized at 10% by weight platinum …

Pt-Cu Catalysts For Catalytic Dehydrogenation Of Alkanes For Energy Production, Zixue Ma, Zhenwei Wu, Jeffrey T. Miller

The Summer Undergraduate Research Fellowship (SURF) Symposium

More active, selective and stable catalysts are in demand to increase the yields of olefins production from light alkane dehydrogenation. Cu was reported to promote Pt catalysts and Pt-Cu catalysts has been shown to achieve increased olefin selectivity and decreased deactivation rate. Pt-Cu catalysts with different Pt:Cu molar ratios may have different crystal structure and performance. This study seeks to understand of the promotion effect of Cu on Pt alkane dehydrogenation catalysts. Four different Pt-Cu catalysts with different atomic ratios were prepared and tested for propane dehydrogenation at 550℃. Synchrotron in situ X-ray diffraction and X-ray absorption spectroscopy are used …

Multi-Scaled Carbon Supported Platinum As A Stable Electrocatalyst For Oxygen Reduction Reaction, Yu-Ping Li, Lu-Hua Jiang, Su-Li Wang, Gong-Quan Sun

Journal of Electrochemistry

The stability of carbon supports is essential for electrocatalysts of fuel cells. Herein, the mesoporous carbon with the high graphitic degree (highly graphitic mesoporous carbon, HGMC) was synthesized by using resorcinol as the carbon precursor, SiO₂ as the templates and urea as the reducing agent. The as-prepared HGMC was characterized by XRD, Raman spectroscopy, TEM, N2 adsorption. The stability of HGMC was evaluated by mimicking the start-up/shut-down conditions of fuel cells in a three-electrode system referring to the NREL standard. The obtained HGMC is of moderate surface area (187.4 m²•g^-1) and is chemically stable under …

Enhancing Stability Of Pem Fuel Cell Catalysts Via Support Changing, Xiao-Hong Xie, Zi-Dong Wei

Journal of Electrochemistry

The Pt/C catalyst with highly dispersed Pt nanoparticles supported on carbon has been widely used as the state-of the-art catalyst in proton exchange membrane fuel cells (PEMFCs), while the durability of Pt/C is one of the major barriers for large-scale applications of PEMFCs. Thus, enhancing the stability of Pt/C has been a hot issue in this field. In this review, we summarize the recent progress in enhancing the catalyst stability in the view of support material. The future prospects of the PEMFCs catalyst should focus on adopting more stable supports or strengthening the interactions between Pt and supports.

Electrochemical Fabrication Of Two-Dimensional Flower-Like Pt Nanostructures For Methanol Electrocatalytic Oxidation, Xia Wang, Jun Hu, Yong-Jun Li

Journal of Electrochemistry

Two-dimensional flower-like Pt nanostructures (2D FPNs) were fabricated on glassy carbon substrates by galvanostatical electrochemical technique. The electrolyte was the HAuCl₄ + HClO₄ aqueous solution without addition of any structure-directing organic reagent, which made as-prepared Pt nanostructures cleaner, exhibiting much higher reactivity. Scanning electron microscopic images revealed that 2D FPNs were spherical Pt nano-flowers constructed by the smallest building blocks, nano-leaves. The number density of spherical Pt nano-flowers can be tuned by controlling the electrodeposition time. High resolution transmission electron microscopic images indicated that each nano-leaf was formed by growing along Pt(111) direction. Electrocatalytic activities of as-prepared 2D …

Microkinetic Modeling And Analysis Of Ethanol Partial Oxidation And Reforming Reaction Pathways On Platinum At Short Contact Times, Maura A. Koehle

Master's Theses

No abstract provided.

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.

Platinum Modified With Hydrogen Molybdenum/Tungsten Bronze As Electrocatalysts For Direct Small Organic Molecule Fuel Cell, Wei-Shan Li, Li-Peng Tian, Jun-Hua Du, Hong-Liang Huang, Wei Li, Li-Xia Zhang, Hong-Yan Yang, Pan-Pan Guo, Zhi-Hui Zhou, Xing-De Xiang, Zhao Fu

Journal of Electrochemistry

There are several problems that limit the application of direct small organic fuel cell,including the use of precious platinum and the activity loss of platinum due to the intermediates poisons from the oxidation of small organic molecules.These problems have attracted wide interest and many solutions have been proposed.We have developed a new method to reduce the platinum usage and improve its activity,based on the modification of platinum with hydrogen molybdenum/tungsten bronze(HxMo(W)O₃) was reviewed.

Preparations Of Composite Electrodes Of Pt With HXWo3 And Catalytic Activity Toward Oxygen Reduction Reaction, Pan-Pan Guo, You-Ju Huang, Hong-Yan Yang, Wei Li, Qing-Long Zhang, Wei-Shan Li

Journal of Electrochemistry

Three composite electrodes of platinum with hydrogen tungsten bronze(H_xWO₃)were prepared by voltammetry: hydrogen tungsten bronze deposited on platinum(H_xWO₃/Pt);platinum deposited on hydrogen tungsten bronze(Pt/H_xWO₃) and codeposited platinum and hydrogen tungsten bronze(Pt-H_xWO₃).The eletro-catalytic activities of three electrodes toward oxygen reduction reaction were studied.It is found that the catalytic activity of platinum can be improved by introducing with hydrogen tungsten bronze.Among these composite electrodes Pt/H_xWO₃,and the electrode shows the best eletro-catalytic activity toward oxygen reduction reaction,hence,provides a new way for reducing loading of …

Design And Fabrication Of The High Efficient Platinum-Nanoporous Gold Catalysts, Zhao-Na Liu, Jin-Tao Zhang, Fang Tian, Peng-Peng Liu, Hou-Yi Ma, Yi Ding

Journal of Electrochemistry

The nanoporous gold(NPG) electrodes with uniform pore sizes and ligaments were prepared by using a simple dealloying method.The as-prepared NPG showed high catalytic activity towards the oxidation of formic acid and formaldehyde.After tiny amount of platinum was deposited onto the NPG substrate,not only the structure stability of NPG was greatly improved,but also the Pt-Au bimetallic catalysts displayed the better catalytic activity and the stronger poison resistance towards the electrooxidation of small organic molecules than the bulk platinum due to synergistic effect between Au and Pt compositions.

Electrocatalytic Performance Of Pt/C And Pt/Wo3/C Catalysts For Methanol Oxidation, Yuan-Yuan Chu, Bing Wu, Ya-Wen Tang, Tian-Hong Lu, Ying Gao

Journal of Electrochemistry

The catalysts of Carbon supported Pt(Pt/C) and carbon supported Pt/WO₃(Pt/WO₃/C) were prepared with liquid phase reduction method.It was found that the catalytic activity and stability of the Pt/WO₃/C catalysts were increased with the addition of WO₃.When the atomic ratio of Pt and W was 1∶1,the best electrocatalytic performance of the Pt/WO₃/C catalyst for the methanol oxidation was obtained.This is attributed to the larger electrochemical surface area of Pt/WO₃/C and the weeker adsorption of CO towards the catalyst.

The Study On Carbon Nanotube-Loaded Pt Catalysts For Proton Exchange Membrane Fuel Cells, Hong Zhu, Feng-Juan Ge, Xiao-Hong Kang, Yu-Guo Yang, Yun-Hua Xu

Journal of Electrochemistry

Carbon nanotube-supported-platinum (Pt/CNTs) and carbon-supported-platinum (Pt/C) catalysts were synthesized by in-situ chemical reduction. They were analyzed using TEM and XRD, then made into electrodes to be part of assemable PEMFC for the performence tests. The resulted show that Pt clusters in both catalysts are of small particle size (about 4nm), and Pt/CNTs exhibits a higher catalytic activity than Pt/C.

Electrocatalytic Oxidation Of Formic Acid On Molybdate-Modified Platinum Electrode, Jun-Hua Du, Xue-Hui Xu, Hong Li, Hong-Yu Cheng, Wei-Shan Li

Journal of Electrochemistry

The electrochemical behavior of molybdates on a platinum electrode in H₂SO₄ solutions with different H₂SO₄ concentrations was studied by cyclic voltammetry and double chronoamperometry. Molybdates were reduced to adsorb hydrogen molybdenum bronzes on the platinum electrode in H₂SO₄ solutions during cathodically potential sweep. The hydrogen molybdenum bronzes were oxidized to different forms of hydrogen molybdenum bronzes with less hydrogen, depending on the H₂SO₄ concentration. Platinum electrode was modified by these hydrogen molybdenum bronzes. However, this modified electrode was not stable in H₂SO₄ solutions. The modified …