Chemistry Commons^™

Electrodeposition Of Epitaxial Metal Thin Films On Silicon For Energy Conversion And Flexible Electronics, Qingzhi Chen

Doctoral Dissertations

"This research focuses on epitaxial electrodeposition of two coinage metals: Au and Ag thin films on the silicon surface and their applications in flexible electronics and energy conversion and storage. The first paper: Photoelectrochemistry of ultrathin, semi-transparent, and catalytic gold films electrodeposited epitaxially onto n-silicon (111) describes the epitaxial electrodeposition of Au thin films on n-type Si using a simple HAuCl4 bath and the photoelectrochemical properties of the Au-Si junction barrier. The effect of the Au layer on the interfacial energetics as well as the stability of the photoelectrode as a function of the Au coverage/thickness is determined in a …

Nanomorphology Dependent Optical And Mechanical Properties Of Aerogels, Chandana Mandal

Doctoral Dissertations

"Aerogels are very low density, light weight open pore materials. A hypothesis that is under intense current investigation by the scientific community states that the mechanical properties of nanostructured polymers depend on their nanomorphology. Aerogels are nanostructured ultra-lightweight nanoporous materials with skeletal frameworks that can display a wide range of nanomorphologies. Thereby aerogels comprise a suitable platform for testing not only that hypothesis but also a wide range of other properties such as light scattering for applications, for example, in thermally insulating windows.

To study the mechanical properties of nanostructured matter as a function of nanomorphology, various shape-memory polyurethane aerogels …

Synthesis And Applications Of Ceramic (Silicon Carbide And Silicon Nitride), Metallic (Cobalt(0)) And Polymeric (Polyurethane) Aerogels, Parwani M. Rewatkar

Doctoral Dissertations

"A new method has been demonstrated for the synthesis of monolithic ceramic and purely metallic aerogels from xerogel powder compacts, and the use of polyurethane aerogels based on cyclodextrins as efficient desiccants.

I. Highly porous ( > 80%) monolithic SiC and Si₃N₄, aerogels were prepared from compressed compacts of polyurea-crosslinked silica xerogel powders. The process is time efficient as solvent-exchange through powders is fast, and energy efficient as it bypasses drying with supercritical fluids. The final ceramic objects were chemically pure, sturdy, with compressive moduli at 37 ±7 MPa and 59 ± 7 MPa, and thermal conductivities …

Polyurea Aerogels: From Nanoscopic To Macroscopic Properties, Tahereh Taghvaee

Doctoral Dissertations

"The morphology of a material is intrinsically a qualitative property and in order to relate nanomorphology to synthetic conditions, it is necessary to express nano/micro-structure quantitatively. In this context, polyurea aerogels were chosen as a model system with demonstrated potential for rich nanomorphology and being guided by a statistical Design-of-Experiments model, a large array of materials (208) with identical chemical composition, but quite different nanostructures were prepared. By reflecting upon the SEM images, it was realized that our first pre-verbal impression about a nanostructure is related to its openness and texture; the former is quantified by porosity (Π), and the …

Three-Dimensional Nanotube Arrays For Solar Energy Harvesting And Production Of Solar Fuels, Wipula P. R. Liyanage

Doctoral Dissertations

"Over the past decade extensive research has been carried out on photovoltaic semiconductors to provide a solution towards a renewable energy future. Fabricating high-efficiency photovoltaic devices largely rely on nanostructuring the photoabsorber layers due to the ability of improving photoabsorption, photocurrent generation and transport in nanometer scale. Vertically aligned, highly uniform nanorods and nanowire arrays for solar energy conversion have been explored as potential candidates for solar energy conversion and solar-fuel generation owing to their enhanced photoconversion efficiencies.

However, controlled fabrication of nanorod and especially nanotube arrays with uniform size and shape and a pre-determined distribution density is still a …

A Review: Thermal Stability Of Methylammonium Lead Halide Based Perovskite Solar Cells, Tanzila Tasnim Ava, Abdullah Al Mamun, Sylvain Marsillac, Gon Namkoong

Electrical & Computer Engineering Faculty Publications

Perovskite solar cells have achieved photo-conversion efficiencies greater than 20%, making them a promising candidate as an emerging solar cell technology. While perovskite solar cells are expected to eventually compete with existing silicon-based solar cells on the market, their long-term stability has become a major bottleneck. In particular, perovskite films are found to be very sensitive to external factors such as air, UV light, light soaking, thermal stress and others. Among these stressors, light, oxygen and moisture-induced degradation can be slowed by integrating barrier or interface layers within the device architecture. However, the most representative perovskite absorber material, CH_{3 …}

Metallic Systems At The Nano And Micro Scale: Bimetallic Nanoparticles As Catalysts And Mcraly Bond Coats In Thermal Barrier Coatings, Kenneth Kane

Theses and Dissertations

The dissertation is split into two parts. The first part will be focused on changes in material properties found at the nanoscale, as miscibility and electronic structure can change significantly with size. The formation of classically-immiscible bimetallic nanoparticles (BNPs) becomes favorable at the nanoscale and novel catalytic properties can emerge from the bimetallic alloying. The formation of alloyed and non-alloyed BNPs is achieved through pulse laser ablation (PLA) and a significant increase in catalytic activity is observed for both. Recently discovered, the increased activity in the non-alloyed BNPs, deemed multicomponent photocatalysis, is examined and the proposed mechanism discussed. The second …

Adhesion At Solid/Liquid Interfaces, Neda Ojaghlou

Theses and Dissertations

The adhesion at solid/liquid interface plays a fundamental role in diverse fields and helps explain the structure and physical properties of interfaces, at the atomic scale, for example in catalysis, crystal growth, lubrication, electrochemistry, colloidal system, and in many biological reactions. Unraveling the atomic structure at the solid/liquid interface is, therefore, one of the major challenges facing the surface science today to understand the physical processes in the phenomena such as surface coating, self-cleaning, and oil recovery applications. In this thesis, a variety of theory/computational methods in statistical physics and statistical mechanics are used to improve understanding of water adhesion …

Development Of Flexible Nickel-Zinc And Nickel-Iron Batteries, Xianyang Meng

Dissertations

The fabrication of flexible nickel-zinc batteries using a facile mixing of electroactive components for electrode preparation is presented. Polytetrafluoroethylene (PTFE) is found to be an effective binder by reducing concentration polarization, providing chemical/physical stability and enhancing flexibility. The zinc electrode containing PTFE maintains its original porous morphology even after hundreds of cycles while polymers such as PEO show morphology change. Each component, as well as the assembled flexible cells show desired flexibility and stability even under bending conditions.

The fabrication of flexible nickel-iron batteries using printable composite electrodes embedded with multiwalled carbon nanotubes (CNT) is also presented. All the metal …

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 …

Constructions Of Noble Metal Nanocrystals With Specific Crystal Facets And High Surface Area, Qiao-Li Chen, Hui-Qi Li, Ya-Qi Jiang, Zhao-Xiong Xie

Journal of Electrochemistry

Noble metal nanocrystals (NCs) have widespread applications in catalysis. Their catalytic performances are strongly related to the surface structures while the atomic utilization efficiency of noble metal is considerably correlated with the surface area. Thus, advantages of both specific surface structure and large surface area are highly required to show off simultaneously so as to optimize the catalytic performance and decrease the usage of noble metal. However, it seems that the two advantages are incompatible with each other in one NC since it is difficult for small NCs to keep their specific facets, while NCs with specific surface structure usually …

Stabilization Strategies Of Pt Catalysts Forproton Exchange Membrane Fuel Cells, Da-Ping He, Shi-Chun Mu

Journal of Electrochemistry

The low service lifetime of proton exchange membrane fuel cells (PEMFCs) is the main bottleneck for their commercial applications. One of the main factors is that the expensive metal Pt catalyst is easy to degradation under the harsh working environment of PEMFC (such as variable voltage, strong acidity, gas-liquid two-phase flow), which leads to the inevitable decay of the catalytic performance, thus, seriously restricting the lifetime of PEMFC. Therefore, the electrochemical stability of Pt-based electrocatalysts has become an important and hot topic to improve the PEMFC lifetime. In this paper, we review the recent development in enhancing the stability of …

The Pilot Application Of Electrochemical Impedance Spectroscopy On Dynamic Proton Exchange Membrane Fuel Cell, Jian-Wei Guo, Jian-Long Wang

Journal of Electrochemistry

By analyzing Electrochemical Impedance Spectroscopy (EIS) in applications of dynamic proton exchange membrane fuel cell (PEMFC), bottlenecks which restrict EIS tool development have been pointed out in this paper. Though the high-frequency resistance in EIS is largely accepted as cell inner-resistance, this can only be applied for cell with low current. The low-frequency resistance is difficult to be realized due to its relation with mass transfer. Furthermore, the improved Randles equivalent circuits are built up preliminarily, thus, penetrating into studies for mass transfer reaction, cell operation/degeneration, and high temperature fuel cell. Inspiringly, EIS is becoming an analyzing tool for stack …

Caging Porous Co-N-C Nanocomposites In 3d Graphene As Active And Aggregation-Resistant Electrocatalyst For Oxygen Reduction Reaction, Lu-Yang Xiu, Meng-Zhou Yu, Peng-Ju Yang, Zhi-Yu Wang, Jie-Shan Qiu

Journal of Electrochemistry

Oxygen reduction reaction (ORR) is the cornerstone reaction of many renewable energy technologies such as fuel cells and rechargeable metal-air batteries. The Pt-based electrocatalysts exhibit the highest activity toward ORR, but their large implementation is greatly prohibiting by unaffordable cost and inferior durability. During electrode manufacturing and electrochemical reaction, severe aggregation of catalyst nanoparticles induced by size effect further limits the operational performance of electrocatalysts. We report a new strategy for fabrication of active and aggregation-resistant ORR electrocatalyst by caging metal-organic frameworks derived Co-N-C nanocomposites in permeable and porous 3D graphene cages via sprayed drying the mixed colloids of ZIF-67 …

Voltage Distribution Of Self-Humidifying Air-Cooled Pemfc, Kai-Feng Tan, Wei-Rong Chen, Ming Han, Xue-Xia Zhang

Journal of Electrochemistry

In this work, the self-adaptive characteristics of self-humidifying air-cooled PEMFC stack was investigated. The performance and the unit-cell voltage distribution of the stack were measured and analyzed through the unit-cell I-V curve fitting. The operating conditions for this experimental study were set as follows: hydrogen pressure at the anode was 2 bar, the fan power used for the reactant oxygen feed and stack cooling was at 0.3 W, and the duration and time gap of water purged from hydrogen chamber were 1 s and 10 s, respectively. The experimental results showed that the self-humidifying air-cooled PEMFC stack used for this …

Research Progress In Hydrogen Evolution Low Noble/Non-Precious Metal Catalysts Of Water Electrolysis, Yang Li, Zhao-Yan Luo, Jun-Jie Ge, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

Hydrogen energy technology with hydrogen as an energy carrier is gaining more and more attention due to its cleanliness and high energy density. Hydrogen fuel cell vehicles have been listed as one of the ultimate energy technologies in the 21st century. Among them, sustainable hydrogen production technology is a necessary prerequisite for the future development of hydrogen energy economy. Electrolyzed water technology driven by renewable resources represents an important way to support the sustainable development of hydrogen energy economy. The development and utilization of high activity, low cost hydrogen evolution catalysts is a key factor in improving the efficiency and …

Progress Of Self-Humidifying Membrane Electrode Assembly For Low Temperature Proton Exchange Membrane Fuel Cell, Bin Chi, Yue-Kun Ye, Shi-Jie Jiang, Shi-Jun Liao

Journal of Electrochemistry

The self/non-humidification membrane electrode assembly(SH-MEA)is an important pathway towards the self- humidification fuel cell and plays a crucial role for the large scale commercialization of low temperature proton exchange membrane fuel cell (LT-PEMFC), because it not only can reduce the volume and complexity of fuel cell system, resulting in the decrease of the cost, but also can improve the output power density of the fuel cell system. Currently, the researches on the self-humidifying MEA of LT-PEMFC mainly focus on three aspects: the preparation of self-humidification proton exchange membrane, the construction of self-humidification catalyst layer, and the construction of composite self-humidifying …

Palladium Adatoms On Gold Nanoparticles As Electrocatalysts For Ethanol Electro-Oxidation In Alkaline Solutions, Hui-Mei Chen, Shang-Qian Zhu, Jia-Le Huang, Min-Hua Shao

Journal of Electrochemistry

Palladium (Pd) is a good catalyst for ethanol electro-oxidation in alkaline solutions. The activity of Pd is further improved in this study by modifying the gold (Au) nanoparticles with Pd adatoms using a simple spontaneous deposition process. The Pd overlayer on the Au core (Au@Pd) is un-uniform with some Au atoms exposed to the electrolyte. The activity of Au@Pd/C toward ethanol oxidation reaction (EOR) is much higher than that of Pd/C in an alkaline solution. The peak current density of Au@Pd/C is 4.6 times higher than that of Pd/C with a 100 mV lower onset potential. The enhanced activity may …

Fuel Cells Reactor For Chemicals And Electric Energy Cogeneration, Zhi-Lin Heng, Xiao-Zi Yuan, Yi-Mei Yin, Zi-Feng Ma

Journal of Electrochemistry

As an energy conversion device, fuel cells can efficiently convert chemical energy into electrical energy. With the developing of technology, it is used as a reactor to conduct the synthesis of high value-added chemicals while generating electrical energy. Having benefits such as mild reaction conditions, controllability of the reaction process, high selectivity of the product, as well as high efficiency of energy utilization, it is widely used in many fields such as preparation of high value-added industrial products, gas separation, water treatment, etc. This paper introduces the current trends and statuses of fuel cell reactors in the cogeneration of chemicals …

Durability Performance Of The High-Power Fuel Cell System, Ke-Yong Wang, Wei-Yu Shi, Ren-Fang Wang, Jia Liu, Zhong-Jun Hou

Journal of Electrochemistry

Fuel cell durability is the crucial challenge in fuel cell vehicle, and the lifetime of more than 5000 hours is believed to be necessary for vehicle application. Few works on durability test of the full fuel cell system have been reported. In this work, the long lifetime HySYS-30 fuel cell system was developed in Sunrise Power based on the improved MEA durability and system control strategy. The durability performance of the system was investigated under vehicle duty cycle for more than 6000 hours, and only 8.1% performance loss was observed, implying that the durability of HySYS-30 fuel cell system could …

A Review Of Proton Exchange Membrane Fuel Cell Catalyst Layer By Electrospinning, Yong Liu, Han Ding, De-Chun Si, Jie Peng, Jian-Bo Zhang

Journal of Electrochemistry

The limitation of catalyst layer for proton exchange membrane fuel cell (PEMFC) in cost, durability and performance constitutes the bottleneck for the commercialization of fuel cell vehicles. Electrospun catalyst layer, with high catalyst utilization, increased triple phase boundary (TPB) and triple phase channel (TPC), has been developed by many researchers. This paper reviews the research progress in the electrospun catalyst layer for PEMFC, combined with the author’s work. Firstly, the development progress of catalyst layer is summarized, and the catalyst layer is classified and analyzed based on its fabrication method and structure character. Next, the fabrication process, physical property characterization, …

Fuel Cell Performance Curve After Mea Optimization Structural Optimization Of Low Pt Membrane Electrode Assembly, Yan Rao, Shang Li, Fen Zhou, Tian Tian, Qing Zhong, Zhao-Hui Wan, Jin-Ting Tan, Mu Pan

Journal of Electrochemistry

Membrane electrode assemblies (MEAs) are the key component of proton exchange membrane fuel cell. For a long time, much attention has been paid to develop MEA technology. At present, the research, development and industrialization of fuel cell has entered a new era. More strict requirements for MEA, especially for the reduction of Pt loading with a challenging target of 0.125 mg·W^-1 have to be met. In this paper, the performance losses under low Pt loading are analyzed in terms of activation polarization, ohm polarization and mass-transfer polarization. It is proposed that research should be focused on the activity of …

Morphological Control Of Ptcu2 Octahedron And Oxygen Reduction Electrocatalytic Performance Of Ptcu For Fuel Cell, Long-Sheng Cao, Lei Wan, Zhi-Gang Shao, Hong-Mei Yu, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Platinum acetylacetonate (Pt(acac)₂) and copper acetylacetonate (Cu(acac)₂) were co-reduced to prepare PtCu₂ octahedron alloy catalyst in N,N-dimethylformamiade by solvothermal method. The PtCu₂ showed lattice compression, and high ratio of non-oxidized Pt with high electronic binding energy. All those structural features contributed to weak adsorption strength of oxygen species on Pt and lower d-band centre position. The influence of structure-directing agent on morphology of PtCu alloy was systematically studied. In the half cell test, as a result of the uniform morphology and regular octahedron of PtCu₂ formed, the mass activity and area specific activity …

Effects Of So2 In Air On Performance Of Direct Methanol Fuel Cell, Bin Qin, Fen-Ning Jing, Xue-Jing Sun, Gong-Quan Sun, Hai Sun

Journal of Electrochemistry

Direct methanol fuel cells (DMFC) generally use oxygen as an oxidant. Contaminants such as sulfides and nitrides in the air can affect the performance of the DMFC. In this work, the effects of SO₂ on the performance of DMFC were investigated and the mechanism of poisoning was analyzed, by means of constant current discharge curve, polarization performance curve, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In the CV scan, the permeated methanol was oxidized at a low potential to eliminate its effect on the SO₂ poisoning behavior test. The results showed that the SO₂ poisoning resulted …

Fe-N Doped Hollow Carbon Nanospheres Linked By Carbon Nanotubes For Oxygen Reduction Reaction, Ya-Lin Zhang, Chi Chen, Liang-Liang Zou, Zhi-Qing Zou, Hui Yang

Journal of Electrochemistry

The development of non-precious metal catalysts for oxygen reduction reaction (ORR) is essential for large-scale application of proton exchange membrane fuel cells. Herein, we present the in situ formed Fe-N doped hollow carbon nanospheres linked by carbon nanotubes composite, synthesized by using ZIF-8 as sacrificed template to form polydopamine (PDA) hollow nanospheres, followed by complexing with FeCl₃, high temperature heat-treatment and NH₃-etching. ZIF-8 was gradually decomposed simultaneously with PDA coating due to the loss of Zn²⁺ grabbed by PDA. NH3 etching resulted in the improved surface area, while the reducibility of NH₃ resulted in …

Facile Synthesis Of Pt-Cu Alloy Nanodendrites As High-Performance Electrocatalysts For Oxygen Reduction Reaction, Liu-Xuan Luo, Guang-Hua Wei, Shui-Yun Shen, Feng-Juan Zhu, Chang-Chun Ke, Xiao-Hui Yan, Jun-Liang Zhang

Journal of Electrochemistry

Structures and compositions have significant effects on the catalytic properties of nanomaterials. Herein, a facile etching-based method was employed to synthesize Pt-Cu nanodendrites (NDs) with uniform and homogeneous alloy structures for enhancing oxygen reduction reaction (ORR). The formation of dendritic morphology was ascribed to the etching effect caused by the oxidative etchants of the Br^-/O₂ pair. The atomic ratio of Pt/Cu in Pt-Cu NDs could be easily tuned by altering the ratio of the Pt/Cu precursors, without deteriorating the dendritic morphology. The most active carbon-supported Pt₁Cu₁ NDs (Pt₁Cu₁ NDs/C) exhibited the …

Acid Treated Carbon As Anodic Electrocatalysts Toward Direct Ascorbic Acid Alkaline Membrane Fuel Cells, He-Mu Chen, Chen-Xi Qiu, Yuan-Yuan Cong, Hui-Yuan Liu, Zi-Hui Zhai, Yu-Jiang Song

Journal of Electrochemistry

In order to improve the hydrophilicity and electrocatalytic activity, commercial carbon black (BP 2000) was subjected to acid treatment to obtain acid-treated carbon (ATC). The generation of rich oxygen-containing groups on the surface of the ATC was proved by X-ray photoelectron spectra (XPS), Fourier transform-infra red spectra (FTIR), thermogravimetric analysis (TG) and contact angle measurement. UV-vis spectra were firstly recorded to calculate activation energy (Ea) of ascorbic acid (AA) chemical oxidation in alkaline conditions by oxygen in air and the Ea value was determined to be 37.1 kJ·mol^-1. Additionally, electrochemical impedance spectra (EIS) were used to evaluate unprecedented …

Pd/C Catalysts For Co2 Electroreduction To Co:Pd Loading Effect, Dun-Feng Gao, Cheng-Cheng Yan, Guo-Xiong Wang, Xin-He Bao

Journal of Electrochemistry

Nanostructured heterogeneous catalysts have been widely used in the electrochemical carbon dioxide (CO₂) reduction reaction (CO₂RR), which can simultaneously achieve the electrocatalytic conversion of CO₂ to fuels and the storage of renewable energy sources. Carbon supported palladium nanoparticles (Pd/C) catalysts have been previously reported to show excellent CO₂RR performance. However, the crucial role of the metal loading in supported electrocatalysts has been rarely reported. In this work, we study the Pd loading effect on the structure of Pd/C catalysts as well as their activity and selectivity of CO₂RR to CO. The …

Development And Thermodynamic Analysis Of An Integrated Mild/Partial Gasification Combined Cycle (Impgc) Under Green And Brown Field Conditions With And Without Carbon Capture, Henry A. Long Iii

LSU New Orleans Theses and Dissertations

Coal is a very prominent energy source in the world, but it is environmentally unattractive due to its high sulfur and ash content as well as its alleged contribution towards climate change, but it is affordable, abundant, and has high energy content. Thus, utilizing coal in a cleaner and more efficient way has become necessary. One promising clean coal technology involves fully gasifying coal into synthesis gas, cleaning it, and feeding it into a high-efficiency combined cycle, such as an Integrated Gasification Combined Cycle (IGCC). Inspired by the recent success of warn gas cleanup (WGCU), mild and partial gasification are …

Kcnq1/Kcne1 Interaction In The Cardiac Iks Channel And Its Physiological Consequences, Jiajing Xu

McKelvey School of Engineering Graduate Student Theses & Dissertations

Dynamic conformational changes of ion channel proteins during activation gating determine their function as carriers of current. The relationship between these molecular movements and channel function over the physiological timescale of the action potential (AP) has not been fully established due to limitations of existing techniques. We constructed a library of possible cardiac IKs protein conformations and applied a combination of protein segmentation and energy linearization to study this relationship computationally. Simulations reproduced the effects of the beta-subunit (KCNE1) on the alpha-subunit (KCNQ1) dynamics and function, observed in experiments. Mechanistically, KCNE1 increased the probability of “visiting” conducting pore conformations on …