Materials Chemistry Commons^™

Crystallographically Determined Etching And Its Relevance To The Metal-Assisted Catalytic Etching (Mace) Of Silicon Powders, Kurt W. Kolasinski, Bret A. Unger, Alexis T. Ernst, Mark Aindow

Chemistry Faculty Publications

Metal-assisted catalytic etching (MACE) using Ag nanoparticles as catalysts and H2O2 as oxidant has been performed on single-crystal Si wafers, single-crystal electronics grade Si powders, and polycrystalline metallurgical grade Si powders. The temperature dependence of the etch kinetics has been measured over the range 5–37◦C. Etching is found to proceed preferentially in a h001i direction with an activation energy of ∼0.4 eV on substrates with (001), (110), and (111) orientations. A quantitative model to explain the preference for etching in the h001i direction is developed and found to be consistent with the measured activation energies. Etching of metallurgical grade powders …

Increased Utility Of Ph Sensitive Indicators As High Concentration Co2 Detectors Through The Use Of Polyelectrolyte Complexes As Stabilizing Media, Camden James Johnson

All Master's Theses

Development of plastic materials which produce visible color change when exposed to different environments has recently attracted attention for many biomedical applications.^1,2Many biomedical devices are packaged under high concentrations of carbon dioxide (CO₂) which can lower the pH of the packaging environment. This is similar to the CO₂ chemistry responsible for ocean acidification.³ Dye molecules that are sensitive to environmental changes in pH (known as pH indicators) can be encapsulated in plastics and produce a visible color change when a medical device is removed from the sterile CO₂ environment. Plastics made from large …

Diisopropylammonium Bromide Based Two-Dimensional Ferroelectric Monolayer Molecular Crystal With Large In-Plane Spontaneous Polarization, Liang Ma, Yinglu Jia, Stephen Ducharme, Jinlan Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

In light of their easy processing, light weight and mechanical flexibility, ferroelectric molecular crystal with large spontaneous polarization (P_s) is highly desired for many advanced applications. Herein, we report the first theoretical study of two-dimensional (2D) ferroelectric molecular crystals via ab initio calculations. Specifically, we show that diisopropylammonium bromide (DIPAB) based 2D ferroelectric monolayer molecular crystal with large in-plane P_s of ∼1.5 × 10⁻⁶ μC cm⁻¹ can be achieved by slicing the bulk DIPAB along a specific plane while keeping the space group unchanged. The important roles of hydrogen bonds are …

Synthesis Of N-Heterocyclic Molecules And Their Applicability Towards Ion Sensing: Polymeric Chemosensors, Aikohi M. Ugboya

College of Graduate Studies: Theses & Dissertations

Critical to biological and environmental processes are anions because often times their relative concentration in our body can be an indicator of one’s well-being. Therefore, highly sensitive and cost-efficient methods for ions recognition is necessary for human health. In recent times, polymeric chemosensors have become a vital tool for sensing ions because of its higher sensitivity and good mechanical properties compared to their monomeric counterparts. These sensors are designed to produce a measurable response in the presence of a targeted ion such as an electrochemical or optical signal. The unique structure and the photophysical properties of the 1,2,3-triazole core coupled …

Nanostructured Materials For Photocatalysis, Water Treatment And Solar Desalination, Hiran D. Kiriarachchi

Theses and Dissertations

Maintaining a constant supply of clean drinking water is among the most pressing global challenges in our time. About one-third of the population is affected by the water scarcity and it can only get worse with climate change, rapid industrialization, and the population growth. Even though nearly 70 percent of the planet is covered by water, the consumable freshwater content is only 2.5 percent of it. Unfortunately, the accessible portion of it is only 1 percent. Even so, most of the freshwater bodies are choked with pollution. Considering the vast availability of saline water on the planet and the increasing …

Oxidative Degradation Of Lignin And Investigation Of Utilization Of Lignin-Derived Materials As Building Blocks For Epoxy Resins, Zhen Fang

Theses and Dissertations--Chemistry

Lignin, the second most abundant biopolymer on earth, is potentially a replaceable source for bulky fuels and chemical feedstocks. There have been numerous reports on methods for the oxidative cleavage of β-O-4 linkages but relatively few reports of how those methods affect other linkages that are present in lignin. We investigated how the β-1 and β-5 linkages respond under oxidative conditions proposed for lignin deconstruction based on their effect on β-O-4 linkages. Mechanochemical treatment of lignin can greatly improve the yield of monomer products and we applied a mechanochemical approach, using powerful ring-and-puck milling to promote lignin degradation. Along with …

Synthesis And Characterization Of Carbonaceous Particles From Xylose And Soybean Residuals, Shanshan Wang

Theses and Dissertations--Chemistry

Carbonaceous materials, especially in micro and nanoscale, are useful in optical, energy storage, electronic, and biomedical devices or technologies. Techniques have been developed for preparation and modification of the carbonaceous materials, while it is still challenging to tailor the properties of carbonaceous materials effectively and economically. Laser is a powerful tool in academic and industrial laboratories, which also plays important roles in the preparation and modification of high-performance carbonaceous nanomaterials.

In this study low-cost hydrothermal synthesis, high-temperature annealing, and Laser ablation (LAL) methods are developed to prepare functionalized carbon nanomaterials and modify their electrochemical and optical properties.

Sub-micro hollow carbon …

Lewis Base Promoted Annulations Of Allenoates With 1,4-Naphthoquinones, Nicole Marie Shoup

Electronic Theses and Dissertations

Lewis base promoted cyclization of allenoates with electron deficient olefins open up the possibility to generate more complex organic structures. By generating more complex molecules, we are able to produce new compounds for biomedical and material applications. Both phosphine and amine Lewis bases offer interesting annulations with allenoates resulting in Lu or Morita–Baylis–Hillman type reactions. Once the Lewis base engages with the allenoate there can be several modes of nucleophilic reactivity that allows for the allenic ester to act as a two or three carbon synthon. The allenoate can then react with varying electron deficient olefins generating more complex molecules …

Modeling The Condensed-Phase Behavior Of Π-Conjugated Polymers, Walker Mask

Theses and Dissertations--Chemistry

It is well established that the morphology and physical properties of an organic semiconducting (OSC) material regulate its electronic properties. However, structure-function relationships remain difficult to describe in polymer-based OSC, which are of particular interest due to their robust mechanical properties. If relationships among the molecular and bulk levels of structure can be found, they can aid in the design of improved materials. To explore and detail important structure-function relationships in polymer-based OSC, this work employs molecular dynamics (MD) simulations to study various π-conjugated polymers in different environments. Two independent investigations are discussed in this work. One investigation examines how …

On The Use Of Vibrational Spectroscopy And Scanning Electron Microscopy To Study Phenolic Extractability Of Cooperage Byproducts In Wine, Berta Baca‑Bocanegra, Julio Nogales‑Bueno, Brian Gorey, Francisco José Heredia, Hugh Byrne, José Miguel Hernández‑Hierro

Articles

Wood is an important source of phenolic compounds, which can be transferred to wine during aging process, improving its properties, from an organoleptic point of view. Therefore, understanding and optimizing the extractability of phenolic compounds from wood are crucial in the oenological field. The structural composition of oak wood samples has been evaluated using Raman and attenuated total reflectance Fourier transform infrared (ATR–FTIR) spectroscopies, and their main spectral features have been linked to phenolic compound extractabilities, as measured by classic chemical analyses. To support the analysis, microscopic images of the samples were also recorded using scanning electron microscopy (SEM). The …

Nanoscale Building Blocks: Bridging The Gap Between Potential And Realized Applications, Nicole Ritter

Theses and Dissertations (Comprehensive)

The vast potential of nanoparticles and nanotechnology remains largely untapped; the crucial bottleneck being the knowledge gap between making and using nanoparticles (NPs). This PhD work bridges this gap by focusing on synthesizing nanoparticles with applications at the forefront. Four peer-reviewed publications are presented in Chapters 3-6, a safety and toxicological perspective is given in Chapter 7, and current work and future progress are summarized in Appendix 1. Bimorphic silver nanoparticles were prepared, presenting an innovative method to synthesize diverse nanostructures using polymeric surface blocking to break symmetry in seeded regrowth (Chapter 3).¹ Silver stars with D_5h symmetry …

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 …

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 …

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 …

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 …

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 …