Chemical Engineering Commons^™

Faceted Nanomaterial Synthesis, Characterizations And Applications In Reactive Electrochemical Membrane Filtration, Qingquan Ma

Dissertations

Facet engineering of nanomaterials, especially metals and metal oxides has become an important strategy for tuning catalytic properties and functions from heterogeneous catalysis to electrochemical catalysis, photocatalysis, biomedicine, fuel cells, and gas sensors. The catalytic properties are highly related to the surface electronic structures, surface electron transport characteristics, and active center structures of catalysts, which can be tailored by surface facet control. The aim of this doctoral dissertation research is to study the facet-dependent properties of metal or metal oxide nanoparticles using multiple advanced characterization techniques. Specifically, the novel atomic force microscope-scanning electrochemical microscope (AFM-SECM) and density functional theory (DFT) …

Carbon Fibers From Bio-Based Precursors Derived From Renewable Sources, Sagar Kanhere

All Dissertations

Carbon fibers have the highest strength and modulus among all known fibers and are used as reinforcements in high-performance composites [1]. Carbon fibers also have a very low density relative to metals. Therefore, carbon fibers possess ultrahigh specific strength and modulus, which make them desirable for high-performance light-weight composites. A vast majority of commercial carbon fibers are produced from PAN precursors that are expensive, which limits the use of PAN-derived carbon fibers to aerospace applications (e.g., airplanes). However, for costsensitive applications, there is a need for low-cost, moderate performance carbon fibers. Lignin is a low-cost by-product of pulping and biorefining …

Quantification Of Flows Emerging From Small Pores In Plane Walls, Matia Peter Edwards

Electronic Thesis and Dissertation Repository

Current membrane separation processes are limited in high production and high purity settings due to a trade-off between selectivity and permeance. Methods of creating nanoscale geometries in 2D materials are emerging and present an opportunity for fast, size selective mass transport that can be tailored to a wide array of applications. This thesis develops a method for quantifying flow through small pores in plane walls based on the behaviour of a solute dispersed in a downstream reservoir. This method is validated for a range of micropore diameters, for which flow rates can be calculated with confidence, and is shown to …

Insight Into The Effects Of Cation Disorder And Surface Chemical Residues On The Initial Coulombic Efficiency Of Layered Oxide Cathode, Jin-Li Liu, Han-Feng Wu, Zhi-Bei Liu, Ying-Qiang Wu, Li Wang, Feng-Li Bei, Xiang-Ming He

Journal of Electrochemistry

Lithium layered oxide LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) is one of the most promising cathode materials in high-energy lithium-ion batteries for electric vehicles. However, one drawback for NCM622 is that its initial coulombic efficiency (ICE) is only about 87%, which is at least 6% lower than that of LiCoO₂ or LiFePO₄. In this work, we investigated the effects of surface chemical residues (e.g., LiOH and Li₂CO₃) and Li/Ni cation disorder resulted during the sintering on the ICE. We found that the ICE of the as-prepared samples could be boosted …

Electrochemical Syntheses Of Nanomaterials And Small Molecules For Electrolytic Hydrogen Production, Jia-Qi Wei, Xiao-Dong Chen, Shu-Zhou Li

Journal of Electrochemistry

Hydrogen is a clean, efficient, renewable energy resource and the most promising alternative to fossil fuels for future carbon-neutral energy supply. Therefore, sustainable hydrogen production is highly attractive and urgently demanded, especially via water electrolysis that has clean, abundant precursors and zero emission. However, current water electrolysis is hindered by the sluggish kinetics and low cost/energy efficiency of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this regard, electrochemical synthesis offers prospects to raise the efficiency and benefit of water electrolysis by fabricating advanced electrocatalysts and providing more efficient/value-adding co-electrolysis alternatives. It is an eco-friendly and facile …

Surface Structure Engineering Of Feni-Based Pre-Catalyst For Oxygen Evolution Reaction: A Mini Review, Jia-Xin Li, Li-Gang Feng

Journal of Electrochemistry

Oxygen evolution reaction (OER) is a significant half-reaction for water splitting reaction, and attention is directed to the high-performance non-precious catalysts. Iron nickel (FeNi)-based material is considered as the most promising pre-catalyst, that will be transferred to the real active phase in the form of high valence state metal species. Even so, the catalytic performance is largely influenced by the structure and morphology of the FeNi pre-catalysts, and lots of work has been done to optimize and tune the structure and chemical environment of the FeNi- based pre-catalysts so as to increase the catalytic performance. Herein, based on our work, …

Biobased Packaging Materials From Cellulose Nanofibrils Produced From Virgin Wood Pulp Or Recycled Cardboard Pulp, Md Ikramul Hasan

Electronic Theses and Dissertations

Self-standing cellulose nanofibril (CNF) films are regarded as one of the promising alternatives to current petroleum-based packaging materials. The mechanical and barrier properties of CNF films are not yet up to the mark for certain applications, especially at high relative humidity. Those properties of CNF films can be tuned by the drying methods of films, degree of fibrillation, cross-linking, and controlled shrinkage. A comprehensive understanding of these processes and their influence on the structure and properties of CNF films have been presented in this thesis.

First, we prepared CNF films from CNF suspensions with two different degrees of fibrillation- standard …

Synthesis And Consolidation Of Metal Oxide Nanocrystals Via Nonthermal Plasma, Austin Cendejas

McKelvey School of Engineering Theses & Dissertations

Nonthermal plasmas offer a unique nonequilibrium environment that has been leveraged in a wide variety of applications in the fields of material processing, lighting, and waste management to name a few. In all of these cases, the plasma serves as a source of high energy electrons, ions, reactive gas species, and radicals that interact in several ways with surfaces brought into contact with the plasma. Specifically, nonthermal plasmas have been shown to be very successful in achieving continuous, high-throughput, monodisperse nanocrystals of a wide variety of materials. The crystallinity of nanoparticles synthesized in nonthermal plasmas can be attributed to the …

Augmented Formic Acid Electro-Oxidation At A Co-Electrodeposited Pd/Au Nanoparticle Catalyst, Yaser M. Asal, Ahmad M. Mohammad, Sayed S. Abd El Rehim, Islam M. Al-Akraa

Chemical Engineering

In this study, the formic acid electro-oxidation reaction (FAEOR) was catalyzed on a Pd-Au co-electrodeposited binary catalyst. The kinetics of FAEOR were intensively impacted by changing the Pd2+:Au3+ molar ratio in the deposition medium. The Pd1-Au1 catalyst (for which the Pd2+:Au3+ molar ratio was 1:1) acquired the highest activity with a peak current density for the direct FAEOR (Ip) of 4.14 mA cm−2 (ca. 13- times higher than that (ca. 0.33 mA cm−2) of the pristine Pd1-Au0 catalyst). It also retained the highest stability that was denoted in fulfilling ca. 0.292 mA cm−2 (ca. 19-times higher than 0.015 …

Electrocatalytic “Volcano-Type” Effect Of Nano-Tio2 (A)/(R) Phase Content In Pt/Tio2-CnX Catalyst, Ai-Lin Cui, Yang Bai, Hong-Ying Yu, Hui-Min Meng

Journal of Electrochemistry

The relationship between the electrochemical activity of fuel cell catalysts and Pt particle size, as well as the catalyst support and co-catalyst is still unclear. In this work, FESEM, XRD, BET, TEM and CV techniques were adopted to investigate the effects of TiO₂ anatase (A)/rutile (R) phases content on the electrochemical activity of Pt electrocatalyst. The results showed that the anatase-rutile phase transformation occurred during the heat treatment of TiO₂ at 700 ~ 900 oC accompanied by the growth of two-phase crystalline size, and anatase was completely transformed into rutile at 900 oC. TEM results revealed that the …

Surface Engineering Of Pt Surfaces With Au And Cobalt Oxide Nanostructures For Enhanced Formic Acid Electro-Oxidation, Yaser M. Asal, Islam M. Al-Akraa, Ahmad M. Mohammad

Chemical Engineering

This study aims to mitigate the CO poisoning of platinum (Pt) surfaces during formic acid electro-oxidation (FAEO), the essential anodic reaction in the direct formic acid fuel cells (DFAFCs). For this purpose, a glassy carbon (GC) electrode was amended sequentially with Pt (n-Pt), gold (n-Au), and cobalt oxide (n-CoOx) nanostructures. Fascinatingly, the ternary modified n-CoOx/n-Au/n-Pt/GC catalyst (for which n-Pt, n-Au, and n-CoOx were sequentially and respectively assembled onto the GC surface) exhibited a remarkable electrocatalytic enhancement toward FAEO, which surpassed ca. 53 times that of the Pt/GC catalyst. Additionally, it exhibited a much (ca. 18 times) higher stability after 3000 …

Photocatalytic Degradation Of Organic Contaminants By Titania Particles Produced By Flame Spray Pyrolysis, Noah Babik

Theses and Dissertations

Advanced oxidation of organic pollutants with TiO2 photocatalysts is limited due to the wide bandgap of TiO2, 3.2 eV, which requires ultraviolet (UV) radiation. When nanosized TiO2 is modified by carbon doping, charge recombination is inhibited and the bandgap is narrowed, allowing for efficient photodegradation under visible light. Here, we propose a flame spray pyrolysis (FSP) technique to create TiO2. The facile process of FSP has been successful in preparing highly crystalline TiO2 nanoparticles. Using the same procedure to deposit TiO2 onto biochar, the photocatalyst was doped by the carbonaceous material. The morphology, crystalline and electronic structure of the FSP …

Surface-Functionalized Chemiresistive Films That Exploit H-Bonding, Cation-Pi, And Metal-Halide Interactions., Prasadanie Karunarathna Adhihetty

Electronic Theses and Dissertations

The development of gas sensors for detection of volatile organic compounds (VOCs) has been of interest in the sensing field for decades. To date, the use of metal nanoparticle-based chemiresistors for trace VOC detection, particularly gold nanoparticle-based sensors, is of great interest due to their high chemical stability, ease of synthesis, unique optical properties, large surface to volume ratio, and high level of conductivity. Much effort has been devoted towards gold monolayer protected clusters (Au MPCs) as chemiresistors to detect harmful VOCs. The present thesis documents the results of our efforts to exploit the advantages of functionalized Au MPCs chemiresistors …

Preparation Of Pt@Basrtio3 Nanostructure And Its Properties Towards Photoelectrochemical Ammonia Synthesis, Jing Zhang, Rui-Xia Guo, Jian-Jun Fu, Shi-Bin Yin, Pei-Kang Shen, Xin-Yi Zhang

Journal of Electrochemistry

Ammonia is an important industrial raw material and a potential green energy. Using renewable energy to convert nitrogen into ammonia under ambient condition is an attractive method. However, the development of efficient photoelectrochemical ammonia synthesis catalysts remains a challenge. Perovskite such as BaSrTiO₃ (BST) is a good photocatalytic material. However, BST is active under ultraviolet light and has a high recombination rate of photogenerated electron-hole pairs. By dispersing precious metals, it can effectively regulate the absorption of sunlight by BST. In this work, we used a two-step method to prepare BST. The H₂PtCl₆·6H₂O …

Effect Of Palladium Loading On Catalytic Properties Of Pd/Gce For The Electro-Oxidation Of Methanol, Formic Acid, And Ethylene Glycol, Islam M. Al-Akraa, Yaser M. Asal, Sohir A. Darwish, Rafik M. Fikry, Reem H. Mahmoud, Mohamed Hassan, Ahmad M. Mohammad

Chemical Engineering

This study investigates the influence of the catalyst (Palladium, Pd) mass that loaded onto a glassy carbon electrode (GCE) on the catalytic activity of methanol (MEO), formic acid (FAEO), and ethylene glycol (EGEO) electro-oxidation, the corresponding principal anodic reactions in the direct methanol (DMFCs), formic acid (DFAFCs), and ethylene glycol (DEGFCs) fuel cells, respectively. By increasing the Pd loading at 0.1 V, the Pd surface area increased from 0.55 cm2 (2 min Pd deposition) to 1.94 cm2 (25 min Pd deposition) which increased the peak currents (IP) of MEO (from 0.181 to 0.608 mA), FAEO (from 0.236 to …

In Situ Characterization Of Electrode Structure And Catalytic Processes In The Electrocatalytic Oxygen Reduction Reaction, Ya-Chen Feng, Xiang Wang, Yu-Qi Wang, Hui-Juan Yan, Dong Wang

Journal of Electrochemistry

As an electrochemical energy conversion system, fuel cell has the advantages of high energy conversion efficiency and high cleanliness. Oxygen reduction reaction (ORR), as an important cathode reaction in fuel cells, has received extensive attention. At present, the electrocatalysts are still one of the key materials restricting the further commercialization of fuel cells. The fundamental understanding on the catalytic mechanism of ORR is conducive to the development of electrocatalysts with the enhanced activity and high selectivity. This review aims to summarize the in situ characterization techniques used to study ORR. From this perspective, we first briefly introduce the advantages of …

In-Situ/Operando57Fe Mössbauer Spectroscopic Technique And Its Applications In Nife-Based Electrocatalysts For Oxygen Evolution Reaction, Jafar Hussain Shah, Qi-Xian Xie, Zhi-Chong Kuang, Ri-Le Ge, Wen-Hui Zhou, Duo-Rong Liu, Alexandre I. Rykov, Xu-Ning Li, Jing-Shan Luo, Jun-Hu Wang

Journal of Electrochemistry

The development of highly efficient and cost-effective electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier to establish effective utilization of renewable energy storage systems and water splitting to produce clean fuel. The current status of the research in developing OER catalysts shows that NiFe-based oxygen evolution catalysts (OECs) have been proven as excellent and remarkable candidates for this purpose. But it is critically important to understand the factors that influence their activity and underlying mechanism for the development of state-of-the-art OER catalysts. Therefore, the development of in-situ/operando characterizations is urgently required to detect key …

A Competent Mwcnt-Grafted Mnox/Pt Nanoanode For The Direct Formic Acid Fuel Cells, Islam M. Al-Akraa, Mamdouh M. Moutaz, Ahmad M. Mohammad, Yaser M. Asal

Chemical Engineering

A novel “MnOx/Pt/MWCNT-GC” nanocatalyst is recommended for the electrooxidation of formic acid (EOFA), the principal anodic reaction in the direct formic acid fuel cells (DFAFCs). The sequential (layer-by-layer) protocol was employed to prepare the catalyst through the electrodeposition of Pt (nano-Pt) and manganese oxide (nano-MnOx) nanoparticles onto the surface of a glassy carbon (GC) electrode supported with multiwalled carbon nanotubes (MWCNTs). The nano-MnOx could successfully mediate the mechanism of EOFA by accelerating the charge transfer, “electronic effect”. On the other hand, MWCNTs could enhance the catalytic performance by changing the surface geometry that inhibited the adsorption of poisoning CO, which …

Computational Rational Design Of Electrocatalysts For Electrochemical Ammonia And Hydrogen Synthesis, Akash Jain

Doctoral Dissertations

The electrochemical hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR) offer fossil-fuel-free routes for hydrogen and ammonia synthesis, respectively. However, currently, both processes lack suitable electrocatalysts for practical applications. Thus, this dissertation focuses on the computational rational design of HER and NRR electrocatalysts. HER is most efficiently catalyzed by platinum (Pt), which is expensive. To reduce the catalyst cost, we investigate core-shell nanoparticles of inexpensive tungsten-carbide (WC) and Pt (WC@Pt). Using first-principles density functional theory (DFT) calculations, we compare the suitability of two WC phases, α-WC and β-WC as support materials for Pt overlayers. We dope WC with titanium …

Selective Co2 Reduction To Formate On Heterostructured Sn/Sno2 Nanoparticles Promoted By Carbon Layer Networks, Xue Teng, Yanli Niu, Shuaiqi Gong, Xuan Liu, Zuofeng Chen

Journal of Electrochemistry

Tin (Sn)-based materials have emerged as promising electrocatalysts for selective reduction of CO₂ to formate, but their overall performances are still limited by electrode structures which govern the accessibility to active sites, the electron transfer kinetics, and the catalytic stability. In this study, the heterostructured Sn/SnO₂ nanoparticles dispersed by N-doped carbon layer networks (Sn/SnO₂@NC) were synthesized by a melt-recrystallization method taking the low melting point of Sn (m.p. 232oC). The N-doped carbon layer networks derived from polydopamine could attract more electrons on the electrocatalyst, serve as conductive agents and protect the ultrafine nanoparticles from agglomeration and …

Synergistic Enhancement Of Formic Acid Electro-Oxidation On Ptxcuy Co-Electrodeposited Binary Catalysts, Yaser M. Asal, Ahmad M. Mohammad, Sayed S. Abd El Rehim, Islam M. Al-Akraa

Chemical Engineering

A propitious binary catalyst composed of Pt and Cu which were electrodeposited simultaneously onto a glassy carbon (GC) substrate was recommended for the formic acid (FA) electro-oxidation reaction (FAOR); the principal anodic reaction in the direct FA fuel cells (DFAFCs). The simultaneous co-electrodeposition of Pt and Cu in the catalyst provided an opportunity to tune the geometric functionality of the catalyst to resist the adsorption of poisoning CO at the Pt surface that represented the major impediment for DFAFCs marketing. The catalytic activity of the catalyst toward FAOR was significantly influenced by the (Pt4+/Cu2+) molar ratio of the electrolyte during …

Controlling The Emission Of Volatile Platinum Oxides To The Vapor Phase In Diesel Oxidation Catalysts, Arnab Ghosh

Nanoscience and Microsystems ETDs

Pt-based catalysts are used for the treatment of emissions from vehicles, particularly in Diesel oxidation catalysts (DOCs). Three-way catalysts are treated at temperatures ranging from 950℃-1050℃ while DOCs are aged at 800℃ for 50 hrs. At 800°C, Pt reacts with O₂ to form PtO₂ which has a high vapor pressure and can be transported through the vapor phase. These accelerated aging conditions lead to the formation of large Pt particles causing a loss of catalytic activity. In this thesis, we used model thin-film catalysts that made it possible to quantify the emission of Pt to the vapor phase …

Molecular Modeling Of High-Performance Thermoset Polymer Matrix Composites For Aerospace Applications, Prathamesh P. Deshpande

Dissertations, Master's Theses and Master's Reports

The global efforts from major space agencies to transport humans to Mars will require a novel lightweight and ultra-high strength material for the spacecraft structure. Three decades of research with the carbon nanotubes (CNTs) have proved that the material can be an ideal candidate for the composite reinforcement if certain shortcomings are overcome. Also, the rapid development of the polymer resin industry has introduced a wide range of high-performance resins that show high compatibility with the graphitic surface of the CNTs. This research explores the computational design of these materials and evaluates their efficacy as the next generation of aerospace …