Catalysis and Reaction Engineering Commons^™

A Co Porphyrin With Electron-Withdrawing And Hydrophilic Substituents For Improved Electrocatalytic Oxygen Reduction, Hong-Bo Guo, Ya-Ni Wang, Kai Guo, Hai-Tao Lei, Zuo-Zhong Liang, Xue-Peng Zhang, Rui Cao

Journal of Electrochemistry

Understanding factors that influence the catalyst activity for oxygen reduction reaction (ORR) is essential for the rational design of efficient ORR catalysts. Regulating catalyst electronic structure is commonly used to fine-tune electrocatalytic ORR activity. However, modifying the hydrophilicity of catalysts has been rarely reported to improve ORR, which happens at the liquid/gas/solid interface. Herein, we report on two Co porphyrins, namely, NO₂-CoP (Co complex of 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin) and 5F-CoP (Co complex of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin), and their electrocatalytic ORR features. By simultaneously controlling the electronic structure and hydrophilic property of the meso-substituents, the NO₂-CoP showed higher electrocatalytic activity than …

Recent Development Of Low Iridium Electrocatalysts Toward Efficient Water Oxidation, Jing Ni, Zhao-Ping Shi, Xian Wang, Yi-Bo Wang, Hong-Xiang Wu, Chang-Peng Liu, Jun-Jie Ge, Wei Xing

Journal of Electrochemistry

Developing high-performance and low-cost electrocatalysts for oxygen evolution reaction (OER) is the key to implementing polymer electrolyte membrane water electrolyzer (PEMWE) for hydrogen production. To date, iridium (Ir) is the state-of-the-art OER catalyst, but still suffers from the insufficient activity and scarce earth abundance, which results in high cost both in stack and electricity. Design low-Ir catalysts with enhanced activity and stability that can match the requirements of high current and long-term operation in PEMWE is thus highly desired, which necessitate a deep understanding of acidic OER mechanisms, unique insights of material design strategies, and reliable performance evaluation norm, especially …

Perovskite-Type Water Oxidation Electrocatalysts, Xiao Liang, Ke-Xin Zhang, Yu-Cheng Shen, Ke Sun, Lei Shi, Hui Chen, Ke-Yan Zheng, Xiao-Xin Zou

Journal of Electrochemistry

The development of energy conversion/storage technologies can achieve the reliable and stable renewable energy supply, and bring us a sustainable future. As the core half-reaction of many energy-related systems, water oxidation is the bottleneck due to its sluggish kinetics of the four-concerted proton-electron transfer (CPET) process. This necessitates the exploitation of low cost, highly active and stable water oxidation electrocatalysts. Perovskite-type oxides possess diverse crystal structures, flexible compositions and unique electronic properties, enabling them ideal material platform for the optimization of catalytic performance. In this review, we provide a comprehensive summary for the crystal structures, electronic structures and synthetic methods …

Facile One-Step Solid-State Synthesis Of Ni-Rich Layered Oxide Cathodes For Lithium-Ion Batteries, Jing-Yue Wang, Rui Wang, Shi-Qi Wang, Li-Fan Wang, Chun Zhan

Journal of Electrochemistry

Nickel-rich layered oxide is one of the dominate cathode materials in the lithium ion batteries, due to its high specific energy density meeting the range requirement of the electric vehicles. Typically, the commercial Ni-rich layered oxides are synthesized from co-precipitated precursors, while precision control is required in the co-precipitation process to ensure the atomic level mixing of the cations such as Ni, Co and Mn, et.al. In this work, a one-step solid-state method was successfully applied to synthesize the Ni-rich layered oxide materials with ultra-high Ni content. By choosing the nickel hydroxides as the precursor with layered structure similar to …

Low-Crystallinity And Heterostructured Aupt-Ru@Cnts As Highly Efficient Multifunctional Electrocatalyst, Tuan-Jie Gan, Jian-Ping Wu, Shi Liu, Wen-Jun Ou, Ling Bin, Xiong-Wu Kang

Journal of Electrochemistry

The catalytic activity of the catalysts is strongly dependent on the structure of the catalysts, and the exploration of their correlation and structure-controlled synthesis of the high-performance catalysts are always at the central. Currently, platinum (Pt) is the optimum catalyst for hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and alcohol oxidation reaction, while ruthenium (Ru) behaves as the champion catalyst for oxygen evolution reaction (OER) during water splitting. Preparing alloy catalysts with these precious metals can modulate the catalytic activity of these catalysts from the perspective of strain effect, ensemble effect and ligand effect. Here, we developed a strategy …

Modeling Solvent Extraction Of Lignin From Hardwoods, Su Pan

McKelvey School of Engineering Graduate Student Theses & Dissertations

This study interprets the observed behavior of solvent extraction of lignin from hardwoods by adapting the framework of the FLASHCHAIN theory (Niksa and Kerstein, 1991; Niksa, 2017). A constitution submodel specifies distributions of molecular weight and reactive sites for native lignin. The model simulates delignification as depolymerization of lignin macromolecules into fragments small enough to be soluble. This process competes with intrachain condensation that consumes labile bridges without forming new fragments, and with recombination that forms larger chains and inhibits further depolymerization. After the soluble fragments are transported from the particle into the bulk solvent, all chemistry continues as long …

Performance And Fouling During Bioreactor Harvesting, Da Zhang

Graduate Theses and Dissertations

Tangential flow filtration has many advantages for bioreactor harvesting as the permeate could be introduced directly to the subsequent capture step, the process is easy to scale up, and fouling of the filter is limited by the cross flow. However, membrane fouling has limited its widespread use. This is particularly problematic given the high cell densities encountered today. Here a reverse asymmetric commercial membrane, BioOptimal™ MF-SL (Asahi Kasei), where the more open surface faces the feed stream, and the tighter barrier layer faces the permeate stream, has been investigated for bioreactor harvesting. The open surface contains pores up to 40 …

Wind Tunnel Modeling Of Jack Rabbit Ii Mock Urban Environment Gas Concentration Measurements, Sami S. Fares

Graduate Theses and Dissertations

The 2015 Jack Rabbit (JR) II field trials were conducted to improve understanding of the denser-than-air dispersion of chlorine in an urban environment. The field study involved five large-scale, outdoor release trials of chlorine in a mock urban environment (MUE) at Dugway Proving Ground (DPG). Various instrumentation was deployed, including JazTM Ultraviolet-Visible (UV-Vis) point sensors capable of measuring gas-phase chlorine concentration throughout the mock urban array.

The Chemical Hazards Research Center (CHRC) was tasked by the Chemical Security Analysis Center (CSAC) with the Mock Urban Wind Tunnel (MUWT) program to study the 2015 JR II Trials at wind tunnel scale. …

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 …

Designing The Electrode Geometry And Electrolyte To Enhance The Product Selectivity And Activity In Carbon Dioxide Electroreduction, Samaneh Sharifi Golru

Dissertations, Theses, and Capstone Projects

Excessive utilization of the fossil fuels due to the rapid growth of the global population has resulted in a dramatic increase in the carbon dioxide (CO₂) level in the atmosphere which is the main reason for global warming and climate change. Therefore, green technologies are in high demand to develop carbon-neutral energy cycles. In this regard, CO₂ electroreduction (CO2ER) has been proposed as a promising approach for CO₂ utilization. CO2ER can mitigate the CO₂ level in the atmosphere as well as produce value-added chemicals and fuels at ambient conditions. Despite the benefits of CO_{2 …}

Electrochemical Synthesis Of Acetylpyrazine, Lin Mao, Dong-Fang Niu, Shuo-Zhen Hu, Xin-Sheng Zhang

Journal of Electrochemistry

Acetylpyrazine is naturally presented in hazelnuts, peanuts, and sesame seeds. As an important food additive, it is widely used in baked foods, meat, sesame and tobacco. At the same time, acetylpyrazine is also an important pharmaceutical intermediate, which is used in the syntheses of anti-tuberculosis drugs, anti-tumor, anti-malaria, anti-viral, antibacterial and treatments of epilepsy, pain and Parkinson’s drugs. At present, the synthesis methods of acetylpyrazine include oxidation method, multi-step method and Grignard reagent method, which have the disadvantages of low yield, cumbersome process, severe reaction conditions and high cost. In this study, acetylation of pyrazine was used to synthesize acetylpyrazine …

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 …

Study And Improvement On Expansion Property Of Silicon Oxide, Wei-Chuan Qiao, Fang-Ru Li, Jin-Lin Xiao, Li-Juan Qu, Xiao Zhao, Meng Zhang, Chun-Lei Pang, Zi-Kun Li, Jian-Guo Ren, Xue-Qin He

Journal of Electrochemistry

The silicon-based anode materials have the potential to meet the ever-increasing demand for energy density in lithium-ion batteries market owing to their high theoretical specific capacity. Unfortunately, their commercialization was hindered by the continuous volume expansion. Herein, the expansion characteristics and corresponding mechanism of the silicon oxide and graphite-silicon oxide composites were investigated by in-situ displacement detection systematically. The results showed that the expansion property was improved by material process modifications. During the de/lithiation processes of graphite, the expansion ratio in 30% ~ 50% SOC changed little because of the small interlayer spacing variation of the intercalated graphite. …

Preparation And Properties Of Gcp-Supported Palladium Particles Composite Towards Electrochemical Ammonia Synthesis, Ying-Chao Wang, Zi-Zai Ma, Yi-Fan Wu, Xiao-Guang Wang

Journal of Electrochemistry

Ammonia (NH₃) plays an essential role in agriculture and modern industries. Electrochemical fixation of nitrogen (N₂) to ammonia (NRR) under ambient conditions with renewable electricity is a promising strategy to replace the industrial Haber-Bosch method. However, it usually suffers from extremely poor ammonia yield and low Faraday efficiency due to the poor electrocatalysts. Therefore, intensive studies have been devoted to developing efficient NRR catalysts till now. Among them, palladium (Pd) can capture protons in the aqueous phase to form stable α-PdH, which balances the competitive adsorption between nitrogen and protons as well as reduces the …

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 …

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 …

Optimization Of Styrene From Ethylbenzene Case Study, Jabria Daria Thompson

Honors Theses

The following pages detail the optimization process of styrene from ethylbenzene in the Styrene Production Plant, Unit 500. There were two parts of the assignment, each with slightly different end goals. The goal of the first part of the assignment, was to create a process that would effectively and efficiently increase the negative Net Present Value (NPV) of the production plant. Procedures taken in this process included developing a working kinetic process simulation model and optimizing this model through unit operations and heat integration, as well as developing an accurate economic model that will be used to evaluate the proposed …

Kinetics Of Carboxymethylation Reaction Of Cellulose Samples With Different Degree Of Crystallinity, Ilkhom Goyibnazarov, Sherzod Yuldoshov, Abdushukhur Sarimsokov

CHEMISTRY AND CHEMICAL ENGINEERING

No abstract provided.

Mathematical Modeling Of Synthesis 4´,4´´-Di-(1-Methyl-1-Hydroxy-2-Phenylethynyl)-Dibenzo-18-Crown-6, Lyubov Kozinskaya, Dilorom Mirkhamitova

CHEMISTRY AND CHEMICAL ENGINEERING

The main goal of this study is the mathematical modeling of the optimal conditions for the synthesis of 4´,4´´-di-(1-methyl-1-hydroxy-2-phenylethynyl)-dibenzo-18-crown-6 by the least squares method. In the STAT program, iconograms of mathematical modeling of the synthesis and the dependence of the rate of formation of 4´,4´´-di-(1-methyl-1-hydroxy-2-phenylethynyl)-dibenzo-18-crown-6 on temperature and reaction time were obtained, the corresponding analytical dependencies are determined. Mathematical processing of the results of the synthesis of 4´,4´´-di-(1-methyl-1-hydroxy-2-phenylethynyl)-dibenzo-18-crown-6 was carried out, a system of linear equations was compiled using the matrix method. The average reaction rate and the optimum of the mathematical model were determined, and the experimental and calculated …

Optimization Of A Fluidized Bed Reactor For The Production Of Styrene From Ethylbenzene, Gregory Espenan

Honors Theses

In order to optimize Unit 500, a styrene production plant, the Net Present Value (NPV) was used as the objective function to ensure every optimization strategy had a positive economic effect. To optimize a chemical plant, it is important to note efficiency, economics, product specifications, and production requirements. The goal of this project was to make changes to the base case of Unit 500 to minimize the cost to produce styrene for an upstream unit. PRO/II was used to simulate various points in different unit operations throughout the process. The NPV was measured after each unit operation was simulated to …