Materials Science and Engineering Commons^™

Direct Activation Of Light Alkanes To Value-Added Chemicals Using Supported Metal Oxide Catalysts, Md Ashraful Abedin

LSU Doctoral Dissertations

One of the most challenging aspects of modern-day catalysis is the conversion of methane. Direct conversion of methane via dehydroaromatization (MDHA) is a well-known process which can produce valuable hydrocarbons. Mo oxide supported on ZSM-5/MCM-22 has been studied extensively in recent years for MDHA. Mo carbides are responsible for activating methane by forming CHx species. These are dimerized into C2Hy and oligomerized on ZSM-5/MCM-22 Brønsted acid sites to form aromatics. Sulfated zirconia (SZ) supported Mo catalyst contains the acid sites necessary to produce benzene in MDHA. Here, sulfated hafnia (SH), a homologous oxide like SZ, has been proposed to provide …

Electrochemical Deposition In Energy Storage Devices, Witness Atutala Martin

Graduate Theses and Dissertations

Metals, whether in a solid or soluble ion form, are a vital part of any electrochemical storage system. More so, Li metal is widely considered as the ideal anode because of its low density and low electrochemical potential (-3.04 V vs. the standard hydrogen electrode – SHE). However, just like most metals, it does not plate or strip evenly during cycling which can lead to cycling performance issues, short cycling lifespans, and even safety concerns brought about by dendrites that can cause internal short-circuiting within cells. This research focused on investigating the electroplating of metals in both aqueous and non-aqueous …

Synthesis And Electrochemical Study Of Cuau Nanodendrites For Co2 Reduction, Dylan Siltamaki, Shuai Chen, Farnood Rahmati, Jacek Lipkowski, Ai-Cheng Chen

Journal of Electrochemistry

The conversion of carbon dioxide (CO₂) to carbon monoxide (CO) and other value-added products is an interesting approach for carbon-containing fuel synthesis using renewable and clean energy. The electrochemical reduction of CO₂ is one of the promising strategies for the storage of intermittent renewable energy resources. The development of electrocatalysts with high activity and stability is vital in the electrochemical CO₂ reduction process. In this study, copper and gold alloyed (CuAu) electrodes with nanodendritic structures were synthesized using a facile electrodeposition method. The CuAu nanodendrites with the atomic ratio of Cu to Au being approximately 1:1 …

Recent Advances In Glycerol Electrooxidation On Pt And Pd: From Reaction Mechanisms To Catalytic Materials, Wei-Yi Zhang, Xian-Yin Ma, Shou-Zhong Zou, Wen-Bin Cai

Journal of Electrochemistry

The conversion of glycerol to value-added products has received considerable attention recently because the booming biodiesel industry produces a large amount of glycerol as a byproduct. Among various means, electrocatalytic oxidation of glycerol is appealing owing to its environmental friendliness and high efficiency. However, electrooxidation of glycerol is very complex, involving multiple electron and proton transfer processes with many reaction pathways. How to rationally design catalysts with high selectivity toward targeted products is an overarching challenge, and of both fundamental and practical significance. In this minireview we aim to provide an overview of recent advancements in electrooxidation of glycerol focusing …

Preparation Of Co1-XS-Mns@Cnts/Cnfs For Electrocatalytic Oxygen Reduction Reaction, Fang-Yan Liu, Qian Zhang, Yue-Kun Li, Feng Huang, Meng-Ye Wang

Journal of Electrochemistry

As an important cathode reaction in fuel cells and metal-air batteries, oxygen reduction reaction (ORR) is a complex reaction of slow kinetics, which severely limits performances of fuel cells and metal-air batteries. Therefore, it is of key importance to find an efficient and stable electrocatalyst to promote ORR. Carbon-based materials, which possess high conductivity, good stability and large specific surface area, are usually used in electrocatalytic ORR. However, pure carbon-based materials exhibit low efficiency. Coupling carbon-based materials with manganese (Mn) and cobalt (Co) transition metals containing 3d orbitals is an effective way to improve electrocatalytic performance. Herein, carbon nanofibers containing …

Oxygen-Exposure Induced Rapid Oxidation Of Spiro-Ometad In Cspbibr2 Perovskite Solar Cells, Wei-Guo Wang, Tian Bai, Gao-Fei Xue, Mei-Dan Ye

Journal of Electrochemistry

2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (Spiro-OMeTAD) is the most widely used hole transport material in perovskite solar cells (PSCs). However, its oxidation in the air takes a long time and results in the attack of perovskite by water. In this regard, we performed the oxidation process of Spiro-OMeTAD in oxygen, where perovskite can be protected from water, guaranteeing the integrity of perovskite. It was demonstrated that the champion Spiro-OMeTAD based CsPbIBr₂ PSCs after oxygen oxidation achieved a 7.19% power conversion efficiency (PCE), showing a higher PCE than 6.29% of the champion device oxidized in air. A series of electrochemical characterization methods were applied …

Application Of Atomically Precise Metal Nanoclusters In Electrocatalysis, Zhi-Hua Zhuang, Wei Chen

Journal of Electrochemistry

Metal nanoclusters (M NCs) consist of only several to a few hundred of metal atoms and possess core sizes less than 2 nm. Owing to the quantum size effect, the electronic states of M NCs evolve to discrete levels similar to the molecule energy gaps, other than a continuous density of states to produce plasmon characteristic of bulk metal nanoparticles (M NPs). In comparison with the conventional M NPs, M NCs exhibit dramatically unique electronic and optical properties, such as molecule-like energy gaps, strong photoluminescence and high catalytic properties, which make them promising for potential application in numerous fields, such …

Pd-Based Electrocatalysts For Oxygen Reduction And Ethanol Oxidation Reactions: Some Recent Insights Into Structures And Mechanisms, Zhi-Peng Wu, Chuan-Jian Zhong

Journal of Electrochemistry

The development of efficient electrocatalysts for applications in fuel cells, including proton-exchange membrane fuel cell (PEMFC) and direct ethanol fuel cell (DEFC), has attracted extensive research attention in recent years. Oxygen reduction reaction and ethanol oxidation reaction are two of the key reactions where the design of active, stable and low-cost electrocatalysts is critical for the mass commercializations of PEMFCs and DEFCs. This challenge stems largely from the limited understanding of the catalyst structures and reaction mechanisms. Progress has been made in investigations of electrocatalysts derived from Pd-based alloy nanomaterials both experimentally and computationally. We highlight herein some of the …

Theoretical Studies Of Metal-N-C For Oxygen Reduction And Hydrogen Evolution Reactions In Acid And Alkaline Solutions, Xue-Ping Qin, Shang-Qian Zhu, Lu-Lu Zhang, Shu-Hui Sun, Min-Hua Shao

Journal of Electrochemistry

Single atom catalysts (SAC) have been regarded as the promising alternatives to platinum group metals due to their low costs and potentially high catalytic activities in various electrocatalytic reactions. The atomic mechanism understanding of activity discrepancy among different metal and nitrogen co-doped carbon-based catalysts is still lacking. Here, non-precious metal and nitrogen co-doped carbons (Me-N-C, Me = Fe and Co) as the model catalysts are investigated by combining experimental and theoretical studies to explore the catalytic activities and corresponding reaction mechanisms toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at universal pHs. Atomic theoretical simulations suggest that Fe-N-C …

Research Progress In Electrodeposition Technology Of Titanium-Based Iridium Oxide Electrode, Dan-Dan Wu, Xu Wu

Journal of Electrochemistry

Titanium-based iridium oxide electrode has been widely used in various fields, such as electrocatalytic oxidation, biomedical applications, hydrometallurgical metal recovery, electro-osmotic dewatering, etc. At present, it is mainly prepared by traditional thermal decomposition method, however, which has high cost, cumbersome process, mainly relying on manual labor and cannot be mass-produced yet. It is, therefore, urgently necessary to explore new preparation technologies by focusing on electrodeposition technology, with technological characteristics such as eco-friendly and sustainable development. This article systematically discusses the research progress in iridium oxide electrodeposition preparation technology from the aspects of deposition solution formulation, base material selection and treatment, …

Preparations And Electrocatalytic Ethanol Properties Of Palladium Intercalated Hydrotalcite, Shou-Xun Hu, Liang Li, Jun-Hao Yang, Liu-Qiang Li, Zhi-Hao Jin

Journal of Electrochemistry

High-performance electrocatalysts play a vital role in the commercial application of direct fuel cells. Current anode materials still have such problems as low activity, easy poisoning and high cost. In this study, a new type of nano- palladium (Pd) catalyst was prepared by dipping method using layered double hydroxides (LDHs) as the carrier. X-ray diffractometer, scanning electron microscope (SEM), inductively coupled plasma mass spectrometer (ICP-MS), energy spectrometer, transmission electron microscope (TEM), cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscope were used to analyze the structure and electrocatalytic performance of the catalyst. The results showed that the newly prepared Pd/Mg-Al-LDHs still maintained …

Preparation Of Pdcoir Tetrahedron Nanocatalysts And Its Performance Toward Ethanol Oxidation Reaction, Zhi-Yuan Yu, Rui Huang, Jie Liu, Guang Li, Qian-Tong Song, Shi-Gang Sun

Journal of Electrochemistry

As a new energy conversion device, direct ethanol fuel cells (DEFCs) are widely concerned because of their remarkable advantages such as high theoretical energy density and wide fuel sources. However, the rapid development of DEFCs has been severely impeded due to the sluggish kinetic process and toxic intermediates especially in their anodic reactions. Palladium (Pd)-based materials are considered to be excellent anode catalysts for DEFCs, especially under alkaline conditions. And further improving their performance is an important direction to promote the development of DEFCs. Surface structure and composition are the key factors affecting the performance of catalysts which can be …

Syntheses Of Na3V2(Po4)2O2F As A Cathode For Sodium Ion Battery Application, Kai Wu

Journal of Electrochemistry

High-temperature solid-state method, hydro-thermal method and solvo-thermal method have been mainly employed to synthesize Na₃V₂(PO₄)₂O₂F (NVPF) cathode materials. However, these methods are energy consuming and complicated, which is not applicable for a large scale industrial production. In this study, a rather low-temperature (70℃) co-precipitation strategy was proposed to synthesize NVPF cathode materials. The as-prepared NVPF cathode materials showed a spherical shape with a diameter of 400 ~ 500 nm, and exhibited a sodium storage of 105.6 mAh·g^-1 and an efficiency of 90.06%. After a simple thermal process, the specific …

Assessment Of Heavy Metal Concentration In Soils Around Geita The Gold Mine, Tanzania, Mariam G. Mgendi, Mkabwa L. K Manoko, W.J.S. Mwegoha, C. Southway C. Southway

Journal of Humanities and Social Sciences

Health issues related to gold mining cannot be underestimated. Gold mining produce acid mine drainage (AMD), which in turn releases heavy metals into the nearby environment, hence causing environmental pollution. Heavy metals are naturally very toxic, thus pose a great health concern especially when their concentration exceeds the recommended permissible limits. In this study, concentrations of five heavy metals—including Pb, Ni, Cr, Cu and Zn—were assessed in the soil around Geita Gold Mine (GGM). A total of 17 sampling sites were established from which the soil samples were collected at 0-15cm and 15-30cm soil depth. The concentration of both total …

Continuous Preparation And Application Of Novel Heterogeneous Catalysis, Michael B. Burkholder

Theses and Dissertations

Transition metal heterogeneous catalysts are widely used across many chemical industries to reduce waste and emissions and reduce production time while increasing rate. The prevalence of these materials results from the complex relationship between metal nanoparticles and supports affecting final catalytic performance. Rational catalyst synthesis describes the ability to precisely engineer structures through controlled preparation. Novel materials and continuous processing represent a promising approach for rational catalyst synthesis.

The application of these catalysts in continuous, multiphase processes, such as cross-coupling reactions, oxidation chemistry, and nitroreduction processes, are paramount to developing new commercial routes for high-value products. Pd/G catalysts synthesized by …

New Horizons For Processing And Utilizing Red Mud, M. Archambo

Dissertations, Master's Theses and Master's Reports

Red mud is an industrial slurry waste that is produced as a byproduct of the Bayer process for alumina. The waste is generated in large quantities, up to a ratio of 2:1 against the valued product alumina. Red mud exhibits many chemical and physical properties that categorize it as a hazardous material. Due to the addition of sodium hydroxide in processing, the pH is typically at values close to 13. Small particle size discourages separation from water for disposal, so drying red mud happens over many years.

The pH of red mud can be reduced with inexpensive reagents. Carbon dioxide …

Valorization Of Xylan In Agroforestry Waste Streams, Harrison Appiah

Graduate Theses, Dissertations, and Problem Reports (ETD)

Valorization of Xylan in Agroforestry Waste Streams.

Harrison Appiah

Microwave-assisted deep eutectic solvent and gamma-valerolactone metallic chloride catalyzed conversion of xylan to furfural were investigated using a 2x3 factorial experimental design at two levels of percent microwave power, reaction time, and catalyst concentration. The levels of each factor studied were (20%, 60% microwave power, 2, 4 minutes, and 10, 20mg) respectively. The effect of three metallic chloride catalysts (LiCl, FeCl3.6H20, CuCl2) on the conversion of xylan to furfural was also investigated. The gamma-valerolactone-ferric chloride sent system exhibited the highest mean yield of furfural (56.50%). The next highest furfural yield of …

Improving Performance And Durability Of Intermediate Temperature Proton‐Conducting Solid Oxide Electrolysis Cells Via Materials Design And Catalyst Surface Engineering, Hanchen Tian

Graduate Theses, Dissertations, and Problem Reports (ETD)

Solid oxide steam electrolysis cell, a promising electrical-chemical conversion device for the next generation efficient hydrogen production and energy storage, has been actively studied because of their high energy conversion efficiencies and prospective applications as electrochemical reactors. After decades of research on protonic ceramic materials, remarkable advances have been made in the protonic ceramic electrochemical cells (PCECs) air electrode and electrolyte. However, the existing air electrodes are far from satisfying the requirements of practical applications, a series of issues, including the lack of active and durable electrodes, greatly limit the commercialization. To date, the systematic development of triple conducting catalysts …

Dry Reforming Of Methane Using Microwave Irradiated Metal Oxide/Coal Char Catalysts, Anthony Carter

Graduate Theses, Dissertations, and Problem Reports (ETD)

This research focuses on the synthesis of both shaped and amorphous powder materials, the combination of these materials with dried Powder River Basin (PRB) coal char, and their reactionary properties with methane and carbon dioxide gasses with conventional and microwave (MW) heating. The first goal of this project was to synthesize shaped micro and nano sized particles with ideal dielectric properties for converting electromagnetic energy into heat and proven capabilities of activating methane. These particles were synthesized via solvothermal, hydrothermal, and co-preceptory treatments alone and onto the surface of dried PRB coal char. PRB is a sub-bituminous, low-ranking coal (LRC) …

Core-Shell Structured Ru@Ptru Nanoflower Electrocatalysts Toward Alkaline Hydrogen Evolution Reaction, Xue-Liang Wang, Yuan-Yuan Cong, Chen-Xi Qiu, Sheng-Jie Wang, Jia-Qi Qin, Yu-Jiang Song

Journal of Electrochemistry

Water electrolysis for hydrogen production is beneficial for solving the problem of energy crisis and environmental issues. It is necessary to study highly active and cost-effective catalysts toward hydrogen evolution reaction (HER) to reduce the consumption of noble metals. Herein, we report the synthesis of core-shell structured Ru@Pt_0.24Ru nanoflowers electrocatalyst by stepwise reduction of Ru and Pt precursors in the mixture of oleylamine and benzyl alcohol at 160 ^oC. The average diameter of the resultant Ru@Pt_0.24Ru was 16.5±4.0 nm with a bulk atomic ratio between Pt and Ru of 0.24:1 and a surface ratio of …

Effect Of Reaction Conditions On Cu⁃Catalyzed Co2 Electroreduction, Chang Zhu, Wei Chen, Yan-Fang Song, Xiao Dong, Gui-Hua Li, Wei Wei, Yu-Han Sun

Journal of Electrochemistry

Electrochemical conversion of carbon dioxide (CO₂) driven by renewable electricity that can meet both carbon emission reduction and renewable energy utilization has been rapidly developed in recent years. Copper (Cu) catalyst has long been a promising candidate for CO₂ electroreduction applications because of its natural abundance and specific capability of producing a substantial amount of C2 products. However, various metallic Cu electrodes reported have been significantly influenced by the adsorption of certain cation/anion ions, resulting in wide-span catalytic activities and selectivity for various products. In addition, a recent report demonstrated that by virtue of gas-diffusion flow cell …

Numerical Simulations Of Current And Temperature Distribution Of Symmetrical Double-Cathode Solid Oxide Fuel Cell Stacks Based On The Theory Of Electric-Chemical-Thermal Coupling, Cheng-Rong Yu, Jian-Guo Zhu, Cong-Ying Jiang, Yu-Chen Gu, Ye-Xin Zhou, Zhuo-Bin Li, Rong-Min Wu, Zheng Zhong, Wan-Bing Guan

Journal of Electrochemistry

Solid oxide fuel cell (SOFC) is a high-efficient clean conversion device for future energy management. Because of the low antioxidant reduction ability and complex thermal stress, the structure of traditional asymmetrical thin anode-supported planar SOFC is easily to be broken under stack operating conditions. To overcome these defects, a new complete symmetrical SOFC based on double-sided cathodes was developed. To study the influences of gas flow direction and current collection mode on the cell performance inside stack, a numerical model was established by finite element method based on the theory of electro-thermo-chemo multiphysical coupling. By applying this model, the molar …

Atom Trapping And Its Role On The Nucleation & Growth Of Platinum Nanoparticles, Deepak Kunwar

Chemistry and Chemical Biology ETDs

Diesel oxidation catalysts deactivate due to Pt sintering, a major problem in automotive industries. To make sure they operate effectively throughout the lifetime of the vehicle, automotive industries are putting an excessive amount of Pt. There is a need to develop a catalyst that serves long term performance with minimal use of Pt. Jones et al^.1 demonstrated that ceria traps Pt atoms. His work generated some logical and valid questions such as what is the mechanism for the formation of anomalously large Pt particles? What is the upper limit of Pt metal loading in the form of single atoms …

A Model For The Anodic Carbonization Of Alkaline Polymer Electrolyte Fuel Cells, Qi-Hao Li, Ying-Ming Wang, Hua-Long Ma, Li Xiao, Gong-Wei Wang, Jun-Tao Lu, Lin Zhuang

Journal of Electrochemistry

The alkaline polymer electrolyte fuel cell (APEFC) has made appreciable progress in recent years but is still suffering performance loss during discharge with air as the oxidant. Several theories have been suggested to interpret the loss. However, efforts are still needed to reach a clear quantitative understanding. Based on the major experimental findings in combination with thermodynamics and kinetics of the reactions involved in the anode, this paper presents a model featuring layered carbonization in the anode and relevant grouped equations. The simulation results generated from the latter are compared with experiments, and possible principles to suppress the performance loss …

Facile Synthesis Of Nitrogen-Doped Graphene-Like Active Carbon Materials For High Performance Lithium-Sulfur Battery, Quan-Hua Meng, Wen-Wen Deng, Chang-Ming Li

Journal of Electrochemistry

Lithium-sulphur (Li-S) battery is regarded as a promising energy storage device because of its high theoretical capacity. However, the low S utilization and short cycling life limit the commercial applications. In this work, nitrogen-doped graphene-like carbon (NGC) materials were synthesized by simply pyrolyzing and carbonizing the mixture of melamine (C₃H₆N₆) and L-cysteine (C₃H₇NO₂S). The graphene-like structure in NGC effectively buffered the volume change of S during the discharge/charge process and improved the cycling stability. Meanwhile, nitrogen-containing functional groups in NGC facilitated the transportation of ions and suppressed the …

Recent Progress In Bifunctional Catalysts For Zinc-Air Batteries, Neng-Neng Xu, Jin-Li Qiao

Journal of Electrochemistry

Zinc-air battery has attracted great attention from researchers due to its high energy density and power density, which is expected to be widely used in energy conversion and storage. Air electrode as the core area of oxygen catalytic reaction is the focus of the entire zinc-air battery research. Recently, many research achievements have been made in non-noble metal bifunctional catalysts/electrodes with high activity, low cost and abundant species. In this review, we mainly focus on the reaction mechanism and the recent progress in non-noble metal oxide catalyst, carbon-based catalyst, and carbon-based transition metal compound composite and self-supporting electrode. In addition, …

Recent Progress On Enhancing Effect Of Nanosized Metals For Electrochemical Co2 Reduction, Yu-Ning Zhang, Dong-Fang Niu, Shuo-Zhen Hu, Xin-Sheng Zhang

Journal of Electrochemistry

The electrochemical conversion of CO₂ to chemical raw material for further utilization shows promising future to alleviate global warming and realize carbon cycle in nature, which is of great significance to the green chemistry and sustainable development. This review briefly introduces the advantages of CO₂ electrochemical reduction (CO₂ER) and its basic reaction principles, and summarizes the recent progress in a series of activity enhancement strategies based on nanosized metal catalysts. The influences of alloy effect, interface engineering, synergistic effect, surface defect engineering and support effect on the catalytic performance of nanosized metals for CO₂ER …

Research Progress Of Metal-Nitrogen-Carbon Catalysts Toward Oxygen Reduction Reaction Inm Changchun Institute Of Applied Chemistry, Ming-Jun Xu, Jie Liu, Jun-Jie Ge, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

The development of highly active and stable catalysts toward oxygen reduction reaction (ORR) has been facing severe challenges. In recent years, pyrolytic M-N-C catalysts and metal-organic framework derived materials made the performance of non-noble metal catalysts greatly improved, however, the molecular and atomic level understanding in the reaction active sites and the mechanism are still lacking. Here, we summarize the recent research progress made in the Changchun Institute of Applied Chemistry. We present a microporous metal-organic-framework confined strategy toward the preferable formation of ORR catalysts. Firstly, we studied the active site and proposed a new active site structure for the …

Electrochemical Carbon Dioxide Reduction In Flow Cells, Jia Fan, Na Han, Yan-Guang Li

Journal of Electrochemistry

Electrochemical carbon dioxide reduction (CO₂RR) is an appealing approach to convert atmospheric CO₂ to value-added fuels and industrial chemicals, and may play an important role during the transition to a carbon-neutral economy. In order to make this technology commercially viable, it is essential to pursue CO₂RR in flow reactors instead of conventional H-type reactors, and to combine electrocatalyst development with system engineering. In this review, we overview the cell configurations and performance advantages of the two types of flow reactors, analyze their shortcomings, and discuss the effects of their different components including gas diffusion electrode …

Electrolyte Tailoring For Electrocatalytic Reduction Of Stable Molecules, Jin-Han Li, Fang-Yi Cheng

Journal of Electrochemistry

Reduction of stable molecules such as CO₂ and N₂ is important process in electrochemical energy conversion and storage technologies for electrofuels production. However, for the inert nature of CO₂/N₂ molecule and competitive proton reduction in conventional aqueous electrolytes, selective electrochemical carbon/nitrogen fixation suffers from high overpotential, low reaction rate and low selectivity. While addressing these issues has witnessed substantial advances in electrocatalysts, much less attention has been placed on the electrolytes, which play an important role in regulating the local environment and thus the performance of catalysts under operating conditions. Rational design of electrolytes has …