Engineering Science and Materials Commons^™

Effect Of Fe2+/Fe3+Interconvertion On Reduction Behavior Of Fe3+ In Acidic Electrolytes, Jian-Xin Qin, Feng Lin, Wen-Ping Liu, Chao Chen, Meng-De Ren

Journal of Electrochemistry

The influences of ferrous/ferric (Fe²⁺/Fe³⁺) interconvertion on electrochemical reduction and electrode reaction of Fe³⁺ were investigated by using linear sweep voltammetry, potentiostatic method and cyclic voltammetry (CV) in acidic electrolytes containing chloride ion (Cl^- ) and sulfate ion (SO₄^2-). It was shown that the reduction process of Fe³⁺/Fe²⁺ would take place in two independent stages: (1) the reduction of Fe³⁺ to Fe²⁺ at E=0.35V and (2) the co-precipitation of Fe²⁺ by forming Fe(OH)₂ (E≤-0.3 V) instead of Fe. The major effect of Fe^{2+ …}

Cobalt-Based Nitrogen-Doped Carbon Non-Noble Metal Catalysts For Oxygen Reduction Reaction, Meng-Xiu Jiang, Jing Zhang, Yue-Hua Li, Rong Zhang

Journal of Electrochemistry

Transition metal-nitrogen co-doped carbon catalysts have attracted significant attention because of their reasonable activity and remarkable selectivity toward oxygen reduction reaction (ORR) as cathodic reaction in fuel cells. However, the role of transition metal in the active sites of the catalysts still is uncertain. In this work, the Co_x-N_y/C-T catalysts were prepared with BP2000 as a carbon source, urea (Ur) as a nitrogen source and Co(OAc)₂•4H₂O as a metal precursor by a simple chemical method. Meanwhile, in order to optimize the ORR activity, the catalysts were synthesized with different amounts of Co …

Core-Shell Pd@Pt Ultrathin Nanowires As Durable Oxygen Reduction Electrocatalysts, Xin Wang, Yun-Jie Xiong, Liang-Liang Zou, Qing-Hong Huang, Zhi-Qing Zou, Hui Yang

Journal of Electrochemistry

This paper describes a simple CO-assisted reduction approach for the controllable synthesis of ultrathin Pd nanowires along the one-dimensional (1D) direction. Ultrathin Pt films from one to several atomic layers were successfully decorated onto ultrathin Pd nanowires by utilizing Cu UPD deposition, and followed by in-situ redox replacement reaction of UPD Cu by Pt. The core–shell structure and composition of the Pd@Pt ultrathin nanowires have been verified using transmission electron microscopy and energy dispersive X-ray spectrometry. The core–shell Pd@Pt ultrathin nanowires exhibited comparative electrocatalytic activity and improved durability for the oxygen reduction reaction in comparison with commercial Pt black. The …

Kinetics And Mechanism Toward Electrochemical Reductions Of Sodium Bromide And Methanol Over Iron Electrodes, Qun Liao, Shu-Feng Zhang, Wen-Hua Leng

Journal of Electrochemistry

It is of technological value and scientific interest to the electro-synthesis of ferrocene, conversion of carbon dioxide (CO₂) and organic electro-synthesis in non-aqueous solutions by investigating the kinetics and mechanism toward electrochemical reductions of sodium bromide (NaBr) and methanol over iron electrodes. However, few reports in the related researches are available. In this article, the kinetics and mechanism toward electrochemical reductions of NaBr and methanol over iron electrodes were examined in detail by carrying out the polarization curve and electrochemical impedance spectroscopic measurements. The results showed that methanol was the reactant, while Na⁺ ions were functioned only …

Electroactivities Of Pd/Fe3O4-C Catalysts For Electro-Oxidation Of Methanol, Ethanol And Propanol, Tao Zou, Qing-Feng Yi, Yuan-Yuan Zhang, Xiao-Ping Liu, Guo-Rong Xu, Hui-Dong Nie, Xiu-Lin Zhou

Journal of Electrochemistry

Development of palladium (Pd) catalysts with high electroactivity for alcohol oxidation is significant for alcohol fuel cells. In this work, Pd nanoparticles were formed by sodium borohydride (NaBH₄) reduction method and subsequently deposited on the surface of carbon supported ferriferrous oxide (Fe₃O₄/C) composites to obtain the Pd/Fe₃O₄-C catalysts with different Fe₃O₄ loadings. Their transmission electron microscopic (TEM) images show that the Pd nanoparticles were uniformly dispersed on the Fe₃O₄/C. Electroactivities of the prepared Pd/Fe₃O₄-C catalysts toward oxidations of C1-C3 …

Computational Studies Of Structure–Function Relationships Of Supported And Unsupported Metal Nanoclusters, Hongbo Shi

Doctoral Dissertations

Fuel cells have been demonstrated to be promising power generation devices to address the current global energy and environmental challenges. One of the many barriers to commercialization is the cost of precious catalysts needed to achieve sufficient power output. Platinum-based materials play an important role as electrocatalysts in energy conversion technologies. In order to improve catalytic efficiency and facilitate rational design and development of new catalysts, structure–function relationships that underpin catalytic activity must be understood at a fundamental level. First, we present a systematic analysis of CO adsorption on Pt nanoclusters in the 0.2-1.5 nm size range with the aim …

Analyses Of Densely Crosslinked Phenolic Systems Using Low Field Nmr, Jigneshkumar Patel

Doctoral Dissertations

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multi-components, especially for the crosslinking of rigid high-performance materials. In these reactions, miscibility is crucial for curing efficiency. This miscibility is typically enhanced by adding a third component, a plasticizer. For the reaction of the highly crystalline crosslinking agent hexamethylenetetramine (HMTA) with a strongly hydrogen-bonded phenol formaldehyde resin, furfural has been traditionally used as the plasticizer. However, the reason for its effectiveness is not clear. In this doctoral thesis work, miscibility and crosslinking efficiency of plasticizers in phenolic curing reactions are studied by thermal analysis and spectroscopic …

Thermo-Stability And Active Site Structure Of Fe/N/C Electrocatalyst For Oxygen Reduction Reaction, Chi Chen, Yu-Jiao Lai, Zhi-You Zhou, Xin-Sheng Zhang, Shi-Gang Sun

Journal of Electrochemistry

The development of Fe/N/C electrocatalyst for oxygen reduction reaction (ORR) is vital for the large-scale applications of proton exchange membrane fuel cells. Understanding the active site structure will contribute to the rational design of highly active catalysts. In this study, the as-prepared Fe/N/C catalyst based on poly-m-phenylenediamine (PmPDA-FeN_x/C) catalyst with the high ORR activity was subjected to the high-temperature heat treatment again at 1000 ~1500 ^oC. The degradation of in the ORR activity of PmPDA-FeN_x/C by with various heat treatments was correlated to the change of elemental compositions, chemical states and textural properties. As the …

A New Type Carbon Composited Molybdenum Doped Vanadium Oxide Nanowires As A Cathode Material For Sodium Ion Batteries, Guang-Rui Zhang, Li-Qiang Hu, Bao-Zhu Zhang

Journal of Electrochemistry

In recent years, the development of lithium ion batteries (LIBs) has been limited due to the insufficient lithium resource and increasing cost. As a promising candidate, sodium ion batteries (SIBs) with the similar electrochemical mechanism and lower cost than LIBs are developing rapidly. However, as a result of the larger radius of Na⁺ compared with Li⁺, the crystalline structures of the most electrode materials are damaged severely during the intercalation of Na⁺, which limits the electrochemical properties of SIBs. Thus, developing new types of electrode materials for SIBs is particularly important. Among the cathode materials, …

Bubble-Induced Inverse Gas-Liquid-Solid Fluidized Bed, Xiliang Sun

Electronic Thesis and Dissertation Repository

Gas-liquid-solid fluidized beds have been widely applied in wastewater treatment, however, the current method of wastewater process has several limitations. Hence, an improved method is in demand. A 3.5 height and 0.1534m inner diameter column was used to study the hydrodynamic characteristics of a bubble-induced three-phase inverse fluidized bed. Air, water and three types of low-density particles were employed as gas, liquid and solid phases.

The hydrodynamic properties in the bubble-induced three-phase fluidized bed were investigated to provide the basic information for the industrial process, such as flow regime, bed expansion ratio and phase holdups. A flow regime map containing …

Correlating Long-Term Lithium Ion Battery Performance With Solid Electrolyte Interphase (Sei) Layer Properties, Seong Jin An

Doctoral Dissertations

This study was conducted to understand effects of some of key factors (i.e., anode surface properties, formation cycling conditions, and electrolyte conditions) on solid electrolyte interphase (SEI) formation in lithium ion batteries (LIBs) and the battery cycle life. The SEI layer passivates electrode surfaces and prevents electron transfer and electrolyte diffusion through it while allowing lithium ion diffusion, which is essential for stable reversible capacities. It also influences initial capacity loss, self-discharge, cycle life, rate capability and safety. Thus, SEI layer formation and electrochemical stability are primary topics in LIB development. This research involves experiments and discussions on key factors …

Electrochemical Synthesis Of Homoallylic Alcohols And Homoallylic Amines, Wei-Qiang Zhong, Xiang-Hui Liang, Jing-Mei Huang

Journal of Electrochemistry

Electrochemical technique has been widely applied in the organic synthesis. This review focuses on the electrochemical synthesis of homoallylic alcohols and homoallylic amines from the allylation of carbonyl compounds and imines. This method has been developed impressively, especially in the field of electrochemical allylation in a green solvent of aqueous media. Improvement of the efficiency of the electricity, regio-selectivity and chiral synthesis are expected.

Ionic Liquid-Supported Tempo/Polymeric Ionic-Liquid/Carbon Black Ternary Composites: Preparations And Applications In Electrochemical Oxidation Of Alcohols, Xin Lin, Cao-Cao Sun, Zhi-Rong Liu, Cheng-Chu Zeng

Journal of Electrochemistry

To effectively recover redox catalyst and supporting electrolyte, a novel ternary composite consisting of ionic liquid-supported TEMPO, polymeric ionic-liquid and carbon black was prepared. The ionic-liquid supported redox catalyst TEMPO-IL-BF₄ was firstly synthesized from 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and followed by the reaction of polydimethyldiallylammonium chloride (PDDA) and bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) to form poly[diallyldimethylammonium bis(trifluoromethanesulfonyl)imide] (PDDA(Tf₂N)). A combination of the above mentioned two synthesized materials and carbon black afforded to obtain the ternary composite, which was used as the recoverable supporting electrolyte and mediator for the electrochemical oxidation of alcohol. The results indicate that various alcohols could be oxidized …

Preparations And Applications Of Irsnox Electrode In Electrochemical Synthesis Of 2,5-Dichlorophenol, Xiang-Yu Ma, Xu-Guo Tu, Rui-Nan He, Ya Chen, Gui-Sheng Zhu, Shou-Yan Shao, Song Chen

Journal of Electrochemistry

The electrodes of titanium based iridium tin oxides (IrSnOx) have been prepared by traditional thermal decomposition method and further applied to the electrosynthsis of 2,5-dichlorophenol in order to explore a green and high efficient synthesis route. The results showed that the electrode surface existed apparent cracks, while the intermediate layer prepared with Sn:Sb=94:6 existed less cracks and longer life time. The main products of the electrolytic reaction were 2,5-dichlorophenol, p-chlorophenol, and 1,2,4-trichlorobenzene. The electrosynthsis yield of 2,5-dichlorophenol reached 57% and the selectivity of 2,5-dichlorophenol was as high as 93% by using the IrSnOx as an anode, which is obviously better …

Selective Direct Electro-Oxidation Of C-H Bond, Yan-Mei Liao, Qian-Qian Wu, An-Lun Zhang, Ying-Hong Zhu, Chun-An Ma

Journal of Electrochemistry

Carbon-hydrogen (C-H) bond is the most basic chemical bond in organic compounds. The activation and direct conversion of C-H bond are the effective methodology for synthesis of different kinds of organic compounds from alkane compounds. The oxidative activation and functionalization of C-H bonds constitute an important and challenging area of investigation. The electro-oxidative activation of C-H bonds to form new C-O, C-C and C-N bonds has proven to be interesting and important in organic chemistry using the clean electron as the oxidant. The target C-O, C-C and C-N compounds could be selectively achieved by choosing the appropriate electrode, supporting electrolyte …

Electrocatalysis Of Nanotin Dioxide In The Battery Reaction Of Zinc-Nitrobenzene, Xu-Guo Tu, Xiang-Yu Ma, Rui-Nan He, Xiao-Juan Wang, Chen Ling, Yun-Xia Sun, Song Chen

Journal of Electrochemistry

The tin dioxide (SnO₂) nanoparticles were synthesized by using a simple hydrothermal route in the presence of tetrapropyl ammonium bromide (TPAB) as a surfactant. Accordingly, the titanium mesh based SnO₂ catalyst electrode was prepared. The morphologies and structures of SnO₂ nanostructures were characterized by scanning electron microscopy and X-ray diffraction spectrometry. The influences of reactant concentration, reaction temperature and time on the morphology of the products were investigated in detail. The electrocatalytic performance of SnO₂ for the reduction of nitrobenzene with zinc was studied. Possible formation process and growth mechanism for such hierarchical SnO_{2 …}

Data Driven Discovery Of Materials Properties., Fadoua Khmaissia

Electronic Theses and Dissertations

The high pace of nowadays industrial evolution is creating an urgent need to design new cost efficient materials that can satisfy both current and future demands. However, with the increase of structural and functional complexity of materials, the ability to rationally design new materials with a precise set of properties has become increasingly challenging. This basic observation has triggered the idea of applying machine learning techniques in the field, which was further encouraged by the launch of the Materials Genome Initiative (MGI) by the US government since 2011. In this work, we present a novel approach to apply machine learning …

Comparative Studies Of Fe, Ni, Co And Their Bimetallic Nanoparticles For Electrochemical Water Oxidation, Maduraiveeran Govindhan, Brennan Mao, Aicheng Chen

Journal of Electrochemistry

The design of efficient, durable, and earth-abundant electrocatalysts via environmentally compatible strategies for the oxygen evolution reaction (OER) is a vital for energy conversion processes. Herein we report a facile approach for the fabrication of low-cost and earth abundant metal catalysts, including iron (Fe), nickel (Ni), cobalt (Co), CoNi, and CoFe nanoparticles (NPs) on titanium (Ti) substrates through a one-step electrochemical deposition. Field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) spectrocopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques were employed to characterize these nanoparticles. Our electrochemical results revealed that among the five synthesized nanomaterials, the …

Impact Of Nafion Loading And Anion Adsorption On The Synthesis Of Pt Monolayer Core-Shell Catalysts, Lijun Yang, Dustin Banham, Elod Gyenge, Siyu Ye

Journal of Electrochemistry

Carbon supported palladium (Pd) nanoparticles were used as a model core material for the synthesis of platinum (Pt) monolayer core-shell catalysts using rotating disk electrode method and a copper (Cu) under potential deposition technique. The impact of Nafion on the synthesis process was revealed by electrochemical testing with various Nafion contents. The existence of Nafion influenced the Cu under potential deposition, galvanic replacement and eventually the oxygen reduction reaction activity of the core-shell catalyst. However, as long as the Nafion content was less than 5 wt% in the test film, adding Nafion could help to bind catalyst onto the surface …

Comparison Of Oxygen Reduction Reaction Activity Of Pt-Alloy Nanocubes, Yongan Tang, Lin Dai, Shouzhong Zou

Journal of Electrochemistry

Alloying Pt with the first row non-noble transition metals has been demonstrated to increase the catalytic activity toward oxygen reduction reaction (ORR), which is the cathode reaction of the proton exchange membrane fuel cells (PEMFCs) and metal-air batteries. However, how much the ORR activity improvement comes from the alloying elements remains controversial. In this paper, the nanocubes of PtMn, PtFe, PtCo, and PtNi with the similar size and composition were prepared and their ORR activities were explored, in order to investigate the effects of alloying elements on the catalytic activity. The use of cubic shape particles minimizes the contribution to …

Designing Pt-Skin Of Pt-Based Bimetallic Electrocatalysts For Oxygen Reduction Reaction, Binwei Zhang, Yunxiao Wang, Yanfei Xu, Huakun Liu, Shixue Dou

Journal of Electrochemistry

In the past decade, great advancement has been made in the development of nanocatalysts for energy conversion and storage. Pt-skin of Pt-based bimetallic has shown a great potential in the tuning the electronic structures of electrocatalytically active materials toward oxygen reduction reaction. Here, we offer a brief overview of the recent research on the design and preparation of catalysts. Our focus is paid on the systematic studies of preparation and performance of Pt-skin catalysts towards oxygen reduction reaction.

Recent Progress In Template-Assisted Synthesis Of Nitrogen-Doped Porous Carbons For Oxygen Electroreduction, Niu Wenhan, Li Ligui, Shaowei Chen And

Journal of Electrochemistry

Nitrogen (N)-doped porous carbons are potential alternatives to precious metal catalysts for oxygen reduction reaction (ORR) at the cathodes of proton exchange membrane fuel cells and metal-air batteries. Template-assisted synthesis has been used extensively as a robust and versatile method in the preparation of such carbon catalysts, where the ORR activity has been found to be dependent on various structural parameters, such as the concentrations and molecular configurations of the dopants, and the porosity, surface accessibility and electrical conductivity of the carbon materials. In this review, we summarize recent progress in this area of research focusing on the design, preparation …

Electrodeposition Of Ruo2 Layers On Tio2 Nanotube Array Toward Co2 Electroreduction, Bei Jiang, Lina Zhang, Xianxian Qin, Wenbin Cai

Journal of Electrochemistry

RuO₂/TiO₂ composite materials have multitude of electrocatalytic applications including but not limited to CO₂ reduction reaction (CO₂RR). RuO₂/TiO₂ electrodes were previously prepared by repetitive coating and thermal decomposition (TD) of a Ru(III) precursor solution on Ti substrate. In this work, electrochemical potential cycling is applied to deposit amorphous RuO₂ (α-RuO₂) layers onto TiO₂ nanotube array (TNA) (RuO₂^CV/TNA) preformed on Ti foil. SEM, GIXRD, and voltammetry are applied to characterize the structures of the resulting Ru_O2^CV/TNA. Ru loading on the RuO_{2 …}

Deformation And Adhesion Of Soft Composite Systems For Bio-Inspired Adhesives And Wrinkled Surface Fabrication, Michael Imburgia

Doctoral Dissertations

The study of soft material deformation and adhesion has broad applicability to industries ranging from automobile tires to medical prosthetics and implants. When a mechanical load is imposed on a soft material system, a variety of issues can arise, including non-linear deformations at interfaces between soft and rigid components. The work presented in this dissertation embraces the occurrence of these non-linear deformations, leading to the design of functional systems that incorporate a soft elastomer layer with application to bio-inspired adhesives and wrinkled surface fabrication. Understanding the deformation of a soft elastomer layer and how the system loading and geometry influence …

Application Of Composite Ionic Liquid In Electro-Oxidation Activation Of A C-H Bond, Zi-Ying Chen, Qian-Qian Wu, Jian-Qing Zhang, Ying-Hong Zhu, Chun-An Ma

Journal of Electrochemistry

In this paper, the ionic liquid/carbon nanotube composite material was prepared through modifying the ionic liquid 1-ethyl-3-methylimidazolium acetate to multi-walled carbon nanotubes. The electro-oxidation properties of p-methoxy toluene (p-MT) were studied using the composite as an electrolyte. The effects of scanning speed, temperature and substrate concentration were studied by cyclic voltammetry and chronoamperometry. The electrochemical kinetics of p-MT in this system was also studied. The results showed that the electrochemical oxidation of p-MT in the composite electrolyte solution was irreversible. The process was mainly controlled by diffusion, and the diffusion coefficient (D) was 7.69×10-10 cm2.s-1. Increasing the reaction temperature and …

Sn-Doped Α-Fe2O3 Photocatalyst Containing Oxygen Vacancy For Water-Splitting, Zu-Hua Wang, Dong-Fang Niu, Hui-Cheng Li, Rong-Bin Du, Heng Xu, Xin-Sheng Zhang

Journal of Electrochemistry

The α-Fe₂O₃ nanoparticles containing oxygen vacancies were synthesized in atmospheric N₂ by dip-dropping method without a high vacuum employed before annealing. The influences of annealing atmosphere and Sn-doping on the photocatalytic performance of α-Fe₂O₃ nanoparticles were studied by annealing the photocatalyst in N₂ or air and adding SnCl₄ to the precursor directly. The results showed that the current density of Sn-doping α-Fe₂O₃ annealed in N₂ at 550 °C and 1.23 V (vs. RHE) was 35 times greater than that of pristine α-Fe_{2 …}

Electrochemical Synthesis Of Porous Polyaniline Electrodes Using Hkust-1 As A Template And Their Electrochemical Supercapacitor Property, Qiong Luan, Chun-Feng Xue, Hong-Ye Zhu, Fu-Juan Yang, Xu-Li Ma, Xiao-Gang Hao

Journal of Electrochemistry

Excellent electrode plays vital important role in the performance of supercapacitors. Polyaniline (PANI) with good conductivity is often used to prepare electrode. However, its available surface is limited and results in a poor supercapacitance in many cases. It is desirable to fabricate an electrode containing electroactive PANI with high surface area deriving from its porous structure. Here, the metal-organic framework (MOF) material with high surface area was selected as a hard template for synthesizing porous PANI. Microporous PANI composite electrodes (Micro-PANI/CC) were fabricated by depositing aniline on to carbon cloth (CC) pre-coated with MOF material of HKUST-1 using a unipolar …

Direct Electrochemistry Of Glucose Oxidase Based On Ws2 Quantum Dots And Its Biosensing Application, Chen-Lu Li, Hua-Ping Peng, Zhong-Nan Huang, Yi-Lun Sheng, Pei-Wen Wu, Xin-Hua Lin

Journal of Electrochemistry

In this study, a novel electrochemical glucose biosensor has been developed by immobilizing glucose oxidase (GOx) on tungsten disulfide quantum dots (WS₂ QDs) on the surface of glassy carbon electrode (GCE). Transmission electron microscopy, UV-vis spectroscopy and cyclic voltammetry were employed to characterize the morphology, structure, and electrochemical behaviors of the as-prepared WS₂ QDs and the biofilm modified electrode. The results suggested that the WS₂ QDs could accelerate the electron transfer between the electrode and the immobilized enzyme, which enabled the direct electrochemistry of GOx without any electron mediator. Besides, the immobilized GOx in WS₂ QDsfilm …

The Problem Of The Anode Electrolyte In H-Type Electrolytic Cell For Electrochemical Reduction Of Carbon Dioxide, Rui Zhang, Wei-Xin Lv, Li-Xu Lei

Journal of Electrochemistry

Electrochemical reduction of carbon dioxide (CO₂) was studied in the H-type electrolytic cell. It was found that the voltage between the cathode and the anode would increase during the long time electrolysis process, for this reason the electrolytic process would be unsustainable. After the experimental investigations carried out by constant potential electrolysis, constant current electrolysis, pH test and KHCO₃ concentration analysis of anode electrolyte before and after the electrolysis, the increase in cell voltage might be caused by the following process: H⁺, that was generated from the anodic oxygen evolution reaction, reacted with HCO_{3 …}

Application Of Adamantane Schiff Base Nickel Complexes/Graphene Oxide/Glassy Carbon Modified Electrode In Detection Of Carmine, Peng Guo, Zheng Liu, Hai-Ying Li, Li-Ming Ma

Journal of Electrochemistry

The Schiff base nickel complexes/graphene oxide/glassy carbon electrodes were prepared by embedded method and electrodeposition on which were used to quantitatively detect the contents of carmine. Cyclic voltammetry, chronoamperometry, scanning electron microscopy (SEM) and other methods were employed to characterize properties and morphologies of the modified electrodes. The results show that the adamantane double Schiff base nickel complexes/graphene oxide/glassy carbon electrode had high electric catalytic activity toward carmine oxidation reaction, and might provide an easy and quick way to detect carmine content with good reproducibility.