Chemical Engineering Commons^™

Band Alignments Of Metal/Oxides-Water Interfaces Using Ab Initio Molecular Dynamics, Yong-Bin Zhuang, Jun Cheng

Journal of Electrochemistry

Band alignments of electrode-water interfaces are of crucial importance for understanding electrochemical interfaces. In the scenario of electrocatalysis, applied potentials are equivalent to the Fermi levels of metals in the electrochemical cells; in the scenario of photo(electro)catalysis, semiconducting oxides under illumination have chemical reactivities toward redox reactions if the redox potentials of the reactions straddle the conduction band minimums (CBMs) or valence band maximums (VBMs) of the oxides. Computational band alignments allow us to obtain the Fermi level of metals, as well as the CBM and VBM of semiconducting oxides with respect to reference electrodes. In this tutorial, we describe …

From Waste To Energy: The Electrochemical Reduction Of Co2 Using Recycled Nanostructured Catalysts, Ibrahim Badawy

Theses and Dissertations

The reduction of carbon dioxide (CO₂RR) using electrochemistry is a promising solution for the burgeoning global energy crisis. The overall vision of its implementation relies on renewable energy sources to power the reaction creating carbon neutral products and effectively closing the carbon cycle. Research in this field has come a long way since its inception in the mid-1900s. However, there remain significant hurdles and important considerations to overcome in order to reach full commercialization. Most electrocatalysts tested for CO₂RR have been designed solely for maximum performance while ignoring the environmental consequences if such a material were …

The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels

Electronic Theses and Dissertations

The purpose of this study was to investigate and compare the corrosion mechanisms between wrought and additive-manufactured (3D-printed) copper and stainless steel. The experimental procedure consisted of measuring the open circuit potential, electrochemical impedance spectroscopy, linear sweep voltammetry, Tafel analysis, surface topology, and scanning electron microscopy for each metal within salt water, tap water, sulfuric acid, and synthetic body fluid (excluding copper in synthetic body fluid).

Overall, printed stainless steel was more corrosion-resistant than wrought stainless steel in tap water and synthetic body fluid based on OCP, LSV, and surface topology results. Additionally, printed copper was more corrosion-resistant than wrought …

Surface Immobilization Of Terpyridine Compounds, Elizabeth Hallett

Chemical Engineering Undergraduate Honors Theses

The deoxydehydration (DODH) of polyols to alkenes is a promising method of producing high-value chemical feedstocks from biomass-derived materials. Current catalytic systems for DODH require the use of costly reducing agents that generate stoichiometric amounts of chemical waste. Immobilizing catalysts on electrode surfaces using chemical linking groups eliminates the need for sacrificial reductants. In this work, glassy carbon electrodes were modified with 4’-(3,4-dihydroxyphenyl)-2,2’:6’,2’’-terpyridine to investigate o-benzoquinone as a potential linking group for DODH, and possibly for other reactions. Previous studies involving electrodes modified with quinone-containing compounds have primarily been focused on catalyzing the oxidation of NADH; the nature or …

Biomimetic Devices To Drive A Thermodynamically Uphill Reaction Using Light And To Degrade Industrial Waste Stream Components, Madison Joanne Sloan

Theses and Dissertations--Chemistry

Given the amount of industrial waste produced each year, as well as the accruing amount of greenhouse gases in our atmosphere produced by the burning of fossil fuels, it is imperative that humanity develop environmentally-sustainable sources of energy and methods of remediation. Nature achieves both of these by use of enzymes as catalysts, inspiring interest in designing biomimetic systems capable of harnessing clean energy and remediating industrial waste. This study examined the ability of enzymes in electrochemical and convective flow systems to achieve these tasks. The first portion studied the incorporation of enzymes into an electrochemical system to drive the …

Synthesis, Structural Diversity, And Redox Control Of Cyclometalated Monoruthenium Complexes, Zhong-Liang Gong, Jiang-Yang Shao, Zhong Yu-Wu

Journal of Electrochemistry

Cyclometalated ruthenium complexes have received increasing attractions recently due to their excellent redox and photophysical properties. One structural feature of these complexes is that there is a ruthenium-carbon (Ru-C) σ bond presented in the molecule. Three common methods, namely, the “late metalation”, “early metalation”, and “transmetalation” methods, for the synthesis of cyclometalated ruthenium complexes are discussed and summarized. General strategies for the design of cyclometalating ligand and cyclometalated ruthenium complexes are introduced. By using different ancillary ligands, such as pyridine, imidazole, triazole, and pyrimidine, a great number of ruthenium complexes can be prepared. The presence of the Ru-C bond significantly …

High Temperature Electrochemical Engineering And Clean Energy Systems, Brenda L. Garcia-Diaz, Luke Olson, Michael Martinez-Rodriguez, Roderick Fuentes, Hector Colon-Mercado, Josh Gray

Journal of the South Carolina Academy of Science

Global power demand is projected to more than double by 2050 and meeting this increased power demand will require maintaining or increasing power output from all existing energy sources while adding a large amount of new capacity. The power sources that have the greatest opportunity to fulfill this demand gap over this time period are clean energy sources including solar and nuclear power. One of the areas of expertise that SRNL has been applying to help with a variety of clean energy technologies is in high temperature electrochemistry. Savannah River National Laboratory (SRNL) in collaboration with industrial and university partners …

Oxygen Reduction Reaction By Copper Complex Based Electrocatalysts, Congling Zhang

Doctoral Dissertations

My research focuses on catalysis of oxygen reduction reaction (ORR) by a series of Cu(II) [copper with positive two valence] -1,2,4-triazole complex-based electrocatalysts at the cathode of PEMFC (polymer electrolyte membrane fuel cell), an efficient and environmental friendly energy conversion system compared to internal combustion engines in use today. The sluggish kinetics of ORR considerably limited the performance of PEMFCs. Understanding of ORR mechanism is important for developing affordable, active and durable ORR catalysts for such devices.

The first part of my work focused on improving the ORR performance of Cu(II)-1,2,4-triazole complex-based catalysts in an acidic environment by exploring synthesis …

Electrochemistry Of Glucose Oxidase Modified On Porin-Phospholipid Biomimic Membrane, Kun-Qi Wang, Zuo-Ming Zhang, Wei Xing, Chang-Peng Liu, Xing Zhou

Journal of Electrochemistry

Biomimic membrane with nano-channels, which is made up of porin MspA and 1,2-Dimyristoyl-sn-glycero-3-phosphocholine (DMPC) is constructed on glassy carbon substrate, and glucose oxidase (GOD) is modified on it. The direct electrochemical reaction and electrocatalytic behavior to oxygen and glucose of GOD on the GOD/MspA-DMPC/GC electreode are expounded by the cyclic voltammetric method. The study shows that GOD immobilized on porin MspA and DMPC biomimic membrane displays direct and surface-controlled electrochemical reaction nearby formal potential (E0′) of the flavoprotein active centre (FAD/FADH), and the electrochemical reaction contains two electrons and two protons exchange in 0.1 mmol?L^-1 phosphate buffer solution (PBS) …

Electro-Catalytic Oxidation Of Hydrogen Peroxide On Au/ L-Methionine /Gc Electrode, Jian-Feng Fan, Xue-Mei Luo, Jing Li, Lou-Zhen Fan

Journal of Electrochemistry

The modified electrodes have been fabricated by generation of Au nanoparticle chains, which was produced by reaction between HAuCl4 and sodium citrate without any additional capping agents or surfactants. The self-assembled Au nanoparticles were attached to the surface of glassy carbon electrode (GCE) layer by layer, using L-methionine (L-Met), thiourea (TU), allyl thiourea (ATU) and polyvinylpyrrolidone (PVP) as a crosslinking agent, respectively. The experimental results showed that the electrochemical performance of the different modified electrodes varied in [Fe(CN)₆]^3-/4- solution. The Au/L-Met/GCE exhibited an excellent electrochemical property, which is superior to other modified electrodes. In addition, the catalysis …

Electrochemical Deposition Of Zinc Oxide Crystal Whiskers, Peng-Zeng Lu, Su Li, Jin-Qian Jia, Zhen-Hai Liang

Journal of Electrochemistry

Pine needle ZnO crystal whiskers were electrodeposited by anodization of zinc foil.The crystal whiskers were characterized by scanning electron microscopy(SEM) and X-ray diffraction(XRD) spectroscopy.The results show that the lengths and diameters of ZnO crystal whiskers are 200~300 nm and 20~50 nm,respectively,with the ratio of the length to diameter ranging from 10~15.The whiskers belong to wurtzite ZnO(JCPDS 36-1451) with good crystallinity and high purity.The crystalization behavior of ZnO was studied by cyclic voltammetry.The effects of the surface oxide layer at the zinc substrates and the [Zn(OH)4]2-concentration of the aqueous electrolyte on the formation of zinc oxide whiskers were investigated.

Template Synthesis And Electrochemical Studies Of Ag_(Core)Au_(Shell) Nanowires, Li Ling, Ya-Xian Yuan, Min-Min Xu, Jian-Lin Yao, Ren-Ao Gu

Journal of Electrochemistry

Agcore Aushell nanowires with different thicknesses were prepared by combining template synthesis and chemical reduction method,and characterized by SEM and cyclic voltammetry(CV).The CV results revealed that the AgcoreAushell nanowires with pinhole were transferred to pinhole free structure after several potential scans.By using thiophenol(TP)and p-aminothiophenol(PATP)as probe,the surface enhanced Raman scattering(SERS)effect was investigated on the core-shell nanowires.The results indicated that AgcoreAushell nanowires could be served as a potential SERS substrate,and the difference in the spectral feature of PATP adsorbed onto Au and Ag nanowires enable us to diagnose the pinhole effect of core-shell nanowires by SERS.

Electrochemical Reduction Behavior Of Benzaldehyde In The Ionic Liquids, Ning Zhao, Wen-Ju Dong

Journal of Electrochemistry

In this paper,the electrochemical reduction of benzaldehyde was investigated in C_4MIMBF_(4)、(C_(6)MIMBF_(4)) and C_(8)MIMBF_(4) ionic liquids by cyclic linear sweep voltammetry,cyclic square-wave voltammetry and chronocoulometry.Benzaldehyde exhibits two successive one-electron irreversible reduction(E_(P1)=-1.39 V,E_(P2)=1.69 V) with GC electrode in C_(4)MIMBF_(4),the voltammetric data for benzaldehyde give diffusion coefficients of 1.5 10~(-8)cm~(2)/s and 1.3 10~(8)cm~2/s.There is one current peak in C_(6)MIMBF_(4)and C_8MIMBF_4 ionic liquids due to their stronger alkalinity then C_4MIMBF_4.The decay time of the charging current became longer in C_(4)MIMBF_(4)、C_(6)MIMBF_(4)、C_(8)MIMBF_(4),and slower heterogeneous kinetics in(C_(6)MIMBF_(4)) and C_(8)MIMBF_(4) ionic liquids.

The Electrocatalystic Investigation Of 3,4-Dihydroxybenzoic Acid On The Modified Multiply Wall Carbon Nanotubes, Ming-Qi Li

Journal of Electrochemistry

The electrochemical behavior of 3,4-Dihydroxybenzoic acid(DHBA)on modified multiply wall carbon nanotubes electrode was investigated by cyclic voltammetry(CV) and square wave voltammetry(SWV).Results show that in 0.1 mol/L HCl solutions the modified carbon nanotube electrode has an obvious electrocatalytic effect on the oxidation and deoxidization of DHBA.The oxidation current of DHBA is linear to it's concentration in the range of 4.0×10~(-6)～1.0×10~(-4) mol/L and 2.0×10~(-4)～8.0×10~(-4)1mol/L with correlation coefficient of 0.9995 and 0.9992.The detection limit is 1.0 ×10~(-6)mol/ L.

Synthesis Of (S)-3-Phenylpropane-2-Tert-Butoxycarbonylamino- 1-Thiol And Its Electrochemical Behavior Self-Assembled On Gold, Sun Ru

Journal of Electrochemistry

The synthesis of (S)-3-Phenylpropane-2-tert-butoxycarbonylamino- 1-thiol(N-Boc-APT) from L-phenylalanine was reported. L-Phenylalanine was reduced to the corresponding amino alcohol, protection of the amino group using tert-butyl pyrocarbonate gave (S)-2-tert-butoxycarbonylamino-3-phenylpropane-1-ol, which was then O-mesylated and treated with potassium thioacetate in DMF to give 3-phenylpropane-2-tert- butoxycarbonylamino-1-etylmercapto. After the acetyl group was removed with ammonia in alcohol, the desired target molecular was obtained. The structure of intermediate and target molecular was conformed by IR and ~(1)HNMR. We made N-Boc-APT self-assemble-modificated gold electrode and investigated its electrochemical behavior. The CV results of methylene blue on nano-Au/N-Boc-APT SAM/Au electrode showed that nano-Au could speed this electron transfer …