Analytical Chemistry Commons^™

An In Situ Fourier Transform Infrared Spectroelectrochemical Study On Alcohols Electrocatalytic Oxidation At Pd Electrode In Acidic Solution, Hai-Ping Huang, Lian-Qin Wang, Pei-Kang Shen

Journal of Electrochemistry

The methanol and ethylene glycol electrooxidation on palladium electrode in acidic solution has been investigated by cyclic voltammetry and in situ Fourier transform infrared spectroelectrochemistry. It shows that the oxidation of methanol and ethylene glycol at Pd electrode cannot proceed until over 1.5 V in acidic and neutral media. The overpotential decreases and the peak current density increases with the reduction in pH values. The formation of the oxygen-containing species significantly affects the alcohol oxidation on Pd electrode. The in situ FTIR spectroscopic measurements show that the oxidation products of ethylene glycol on Pd electrode are CO₂ and oxalic …

In-Situ Surface Enhanced Raman Scattering Electrochemical Investigation Of 4-Aminoantipyrine On Silver Electrode, Li-Jun Zhang, Wei Song, Ling Chen, Zong-Rang Zhang, Hai-Feng Yang

Journal of Electrochemistry

In this paper, 4-AAP was self-assembled on silver surface to form monolayers. Surface-enhanced Raman Spectroscopy (SERS) was used to in-situ investigate the adsorption mechanism of the 4-aminoantipyrine(4-AAP) on silver surface dependent on shifting potentials and the effect of solution pH. Based on density functional theory(DFT) calculation of vibration modes,approximate assignment of 4-AAP SERS spectrum was conducted. In situ SERS spectral electrochemical experiments indicated that the 4-AAP monolayers experience a dynamic adsorption process from a tilted fashion to a more vertical mode for benzene ring and more parallel for pyrine ring with the potential applied toward more negative voltages. The complete …

Phenomena Characterization Of Energy Materials By X-Ray Absorption Spectroscopy, Ming-Yao Cheng, Chun-Jen Pan, Ju-Hsiang Cheng, Bing-Joe Hwang

Journal of Electrochemistry

The aim of this review is to introduce the characterization of energy materials by X-ray absorption spectroscopy (XAS) . This technique allows us to probe changes in the valance state and the local environment of the targeted element in the active material; thereby,leading to a better understanding of its electrochemical behavior,and hopefully showing the way to improved performance. Here,electrocatalysts for fuel cells and active electrode materials for Li-ion batteries are taken as the examples that illustrate the capability of XAS and allow observation and theory to be correlated with electrochemical phenomena.

Comparative Study Of Nanoporous Pt, Ptru And Ptruir Catalysts Using Electrochemical Ftir Spectroscopy, M. Amussen Robert, Holt-Hindle Peter, Nigro Samantha, Aicheng Chen

Journal of Electrochemistry

In recent years much effort has been put towards developing efficient Pt-based electrocatalysts for applications in fuel cells. With the rising cost of precious metals such as Pt,the need to enhance the activity and to decrease the load of catalysts is prominent. Herein we report on the synthesis and comparative study of nanoporous Pt,PtRu and PtRuIr electrocatalysts. The nanoporous electrodes were fabricated using a hydrothermal method and characterized by scanning electron microscopy (SEM) ,energy dispersive spectroscopy (EDS) ,X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) . The electrocatalytic activity of the fabricated nanopo- rous materials was evaluated using both CO …

Electrochemical Surface-Enhanced Raman Spectroscopy—Current Status And Perspective, Bin Ren, Jian-Feng Li, Yi-Fan Huang, Zhi-Cong Zeng, Zhong-Qun Tian

Journal of Electrochemistry

Electrochemical interface is a very important interface closely related to various energy and life processes. Surface-enhanced Raman scattering was widely used in electrochemistry soon after its discovery to understand the surface bonding,configuration,and orientation of the surface species. In recent 10 years,the fast development of nanoscience and nanotechnology has offered SERS with abundant substrates and characterization methods,which has allowed impressive development of electrochemical SERS. This articles will follow the time line to make systematically overview of SERS on Au and Ag,thin-layer transition-metal SERS,pure transition metal SERS,core-shell SERS and those methods for studying single crystal surfaces,including gap-mode SERS, TERS and SHINERS. Emphasis …

Electrochemical Sers Studies On The Adsorption Of Benzoimidazole And Derivative In Nonaqueous Solution, Ya-Xian Yuan, Feng-Zhu Yang, Wei Liu, Ping-Jie Wei, Jian-Lin Yao, Ren-Ao Gu

Journal of Electrochemistry

The surface adsorption of benzoimidazole (BIMH) and 2-mercaptobenzimidazole(MBI) was investigated by electrochemical in-situ surface enhanced Raman spectroscopy (SERS) and direct electrochemical synthesis on Cu electrode. The influence of the neutral ligand of triphenylphosphine (pph₃) on the adsorption and surface coordination of BIMH and MBI were investigated respectively. BIMH interacted with metal surface by the neutral molecule to form chemical adlayer in the extremely negative potential,while it adsorbed onto metal surface through the N atoms to form a polymer film which may suppress the corrosion of the metal. The introduction of pph₃ destroyed the film formation of BIMH …

In Situ Surface-Enhanced Raman Scattering Spectroscopic Study Of Sulfur Adsorption On Polycrystalline Platinum Electrode Surface, Bolian Xu, In-Su Park, Ying Li, De-Jun Chen, Yuye J. Tong

Journal of Electrochemistry

The paper reports the first in situ surface enhanced Raman scattering (SERS) spectroelectrochemistry study of sulfur adsorption and electro-oxidation on highly roughened polycrystalline Pt surface in both acidic and basic supporting electrolytes. The SERS spectra were taken at a constant electrode potential after accumulative electro-oxidation CVs of the Pt electrode with pre-adsorbed sulfur species and at different electrode potentials that were varied stepwise of the Pt electrode immersed in sulfur-containing electrolytes without pre-adsorbed sulfur species. In both cases,a dominant vibrational band at 299 cm^-1 in acidic electrolyte but at 310 cm^-1 in basic electrolyte was observed,which was assigned …

Preliminary Investigation Of Iron Protoporphyrin Sams On Platinum Electrodes By Surface Enhanced Vibrational Spectroscopies, Min Ma, Yao-Yue Yang, Han-Xuan Zhang, Wen-Bin Cai

Journal of Electrochemistry

In situ SERS and ATR-SEIRAS were applied to investigate the electrochemical and structural properties of iron protoporphyrin IX (FePP) self-assembled monolayers (SAMs) on Pt electrodes in 0. 1 mol· L -1 HClO₄. The potential dependent SERS spectra of the FePP SAM on a roughened Pt electrode with the enhancement factor of ca. 40 were acquired with the excitation line of 514 nm. Analyses of SERS data over the potential region from 0. 5 to -0. 3 V enabled to obtain potential dependent adsorption isotherms,from which the formal redox potential could be estimated to be ca. -0. 2 V. …

Studies Of Oxidation Processes Of Adsorbed And Solution Co On Pt(110) Electrode By Cyclic Voltammetry And In Situ Ftirs, Li Tian, Jun-Tao Li, Jin-Yu Ye, Chun-Hua Zhen, Shi-Gang Sun

Journal of Electrochemistry

The oxidation processes of adsorbed CO (COad) and solution phase CO (COsol) on Pt(110) electrode were investigated by cyclic voltammetry and in-situ FTIR spectroscopy. It has revealed that in comparison with COad on Pt(110) in a CO-free solution,the oxidation current peak of COsol in a CO-saturated solution is positively shifted ca. 168 mV,and the peak current density has been increased by 6. 70 times. Linear adsorbed CO (COL) is determined by in-situ FTIR spectroscopy as the main species,which is uniformly distributed on Pt (110) surface. In a CO-free solution,the onset potential of COL is measured by in-situ FTIRS ca. 0. …

Density Functional Theory Studies Of Surface-Enhanced Raman Spectroscopy In Electrochemical Interfaces, Liu-Bin Zhao, De-Yin Wu, Bin Ren, Zhong-Qun Tian

Journal of Electrochemistry

Quantum chemical density functional theory and Raman scattering theory were used to study the bonding mechanism and surface-enhanced Raman spectroscopy of pyridine adsorbed on transition metals (Ⅷ group) and coinage metals (IB group) . SERS studies of pyridine-metal systems have been reviewed. Chemical bonding mechanism as well as photo-driven charge transfer mechanism was considered to investigate the vibrational frequency shift and the enhancement of SERS intensity in electrochemical interfaces. Our theoretical results can be used to interpret the SERS phenomena dependent on metals,excitation wavelengths,and applied potentials.

Full Multiple Scattering Analysis Of Xanes At The Cd L 3- And O K- Edges In Cdo Films Combined With A Soft-X-Ray Emission Investigation, I. N. Demchenko, J. D. Denlinger, M. Chernyshova, K. M. Yu, D. T. Speaks, P. Olalde-Velasco, Oliver Hemmers, W. Walukiewicz, A. Derkachova, K. Lawniczak-Jablonska

Environmental Studies Faculty Publications

X-ray absorption near edge structure (XANES) at the cadmium L3 and oxygen K edges for CdO thin films grown by pulsed laser deposition method, is interpreted within the real-space multiple scattering formalism, FEFF code. The features in the experimental spectra are well reproduced by calculations for a cluster of about six and ten coordination shells around the absorber for L3 edge of Cd and K edge of O, respectively. The calculated projected electronic density of states is found to be in good agreement with unoccupied electronic states in experimental data and allows to conclude that the orbital character of the …

Spectroelectrochemical Studies Of Metalloporphyrins In Room Temperature Ionic Liquid, Yong Soo Hoo

Master's Theses (2009 -)

The oxidation/reduction reactions of porphyrins and metalloporphyrins play an important role in medicinal, industrial and biochemical reactions. Metalloporphyrins are particularly useful as potential catalysts for a variety of processes including catalytic oxidations. The unique properties of metalloporphyrins make them good candidates as electrocatalysts for fuel cells. Metalloporphyrins also play some important roles in biological functions.

By incorporating spectroscopic experiments such as UV-visible or infra-red spectroscopy along with electrochemical experiments such as cyclic voltammetry, one is able to determine the structural changes of the molecule when oxidation or reduction reaction is carried out.

Perfluoroalkyl Phosphonic And Phosphinic Acid Electrolytes For Proton Exchange Membrane Fuel Cells, Mahesha Herath

All Dissertations

Perfluorinated sulfonic acid polymers have been considered as the state-of-art membrane materials for proton exchange membrane fuel cells. A major technical issue with these polymers is that they do not function well at temperatures above 80 °C and at low humidities. Therefore, research has been focused on developing PEM materials that can operate independent of hydration requirements. The operation of fuel cells at high temperature (e.g. 120 oC) increases fuel cell system efficiency due to faster electrode kinetics and better CO tolerance. This dissertation will describe a study of proton-transport rates and mechanisms under anhydrous and aqueous conditions using a …

Rapid Multi-Class Multi-Residue Method For The Confirmation Of Chloramphenicol And Eleven Nitroimidazoles In Milk And Honey By Liquid Chromatography Tandem Mass Spectrometry, Mark Cronly, Patrice Behan, Barry Foley, Liam Regan, Sheila Martin, Michael Doyle, Edward Malone

Articles

A confirmatory method has been developed to allow for the analysis of eleven nitroimidazoles and also chloramphenicol in milk and honey samples. These compounds are classified as A6 compounds in annex IV of council regulation 2377/90 and therefore prohibited for the use in animal husbandry. Milk samples are extracted by acetonitrile with addition of NaCl, while honey samples are first dissolved in water before a similar extraction. Honey extracts undergo a hexane wash to remove impurities. Both milk and honey extracts are evaporated to dryness and reconstituted in initial mobile phase. These are then injected onto an LC-MS/MS system and …

Blocking Method In Enzyme-Amplified Amperometric Dna Biosensor, Miao He, Wei Chen, Xiong-Wei Xu, Ai-Lin Liu, Xin-Hua Lin

Journal of Electrochemistry

Non-specific absorption of enzyme and nucleotide is a main source leading to the background staining in enzyme-amplified amperometric detection of DNA. To eliminate the background staining in this system, the blocking procedure by mercapto-hexanol (MCH) and bovine serum albumin (BSA) was studied systematically. The results show that the anti-fouling effect of BSA is better than that of MCH. A simple and efficient blocking strategy employing BSA as the sole blocking reagent was established and applied in the detection of PMLRARα fusion gene in acute promyelocytic leukemia. It can effectively eliminate the background staining,shorten the pre-processing time,and achieve strong signal amplification.

Measurement And Wavelet Analysis Of The Electrochemical Noise Of Rebar Steel In Simulated Concrete Pore Solution, Rong-Gang Hu, Chen-Qing Ye, Shi-Gang Dong, Chang-Jian Lin

Journal of Electrochemistry

Electrochemical noise (ECN) measurement can provide information about both corrosion rate and corrosion type while inflicting no perturbation on the studied system. The ECN data of steel rebar in SPS with different amount of Cl-were collected and treated by discrete wavelet transformation to evaluate the contribution from transients in different frequency in the overall signals. Energy distribution plot (EDP) indicated in SPS with 0.0001 mol/L NaCl, the transients with time constant between 16 ～ 32 s were found to be predominant over other processes; while in SPS with higher Cl-concentration, the trend toward active corrosion became the main process. It …

Fabrication Of Electrochemically Activated Glassy Carbon/Bismuth Film Electrodes For Sensitive Analysis Of Pb(2+) And Cd(2+), Kang Shi, Wen-Jing Wang, Kun Hu

Journal of Electrochemistry

The application of electrochemically activated glassy carbon (GC) in the in-situ preparing of bismuth film electrodes (BiFEs) to analyze Pb^{2 +} and Cd^{2 +} was investigated. The glassy carbon electrodes were electrochemically activated by either potentiostic or cyclic polarization in 1 mol·L^-1 NaOH solution. Experimental results show that employment of HCl solution as the analytical solution not only can reproducibly renew the electrochemically activated GC electrode surface with an electrochemical clear procedure, but also can greatly enhance the sensitivity of BiFes method for analysis of Pb^{2 +} and Cd^{2 +}. The test range thus …

A Preliminary Study In Probing Rapid Method Of Isotope 87sr/86sr Analysis By Electrospray Ionization -Quadrupole Ion Trap - Mass Spectrometry, Sheng Song

Student Theses and Dissertations

The isotope ratio 87Sr/86Sr, typically reported in geologic investigations, is obtained by direct electrospray ionization of aqueous sample containing Sr(II), Rb(I) and 18c6. At relatively high concentrations, we observed favorable formation of Sr2+(18c6)₂ and Rb+(18c6) over Sr2+(18c6) complexes. Physical separation of Sr2+(18c6)₂ and Rb+(18c6) as well as separation of Sr2+(18c6)₂ is observed by simply injecting the sample solution to ESI source using simple PEEK tubing in neutral pH. These phenomena are caused by the difference in mobility of the complexes and masked by the gas phase association reactions. ESI-QITMS successfully obtained the expected isotope distribution of Sr(II) …

Chemical Characterization Of Botanical Products: Comprehensive Speciation By Liquid Chromatography Particle Beam Mass Spectrometry, Joaudimir Castro Georgi

All Dissertations

The dietary supplement industry has expanded and many of these supplements have become an important aspect of people's everyday lives. In 1994, the U.S. Dietary Supplement Health and Education Act (DSHEA) classified numerous nutraceutical/botanical products as dietary supplements because of their beneficial medicinal properties and provided the necessary regulation to the supplement producers. Since then, the interest of the scientific community towards dietary supplements has grown intensively and numerous studies have been carried out in order to understand the chemical behavior of the active molecules in the human body. The development towards analytical methods for the quantification of the active …

Analysis Of Ammonia And Volatile Organic Amine Emissions In A Confined Poultry Facility, Hanh Hong Thi Dinh

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The National Air Emission Monitoring Study (NAEMS) project was funded by the Agricultural Air Research Council (AARC) to evaluate agricultural emissions nationwide. Utah State University (USU) is conducting a parallel study on agricultural emissions at a Cache Valley poultry facility. As part of this parallel study, samples of animal feed, eggs and animal waste were collected weekly from three manure barns (designated: manure barn, barn 4 - manure belt and barn 5 - high rise) from May 2008 to November 2009.

These samples were analyzed to determine ammonia content, total Kjeldahl nitrogen content and ammonia emission. The yearly average calculated …