Materials Chemistry Commons^™

Stm Investigation Of Oxygen Reduction Reaction On Solid Interface In Fuel Cell, Zhen-Feng Cai, Bing Sun, Wen-Jie Jiang, Ting Chen, Dong Wang, Li-Jun Wan

Journal of Electrochemistry

An electrocatalyst for oxygen reduction reaction (ORR) is an important component for fuel cells. An investigation at interfacial electrochemical reactions toward ORR at a molecular scale benefits mechanistic understanding as well as rational design of catalysts. Scanning tunneling microscopy (STM) has been proven to be a powerful tool to monitor chemical reactions and to provide in-situ information about the interfacial electrochemical reactions at a molecular level. This review summarizes the recent STM studies in monitoring the interface processes such as morphological changes, molecular changes, reaction intermediates, and oxidation products. The prospects of future development in this field are outlined.

Synthesis Of Ultrathin Co3O4 Nanoflakes Film Material For Electrochemical Sensing, Hui-Juan Wang

Journal of Electrochemistry

Ultrathin cobalt oxide (Co₃O₄) nanoflakes film material was synthesized by using an electro-deposited cobalt layer as a raw material through a simple oxidation method and followed by a heat treatment at 350 ^oC. The physical characterizations of the Co₃O₄ nanoflakes film were performed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) technologies, and the electrochemical activity was measured by cyclic voltammetry (CV). As a promising material for electrochemical sensing, the as-synthesized ultrathin Co₃O₄ nanoflakes film material exhibited excellent electrochemical activity for H₂O …

Polyol Induced Partitioning Of Essential Oils In Aqueous Organic Solvent Mixtures, Thomas Delmastro

Seton Hall University Dissertations and Theses (ETDs)

Polyol Induced Extraction (PIE) was developed and patented at Seton Hall University by Drs. John R. Sowa Jr., Wyatt R. Murphy, and Mithilesh Deshpande. It was originally discovered and implemented as a method to recycle and reuse waste acetonitrile during the production shortage in 2008. Through the use of PIE, a solvent mixture containing acetonitrile and water can be separated by employing a polyol mass separating agent, which induces a phase separation. The system is separated into its corresponding aqueous and organic phases, with the organic phase being a highly purified organic liquid. Based on the successful experimental results that …

A Grand Unified Model For Liganded Gold Clusters, Wen Wu Xu, Beien Zhu, Xiao Cheng Zeng, Yi Gao

Xiao Cheng Zeng Publications

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three ‘flavours’ (namely, bottom, middle and top) to represent three possible valence states. The ‘composite particles’ in GUM are categorized into two groups: variants of triangular elementary block Au₃(2e) and tetrahedral elementary block Au₄(2e), all satisfying the duet rule (2e) of the valence shell, akin to …

Electrogenerated Chemiluminescence Study Of Semiconductor Nanoparticles Towards Sensitive Detection Of Biomolecules, Yiliyasi Wusimanjiang

Dissertations

The main focus of this dissertation is to unfold the fundamental aspects of electrogenerated chemiluminescence (ECL) generation from semiconductor nanoparticles (also known as quantum dots or QDs) within different ECL systems. The ECL and photo-physical interactions between the CdTe QDs (λ_emission= ~760 nm) and the CdSe QDs (λ_emission= ~550 nm), as well as the effects of carbon nanotubes on ECL of QDs were separately investigated. Optimum experimental conditions for peptide bond formation on an electrode surface through EDC (1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide hydrochloride)/NHS (N-Hydroxysulfosuccinimide) coupling were also revealed using cyclic voltammetry technique. Based on the information …

Graphene Quantum Dots Electrochemistry And Development Of Sensitive Electrochemical Biosensor [Hybrid Poster 1-B], Tyler Smith, Alexander Banaszak

Posters-at-the-Capitol

Graphene quantum dots (GQDs) are zero-dimensional material derived from graphene derivatives with characteristics from the structure of graphene with quantum confinement and edge effects possessing unique properties. Intense research activity in GQDs is attributed to their novel physical-chemical phenomena arising from the sp²-bonded carbon core surrounded with edge functional moieties. In this work, GQDs of optimal 5-7 nm size are investigated for their fundamental electrochemical properties and use in electrochemical sensing including enzyme-based glucose biosensor. Glucose oxidase (GO_x) was immobilized on GQDs modified glassy carbon (GC) and the UV-Vis absorption and fluorescence spectroscopy, electron microscopy, cyclic …

The Study Of Dynamical Electrochemical Impedance Spectroscopy For Oxygen Reduction Reaction On Pt/C Catalyst, Kun-Ming Shi, Jian-Wei Guo, Jia Wang

Journal of Electrochemistry

With joint techniques of rotating disc electrode(RDE) and electrochemical impedance spectroscopy(EIS), and further establishment on equivalent circuit model, this paper studied oxygen reduction reaction(ORR) on commercial Pt/C catalyst in acid medium. Our results found that the dynamical interface on Pt/C consists of two independent processes: 1) the PtO reduction from Pt surface, 2) the new PtO formation from ORR, thus providing key clues for catalyst stability and activity. This also implied that the dynamical interface facilitates reconstruction for porous electrode, and matches with mass transfer. One important issue is discovered that at high overpotential, the high reaction rate for ORR …

A Comparison Of Solvent And Water-Borne Alkyd Coatings And The History Of Voc Regulations In The United States, Molly Elise Burns

Master's Theses

A Comparison of Solvent and Water-Borne Alkyd Coatings Abstract

Conventional solvent based alkyd coatings have gone out of favor due to concerns over volatile organic compound (VOC) content. However, due to recent focus on renewable raw materials, alkyds are making a comeback in waterborne form. Water based alkyd coatings are known to have poor shelf stability and corrosion resistance, as well as other problems during the formulation process. This project focused on comparing solvent borne to two types of water-borne alkyds, water reducible alkyds and alkyds emulsions. The purpose was to understand the differences between the three types of alkyds …

Using In Situ Liquid Single Photon Ionization Mass Spectrometry (Spi-Ms) To Probe Lithium Polysulfide Electrolyte In Motion, Aala M. Al Hasan, Jiachao Yu, Juan Yao, Vijayakumar Murugesan, Manjula Nandasiri, Xiao-Ying Yu

STAR Program Research Presentations

The solid-liquid (s-l) interface is the most common interface encountered in electrochemical systems. The s-l interface has wide applications in energy storage, catalysis, and material sciences. In situ studies of chemical reactions taking place on the s-l interfaces can further our understanding of electron transfer and link to real-world device functions under challenging conditions. Direct probing of the solid electrode and liquid electrolyte interface has been realized using a vacuum compatible electrochemical microfluidic reactor, system for analysis at the liquid vacuum interface (SALVI) with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Most recently, the electrochemical version of SALVI was integrated to …

Mida Boronates Are Hydrolysed Fast And Slow By Two Different Mechanisms, Jorge A. Gonzalez, O. Maduka Ogba, Gregory F. Morehouse, Nicholas Rosson, Kendall N. Houk, Andrew G. Leach, Paul H.-Y. Cheong, Martin D. Burke, Guy C. Lloyd-Jones

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

MIDA boronates (N-methylimidodiacetic boronic acid esters) serve as an increasingly general platform for building-block-based small molecule construction, largely due to the dramatic and general rate differences with which they are hydrolysed under various basic conditions. Yet the mechanistic underpinnings of these rate differences have remained unclear, hindering efforts to address current limitations of this chemistry. Here we show that there are two distinct mechanisms for this hydrolysis: one is base-mediated and the other neutral. The former can proceed more than three orders of magnitude faster, and involves rate-limiting attack at a MIDA carbonyl carbon by hydroxide. The alternative ‘neutral’ hydrolysis …

Electrochemical And In Situ X-Ray Absorption Fine Structure Study Of Li-Rich Cathode Materials, Meng-Yan Hou, Hong-Liang Bao, Ke Wang, Jian-Qiang Wang, Yong-Yao Xia

Journal of Electrochemistry

A series of the lithium-rich and manganese-based layered structure xLi₂MnO₃•(1-x)LiMn_1/3Ni_1/3Co_1/3O₂ (x = 0.3,0.5,0.7) materials were synthesized by a co-precipitation method, and followed by a solid-state reaction process. By comparing the first cycle efficiency, the reversible discharge capacity, the cycling stability and the voltage decay during the charge/discharge cycling process, the material with the composition of 0.5Li₂MnO₃•0.5LiMn_1/3Ni_1/3Co_1/3O₂was found to show the best electrochemical performance. The lithium storage mechanism and thermal stability of the de-lithiated compound were also investigated …

Electrochemiluminescence Immunosensor Based On Platinum Nanoparticles For The Determination Of Apolipoprotein A1, Ni Liao, Ying Zhuo, Ruo Yuan

Journal of Electrochemistry

In this paper, a novel electrochemiluminescence (ECL) immunosensor for the detection of apolipoprotein A1 was constructed based on flower-like platinum nanoparticles (PtNFs) via a one-pot chemical synthesis method. The PtNFs was used to immobilize the secondary antibody and enzyme (GOD). Then the prepared bioconjugates were introduced onto the electrode via sandwich immunoreactions. Accordingly, the ECL luminophore peroxydisulfate (S₂O₈^2-) was presented in the working buffer solution containing an appropriate amount of glucose. Through the ECL responses of S₂O₈^2- and O₂, a dramatically amplified ECL signal was obtained for the reason …

Development And Characterization Of Reagent Pencils For Microfluidic Paper Based Analytical Devices, Cheyenne H. Liu

Master's Theses

Microfluidic paper based analytical devices (microPADs) are a novel platform for point of care (POC) diagnostics. Limitations of reagent shelf life have been overcome with the introduction of reagent pencils as a method for solid-based reagent deposition. While useful, little work has been reported on the characterization and optimization of reagent pencils. Herein, an investigation on reagent pencil composition and efficiency is conducted via colorimetric release profile tests utilizing an erioglaucine disodium salt that yields a quantifiable blue colored product in the presence of water. Within this work, an investigation on the molecular weight dependence, polymer chain end functionality, and …

Quantifying The Use Of Chloroform Vapor Exposure To Improve The Adhesion Of Au Thin Films Onto Pmma, Kathleen T. Krist

Senior Honors Projects, 2010-2019

The metallization of Au onto plastics is an important processing step in applications such as the aerospace and automotive industries, the field of microelectronics, and the fabrication of microfluidic devices. While its corrosion resistance and excellent electrical and thermal conductivity make Au a useful choice, its inertness results in poor adhesion to polymer surfaces. Previous studies have indicated that exposing commercially available poly(methyl methacrylate) (PMMA) sheets to chloroform vapor following Au deposition significantly improves adhesion. In this study, we utilized electron-beam evaporation and magnetron sputtering to deposit Au thin films onto 1.50 mm thick PMMA and exposed the samples to …

Curing Of Polymer Thermosets Via Click Reactions, Mark Richard Brei

Dissertations

In the first project, an azide functional resin and tetra propargyl aromatic diamines were fabricated for use as a composite matrix. These systems take already established epoxy/amine matrices and functionalize them with click moieties. This allows lower temperatures to be used in the production of a thermoset part. These new systems yield many better mechanical properties than their epoxy/amine derivatives, but their T_gs are low in comparison.

The second project investigates the characterization of a linear system based off of the above azide functional resin and a difunctional alkyne. Through selectively choosing catalyst the linear system can show …

Immobilization Of Heteropolyacids In Silica Gel, Opeyemi Adetola

Electronic Theses and Dissertations

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using sol-gel technique. Effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were some lower as compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin’s structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 800-1100 nm excepting for W-containing sample obtained with trimethylstearylammonium chloride. …

Photocatalytic Properties Of G-C3n4–Tio2 Heterojunctions Under Uv And Visible Light Conditions, Rachel Fagan, Declan Mccormack, Steven J. Hinder, Suresh Pillai

Articles

Graphitic carbon nitride (g-C3N4) and titanium dioxide (TiO2) were chosen as a model system to investigate photocatalytic abilities of heterojunction system under UV and visible light conditions. The use of g-C3N4 has been shown to be effective in the reduction in recombination through the interaction between the two interfaces of TiO2 andg-C3N4. A simple method of preparing g-C3N4 through the pyrolysis of melamine was employed, which was then added to undoped TiO2 material to form the g-C3N4–TiO2 system. These materials were then fully characterized by X-ray diffraction (XRD), Brunauer Emmett Teller (BET), and various spectroscopic techniques including Raman, X-ray photoelectron …

An Effective Method For The Preparation Of High Temperature Stable Anatase Tio2 Photocatalysts, Rachel Fagan, Declan Mccormack, Suresh Pillai, Damian Synnott

Articles

An efficient, rapid and straightforward method for the preparation of nitrogen and fluorine (N, F) codoped high temperature stable anatase using a microwave pre-treatment is reported. Using a single source, ammonium fluoride (NH₄F) for both nitrogen and fluorine, effective doping of the precursor titanium isopropoxide (TTIP) was possible. These samples were characterised for their structural and optical properties using X-ray diffraction (XRD), Fourier transform IR (FTIR), Raman spectroscopy and UV-vis spectroscopy. In terms of the anatase to rutile transition enhancement using a novel microwave assisted technique, the sample prepared in a composition of 1:8 TiO₂: NH …

Electrochemical H2O2 Sensor Based On The Co-Immobilization Of Phosphmolybdic Acid And Graphene On Pedot Film Electrode With Nafion, Hao-Xian Zhou, Jun-Ming Zhang, Zhi-Yu Qu, Pan-Yu Zhang, You-Jun Fan

Journal of Electrochemistry

With a glassy carbon electrode (GCE) as the substrate, the poly(3,4-ethylenedioxythiophene) (PEDOT) film electrode was prepared through the electrochemical polymerization method, then a novel non-enzymatic electrochemical H₂O₂ sensor was fabricated by co-immobilizing phosphomolybdic acid and graphene with Nafion on the PEDOT/GCE electrode. The modified electrodes were characterized by scanning electron microscopy (SEM), while the responsive properties of the sensor to H₂O₂ were investigated by cyclic voltammetry and chronoamperometry. The results demonstrated that, under the optimized conditions, the sensor exhibited good electrocatalytic performance for H₂O₂ reduction. The current response of the sensor …

Adsorption Behavior Of Rhodamine 6g On Silver Surfaces Studied By Electrochemical Surface-Enhanced Raman Spectroscopy, Chan-Juan Chen, Cheng Zong, Guo-Kun Liu, Bin Ren

Journal of Electrochemistry

Rhodamine 6G (R6G) is one of the most common probe molecules employed in single molecule surface-enhanced Raman spectroscopy (SM-SERS). The study in adsorption behavior of R6G will help understand the interactions between R6G and surface. In this paper, we used electrochemical surface-enhanced Raman spectroscopy (SERS) to study the potential-dependent adsorption behavior of R6G on silver electrodes. Our results show that when the potential moved negatively, the orientation of R6G on silver surface changed from vertical to inclined adsorption. This result indicates that the abnormal SM-SERS spectra of R6G observed in the former SM-SERS studies from other research groups are due …

Electrochemical Detection Of Hydrogen Peroxide At Aunps Modified Electrode Using P-Hydroxyphenylboronic Acid As A Precursor, Chun-Yan Wang, Xiao-Qiu Liu, Ying-Xin Qi

Journal of Electrochemistry

We developed a new method for electrochemical detection of hydrogen peroxide (H₂O₂) based on boronate oxidation of p-hydroxyphenylboronic acid. This method using p-aminophenol which is produced from the reaction of H₂O₂ and p-aminophenylboronic acid as a well electrochemical probe, combined with a gold nanoparticles (AuNPs) modified electrode for an indirect detection of H₂O₂. Because of the large surface area and enhanced electrocatalytic behavior by the AuNPs modified electrode, the detection sensitivity was improved. The method could detect H₂O₂ in the concentration range of 1 ~ 100 …

Fabrication Of Riboflavin Electrochemical Sensor Based On Au Nanoparticles/Polydopamine/Carbon Nanotubes Modified Glassy Carbon Electrode, Hua-Ping Peng, Mei-Ling Yu, Xin Liu, Pan Liu, Wei Chen, Ai-Lin Liu, Xin-Hua Lin

Journal of Electrochemistry

A novel electrochemical platform for the high sensitivity detection of riboflavin was constructed by Au nanoparticles/polydopamine/carbon nanotubes (Au-PDA-MWCNTs) nanocomposite modified glassy carbon electrode. The Au-PDA-MWCNTs nanocomposite was synthesized by in situ reduction method. The characteristics of the as-prepared Au-PDA-MWCNTs nanocomposite modified electrodes were investigated by using UV-Vis spectroscopy, scanning electron microscopy (SEM) and electrochemical methods. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to study the electrochemical behavior of riboflavin (RF) at Au-PDA-MWCNTs nanocomposite modified electrodes. The results demonstrated that the present electrochemical sensor exhibited a wide linear range from 5×10^-9 mol•L^-1to 1×10^-5 mol•L …

Unraveling A Generic Growth Pattern In Structure Evolution Of Thiolate-Protected Gold Nanoclusters, Wen Wu Xu, Yadong Li, Yi Gao, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Precise control of the growth of thiolate-protected gold nanoclusters is a prerequisite for their applications in catalysis and bioengineering. Here, we bring to bear a new series of thiolateprotected nanoclusters with a unique growth pattern, i.e., Au₂₀(SR)₁₆, Au₂₈(SR)₂₀, Au₃₆(SR)₂₄, Au₄₄(SR)₂₈, and Au₅₂(SR)₃₂. These nanoclusters can be viewed as resulting from the stepwise addition of a common structural motif [Au₈(SR)₄]. The highly negative values of the nucleus-independent chemical shift (NICS) in the center of the tetrahedral Au4 …

Tuning The Electronic Properties Of Monolayer And Bilayer Ptse2 Via Strain Engineering, Pengfei Li, Lei Li, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The recently synthesized monolayer PtSe₂ belongs to the class of two-dimensional transition metal dichalcogenide (TMDC) materials (Nano Lett., 2015, 15, 4013). Based on first-principles calculations, we show that the band gaps of monolayer and bilayer PtSe₂ can be tuned over a wide range via strain engineering. Both isotropic and uniaxial strains are investigated. For bilayer PtSe₂, the vertical out-of-plane strain is also considered. In most cases, the strain can reduce the band gap except for the bilayer PtSe₂ under the isotropic strain (Ɛ≤ 4%) for which the band gap can be slightly enlarged. Importantly, the …

Unraveling A Generic Growth Pattern In Structure Evolution Of Thiolate-Protected Gold Nanoclusters, Wen Wu Xu, Yadong Li, Yi Gao, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Precise control of the growth of thiolate-protected gold nanoclusters is a prerequisite for their applications in catalysis and bioengineering. Here, we bring to bear a new series of thiolateprotected nanoclusters with a unique growth pattern, i.e., Au₂₀(SR)₁₆, Au₂₈(SR)₂₀, Au₃₆(SR)₂₄, Au₄₄(SR)₂₈, and Au₅₂(SR)₃₂. These nanoclusters can be viewed as resulting from the stepwise addition of a common structural motif [Au₈(SR)₄]. The highly negative values of the nucleus-independent chemical shift (NICS) in the center of the tetrahedral Au …

Mechanistic Study Of Pressure And Temperature Dependent Structural Changes In Reactive Formation Of Silicon Carbonate, Bingyan Qu, Dongdong Li, Lei Wang, Jili Wu, Rulong Zhou, Bo Zhang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The discovery of the silicon carbonate through chemical reaction between porous SiO₂ and gaseous CO₂ addressed a long-standing question regarding whether the reaction between CO₂ and SiO₂ is possible. However, the detailed atomic structure of silicon carbonate and associated reaction mechanism are still largely unknown. We explore structure changes of silicon carbonate with pressure and temperature based on systematic ab initio molecular dynamics simulations. Our simulations suggest that the reaction proceeds at the surface of the porous SiO₂. Increasing number of CO₂ molecules can take part in the reaction by increasing either the …

Surprising Impact Of Remote Groups On The Folding–Unfolding And Dimer-Chain Equilibria Of Bifunctional H-Bonding Unimers, Rui Liu, Shuang Cheng, Erin S. Baker, Richard D. Smith, Xiao Cheng Zeng, Rui Liu

Xiao Cheng Zeng Publications

Oligoamide 1, consisting of two H-bonding units linked by a trimethylene linker, was previously found to form a very stable, folded dimer. In this work, replacing the side chains and end groups of 1 led to derivatives that show the surprising impact of end groups on the folding and dimer-chain equilibria of the resultant molecules.

Hydrogen Bonding And Orientation Effects On The Accommodation Of Methylamine At The Air-Water Interface, Ross D. Hoehn, Marcelo A. Carignano, Sabre Kais, Chongjing Zhu, Xiao Cheng Zeng, Joseph S. Francisco, Ivan Gladich

Xiao Cheng Zeng Publications

Methylamine is an abundant amine compound detected in the atmosphere which can affect the nature of atmospheric aerosol surfaces, changing their chemical and optical properties. Molecular dynamics simulation results show that methylamine accommodation on water is close to unity with the hydrophilic head group solvated in the interfacial environment and the methyl group pointing into the air phase. A detailed analysis of the hydrogen bond network indicates stronger hydrogen bonds between water and the primary amine group at the interface, suggesting that atmospheric trace gases will likely react with the methyl group instead of the solvated amine site. These findings …

Medium-Sized Au40(Sr)24 And Au52(Sr)32 Nanoclusters With Distinct Gold-Kernel Structures And Spectroscopic Features, Wen Wu Xu, Yadong Li, Yi Gao, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We have analyzed the structures of two medium-sized thiolateprotected gold nanoparticles (RS-AuNPs) Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ and identified the distinct structural features in their Au kernels [Sci. Adv., 2015, 1, e1500425]. We find that both Au kernels of the Au₄₀(SR)₂₄ and Au₅₂(SR)₃₂ nanoclusters can be classified as interpenetrating cuboctahedra. Simulated X-ray diffraction patterns of the RS-AuNPs with the cuboctahedral kernel are collected and then compared with the X-ray diffraction patterns of the RS-AuNPs of two other prevailing Au-kernels identified from previous experiments, namely the Ino-decahedral kernel and icosahedral kernel. …

Correction: Surprising Impact Of Remote Groups On The Folding–Unfolding And Dimer-Chain Equilibria Of Bifunctional H-Bonding Unimers, Rui Liu, Shuang Chen, Erin S. Baker, Richard D. Smith, Xiao Cheng Zeng, Bing Gong

Xiao Cheng Zeng Publications

The authors regret that in the original article the spelling of one author’s surname is incorrect. The correct name of the author is ‘Shuang Chen’.

The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.