Analytical Chemistry Commons^™

Ionic Liquid Enhanced Proton Transfer For Neutral Oxygen Evolution Reaction, Ming-Xing Chen, Nian Liu, Zi-He Dua, Jing Qi, Rui Cao

Journal of Electrochemistry

The development of highly active catalyst in pH-neutral media for oxygen evolution reaction (OER) is critical in the field of renewable energy storage and conversion. Nevertheless, the slow kinetics of proton-coupled electron transfer (PCET) hinders the overall OER efficiency. Herein, we report an ionic liquid (IL) modified CoSn(OH)₆ nanocubes (denoted as CoSn(OH)₆-IL), which could be prepared through a facile strategy. The modified IL would not change the structural characteristics of CoSn(OH)₆, but could effectively regulate the local proton activity near the active sites. The CoSn(OH)₆-IL exhibited higher intrinsic OER performances than the pristine …

Single Nanobubble Formation On Au Nanoelectrodes And Au@Ws2 Nanoelectrodes: Voltammetric Analysis And Electrocatalysis, Xian-Zhun Luo, Xiao-Hu Chen, Yong-Xin Li

Journal of Electrochemistry

Taking advantage of the extremely small size of the gold nanodisk electrode, the single hydrogen nanobubble generated on the surface of the nanoelectrode was studied to evaluate its hydrogen evolution performance. It was found that compared with the bare gold nanodisk electrode, the bubble formation potential of the gold nanodisk electrode modified with tungsten disulfide quantum dots (WS₂ QDs) on the surface was more positive, indicating that its hydrogen evolution activity was higher. Microdynamic model analysis shows that the average standard rate constant of the rate-determining step of the hydrogen evolution reaction of gold nanoelectrodes modified with WS_{2 …}

Electrochemical Advanced Treatment Of Desulfurization Wastewater From Coal-Fired Power Plants, Ju-Cai Wei, Juan Yi, Xu Wu

Journal of Electrochemistry

Zero-emission of desulfurization wastewater is one of the main demands for coal-fired power plants. As typical high salinity wastewater, it is hard to purify the desulfurization wastewater from coal-fired power plants through traditional physicochemical treatment or biochemical treatment, e.g., COD and Cl^–. A high concentration of Cl^– ion in desulfurization wastewater restricts wastewater reuse and zero-emission. Electrochemical technology is an attractive method for high salinity wastewater zero-emission, which provides a versatile, efficient, cost-effective, easily automatable, and clean industrial process. For advanced treatment of effluent after triple box process treatment in power plants, this paper reports an electrochemical …

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 …

Facile Nitrogen-Doping Of Screen-Printed Carbon Electrodes For Detection Of Hydrogen Peroxide, Emmanuel Nkyaagye

Electronic Theses and Dissertations

Screen-printed carbon electrodes (SPCEs) have garnered much attention as sensors due to their simplicity and relatively low cost. However, to impart necessary selectivity and sensitivity for specific applications, modification of the SPCE surface, which can involve time-consuming procedures or costly equipment/materials, is typically required. Here, a simple nitrogen-doping process based on NH₄OH was used to modify SPCEs prepared from commercially available ink for electrochemical detection of H₂O₂, a common target for biosensing strategies and indicator of cell stress. XPS studies showed that NH₄OH treatment of SPCEs led to a nearly 5-fold increase …

Electrochemical Impedance Spectroscopy For Electrocatalytic Interfaces And Reactions: Classics Never Die, Jun Huang

Journal of Electrochemistry

This review article recapitulates electrochemical impedance spectroscopy (EIS) studies in the field of electrocatalysis. The history of this specialized field, ranging from the beginning of the twentieth century to now, is outlined. We then chronicle milestones of the impedance theory. Special emphases are put on the Dolin-Ershler model, the prevailing model for analyzing adsorption impedance data. Afterwards, we narrow into a very specific and fundamental topic, the double-layer capacitance at platinum (Pt) single crystals. We discuss the challenges in experimentation and theoretical understanding thereof. We cast doubts into the validity of using the Dolin-Ershler model to obtain the double-layer capacitance …

Immobilization Of Electrocatalytically Active Gold Nanoparticles On Nitrogen-Doped Carbon Fiber Electrodes, Daniel Mawudoku

Electronic Theses and Dissertations

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a …

Carbon Quantum Dots: Bridging The Gap Between Chemical Structure And Material Properties, Timothy J. Pillar-Little Jr.

Theses and Dissertations--Chemistry

Carbon quantum dots (CQDs) are the latest generation of carbon nanomaterials in applications where fullerenes, carbon nanotubes, and graphene are abundantly used. With several attractive properties such as tunable optical property, edge-functionalization, and defect-rich chemical structure, CQDs have the potential to revolutionize optoelectronics, electro- and photocatalysis, and biomedical applications. Chemical modifications through the addition of heteroatoms, chemical reduction, and surface passivation are found to alter the band gap, spectral position, and emission pathways of CQDs. Despite extensive studies, fundamental understanding of structure-property relationship remains unclear due to the inhomogeneity in chemical structure and a complex emission mechanism for CQDs.

This …

Homogeneous Ligand-Centered Hydrogen Evolution And Hydrogen Oxidation : Exploiting Redox Non-Innocence To Drive Catalysis., Andrew Z. Haddad

Electronic Theses and Dissertations

Hydrogen is a promising carbon-free fuel / energy carrier and is an essential building block for many industrial and agricultural processes. Rising energy demands have ignited interest in the development of carbon-free and carbon neutral energy sources. In this context, hydrogen is an attractive candidate—being energy-dense, carbon-free—and easily accessible through a two-electron reduction of water. Accordingly, many electrochemical homogeneous catalyst systems have been studied, with a focus on understanding the mechanism of hydrogen evolution proceeding through metal-hydride intermediates. However, there has been a renaissance in hydrogen evolution reaction (HER) catalyst design, with many groups implicating ligand redox non-innocence as a …

Electrochemical Nanoprobes For Electron Transfer Kinetics And Electrocatalysis Study, Yun Yu

Dissertations, Theses, and Capstone Projects

The studies of electrochemical processes on the nanoscale have led to a significant progress in understanding of electrochemical mechanisms and characterization of nanomaterials in the fields of energy, catalysis, and biological research. Electrochemical experiments at nanoscale require the fabrication and characterization of nanometer-sized electrochemical probes. The main advantages of the nanoprobes include very fast mass-transfer rate, high signal-to-noise ratio and extremely fine spatial resolution of electrochemical imaging. In the course of my Ph.D. research, different types of electrochemical probes were developed for measuring electron-transfer kinetics, probing single catalytic nanoparticles and sampling ultra-small volume of liquids.

We developed methodologies to fabricate …

Electrochemical And Spectroscopic Studies Of Ethanol Oxidation On Nano-Cubic Pt Modified By Tin Adatoms, Lu Rao, Bin-Wei Zhang, Yan-Yan Li, Yan-Xia Jiang, Shi-Gang Sun

Journal of Electrochemistry

The nano-cubic Pt modified by tin (Sn) was synthesized and used to investigate the role of this adatom played in the ethanol oxidation. The onset potential of ethanol oxidation was significantly shifted negatively which can be forward about 300 mV when the coverage of Sn (θSn)was 0.9. The electrtochemical in situ FTIR result demonstrated that the amount of CO₂ increased first, and then decreased with θSn increased, and reached the maximun when θSn was 0.38. Furthermore, the formation of acetic acid could be observed at very low potential (-0.05 V) after modifying Sn adatom, and the amount of acetic …

An In Situ Ftir Spectroelectrochemical Study On Methanol Oxidation At Pt-Mo2C/Gc Catalyst, Hai-Ping Huang, Xi-Yu Yao, Pei-Kang Shen

Journal of Electrochemistry

A 40% Pt on Mo₂C/GC catalyst has been prepared by ion exchange method. The mechanism of methanol electrooxidation on Pt-Mo₂C/GC and commercial Pt/C catalysts in acidic media was studied by cyclic voltammetry, XRD measurements and in-situ Fourier transform infrared spectroelectrochemistry. The results revealed that the Pt nanoparticles were uniformly dispersed on Mo₂C/GC with an average particle size of 3 nm. The cyclic voltammetric and chronopotentiometric experiments indicated that Pt-Mo₂C/GC catalyst exhibited a better performance for methanol oxidation than that of Pt/C in acid solution. A negative shift over 90 mV of the …

Development Of Dehydrogenase-Based Bioanode Using Poly(Phenosafranin)-Functionalized Swcnt Nanocomposites And Its Application To Ethanol Biosensor, S. Saleh Farhana, Okajima Takeyoshi, Lanqun Mao, Takeo Ohsaka

Journal of Electrochemistry

A New type of dehydrogenase-based amperometric ethanol biosensor was constructed using alcohol dehydrogenase (ADH) which was immobilized on the edge-plane pyrolytic graphite (EPPG) electrode modified with poly(phenosafranin)-functionalized single-walled carbon nanotube (PPS-SWCNT). The PPS-SWCNT modified EPPG electrode was prepared by electropolymerization of phenosafranin on the EPPG electrode which was previously coated with SWCNT. The performance of the ADH/PPS-SWCNT/EPPG electrode was evaluated using cyclic voltammetry and amperometry in the presence of ethanol. The fabricated ethanol biosensor provided a reasonable sensitivity of 2.0 μA cm–2 mM–1 and a low detection limit (36 μM) for the electrocatalytic oxidation of ethanol with a linear concentration …

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 …

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 …