Chemistry Commons^™

Acid Treated Carbon As Anodic Electrocatalysts Toward Direct Ascorbic Acid Alkaline Membrane Fuel Cells, He-Mu Chen, Chen-Xi Qiu, Yuan-Yuan Cong, Hui-Yuan Liu, Zi-Hui Zhai, Yu-Jiang Song

Journal of Electrochemistry

In order to improve the hydrophilicity and electrocatalytic activity, commercial carbon black (BP 2000) was subjected to acid treatment to obtain acid-treated carbon (ATC). The generation of rich oxygen-containing groups on the surface of the ATC was proved by X-ray photoelectron spectra (XPS), Fourier transform-infra red spectra (FTIR), thermogravimetric analysis (TG) and contact angle measurement. UV-vis spectra were firstly recorded to calculate activation energy (Ea) of ascorbic acid (AA) chemical oxidation in alkaline conditions by oxygen in air and the Ea value was determined to be 37.1 kJ·mol^-1. Additionally, electrochemical impedance spectra (EIS) were used to evaluate unprecedented …

Pd/C Catalysts For Co2 Electroreduction To Co:Pd Loading Effect, Dun-Feng Gao, Cheng-Cheng Yan, Guo-Xiong Wang, Xin-He Bao

Journal of Electrochemistry

Nanostructured heterogeneous catalysts have been widely used in the electrochemical carbon dioxide (CO₂) reduction reaction (CO₂RR), which can simultaneously achieve the electrocatalytic conversion of CO₂ to fuels and the storage of renewable energy sources. Carbon supported palladium nanoparticles (Pd/C) catalysts have been previously reported to show excellent CO₂RR performance. However, the crucial role of the metal loading in supported electrocatalysts has been rarely reported. In this work, we study the Pd loading effect on the structure of Pd/C catalysts as well as their activity and selectivity of CO₂RR to CO. The …

Recent Progress In Pt-Based Catalysts For Oxygen Reduction Reaction, Jing Li, Xin Feng, Zi-Dong Wei

Journal of Electrochemistry

One major challenge for a large-scale commercialization of the proton-exchange membrane fuel cells (PEMFCs) technologies that enable a shift to ‘zero-emission’ personal transportation, is the expensive and unstable Pt catalysts, which are mainly used to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) occurred on the air electrode of PEMFCs. Many research works have targets to improve the stability of Pt-based catalysts and to construct Pt/transitional metal alloys with low Pt loading amount. Herein, we provide a minireview for the Pt-based ORR catalysts based on our recent work, which covers a brief background introduction, the stability improvement of …

Facile Synthesis Of Pt-Cu Alloy Nanodendrites As High-Performance Electrocatalysts For Oxygen Reduction Reaction, Liu-Xuan Luo, Guang-Hua Wei, Shui-Yun Shen, Feng-Juan Zhu, Chang-Chun Ke, Xiao-Hui Yan, Jun-Liang Zhang

Journal of Electrochemistry

Structures and compositions have significant effects on the catalytic properties of nanomaterials. Herein, a facile etching-based method was employed to synthesize Pt-Cu nanodendrites (NDs) with uniform and homogeneous alloy structures for enhancing oxygen reduction reaction (ORR). The formation of dendritic morphology was ascribed to the etching effect caused by the oxidative etchants of the Br^-/O₂ pair. The atomic ratio of Pt/Cu in Pt-Cu NDs could be easily tuned by altering the ratio of the Pt/Cu precursors, without deteriorating the dendritic morphology. The most active carbon-supported Pt₁Cu₁ NDs (Pt₁Cu₁ NDs/C) exhibited the …

Progress Of Self-Humidifying Membrane Electrode Assembly For Low Temperature Proton Exchange Membrane Fuel Cell, Bin Chi, Yue-Kun Ye, Shi-Jie Jiang, Shi-Jun Liao

Journal of Electrochemistry

The self/non-humidification membrane electrode assembly(SH-MEA)is an important pathway towards the self- humidification fuel cell and plays a crucial role for the large scale commercialization of low temperature proton exchange membrane fuel cell (LT-PEMFC), because it not only can reduce the volume and complexity of fuel cell system, resulting in the decrease of the cost, but also can improve the output power density of the fuel cell system. Currently, the researches on the self-humidifying MEA of LT-PEMFC mainly focus on three aspects: the preparation of self-humidification proton exchange membrane, the construction of self-humidification catalyst layer, and the construction of composite self-humidifying …

Palladium Adatoms On Gold Nanoparticles As Electrocatalysts For Ethanol Electro-Oxidation In Alkaline Solutions, Hui-Mei Chen, Shang-Qian Zhu, Jia-Le Huang, Min-Hua Shao

Journal of Electrochemistry

Palladium (Pd) is a good catalyst for ethanol electro-oxidation in alkaline solutions. The activity of Pd is further improved in this study by modifying the gold (Au) nanoparticles with Pd adatoms using a simple spontaneous deposition process. The Pd overlayer on the Au core (Au@Pd) is un-uniform with some Au atoms exposed to the electrolyte. The activity of Au@Pd/C toward ethanol oxidation reaction (EOR) is much higher than that of Pd/C in an alkaline solution. The peak current density of Au@Pd/C is 4.6 times higher than that of Pd/C with a 100 mV lower onset potential. The enhanced activity may …

Fuel Cells Reactor For Chemicals And Electric Energy Cogeneration, Zhi-Lin Heng, Xiao-Zi Yuan, Yi-Mei Yin, Zi-Feng Ma

Journal of Electrochemistry

As an energy conversion device, fuel cells can efficiently convert chemical energy into electrical energy. With the developing of technology, it is used as a reactor to conduct the synthesis of high value-added chemicals while generating electrical energy. Having benefits such as mild reaction conditions, controllability of the reaction process, high selectivity of the product, as well as high efficiency of energy utilization, it is widely used in many fields such as preparation of high value-added industrial products, gas separation, water treatment, etc. This paper introduces the current trends and statuses of fuel cell reactors in the cogeneration of chemicals …

Durability Performance Of The High-Power Fuel Cell System, Ke-Yong Wang, Wei-Yu Shi, Ren-Fang Wang, Jia Liu, Zhong-Jun Hou

Journal of Electrochemistry

Fuel cell durability is the crucial challenge in fuel cell vehicle, and the lifetime of more than 5000 hours is believed to be necessary for vehicle application. Few works on durability test of the full fuel cell system have been reported. In this work, the long lifetime HySYS-30 fuel cell system was developed in Sunrise Power based on the improved MEA durability and system control strategy. The durability performance of the system was investigated under vehicle duty cycle for more than 6000 hours, and only 8.1% performance loss was observed, implying that the durability of HySYS-30 fuel cell system could …

Vibrational Analysis Of A Rate-Slowing Conformational Kinetic Isotope Effect, O. Maduka Ogba, Zichen Liu, Daniel J. O'Leary

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

An enthalpy-entropy approach to analyzing a rate-slowing conformational kinetic isotope effect (CKIE) in a deuterated doubly-bridged biaryl system is described. The computed isotope effect (kH/kD = 1.075, 368 K) agrees well with the measured value (kH/kD = 1.06, 368 K). The rateslowing (normal isotope effect) nature of the computed CKIE is shown to originate from a vibrational entropy contribution defined by the twenty lowest frequency normal modes in the ground state and transition state structures. This normal entropy contribution is offset by an inverse vibrational enthalpy contribution, which also arises from the twenty lowest frequency normal modes. Zero point vibrational …

Atom-Specific Activation In Co Oxidation, Simon Schreck, Elias Diesen, Jerry Larue, Hirohito Ogasawara, Kess Marks, Dennis Nordlund, Matthew Weston, Martin Beye, Filippo Cavalca, Fivos Perakis, Jonas Sellberg, André Eilert, Kyung Hwan Kim, Giacomo Coslovich, Ryan Coffee, Jacek Krzywinski, Alex Reid, Stefan Moeller, Alberto Lutman, Henrik Öström, Lars G. M. Pettersson, Anders Nilsson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We report on atom-specific activation of CO oxidation on Ru(0001) via resonant X-ray excitation. We show that resonant 1s core-level excitation of atomically adsorbed oxygen in the co-adsorbed phase of CO and oxygen directly drives CO oxidation. We separate this direct resonant channel from indirectly driven oxidation via X-ray induced substrate heating. Based on density functional theory calculations, we identify the valence-excited state created by the Auger decay as the driving electronic state for direct CO oxidation. We utilized the fresh-slice multi-pulse mode at the Linac Coherent Light Source that provided time-overlapped and 30 fs delayed pairs of soft …

Nano-Based Systems And Biomacromolecules As Carriers For Metallodrugs In Anticancer Therapy, Mina Poursharifi, Marek T. Wlodarczyk, Aneta J. Mieszawska

Publications and Research

Since the discovery of cisplatin and its potency in anticancer therapy, the development of metallodrugs has been an active area of research. The large choice of transition metals, oxidation states, coordinating ligands, and different geometries, allows for the design of metal-based agents with unique mechanisms of action. Many metallodrugs, such as titanium, ruthenium, gallium, tin, gold, and copper-based complexes have been found to have anticancer activities. However, biological application of these agents necessitates aqueous solubility and low systemic toxicity. This minireview highlights the emerging strategies to facilitate the in vivo application of metallodrugs, aimed at enhancing their solubility and bioavailability, …

Development And Thermodynamic Analysis Of An Integrated Mild/Partial Gasification Combined Cycle (Impgc) Under Green And Brown Field Conditions With And Without Carbon Capture, Henry A. Long Iii

LSU New Orleans Theses and Dissertations

Coal is a very prominent energy source in the world, but it is environmentally unattractive due to its high sulfur and ash content as well as its alleged contribution towards climate change, but it is affordable, abundant, and has high energy content. Thus, utilizing coal in a cleaner and more efficient way has become necessary. One promising clean coal technology involves fully gasifying coal into synthesis gas, cleaning it, and feeding it into a high-efficiency combined cycle, such as an Integrated Gasification Combined Cycle (IGCC). Inspired by the recent success of warn gas cleanup (WGCU), mild and partial gasification are …

The Catalytic Mechanism Of Electron-Bifurcating Electron Transfer Flavoproteins (Etfs) Involves An Intermediary Complex With Nad+, Gerrit J. Schut, Nishya Mohamed-Raseek, Monika Tokmina-Lukaszewska, David W. Mulder, Diep M. N. Nguyen, Gina L. Lipscomb, John Patrick Hoben, Angela Patterson, Carolyn E. Lubner, Paul W. King, John W. Peters, Brian Bothner, Anne-Frances Miller, Michael W. W. Adams

Chemistry Faculty Publications

Electron bifurcation plays a key role in anaerobic energy metabolism, but it is a relatively new discovery, and only limited mechanistic information is available on the diverse enzymes that employ it. Herein, we focused on the bifurcating electron transfer flavoprotein (ETF) from the hyperthermophilic archaeon Pyrobaculum aerophilum. The EtfABCX enzyme complex couples NADH oxidation to the endergonic reduction of ferredoxin and exergonic reduction of menaquinone. We developed a model for the enzyme structure by using nondenaturing MS, cross-linking, and homology modeling in which EtfA, -B, and -C each contained FAD, whereas EtfX contained two [4Fe-4S] clusters. On the basis …

Stabilized, Hybrid Solid-State Photocatalysts For Water Purification: Preparation, Properties And Performance Under Visible Light Irradiation, Karpagavalli Ramji

Seton Hall University Dissertations and Theses (ETDs)

Stabilized heterogeneous photocatalysts that use only solar light and air have been prepared and successfully employed to decontaminate water from organic pollutants. Organic dye pollutants present, for example in textile effluents, are one of the major sources of water pollution owing to their limited biodegradability, toxicity and potential carcinogenic risks. Before certifying water for public consumption, reuse in industries or for discharge in surface water the organic pollutants must be degraded, an effort that is energy intensive and currently requires complex methodologies. We report solid-state photocatalysts that use only visible light and air to treat wastewater. Perfluoroalkyl perfluoro-substituted zinc phthalocyanine …

Lipg A Bifunctional Phospholipase/Thioesterase Involved In Mycobacterial Envelope Remodeling, Christopher Spilling, Pierre Santucci, Vanessa Point, Isabelle Poncin, Alexandre Guy, Celine Crauste, Carole Serveau-Avesque, Jean Galano, Jean-Francois Cavalier, Stephane Canaan

Chemistry & Biochemistry Faculty Works

Tuberculosis caused by Mycobacterium tuberculosis is currently one of the leading causes of death from an infectious agent. The main difficulties encountered in eradicating this bacteria are mainly related to (i) a very complex lipid composition of the bacillus cell wall, (ii) its ability to hide from the immune system inside the granulomas, and (iii) the increasing number of resistant strains. In this context, we were interested in the Rv0646c (lipGMTB) gene located upstream to the mmaA cluster which is described as being crucial for the production of cell wall components and required for the bacilli adaptation and survival in …

Side Chain Modifications To Improve Peptide Structure–Activity Relations, Neelam Lahankar

Seton Hall University Dissertations and Theses (ETDs)

While natural peptides, are ideal starting points for peptide-based drug design and development, they suffer from high conformational instability, which results in susceptibility to proteolytic degradation and poor bioavailability. Peptidomimetics in recent years has helped circumvent these shortcomings by improving the pharmacological properties of polypeptides. Peptidomimetics contain essential elements (pharmacophores) that mimic a natural peptide or protein in 3D space and retain the ability to interact with the biological target producing the same biological effect. In contrast, they offer conformationally restricted structures, potentially minimizing cross-target interactions, which leads to better transport properties through biologic membranes and resistance to immune responses. …

Advancements In Fractal Plasmonics: Structures, Optical Properties, And Applications., Gregory Q Wallace, Francois Lagugne-Labarthet

Chemistry Publications

The structural characteristics of plasmonic nanostructures directly influence their plasmonic properties, and therefore, their potential role in applications ranging from sensing and catalysis to light- and energy-harvesting. For a structure to be compatible with a selected application, it is critical to accurately tune the plasmonic properties over a specific spectral range. Fabricating structures that meet these stringent requirements remains a significant challenge as plasmon resonances are generally narrow with respect to the considered selected spectral range. Adapted from their well-established role in GHz applications, plasmonic fractal structures have emerged as architectures of interest due to their ability to support multiple …

Mass-Analyzed Threshold Ionization Of Lanthanide Imide Lnnh (Ln = La And Ce) Radicals From N–H Bond Activation Of Ammonia, Yuchen Zhang, Silver Nyambo, Dong-Sheng Yang

Chemistry Faculty Publications

Ln (Ln = La and Ce) atom reactions with ammonia are carried out in a pulsed laser vaporization supersonic molecular beam source. Lanthanide-containing species are observed with time-of-flight mass spectrometry, and LnNH molecules are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling for the Ce species. The MATI spectrum of LaNH exhibits a single vibronic band system with a strong origin band and two weak vibronic progressions, whereas the spectrum of CeNH displays two band systems …

Photophysical Characterization And Wavelength Tuning Of Natural And Synthetic Oxobacteriochlorins And Biohybrids, Don Hood

Arts & Sciences Graduate Student Theses and Dissertations

ABSTRACT OF THE DISSERTATIONPhotophysical Characterization and Wavelength Tuning of Natural and Synthetic Oxobacteriochlorins and BiohybridsByDonald L. HoodDoctor of Philosophy in ChemistryWashington University in St. Louis, 2018Dr. Dewey Holten, ChairpersonHerein is discussed the theoretical and practical unpinnings of photophysical behaviors and kinetic constants for tetrapyrrole macrocycles, to wit, porphyrins, chlorins, and bacteriochlorins. Understanding the characteristic photophysical response of tetrapyrroles to changes in environment or substituents is important to designing synthetic chromophores with tunable absorption wavelengths and for preparing useful biohybrids of natural photosynthetic light antennas combined with unnatural chromophores attached to the light antenna oligomers. Synthetic oxobacteriochlorins provide simpler synthetic pathway …

Radiolabeled Nanohydroxyapatite As A Platform For The Development Of New Pet Imaging Agents, Stacy Lee Queern

Arts & Sciences Graduate Student Theses and Dissertations

Positron emission tomography (PET) imaging utilizes drugs labeled with positron emitters to target and evaluate different biological processes occurring in the body. Tailoring medicine to the individual allows for higher quality of care with better diagnosis and treatment and is a key purpose for advancing research into developing new platforms for PET imaging agents. A PET nuclide of high interest for the development of these agents is 89Zr. This can be attributed to the long half-life of 3.27 days and low positron energy of 89Zr.In this work, we developed a production method for 89Zr using Y sputtered coins that is …

Anodic Cyclization Reaction: Manipulation Of Reaction Pathway And Efforts To Radical Cation And Radical Intermediate, Ruozhu Feng

Arts & Sciences Graduate Student Theses and Dissertations

In recent years, synthetic chemists have been expressing significant interest in electro-organic synthetic methods. This interest is being fueled by the existence of an increasing number of successful methods in the literature and the availability of new electrochemical equipment that removes the barrier to attempting an electrolysis reaction for the first time. Yet while these developments have fueled growth in some areas of electro-organic synthesis (the recycling of chemical catalysts for example), other areas remain underdeveloped. One such area is the exploration of reactions that can be triggered directly as an electrode surface without the use of any chemical reagent. …

Mechanisms For The Incorporation And Distribution Of Radionuclides In Near-Surface Fallout, Marc Alan Fitzgerald

UNLV Theses, Dissertations, Professional Papers, and Capstones

Fallout is the radioactive glass formed from a mixture of vaporized anthropogenic materials with proximate environmental material. These glassy byproducts constitute a compositional record of environmental materials such as soil and vapor precursors that are responsible for chemical heterogeneity in the glasses. The work of this dissertation is to untangle these different sources of compositional heterogeneity, distinguishing low-abundance vaporized anthropogenic-rich material from natural compositions, in order examine soil behavior and chemical evolution during fallout formation. Unfortunately, mixing convolutes the multivariate elemental relationships in these melts due to overlapping element abundances that might distinguish different source materials and chemical behaviors, making …

Optimization Of Useful Hard X-Ray Photochemistry, David Lewis Goldberger

UNLV Theses, Dissertations, Professional Papers, and Capstones

X-ray induced damage is generally considered a nuisance, but in the field of Useful Hard X-ray Photochemistry we harness the highly ionizing and penetrating properties of hard X-rays (> 7 keV) to initiate novel photochemical decomposition and synthesis at ambient and extreme conditions. Preliminary experiments suggest that the energy of irradiating photons and the sample pressure play roles in determining the nature of X-ray induced damage. Here, we present the X-ray energy dependence of damage induced in strontium oxalate, strontium nitrate, and barium nitrate, as well as the pressure dependence of X-ray induced damage of strontium oxalate. Our results indicate …

Kcnq1/Kcne1 Interaction In The Cardiac Iks Channel And Its Physiological Consequences, Jiajing Xu

McKelvey School of Engineering Graduate Student Theses & Dissertations

Dynamic conformational changes of ion channel proteins during activation gating determine their function as carriers of current. The relationship between these molecular movements and channel function over the physiological timescale of the action potential (AP) has not been fully established due to limitations of existing techniques. We constructed a library of possible cardiac IKs protein conformations and applied a combination of protein segmentation and energy linearization to study this relationship computationally. Simulations reproduced the effects of the beta-subunit (KCNE1) on the alpha-subunit (KCNQ1) dynamics and function, observed in experiments. Mechanistically, KCNE1 increased the probability of “visiting” conducting pore conformations on …

Mechanisms Of Calcium Phosphate Mineralization On Biological Interfaces And Their Engineering Applications, Doyoon Kim

McKelvey School of Engineering Graduate Student Theses & Dissertations

All living organisms utilize phosphorus (P) as an essential component of their cell membranes, DNA and RNA, and adenosine triphosphate. Bones, in addition to bearing loads, play an important role in balancing P levels in our bodies. In bones, a network of collagen templates and calcium phosphate (CaP) nanocrystals builds hierarchical levels, from nano- to macroscale. Within this architecture, the thermodynamic properties of CaP minerals are influential. Despite the importance of nucleation, growth, and crystallization in collagen structures for tissue development, little kinetic study of these processes has been conducted due to the limited in situ techniques for monitoring these …

Syntheses Of A Tin (Iv) Meso-Tetra(4-Pyridyl) Porphyrin Dichloride-Tetrachlorobis (Bipy)2 Ruthenium (Ii) Complex And Studies Of Photophysical Properties Of 1-Nitropyrene, Phillip Sharp

Electronic Theses and Dissertations

Development of a photosensitizer that can work in both aerobic and anaerobic environments would increase the robustness of the cancer treatment known as photodynamic therapy. The development of a photosensitizer was first attempted by synthesizing a tin (IV) meso-tetra (4-pyridyl) porphyrin dichloride-tetrachlorobis (Bipy)₂ ruthenium (II) complex. The synthesize of the tin porphyrin was done by a method from literature and had a percent error of 31.58 and 37.31 when comparing the theoretical percentages of carbon (55.39) and nitrogen (12.92) meaning that photosensitizer was not synthesized.

The second type of chromophore that was studied was 1-nitropyrene do determine if it …

Inequality, Rubber, And Thermodynamics In Indonesia, Ernest M. Oleksy

The Downtown Review: An Interdisciplinary Journal Written and Peer-Reviewed by Mandel Honors College Students at Cleveland State University

Intersectionality has led the charge in ensuring that workplace justice is assured to all people, irrespective of their identities. While intersectionality is a useful theory for explaining inequality, what must not be understated is the contributions that postcolonialism and the blue-collar working identity can have on harsh working conditions. Particularly, miners in Indonesia have had to work in very hostile environments where they are at-risk for sulfur poisoning as they mine for materials to vulcanize rubber. This article serves two purposes. The first is to call attention to how place can help explain the differential experiences of miners in the …

The Chemical Causes And Social Effects Of Acid Rain, Ernest M. Oleksy

The Downtown Review: An Interdisciplinary Journal Written and Peer-Reviewed by Mandel Honors College Students at Cleveland State University

While global warming tends to dominate the collective conscious for environmentalism of academics and the public alike, many other physical phenomena bear serious implications for humanity's future. One such phenomenon, acid rain, has been under-reported considering how damaging it is to the ecosystem and how much politicking is involved when determining how to address it. This article serves two purposes. The first is to inform readers of the basic chemical processes underlying acid rain and why it is damaging to organisms. The second is to inform readers of how acid rain has been portrayed by other publications, like the National …

The Value Of Commodity Products Based On Furfural In The National Economy (Review), M. Аkhмаdaliev, I. Аskarov

Scientific journal of the Fergana State University

The article describes the methods of obtaining furfuralis by recycling of vaste and importance of goods production’s on the base of furfuralis for economy

The Value Of Checking An Infrared Spectrophotometer According To The Program Of Metrological Certification For The Correct Classification Of Motor Oils By Their Chemical Composition, М. Imomova, B. Аbduganiev

Scientific journal of the Fergana State University

In this article the questions of determining the chemical composition of the motor oils after the metrological certification of infrared spectrophotometer are elucidated