Physical Chemistry Commons^™

Minimalistic Supramolecular Proteoglycan Mimics By Co-Assembly Of Aromatic Peptide And Carbohydrate Amphiphiles, Alexandra Brito, Yousef M. Abul-Haija, Diana Soares De Costa, Ramon Novoa-Carballal, Rui L. Reis, Rein V. Ulijn, Ricardo A. Pires, Iva Pashkuleva

Advanced Science Research Center

We report the co-assembly of aromatic carbohydrate and dipeptide amphiphiles under physiological conditions as a strategy to generate minimalistic proteoglycan mimics. The resulting nanofibers present a structural, fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) core and a functional carbohydrate (Fmoc-glucosamine-6-sulfate or -phosphate) shell. The size, degree of bundling and mechanical properties of the assembled structures depend on the chemical nature of the carbohydrate amphiphile used. In cell culture medium, these nanofibers can further organize into supramolecular hydrogels. We demonstrate that, similar to proteoglycans, the assembled gels prolong the stability of growth factors and preserve the viability of cultured cells. Our results demonstrate that this approach …

Atlas Of Experimental And Theoretical High Temperature Methane Cross Sections From T = 295 To 1000k In The Near-Infrared, Andy Wong, Peter F. Bernath, Michael Rey, Andrei V. Nikitin, Vladimir G. Tyuterev

Chemistry & Biochemistry Faculty Publications

Spectra of hot methane were recorded using a tube furnace and a high-resolution Fourier transform spectrometer. We obtained experimental absorption spectra in the 1.85-1.11 μm near-infrared region at eight temperatures ranging from 295 K up to 1000 K. We have converted these into an atlas of absorption cross sections at each temperature for the methane tetradecad, icosad and triacontad polyads, excluding some spectral intervals either strongly contaminated by water or due to baseline fringes. On the theoretical side, the spectra were simulated from the ab initio-based Reims-Tomsk TheoReTS line list for the same experimental conditions. This line list has been …

High Level Thermochemical And Spectroscopic Computations For Molecules Relevant To Combustion And The Atmosphere, Bradley K. Welch

Doctoral Dissertations

"Computational thermochemistry can be a complicated multistep process, but in recent years has become an equal partner with experiment. Many important molecules in combustion systems or in the atmosphere (such as short-lived radicals) are difficult to study experimentally. Predicting highly accurate thermochemistry is a key aspect in understanding these species. In this project, computational thermochemistry was developed into an automated streamlined procedure and then used to understand the methyl and ethyl peroxy families of radicals. This effort involved optimizing a standard workflow for computational thermochemistry. Computational thermochemistry generally requires numerous individual calculations whose cost and scalings vary widely. Conducting such …

The Benefit Of Precise Chemical Shift And Concentration Referencing In Nmr Applications, Ming Huang

Doctoral Dissertations

“In Nuclear Magnetic Resonance (NMR) spectroscopy, the chemical shift and intensity of NMR signals provide critical information about a sample's molecular structure, reaction conditions, and material properties. For the precise determination of structures and properties, it is critical to know sample or reaction conditions such as temperature, pH, concentration, or absolute amount of material. Chemical-shift and signal-intensity calibrations play a key role for extracting the maximum amount of information from NMR experiments. In this dissertation, internal and external reference standards are used to calibrate NMR spectra with respect to chemical shift and signal intensity. Sealed capillary tubes filled with specific …

Accurate Monitoring Of X, Y, And Z Magnetization For Analysis Of Hardware And Pulse Sequence Performance In Nmr Spectroscopy, Emmalou Theresa Schmittzehe

Doctoral Dissertations

"A new nuclear magnetic resonance (NMR) imaging protocol has been developed to independently record the x, y, and z components of the nuclear net magnetization at any point in a pulse sequence while eliminating the observation of the other components. This protocol provides an experimental method of tracking magnetization which then can be used in conjunction with theoretical models to scrutinize the predicted outcome of each step in an NMR pulse sequence and potentially find further improvements to their effectiveness and efficiency. The protocol utilizes a rapid rotating-frame imaging pulse-train technique to obtain RF-field (B₁) and resonance-offset (ΔB …

Non-Covalent And Covalent Interactions Between Phenylacetylene And Quinoline Radical Cations With Polar And Non-Polar Molecules In The Gas Phase, Adam C. Pearcy

Theses and Dissertations

Gas phase molecular clusters present an ideal medium for observing factors that drive chemical reactions without outside interferences from excessive solvent molecules. Introducing an ion into the cluster promotes ion-molecule interactions that may manifest in a variety of non-covalent or even covalent binding motifs and are of significant importance in many fields including atmospheric and astronomical sciences. For instance, in outer space, molecules are subject to ionizing radiation where ion-molecule reactions become increasingly competitive to molecule-molecule interactions. To elucidate individual ion-molecule interaction information, mass spectrometry was used in conjunction with appropriate theoretical calculations.

Three main categories of experiment were conducted …

Metal Nanoparticle Synthesis By Photochemical Reduction With A High-Intensity Focused Laser Beam, Victoria K. Meader

Theses and Dissertations

Colloidal, metallic nanoparticles have myriad applications, but they are most ideal when they are monodisperse, and demonstrate maximum catalytic utility when they are small (< 5 nm) and uncoated; because their surface area is accessible and maximized. Laser- assisted metal nanoparticle synthesis is a ‘green’ method that has become a topic of active research because it is able to produce uncoated or ‘naked’ products. The nanoparticles synthesized in this work were formed through the reduction of metal salts in aqueous solutions; but the reducing agent is an electron-dense microplasma generated by the laser pulse interacting with the media. Because no chemical reducing agents or stabilizers are needed, the products have no surfactants.

The underlying reaction mechanisms that drive this type of synthesis are generally understood, however, there is insufficient detail that would allow control over the formation of ultimate product morphologies and size distributions. The metals examined in this thesis are: gold, whose formation follows an autocatalytic rate law; and silver, whose formation follows a first-order rate law. Through my research, I was able to …

Adhesion At Solid/Liquid Interfaces, Neda Ojaghlou

Theses and Dissertations

The adhesion at solid/liquid interface plays a fundamental role in diverse fields and helps explain the structure and physical properties of interfaces, at the atomic scale, for example in catalysis, crystal growth, lubrication, electrochemistry, colloidal system, and in many biological reactions. Unraveling the atomic structure at the solid/liquid interface is, therefore, one of the major challenges facing the surface science today to understand the physical processes in the phenomena such as surface coating, self-cleaning, and oil recovery applications. In this thesis, a variety of theory/computational methods in statistical physics and statistical mechanics are used to improve understanding of water adhesion …

Temperature-Dependent Kinetic Studies Of Arsenicals Adsorption From Solution To Hematite Nanoparticles, Sara Soldoozy

Theses and Dissertations (Comprehensive)

Surface chemistry is the study of the chemical and physical phenomena that transpire at interfaces such as liquid-solid, solid-gas, liquid-gas, and liquid-liquid. To study the reactions occurred at the surfaces, surface sensitive techniques come to play. Adsorption of arsenical compounds (liquid adsorbate), particularly arsenate (iAs) and dimethylarsinic acid (DMA), to the surface of iron bearing materials (solid adsorbent) that frequently are found in geosorbents such as hematite (Fe₂O₃) has been studied in this thesis. Arsenical compounds can pollute the environment through natural sources and anthropogenic activities, and ultimately contaminate water. Absorbing these pollutants to a material …

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 …

Constructions Of Noble Metal Nanocrystals With Specific Crystal Facets And High Surface Area, Qiao-Li Chen, Hui-Qi Li, Ya-Qi Jiang, Zhao-Xiong Xie

Journal of Electrochemistry

Noble metal nanocrystals (NCs) have widespread applications in catalysis. Their catalytic performances are strongly related to the surface structures while the atomic utilization efficiency of noble metal is considerably correlated with the surface area. Thus, advantages of both specific surface structure and large surface area are highly required to show off simultaneously so as to optimize the catalytic performance and decrease the usage of noble metal. However, it seems that the two advantages are incompatible with each other in one NC since it is difficult for small NCs to keep their specific facets, while NCs with specific surface structure usually …

Stabilization Strategies Of Pt Catalysts Forproton Exchange Membrane Fuel Cells, Da-Ping He, Shi-Chun Mu

Journal of Electrochemistry

The low service lifetime of proton exchange membrane fuel cells (PEMFCs) is the main bottleneck for their commercial applications. One of the main factors is that the expensive metal Pt catalyst is easy to degradation under the harsh working environment of PEMFC (such as variable voltage, strong acidity, gas-liquid two-phase flow), which leads to the inevitable decay of the catalytic performance, thus, seriously restricting the lifetime of PEMFC. Therefore, the electrochemical stability of Pt-based electrocatalysts has become an important and hot topic to improve the PEMFC lifetime. In this paper, we review the recent development in enhancing the stability of …

The Pilot Application Of Electrochemical Impedance Spectroscopy On Dynamic Proton Exchange Membrane Fuel Cell, Jian-Wei Guo, Jian-Long Wang

Journal of Electrochemistry

By analyzing Electrochemical Impedance Spectroscopy (EIS) in applications of dynamic proton exchange membrane fuel cell (PEMFC), bottlenecks which restrict EIS tool development have been pointed out in this paper. Though the high-frequency resistance in EIS is largely accepted as cell inner-resistance, this can only be applied for cell with low current. The low-frequency resistance is difficult to be realized due to its relation with mass transfer. Furthermore, the improved Randles equivalent circuits are built up preliminarily, thus, penetrating into studies for mass transfer reaction, cell operation/degeneration, and high temperature fuel cell. Inspiringly, EIS is becoming an analyzing tool for stack …

Caging Porous Co-N-C Nanocomposites In 3d Graphene As Active And Aggregation-Resistant Electrocatalyst For Oxygen Reduction Reaction, Lu-Yang Xiu, Meng-Zhou Yu, Peng-Ju Yang, Zhi-Yu Wang, Jie-Shan Qiu

Journal of Electrochemistry

Oxygen reduction reaction (ORR) is the cornerstone reaction of many renewable energy technologies such as fuel cells and rechargeable metal-air batteries. The Pt-based electrocatalysts exhibit the highest activity toward ORR, but their large implementation is greatly prohibiting by unaffordable cost and inferior durability. During electrode manufacturing and electrochemical reaction, severe aggregation of catalyst nanoparticles induced by size effect further limits the operational performance of electrocatalysts. We report a new strategy for fabrication of active and aggregation-resistant ORR electrocatalyst by caging metal-organic frameworks derived Co-N-C nanocomposites in permeable and porous 3D graphene cages via sprayed drying the mixed colloids of ZIF-67 …

Voltage Distribution Of Self-Humidifying Air-Cooled Pemfc, Kai-Feng Tan, Wei-Rong Chen, Ming Han, Xue-Xia Zhang

Journal of Electrochemistry

In this work, the self-adaptive characteristics of self-humidifying air-cooled PEMFC stack was investigated. The performance and the unit-cell voltage distribution of the stack were measured and analyzed through the unit-cell I-V curve fitting. The operating conditions for this experimental study were set as follows: hydrogen pressure at the anode was 2 bar, the fan power used for the reactant oxygen feed and stack cooling was at 0.3 W, and the duration and time gap of water purged from hydrogen chamber were 1 s and 10 s, respectively. The experimental results showed that the self-humidifying air-cooled PEMFC stack used for this …

Research Progress In Hydrogen Evolution Low Noble/Non-Precious Metal Catalysts Of Water Electrolysis, Yang Li, Zhao-Yan Luo, Jun-Jie Ge, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

Hydrogen energy technology with hydrogen as an energy carrier is gaining more and more attention due to its cleanliness and high energy density. Hydrogen fuel cell vehicles have been listed as one of the ultimate energy technologies in the 21st century. Among them, sustainable hydrogen production technology is a necessary prerequisite for the future development of hydrogen energy economy. Electrolyzed water technology driven by renewable resources represents an important way to support the sustainable development of hydrogen energy economy. The development and utilization of high activity, low cost hydrogen evolution catalysts is a key factor in improving the efficiency and …

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 …

Special Issue In Honor Of Professor Baolian Yi On His 80th Birthday, Chinese Society Of Electrochemistry (Cse)

Journal of Electrochemistry

No abstract provided.

A Review Of Proton Exchange Membrane Fuel Cell Catalyst Layer By Electrospinning, Yong Liu, Han Ding, De-Chun Si, Jie Peng, Jian-Bo Zhang

Journal of Electrochemistry

The limitation of catalyst layer for proton exchange membrane fuel cell (PEMFC) in cost, durability and performance constitutes the bottleneck for the commercialization of fuel cell vehicles. Electrospun catalyst layer, with high catalyst utilization, increased triple phase boundary (TPB) and triple phase channel (TPC), has been developed by many researchers. This paper reviews the research progress in the electrospun catalyst layer for PEMFC, combined with the author’s work. Firstly, the development progress of catalyst layer is summarized, and the catalyst layer is classified and analyzed based on its fabrication method and structure character. Next, the fabrication process, physical property characterization, …

Fuel Cell Performance Curve After Mea Optimization Structural Optimization Of Low Pt Membrane Electrode Assembly, Yan Rao, Shang Li, Fen Zhou, Tian Tian, Qing Zhong, Zhao-Hui Wan, Jin-Ting Tan, Mu Pan

Journal of Electrochemistry

Membrane electrode assemblies (MEAs) are the key component of proton exchange membrane fuel cell. For a long time, much attention has been paid to develop MEA technology. At present, the research, development and industrialization of fuel cell has entered a new era. More strict requirements for MEA, especially for the reduction of Pt loading with a challenging target of 0.125 mg·W^-1 have to be met. In this paper, the performance losses under low Pt loading are analyzed in terms of activation polarization, ohm polarization and mass-transfer polarization. It is proposed that research should be focused on the activity of …

Morphological Control Of Ptcu2 Octahedron And Oxygen Reduction Electrocatalytic Performance Of Ptcu For Fuel Cell, Long-Sheng Cao, Lei Wan, Zhi-Gang Shao, Hong-Mei Yu, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Platinum acetylacetonate (Pt(acac)₂) and copper acetylacetonate (Cu(acac)₂) were co-reduced to prepare PtCu₂ octahedron alloy catalyst in N,N-dimethylformamiade by solvothermal method. The PtCu₂ showed lattice compression, and high ratio of non-oxidized Pt with high electronic binding energy. All those structural features contributed to weak adsorption strength of oxygen species on Pt and lower d-band centre position. The influence of structure-directing agent on morphology of PtCu alloy was systematically studied. In the half cell test, as a result of the uniform morphology and regular octahedron of PtCu₂ formed, the mass activity and area specific activity …

Effects Of So2 In Air On Performance Of Direct Methanol Fuel Cell, Bin Qin, Fen-Ning Jing, Xue-Jing Sun, Gong-Quan Sun, Hai Sun

Journal of Electrochemistry

Direct methanol fuel cells (DMFC) generally use oxygen as an oxidant. Contaminants such as sulfides and nitrides in the air can affect the performance of the DMFC. In this work, the effects of SO₂ on the performance of DMFC were investigated and the mechanism of poisoning was analyzed, by means of constant current discharge curve, polarization performance curve, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In the CV scan, the permeated methanol was oxidized at a low potential to eliminate its effect on the SO₂ poisoning behavior test. The results showed that the SO₂ poisoning resulted …

Fe-N Doped Hollow Carbon Nanospheres Linked By Carbon Nanotubes For Oxygen Reduction Reaction, Ya-Lin Zhang, Chi Chen, Liang-Liang Zou, Zhi-Qing Zou, Hui Yang

Journal of Electrochemistry

The development of non-precious metal catalysts for oxygen reduction reaction (ORR) is essential for large-scale application of proton exchange membrane fuel cells. Herein, we present the in situ formed Fe-N doped hollow carbon nanospheres linked by carbon nanotubes composite, synthesized by using ZIF-8 as sacrificed template to form polydopamine (PDA) hollow nanospheres, followed by complexing with FeCl₃, high temperature heat-treatment and NH₃-etching. ZIF-8 was gradually decomposed simultaneously with PDA coating due to the loss of Zn²⁺ grabbed by PDA. NH3 etching resulted in the improved surface area, while the reducibility of NH₃ resulted in …

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 …

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 …

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 …