Physical Chemistry Commons^™

Engineering Multifunctional And Morphologically Diverse Polymer Brush Surfaces, Cassandra M. Reese

Dissertations

The combination of surface-initiated polymerization (SIP) and post-polymerization (PPM) serves as a powerful approach to fabricate complex, multifunctional polymer films, which can be precisely tuned for desired surface engineering applications. Careful manipulation of PPM parameters such as reaction conditions, the tethered brush parameters, and the physical properties of the unbound post-modifier greatly influence the depth of penetration of the post-modifier and the polymer brush compositional heterogeneity. This dissertation focuses on engineering polymer brush surfaces with multifunctional chemistries and tunable morphologies by investigating the PPM parameters that dictate the distribution of post-modifiers on grafted polymer brush surfaces.

The first chapter of …

Experimental And Computational Study On Magnetic Nanowires Of Layered Titanates, Caleb Layne Heath

Graduate Theses and Dissertations

The intricate nanostructures of layered titanates are unique among nanomaterials due to their easy and inexpensive syntheses. These nanomaterials have been proven valuable for use in industries as varied as energy, water treatment, and healthcare, and can be produced at industrial scales using already existent equipment. They have complex morphology, and surface structure well suited to chemical modification and doping. However, there is a longstanding debate on their lattice structure after the doping. There is a long-unmet need to understand, using both experimental and simulation methods, how dopants alter the clay-like layered crystal structure and associated physical and chemical properties. …

Surface-Enhanced Infrared Absorption Spectroscopy- Surface Sensitive In Situ Label-Free Spectroelectrochemistry, Lie Wu, Jian-Long Sun, Xiu-E Jiang

Journal of Electrochemistry

Surface-enhanced infrared absorption spectroscopy (SEIRAS), especially in attenuated total reflectance (ATR) mode, taking advantages of surface-enhancement and near-field optical effect of enhancing substrate, is a ultra-sensitive infrared spectroscopy, which could achieve surface-selected detection at a sub-monolayer level. Since the enhancing substrate could simultaneously serve as a working electrode, ATR-SEIRAS is a readily surface-sensitive in situ label-free spectroelectrochemistry technique. With the advantages of small influence from metal species on enhancement effect, good potential reversibility of spectra, simple surface selection rule and sensitivity to polar molecules, ATR-SEIRAS has been widely applied in the fields of orientation analysis and species identification of interfacial …

High-Efficiency Nitrite Sensor Based On Cop Nanowire Array, Fu-Ling Zhou, Xiao-Li Xiong, Xu-Ping Sun

Journal of Electrochemistry

Nitrite has a negative impact on the environment and human health. The long-term consumption of nitrite-containing foods has a carcinogenic risk. Therefore, the analysis and detection of nitrite are important. It is of great significance to develop high-efficiency electrocatalysts to achieve high sensitivity and selectivity for nitrite detection. The cobalt phosphide nano-array (CoP/TM) was obtained by hydrothermal and low-temperature phosphating. The electrochemical test results show that the constructed CoP/TM was a highly efficient electrochemical reduction nitrite catalyst with the excellent sensing performance and response time less than 3 s, as well as the linear detection range of 1.0 μmol·L^{-1 …}

Preparation And Capacitive Property Of Two-Dimensional Multilayer Ti3C2TX-Mxene/Ppy-Nw Composite Material, Lu Chen, Xuan Jian, Min He, Mi-Mi Zhang, Xiao-Die Chen, Lou-Jun Gao, Zhen-Hai Liang

Journal of Electrochemistry

In this paper, the two-dimensional multilayered Ti₃C₂T_x-MXene was obtained by hydrofluoric acid etching method on the bulk phase material MAX(Ti₃AlC₂) substrate. The two-dimensional multilayered Ti₃C₂T_x-MXene/PPy-NW composite electrode materials were successfully prepared by combining the one-dimensional polypyrrole nanowires (PPy-NW) with two-dimensional multilayered Ti₃C₂T_x-MXene. The morphologies and compositions of the synthetic materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Electrochemical tests showed that Ti₃C_{2 …}

In Situ/Operando Visualization Of Electrode Processes In Lithium-Sulfur Batteries: A Review, Shuang-Yan Lang, Xin-Cheng Hu, Rui Wen, Li-Jun Wan

Journal of Electrochemistry

Lithium-sulfur (Li-S) batteries have been regarded as one of the most promising candidates for the next-generation energy storage devices. Fundamental understanding of the structure and evolution processes at electrode-electrolyte interfaces is essential to the further development. In this review, we summarize recent advances in the interfacial observations by means of various in situ/operando visualization techniques, including scanning probe microscopy (SPM), electron microscopy (EM), X-ray microscopy (XRM) and optical microscopy (OM). The real-time investigation provides important evidence for the morphology and component changes including S/Li₂S transformation, polysulfide dissolution on cathodes and Li/solid electrolyte interphase (SEI) evolution on anodes, which …

Recent Progress Of Electrochemiluminescence Sensors Based On Electrically Heated Electrode, Hui-Fang Zhang, Yi-Ting Chen, Fang Luo, Zhen-Yu Lin, Guo-Nan Chen

Journal of Electrochemistry

Electrochemiluminescence (ECL) has broad application in the fields of environmental monitoring and biological analysis due to its intrinsic advantages such as excellent versatility, good detection sensitivity, and high specificity. The intensity of ECL can be influenced by temperature variation in the ECL quantum efficiency and the rate of electrochemical reaction. However, traditional temperature control is commonly realized through bulk solutions heating, which is complicated and unfavorable for detection when the volatile and thermally unstable materials existed. In order to address these problems, electrically heated electrodes are used to adjust the temperature desired. The major character of this technique lies in …

Application Of Nanomaterials In The Detection Of Volatile Organic Compounds In Exhaled Breath For Cancer Diagnosis, Wan-Qiao Bai, Xue-Zhi Qiao, Tie Wang

Journal of Electrochemistry

Volatile organic compounds (VOCs) generated in human body can reflect one’s health state, and numerous diseases are identified by some VOCs biomarkers. More recently, analyses of VOCs biomarkers from exhaled breath have turned into a research frontier worldwide because it offers a noninvasive way for diseases diagnosis. Various kinds of nanomaterials are used to enhance the performance of sensing techniques, and play an essential role in miniaturization detection. In this review, several kinds of nanomaterials (metallic, metal oxide, carbon-based, composites and MOFs-based materials) used in various VOCs detection methods, especially in VOCs sensors are summarized. Learning from the successful utilization …

Sensitive Photoelectrochemical Assay Of Nucleic Acids Based On Catalytic Hairpin Assembly And Ru(Nh3)63+, Ya-Min Fu, Xiao-Xia Yan, Xiao-Hua Zhang, Jin-Hua Chen

Journal of Electrochemistry

A simple “signal-on” photoelectrochemical (PEC) sensing platform for sensitive assay of nucleic acids was developed by coupling catalytic hairpin assembly (CHA) signal amplification strategy with Ru(NH₃)₆³⁺. Herein, cadmium sulfide (CdS) was deposited on the TiO₂/indium tin oxide (ITO) electrode by a method of successive ionic layer adsorption and reaction (SILAR), serving as one kind of photoelectric material to broaden absorption range of TiO₂ and to improve the photoelectric conversion efficiency. Thereafter, the capture DNA (C-DNA) was immobilized on the CdS/TiO₂/ITO electrode. Simultaneously, Au-hairpin DNA probe 1 (Au-HP1) and hairpin DNA …

A Facile Strategy For Two-Step Fabrication Of Gold Nanoelectrode For In Vivo Dopamine Detection, Li-Hao Guan, Chao Wang, Wang Zhang, Yu-Lu Cai, Kai Li, Yu-Qing Lin

Journal of Electrochemistry

In vivo monitoring neurochemicals with microelectrode is invasive and the damage to brain tissue may inevitably cause disturbance signals physiologically to the measurement. It is of great importance to reduce the electrode size and to decrease the damage. This study demonstrates a novel nanoelectrode preparation methodology for in vivo monitoring dopamine (DA) fluctuation in the living brain of rats with high dependability. The fabrication process of the gold nanoelectrode involving a few minutes consists of only two steps: 1) growing gold nanoseeds on surface of tip of glassy capillary by ion sputtering; 2) wet depositing a continuous conductive gold film …

Graphene-Like Secondary-Laser-Etched Polyimide Film Decorated With CuXO Nanocomposites: A Novel Electrode Substrate For Non-Enzymatic Glucose Sensors, Wan-Lin Dai, Zhi-Wei Lu, Jian-Shan Ye

Journal of Electrochemistry

In this work, a novel electrode substrate with graphene-like surface and Cu_xO nanocomposites derived from secondary-laser-etched polyimide (SLEPI) film was synthesized and applied in non-enzymatic glucose detection for the first time. Characterizations indicate that the as-prepared SLEPI/Cu_xO film electrode (SLEPI/Cu_xO-FE) possessed huge surface area, plentiful active sites and excellent electrocatalytic performance. The obtained sensor exhibited the high sensitivity and selectivity for glucose determination with a linear range of 0.05 mmol·L^-1 to 3 mmol·L^-1 and a detection limit of 1.72 μmol·L^-1 (S/N=3), which provides a simple, flexible and low-cost electrochemical sensor for …

Preparation And Electrocatalytic Oxygen Reduction Performance Of Self-Doped Sludge-Derived Carbon, Ya-Li Ye, Wei-Ming Feng, Ge Li, Zhen-Chao Lei, Chun-Hua Feng

Journal of Electrochemistry

The development of low-cost, high-performance cathode catalysts is critical for practical application of fuel cells. Here, the N, P-doped porous graphene-like carbon with outstanding oxygen reduction reaction (ORR) performance was synthesized by pyrolysis of surplus sludge, which functioned as a self-doped, self-activated, and self-templated precursor by acclimation with continuous feedings of phenol. The results show that the amounts of microorganisms were enriched after acclimation, with increasing contents of N, P, Fe, as well as C atoms. The increasing pyrolysis temperature resulted in the formation of an ordered graphitic structure, however, the excessively high temperature induced the drop in the amounts …

The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O₂(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O₂(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. …

Control Strategies For Multi-Evaporator Vapor Compression Cycles, Sunderlin D. Jackson

Theses and Dissertations

Next-generation military aircraft must be able to handle highly transient thermal loads that exceed the ability of current aircraft thermal subsystems. Vapor compression cycle systems are a particular refrigeration technology that is an attractive solution for dealing with this challenge, due primarily to their high efficiency. However, there are several barriers to realizing the benefits of vapor cycles systems for controlling thermal loads in military aircraft. This thesis focuses on addressing the challenge of controlling vapor cycles in the presence of highly transient evaporator heat loads. Specifically, a linear quadratic regulator (LQR) is designed for a simple vapor cycle system, …

Current Status And Prospect Of Battery Configuration In Li-S System, Jia-Hang Chen, Hui-Jun Yang, Cheng Guo, Jiu-Lin Wang

Journal of Electrochemistry

Commercial lithium-ion batteries (LIBs) are incapable of satisfying the increasing demand for emerging electronic devices due to their limited energy density. Among the next-generation batteries, lithium-sulfur (Li-S) batteries are becoming a promising energy-storage system due to their high theoretical energy density and natural abundance of sulfur. However, the shuttle of soluble polysulfide intermediates between two electrodes, as well as the problem on Li metal anode,lower the utilization of active material and lead to the loss of specific capacity and rapid capacity fading. All the above challenges limit the further application of Li-S batteries. Recently, various novel battery configurations have been …

Recent Progress On Tio2-Based Anode Materials For Sodium-Ion Batteries, Si-Tian Lian, Jian-Shuai Lv, Qiang Yu, Guang-Wu Hu, Zhuo Chen, Liang Zhou, Li-Qiang Mai

Journal of Electrochemistry

Titanium dioxide (TiO₂) represents a stable, low-cost, and nontoxic anode material for sodium-ion batteries (SIBs). However, the low electrical conductivity limits its electrochemical activity (specific capacity) and rate capability, hindering its widespread applications. In this article, we show that different crystal forms of TiO₂ have different pore structures, resulting in the distinct sodium storage capacities. Accordingly, the article introduces how TiO₂ microstructures influence sodium storage. The nanoparticle structure can improve the rate performance of the material due to its short ion diffusion distance, and the internal cavity of the hollow structure is beneficial to cycle stability. …

Recent Progress In Vanadium-Based Electrode Materials, Meng-Lei Sun, Da-Qi Zhang, Jin-Kui Feng, Jiang-Feng Ni

Journal of Electrochemistry

It is an important solution to solve energy storage problems by developing inexpensive and safe lithium-ion and sodium-ion batteries with superior performance. Vanadium-based electrode materials are promising electrode materials because of diversified chemical valences, open structures and high theoretical capacities. In the past few years, vanadium-based electrode materials such as oxides, sulfides, and phosphates have achieved a considerable development in the battery field, It is,  therefore, necessary to summarize their recent research progress. In this review, we particularly highlight the key challenges that are facing in the application of vanadium materials, such as low ion diffusion coefficient and poor structural …

Recent Progress In Key Materials For Room-Temperature Sodium-Ion Batteries, Fan-Fan Wang, Xiao-Bin Liu, Long Chen, Cheng-Cheng Chen, Yong-Chang Liu, Li-Zhen Fan

Journal of Electrochemistry

Sodium-ion batteries (SIBs) have attracted tremendous attention in large-scale energy storage applications due to their resource advantages. However, Na+ is larger and heavier than Li+, which will limit its reversible reaction with the electrode materials and result in poor electrochemical performance. Thus, developing stable and high-efficiency electrode materials is the key to promoting the practical application of SIBs. Furthermore, the optimization of electrolyte is essential for the construction of high-safety and long-lifespan SIBs. In this review, we mainly summarize the recent advancements of electrode materials and electrolytes for room-temperature SIBs and discuss their challenges and possible resolution strategies. We hope …

Recent Developments In Surface/Interface Modulation And Structure-Performance Relationship Of Cathode Catalysts For Li-Air Batteries, Rui Gao, Jun-Kai Wang, Zhong-Bo Hu, Xiang-Feng Liu

Journal of Electrochemistry

Lithium-air battery has been considered to be one of the most promising secondary battery systems because of its high energy density. However, the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the cathode, and the high overpotential, poor cycle stability and low rate capacity have severely blocked the development and application of Li-air battery. One of the effective strategies to alleviate these issues is to develop cathode catalysts for Li-air batteries. The design and development of bifunctional cathode catalysts with high activity and efficiency on both ORR and OER is highly desired for Li-air …

A Comparative Study Of Pre-Lithiated Hard Carbon And Soft Carbon As Anodes For Lithium-Ion Capacitors, Zhao Li, Xian-Zhong Sun, Wen-Jie Liu, Xiong Zhang, Kai Wang, Yan-Wei Ma

Journal of Electrochemistry

Lithium-ion capacitor (LIC) has emerged to be one of the most promising electrochemical energy storage devices. Presently, activated carbon (AC) is the mostly used cathode material for LIC. Nevertheless, various carbonaceous materials can be used as anode materials, such as hard carbon (HC) and soft carbon (SC). Therefore, HC and SC with different structural and electrochemical characteristics have been investigated as the anode materials of LICs in this work. Compared with the HC electrode, the SC electrode showed higher electronic conductivity and reversible capacity. The rate capabilities of the two carbonaceous materials as a function of coating thickness have been …

Cvd Preparation And Application Of 3d Graphene In Electrochemical Energy Storage, Yong-Kang Xia, Ming-Yuan Gu, Hong-Guan Yang, Xin-Zhi Yu, Bing-An Lu

Journal of Electrochemistry

Three-dimensional (3D) graphene combinations with the excellent intrinsic properties of graphene and the 3D micro/nano porous structures provide a graphene foam with high specific surface area, excellent mechanical strength and fast electron and mass transports. The 3D graphene foam and its composite nanomaterials are widely used in the fields of nano-electronics, energy storage, chemical and biological sensing. The 3D graphene foam prepared by chemical vapor deposition (CVD) method is of high purity and crystallinity.  In this review, a brief overview in the CVD preparations of 3D graphene and properties of CVD prepared 3D graphene based nanomaterials in electrochemical energy storage …

Applications Of Advanced Imaging Technologies For Critical Issues Of All-Solid-State Lithium Battery Studies, Yi-Bo Zhao, Hui-Hui Liu, Song-Liang Chen, Shou-Hang Bo

Journal of Electrochemistry

All-solid-state lithium batteries have attracted much attention for their high energy density and good safety. To increase their efficiency and prolong their service life, it is necessary to achieve high ion conductivity at the electrode/electrolyte interface and in the electrolyte, as well as to eliminate dendrites growth in the battery. Based on the critical requirements outlined above, this paper discusses the applications of advanced imaging technologies in relevant studies. Recent progresses in investigations of all-solid-state lithium batteries by imaging techniques including electron microscopy, scanning probe microscopy, X-ray tomography, magnetic resonance imaging and optical microscopy are summarized.

Synthesis Of Flower-Like Vanadium Disulfide For Lithium Storage Application, Pan Li, Jian Liu, Wei-Yi Sun, Hai-Xia Li, Zhan-Liang Tao

Journal of Electrochemistry

In order to improve the electrochemical properties of vanadium disulfide (VS₂) as an electrode material in Li-ion battery, the flower-like VS₂ was prepared by a one-step hydrothermal method with the addition of polyethylene glycol 400. The phase and morphology of the product were characterized by using X-ray diffraction and field emission scanning electron microscopy. During the growth process, it was observed that the flower-like VS₂ was interspersed with several hexagonal vanadium disulfide nanosheets, which had a high specific surface area and excellent structural stability. The flower-like VS₂ was used for the cathode material test in …

Ni/Mn3O4/Nimn2O4 Double-Shelled Hollow Spheres Embedded Into Reduced Graphene Oxide As Advanced Anodes For Sodium-Ion Batteries, Chong Yan, Hua-Ri Kou, Bo Yan, Xiao-Jing Liu, De-Jun Li, Xi-Fei Li

Journal of Electrochemistry

Delicately building the unique nanocomposite with the combination of hollow structure and reduced graphene oxide (rGO) is highly desirable and still remains a great challenge in the field of energy conversion and storage. In this work, Ni/Mn₃O₄/NiMn₂O₄ double-shelled hollow spheres coated by rGO (denoted as R-NMN) have been successfully synthetized via one-step rapid solvothermal treatment followed by subsequent annealing for the first time. Served as anodes for sodium ion batteries (SIBs), the R-NMN composite containing 25wt% rGO exhibits a high discharge capacity of 187.8 mAh·g^-1 after 100 cycles at 50 mA·g^{-1 …}

Preface On Special Issue Of Next-Generation Secondary Batteries, Zhen Zhou, Quan-Feng Dong

Journal of Electrochemistry

No abstract provided.

Fundamental Limits Of Measuring Single-Molecule Rotational Mobility, Oumeng Zhang, Matthew D. Lew

Electrical & Systems Engineering Publications and Presentations

Various methods exist for measuring molecular orientation, thereby providing insight into biochemical activities at nanoscale. Since fluorescence intensity and not electric field is detected, these methods are limited to measuring even-order moments of molecular orientation. However, any measurement noise, for example photon shot noise, will result in nonzero measurements of any of these even-order moments, thereby causing rotationally-free molecules to appear to be partially constrained. Here, we build a model to quantify measurement errors in rotational mobility. Our theoretical framework enables scientists to choose the optimal single-molecule orientation measurement technique for any desired measurement accuracy and photon budget.

Substrate-Dependent Photoconductivity Dynamics In A High-Efficiency Hybrid Perovskite Alloy, Ali Moeed Tirmzi, Jeffrey A. Christians, Ryan P. Dwyer, David T. Moore, John A. Marohn

Faculty Publications

Films of (FA_0.79MA_0.16Cs_0.05)_0.97Pb(I_0.84Br_0.16)_2.97 were grown over TiO₂, SnO₂, indium tin oxide (ITO), and NiO. Film conductivity was interrogated by measuring the in-phase and out-of-phase forces acting between the film and a charged microcantilever. We followed the films’ conductivity versus time, frequency, light intensity, and temperature (233−312 K). Perovskite conductivity was high and light-independent over ITO and NiO. Over TiO₂ and SnO₂, the conductivity was low in the dark,increased with light intensity, and persisted for 10’s of seconds after the light …

Facile Synthesis Of A Tailored-Designed Au/Pt Nanoanode For Enhanced Formic Acid, Methanol, And Ethylene Glycol Electrooxidation, Yaser M. Asal Mr., Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof

Chemical Engineering

The recent revolution in nanoscience and global energy demand have motivated research in liquid fuel cells (LFCs) due to their enhanced efficiency, moving flexibility, and reduced contamination. In line with this advancement, a glassy carbon (GC) electrode was modified with platinum (PtNPs) and gold (AuNPs) nanoparticles to fabricate a nanosized anode for formic acid, methanol, and ethylene glycol electrooxidation (abbreviated, respectively, to FAO, MO, and EGO), of the key anodic reactions of LFCs. The deposition sequence of the catalyst’s layers was important where the Au/Pt/GC electrode (in which PtNPs were directly deposited onto the GC surface followed by AuNPs—surface coverage …

A Promising Modification Of Pt Surfaces With Cnts For Decreasing Poisoning Impact In Direct Methanol Fuel Cells, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Aya A. Khalifa Ms.

Chemical Engineering

Direct methanol fuel cells (DMFCs) are clean energy sources that have many applications due to the high energy density of methanol as a fuel. However, this type of fuel cells (FCs) has limitations that are preventing it from being commercialized. One such limitation is the adsorption of intermediates such as CO into the surface of the Platinum (Pt) catalyst during methanol oxidation (MO) which deactivates its active sites, where the reaction is taking place, and leads to poisoning of the electrode over the long term. In this study, multi-walled carbon nanotubes (MWCNTs) have been introduced to the Pt-modified glassy carbon …

Enhanced Electro-Oxidation Of Methanol At Pt-Au Nanocatalyst For Direct Methanol Fuel Cells, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Ahmad M. Mohammad Prof

Chemical Engineering

In this investigation, a Pt-Au nanocatalyst prepared by the coelectrodeposition of Pt (PtNPs) and Au (AuNPs) nanoparticles is assembled onto a glassy carbon (GC) electrode for efficient methanol oxidation (MO). Several molar ratios between PtNPs and AuNPs have been used and the corresponding catalytic activity towards MO is tracked. The Pt1:Au1 catalyst showed the highest catalytic activity (5 times higher oxidation peak current (Ip) and a 126 mV negative shift in the onset potential (Eonset) toward MO). The catalyst’s morphology, composition and activity are investigated and the ehancement mechanism is recognized.