Chemistry Commons^™

Effect Of Reaction Conditions On Cu⁃Catalyzed Co2 Electroreduction, Chang Zhu, Wei Chen, Yan-Fang Song, Xiao Dong, Gui-Hua Li, Wei Wei, Yu-Han Sun

Journal of Electrochemistry

Electrochemical conversion of carbon dioxide (CO₂) driven by renewable electricity that can meet both carbon emission reduction and renewable energy utilization has been rapidly developed in recent years. Copper (Cu) catalyst has long been a promising candidate for CO₂ electroreduction applications because of its natural abundance and specific capability of producing a substantial amount of C2 products. However, various metallic Cu electrodes reported have been significantly influenced by the adsorption of certain cation/anion ions, resulting in wide-span catalytic activities and selectivity for various products. In addition, a recent report demonstrated that by virtue of gas-diffusion flow cell …

Understanding The Role Of Atom Trapping In The Evolution Of Hydrocarbon Transformation Catalyst Morphology, Griffin Alexander Canning

Chemistry and Chemical Biology ETDs

Converting alkanes to other, more chemically and economically valuable molecules requires catalysts that can survive elevated temperatures and highly reducing environments. These environments can cause many metal-nanoparticle based catalysts to sinter rapidly, causing a loss of activity. They must also tolerate the coke formation, as well, since coke can restrict access to active sites by gas phase molecules, thus lowering catalytic activity. While there are routes to improve both the sinter and coke resistance of catalysts, an alternative strategy is to develop a protocol for regenerating the activity of the catalyst in question when coke formation or sintering becomes problematic. …

Atom Trapping And Its Role On The Nucleation & Growth Of Platinum Nanoparticles, Deepak Kunwar

Chemistry and Chemical Biology ETDs

Diesel oxidation catalysts deactivate due to Pt sintering, a major problem in automotive industries. To make sure they operate effectively throughout the lifetime of the vehicle, automotive industries are putting an excessive amount of Pt. There is a need to develop a catalyst that serves long term performance with minimal use of Pt. Jones et al^.1 demonstrated that ceria traps Pt atoms. His work generated some logical and valid questions such as what is the mechanism for the formation of anomalously large Pt particles? What is the upper limit of Pt metal loading in the form of single atoms …

Adsorption And Reconfiguration Of Amphiphiles At Silica-Water Interfaces: Role Of Electrostatic Interactions, Van Der Waals Forces And Hydrogen Bonds, Yao Wu

LSU Doctoral Dissertations

The ability to explore and predict metastable structures of hybrid self-assemblies is of central importance for the next generation of advanced materials with novel properties. As compared to their thermodynamically stable forms, the kinetically stabilized materials show improved functionality potentially over their stable counterparts. The self-assembly processes usually originate from weak intermolecular interactions, involving a dynamic competition between attractive and repulsive interactions. These weak forces, including van der Waals (vdW), electrostatic interaction and the hydrogen bonding (H-bonding), can be tuned by external stimuli, e.g., confinement, temperature and ionization, and consequently driving hybrid materials into different configurations. It is challenging to …

Facile Synthesis Of Nitrogen-Doped Graphene-Like Active Carbon Materials For High Performance Lithium-Sulfur Battery, Quan-Hua Meng, Wen-Wen Deng, Chang-Ming Li

Journal of Electrochemistry

Lithium-sulphur (Li-S) battery is regarded as a promising energy storage device because of its high theoretical capacity. However, the low S utilization and short cycling life limit the commercial applications. In this work, nitrogen-doped graphene-like carbon (NGC) materials were synthesized by simply pyrolyzing and carbonizing the mixture of melamine (C₃H₆N₆) and L-cysteine (C₃H₇NO₂S). The graphene-like structure in NGC effectively buffered the volume change of S during the discharge/charge process and improved the cycling stability. Meanwhile, nitrogen-containing functional groups in NGC facilitated the transportation of ions and suppressed the …

A Model For The Anodic Carbonization Of Alkaline Polymer Electrolyte Fuel Cells, Qi-Hao Li, Ying-Ming Wang, Hua-Long Ma, Li Xiao, Gong-Wei Wang, Jun-Tao Lu, Lin Zhuang

Journal of Electrochemistry

The alkaline polymer electrolyte fuel cell (APEFC) has made appreciable progress in recent years but is still suffering performance loss during discharge with air as the oxidant. Several theories have been suggested to interpret the loss. However, efforts are still needed to reach a clear quantitative understanding. Based on the major experimental findings in combination with thermodynamics and kinetics of the reactions involved in the anode, this paper presents a model featuring layered carbonization in the anode and relevant grouped equations. The simulation results generated from the latter are compared with experiments, and possible principles to suppress the performance loss …

Water-Soluble Graphene In Agar Gel As Electrolyte For Magnesium-Air Battery, Liew Siaw Ying

Student Works (2020-2029)

Presently, ever-increasing demands on energy and the global environmental issues have given the impetus to investigate the new battery systems which are inexpensive, efficient, having high performance, and also green to the environment. Among all the battery technologies, magnesium-air (Mg-air) battery is an attractive battery to be developed owing to the interesting properties of the Mg anode. Mg has high specific energy (6.46 kWh kg-1) and reactivity, apart from its high abundance, lower cost, low toxicity, and comparatively safe to handle in the atmosphere. Nevertheless, Mg-air battery is still not being widely investigated as compared to the other batteries. Electrolyte …

Synthesis And Characterization Of Water-Soluble Polyaniline For Hydrazine Detection / Hazira Hussin, Hazira Hussin

Student Works (2020-2029)

In this study, polyaniline (PAni) was synthesized through the chemical oxidation method using aniline (Ani) as a monomer, hydrochloric acid (HCl) as a dopant, and ammonium persulphate (APS) as an initiator. PAni was rendered water soluble through treating with cellulose derivatives. Cellulose derivatives such as methylcellulose (MC), hydroxypropyl cellulose (HPC), and hydroxypropyl methylcellulose (HPMC) were used as a stabilizer to improve the solubility of PAni in an aqueous medium. The water-soluble PAni-cellulose derivative was applied as a chemical sensor for hydrazine detection. The chemical structures and electrical conducting behaviours of PAni-cellulose derivatives were investigated using Fourier transform infrared (FTIR) and …

Synthesis And Characterization Of Silver Nanoparticles In Lamellar Lyotropic Liquid Crystal, Siti Mariah Mohd Yasin

Student Works (2020-2029)

Lamellar lyotropic liquid crystal-silver nanoparticles (LLLC-AgNPs) are synthesized using the in-situ method. The polarizer microscope showed a mosaic-like pattern with fan shape textures. The high resolution transmission electron microscope (HRTEM) confirmed that the AgNPs are spherical in shape with 4 – 12 nm size. Differential scanning calorimetry (DSC) determined the LLLC-AgNPs transition anisotropic phase to the highly ordered isotropic phase at 300 °C, and crystallinity was completed at 350 °C. Thermogravimetric analysis (TGA) verified that the LLLC-AgNPs were completely decomposed at 700 °C. Ultra-violet visible spectroscopy (UV-vis) found the absorption peaks at around 400 nm and proved that the AgNPs …

Preparation And Characterisation Of Heat Treated Oil Palm-Empty Fruit Bunch/High Density Polyethylene Composites, Nordin Nur Afifah

Student Works (2020-2029)

Natural fibre composites (NFCs) are composite materials, in which the reinforcing fibres are derived from renewable and carbon dioxide neutral resources such as wood or plants. NFC can be made by replacing synthetic fibres with various types of natural fibres. Oil palm empty fruit bunch (OPEFB) fibre and oil palm mesocarp fibre are two important types of fibrous materials left in the palm-oil industry. In this study, EFB will be used as a reinforcement to the high-density polyethylene (HDPE). EFB was heat-treated at 180°C using vacuum oven for one hour, extrusion compounded with HDPE at 10%, 20% and 30% weight …

Recent Progress In Bifunctional Catalysts For Zinc-Air Batteries, Neng-Neng Xu, Jin-Li Qiao

Journal of Electrochemistry

Zinc-air battery has attracted great attention from researchers due to its high energy density and power density, which is expected to be widely used in energy conversion and storage. Air electrode as the core area of oxygen catalytic reaction is the focus of the entire zinc-air battery research. Recently, many research achievements have been made in non-noble metal bifunctional catalysts/electrodes with high activity, low cost and abundant species. In this review, we mainly focus on the reaction mechanism and the recent progress in non-noble metal oxide catalyst, carbon-based catalyst, and carbon-based transition metal compound composite and self-supporting electrode. In addition, …

Research Progress Of Metal-Nitrogen-Carbon Catalysts Toward Oxygen Reduction Reaction Inm Changchun Institute Of Applied Chemistry, Ming-Jun Xu, Jie Liu, Jun-Jie Ge, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

The development of highly active and stable catalysts toward oxygen reduction reaction (ORR) has been facing severe challenges. In recent years, pyrolytic M-N-C catalysts and metal-organic framework derived materials made the performance of non-noble metal catalysts greatly improved, however, the molecular and atomic level understanding in the reaction active sites and the mechanism are still lacking. Here, we summarize the recent research progress made in the Changchun Institute of Applied Chemistry. We present a microporous metal-organic-framework confined strategy toward the preferable formation of ORR catalysts. Firstly, we studied the active site and proposed a new active site structure for the …

Electrochemical Carbon Dioxide Reduction In Flow Cells, Jia Fan, Na Han, Yan-Guang Li

Journal of Electrochemistry

Electrochemical carbon dioxide reduction (CO₂RR) is an appealing approach to convert atmospheric CO₂ to value-added fuels and industrial chemicals, and may play an important role during the transition to a carbon-neutral economy. In order to make this technology commercially viable, it is essential to pursue CO₂RR in flow reactors instead of conventional H-type reactors, and to combine electrocatalyst development with system engineering. In this review, we overview the cell configurations and performance advantages of the two types of flow reactors, analyze their shortcomings, and discuss the effects of their different components including gas diffusion electrode …

Electrolyte Tailoring For Electrocatalytic Reduction Of Stable Molecules, Jin-Han Li, Fang-Yi Cheng

Journal of Electrochemistry

Reduction of stable molecules such as CO₂ and N₂ is important process in electrochemical energy conversion and storage technologies for electrofuels production. However, for the inert nature of CO₂/N₂ molecule and competitive proton reduction in conventional aqueous electrolytes, selective electrochemical carbon/nitrogen fixation suffers from high overpotential, low reaction rate and low selectivity. While addressing these issues has witnessed substantial advances in electrocatalysts, much less attention has been placed on the electrolytes, which play an important role in regulating the local environment and thus the performance of catalysts under operating conditions. Rational design of electrolytes has …

Fuel Cell Performance Of Non-Precious Metal Based Electrocatalysts, Yan-Feng Zhang, Fei Xiao, Guang-Yu Chen, Min-Hua Shao

Journal of Electrochemistry

The commercialization of proton exchange membrane fuel cells (PEMFCs) is hindered by high cost and low durability of Pt based electrocatalysts. Developing efficient and durable non-precious metal catalysts is a promising approach to addressing these conundrums. Among them, transition metals dispersed in a nitrogen (N)-doped carbon support (M-N-C) show good oxygen reduction reaction activity. This article reviews recent progress in M-N-C catalysts development, focusing on the catalysts design, membrane electrode assembly fabrication, fuel cell performance, and durability testing. Template-assisted approach is an efficient way to synthesize M-N-C materials with homogeneously dispersed single atom active site and reduced metal particles, carbides …

Recent Progress On Enhancing Effect Of Nanosized Metals For Electrochemical Co2 Reduction, Yu-Ning Zhang, Dong-Fang Niu, Shuo-Zhen Hu, Xin-Sheng Zhang

Journal of Electrochemistry

The electrochemical conversion of CO₂ to chemical raw material for further utilization shows promising future to alleviate global warming and realize carbon cycle in nature, which is of great significance to the green chemistry and sustainable development. This review briefly introduces the advantages of CO₂ electrochemical reduction (CO₂ER) and its basic reaction principles, and summarizes the recent progress in a series of activity enhancement strategies based on nanosized metal catalysts. The influences of alloy effect, interface engineering, synergistic effect, surface defect engineering and support effect on the catalytic performance of nanosized metals for CO₂ER …

Structural Organization And Chemical Activity Revealed By New Developments In Single-Molecule Fluorescence And Orientation Imaging, Tianben Ding

McKelvey School of Engineering Graduate Student Theses & Dissertations

Single-molecule (SM) fluorescence and its localization are important and versatile tools for understanding and quantifying dynamical nanoscale behavior of nanoparticles and biological systems. By actively controlling the concentration of fluorescent molecules and precisely localizing individual single molecules, it is possible to overcome the classical diffraction limit and achieve 'super-resolution' with image resolution on the order of 10 nanometers.

Single molecules also can be considered as nanoscale sensors since their fluorescence changes in response to their local nanoenvironment. This dissertation discusses extending this SM approach to resolve heterogeneity and dynamics of nanoscale materials and biophysical structures by using positions and orientations …

Nanoceria Distribution And Effects Are Mouse-Strain Dependent, Robert A. Yokel, Michael T. Tseng, D. Allan Butterfield, Matthew L. Hancock, Eric A. Grulke, Jason M. Unrine, Arnold J. Stromberg, Alan K. Dozier, Uschi M. Graham

Pharmaceutical Sciences Faculty Publications

Prior studies showed nanoparticle clearance was different in C57BL/6 versus BALB/c mice, strains prone to Th1 and Th2 immune responses, respectively. Objective: Assess nanoceria (cerium oxide, CeO₂ nanoparticle) uptake time course and organ distribution, cellular and oxidative stress, and bioprocessing as a function of mouse strain. Methods: C57BL/6 and BALB/c female mice were i.p. injected with 10 mg/kg nanoceria or vehicle and terminated 0.5 to 24 h later. Organs were collected for cerium analysis; light and electron microscopy with elemental mapping; and protein carbonyl, IL-1β, and caspase-1 determination. Results: Peripheral organ cerium significantly increased, generally more …

Enhancement Of Graphene Biocompatibility As A Potential Nano-Carrier For Drug Delivery Applications Using Natural Deep Eutectic Solvent, Zainal Abidin Mohamad Hamdi

Student Works (2020-2029)

Graphene has attracted massive interest in numerous biomedical applications such as anti-cancer therapy, drug delivery, bio-imaging and gene delivery. Therefore, it is important to ensure that graphene is nontoxic, and that its cellular biological behavior is safe and biocompatible. Herein, a new route was used to enhance the biocompatibility of graphene as a nano-carrier for potential drug delivery applications, using different compositions of natural deep eutectic solvents (DESs) as functionalizing agents, owing to their capability to introduce various functional groups and surface modifications. To meet this end, eight different combinations of binary and ternary DESs were synthesized using choline chloride …

Plasma And Serum Proteins Bound To Nanoceria: Insights Into Pathways By Which Nanoceria May Exert Its Beneficial And Deleterious Effects In Vivo, D. Allan Butterfield, Binghui Wang, Peng Wu, Sarita S. Hardas, Jason M. Unrine, Eric A. Grulke, Jian Cai, Jon B. Klein, William M. Pierce, Robert A. Yokel, Rukhsana Sultana

Chemistry Faculty Publications

Nanoceria (CeO2, cerium oxide nanoparticles) is proposed as a therapeutic for multiple disorders. In blood, nanoceria becomes protein-coated, changing its surface properties to yield a different presentation to cells. There is little information on the interaction of nanoceria with blood proteins. The current study is the first to report the proteomics identification of plasma and serum proteins adsorbed to nanoceria. The results identify a number of plasma and serum proteins interacting with nanoceria, proteins whose normal activities regulate numerous cell functions: antioxidant/detoxification, energy regulation, lipoproteins, signaling, complement, immune function, coagulation, iron homeostasis, proteolysis, inflammation, protein folding, protease inhibition, adhesion, protein/RNA …

Synthesis Of Polyurethane Incorporated By Calcium Oxide And Magnesium Oxide For Heavy Metal Removal From Water, Fard Mohsen Vafaei

Student Works (2020-2029)

Water contaminated by heavy metals such as copper, lead, nickel, and cadmium has significant adverse impacts on receiving water. In recent years, various methods, such as adsorption, chemical precipitation, and ion exchange, have been extensively studied for the elimination of heavy metals. Adsorption is one of the numerously and diversely reported mechanisms of removing heavy metals due to its simplicity and costeffectiveness. In this study, highly permeable rigid polyurethanes (PU) incorporating calcium oxide (CaO) (PU/CaO) composite materials were prepared via a facile and economic one-pot synthesis method and characterized for remediation of heavy metal from water. To investigate the effect …

Syntheses, Characterisations And Electrochemical Studies Of Nickel(Ii) And Cobalt(Ii)-Ligand Assisted Cooperative Complexes, Subramaniam Jeevithra Dewi

Student Works (2020-2029)

A newly designed tetradentate ligand L1 (L1 = 3,6-bis(pyrazol-1-yl)-pyridazine) which offers multinucleation sites on its moiety structure has been prepared. The reaction of L1 with different molar ratio of nickel and cobalt salts lead to the formation of di- and tetranuclear complexes [NiII 2(L1)2(CH3CN)4](PF6)4 (1), [NiII 4(L1)4(μ-OH)4](ClO4)4 (2) and [CoII/III(L1)4(μ-CH3O)2(μ-O)2](PF6)3(NO3) (3), which served as the attempt to design of catalysts based on cheap and earth-abundant metals for carbon dioxide reduction. The presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the base controls the nuclearity of the complex formation. In the absence of DBU, complex 1 was formed in dinuclear fashion whereas complex 2 …

Poly(Ethylene Oxide) Based Polymer Electrolytes For All-Solid-State Li-S Batteries, Xue Li, Zheng-Liang Gong

Journal of Electrochemistry

In recent years, research on lithium-sulfur (Li-S) batteries has received much attention because the sulfur positive electrode and the lithium metal negative electrode produce a high theoretical specific capacity (lithium metal ~ 3800 mAh·g^-1, sulfur ~ 1675 mAh·g^-1). In addition, sulfur is considered to be the most promising cathode material for secondary lithium batteries, due to its advantages of low price and environmental friendly. However, the practical application of conventional liquid Li-S batteries is still obstructed by several critical issues, such as lithium ploysulfides shuttle effect, long-term stability of lithium metal anode with organic liquid electrolytes, …

Synthesis And Raman Study Of Hollow Core-Shell Ni1.2Co0.8P@N-C As An Anode Material For Sodium-Ion Batteries, Jia-Hui Chen, Xiao-Bin Zhong, Chao He, Xiao-Xiao Wang, Qing-Chi Xu, Jian-Feng Li

Journal of Electrochemistry

With the increasing demand for large-scale energy storage, great progress has been made in discovering new advanced energy storage materials. Sodium-ion batteries (SIBs) have attracted much attention in recent years due to their use of abundant sodium resources and their comparable electrochemical capacity to lithium-ion batteries (LIBs). In this paper, we developed novel hollow core-shell Ni-Co bimetallic phosphide nanocubes with N-doped carbon coatings (Ni_1.2Co_0.8P@N-C) as the anode material for SIBs. The material was synthesized through a low-temperature phosphorization method using resorcinol formaldehyde (RF) resin coating with a Ni-Co Prussian blue analogue (PBA) as a template and …

Preparations Of Nano-MnoX/Ti Electrocatalytic Membrane Electrode For Catalytic Oxidation Of Cyclohexane Using Intermittent Electrodeposition, Xue Zhou, Hong Wang, Zhen Yin, Yu-Jun Zhang, Jian-Xin Li

Journal of Electrochemistry

Cyclohexanone and cyclohexanol (KA oil) obtained from highly selective oxidation of cyclohexane (CHA) show important industrial value and application prospects. In this work, the intermittent electrodeposition was developed to prepare nano-MnO_x catalyst loading porous tubular titanium membrane electrode (MnO_x/Ti), which was employed to constitute an electro-catalytic membrane reactor (ECMR) for the oxidation of cyclohexane to produce cyclohexanol and cyclohexanone. The surface morphology, crystal structure and electrochemical property of the catalysts were characterized by FESEM, XRD and electrochemical workstation, respectively. The results show that the catalyst prepared by the intermittent electrodeposition displayed nano-flower-like γ-MnO₂. Compared with …

Preparation Of Α-Hydroxylated Acetal From 2-Butanone By Indirect Electrooxidation, Hai-Qing Huang, Ye Miao, Xin-Sheng Zhang

Journal of Electrochemistry

Acetoin (3-hydroxy-2-butanone) is an important food spice. As a platform compound, it is widely used in medicine, tobacco, cosmetics, chemical material and other industries. In this paper, α-hydroxylated acetal, an intermediate of acetoin, was prepared from 2-butanone by indirect electrooxidation in the plate and frame electrolytic cell, in which graphite plates were used as both an anode and a cathode, while KOH as an electrolyte and KI as a catalyst. Acetoin could be prepared by hydrolysis in acidic aqueous solution from acetoin intermediate. The effects of current density, electrolyte flow rate between the plates, 2-butanone concentration and electrolysis temperature …

Electrochemical Oxidation Of Metal Chromium In Odium Hydroxide Aqueous Solution, Ping Han, Hai-Tao Feng, Ya-Ping Dong, Sen Tian, Bo Zhang, Wu Li

Journal of Electrochemistry

Ferrochrome electrolysis technology is a novel method for preparing sodium chromate (Na₂CrO₄). Although the method performs well at soft reaction conditions, controllable process, environmentally friendly production process, etc., the electrochemical oxidation process of metal chromium in NaOH aqueous electrolyte is still unclear. At present, there are few research articles about specific electrochemical oxidation of metal chromium in NaOH aqueous electrolyte. It is, therefore, meaningful to carry out the research in electrochemical oxidation mechanism of chromium. The electrochemical oxidation of metal chromium in 0.01 mol·L^-1 ~ 10 mol·L^-1 NaOH aqueous electrolytes at 20 °C was …

Stability Studies For A Membrane Electrode Assembly Type Co2 Electro-Reduction Electrolytic Cell, Qing Mao, Bing-Yu Li, Wei-Yun Jing, Jian Zhao, Song Liu, Yan-Qiang Huang, Zhao-Long Du

Journal of Electrochemistry

Electro-catalytic reduction is an efficient way to achieve resourcable transformation of CO₂, which is one of the important techniques to solve the global environmental problems originated from excessive CO₂ emission. In this study, a membrane electrode assembly(MEA) type CO₂ electro-reduction electrolytic cell was constucted, which enables CO₂ feeding and real-time KHCO₃ aqueous updating on both sides of the cathode gas diffusion electrode (GDE). By means of the electrolytic cell, effects of KHCO₃ concentration and updating inside the liquid electrolytic chamber on CO₂ electro-reduction activity, production distribution and stability were investigated. The experimental …

Catalytic Esterification Of Palm-Based Lauric Acid Diethylene Glycol Via Microwave Heating, Abas Noor Azeerah

Student Works (2020-2029)

Diethylene glycol esters of fatty acids are mixtures of diethylene glycol mono- and di-esters of saturated and unsaturated fatty acids derived from edible oils and fats. The products are produced either by direct esterification of diethylene glycol with fatty acids or by transesterification of diethylene glycol with oils or fats. This study involved in maximizing the conversion of lauric acid to glycol ester via esterification with diethylene glycol, aided by calcined Zn-Mg-Al catalyst in a 250-ml reactor using both conventional and microwave heating. Preliminary catalytic screening involving tin (II) oxalate, Amberlyst-15 and calcined Zn-Mg-Al catalysts in esterification of lauric acid …

Green Synthesis Of Reduced Graphene Oxide For Efficient Adsorption-Photocatalysis Studies In Methylene Blue Dye Degradation, Ling Er Valerie Siong

Student Works (2020-2029)

Dyes are one of the major components of industrial effluents. Owing to the complex structures of these toxic organic compounds, the removal of dyes from effluents possesses a great challenge in wastewater treatment. In order to tackle this issue, one of the effective methods is to remove dyes via the combination of adsorption and photocatalysis processes. In the present work, reduced graphene oxide (rGO) was fabricated from graphene oxide (GO) by using an environmentally friendly solvothermal approach, whereby ethanol was employed as a non-toxic reductant. In order to investigate the formation of rGO, the reduction of GO was carried out …