Catalysis and Reaction Engineering Commons^™

A Metal-Free Approach To Biaryl Compounds: Carbon-Carbon Bond Formation From Diaryliodonium Salts And Aryl Triolborates, Kuruppu Lilanthi Jayatissa

Dissertations and Theses

Biaryl moieties are important structural motifs in many industries, including pharmaceutical, agrochemical, energy and technology. The development of novel and efficient methods to synthesize these carbon-carbon bonds is at the forefront of synthetic methodology. Since Ullmann’s first report of stoichiometric Cu-mediated homo-coupling of aryl halides, there has been a dramatic evolution in transition metal catalyzed biaryl cross-coupling reactions.

Our work focuses on the discovery and development of an unprecedented reagent combination for metal-free cross-coupling. It is hypothesized that direct carbon-carbon bond formation occurs via a triaryl-λ³-iodane and that electrophile/nucleophile pairing is critical for success in the reaction. Proof-of-concept …

An Enzymatic Ethanol/O2 Biofuel Cell Powered By Commercial Vodka Fuel, Yi-Ming Yan, Lan-Qun Mao

Journal of Electrochemistry

This study demonstrates the performance of a new type alcohol/O₂ biofuel cell assembled by using alcohol dehydrogenase (ADH) and bilirubin oxidase (BOD) as the biocatalysts of the bioanode and the biocathode for the bioelectrocatalytic oxidation of alcohol and reduction of oxygen, respectively. To construct the bioanode and the biocathode, single-walled carbon nanotubes (SWCNTs) were used. In the bioanode, SWCNTs were used as the supporting materials for both methylene green (MG) which was used as the electrocatalyst for the oxidation of NADH and ADH. The as-constructed MG/ADH/SWCNTs-based bioanode exhibits a good activity toward the bioelectrocatalytic oxidation of ethanol. In the …

Electrochemical Monitoring Of Cell Wall-Regulated Transient Extracellular Oxidative Burst From Single Plant Cells, Jun-Tao Liu, Yan-Ling Liu, Zhi Cheng, Shi-Jing Chen, Wei-Hua Huang

Journal of Electrochemistry

Oxidative burst by rapid, transient generation of reactive oxygen species (ROS) is a fundamental process for plant disease defense and signal transduction. ROS can be protective or toxic depending on their concentrations, and critical balance between ROS production and scavenging is regulated by complex and perfect mechanisms in plant cells. However, the process of rapid and transient ROS burst from plant cells and their regulatory mechanisms are far from being completely understood, owing to the methodological obstacles in real-time monitoring such a fast process. In this work, we showed the application of microelectrode electrochemistry with high spatiotemporal resolution to monitor …

Naio4 Oxidation Of Mussel Adhesive Protein Film And Its Corrosion Protection For Mg-1.0ca Alloy, Rui-Qing Hou, Ping-Li Jiang, Shi-Gang Dong, Chang-Jian Lin

Journal of Electrochemistry

The effect of oxidation of mussel adhesive protein (Mefp-1) film on the corrosive resistance for Mg-1.0Ca alloy was investigated by scanning electron microscopy (SEM), atom force microscopy (AFM), electron probe microanalysis (EPMA), Infrared reflection absorption spectroscopy (IRAS) and electrochemical methods. The results showed that the NaIO₄ induced oxidation of the pre-formed Mefp-1 film with porous morphology involved structural change of the DOPA group in the protein and resulted in a more uniform film with net-like morphology. The protein film without oxidation had an increasing resistance for the corrosion of Mg-1.0Ca alloy up to 7 days exposure. After oxidation, Epit …

Preparation And Properties Of Titanium Based Metal Oxide Electrodes For Ammonia Nitrogen Wastewater Treatment, Xue Li, Meng Xue, Ling Huang, Jun-Tao Li, Shi-Gang Sun

Journal of Electrochemistry

In this paper, four types of titanium based metal oxides electrodes were prepared by thermal decomposition method: Ti/SnO₂+Sb₂O₃, Ti/SnO₂+Sb₂O₃/SnO₂+IrO₂, Ti/SnO₂+Sb₂O₃/SnO₂+RuO₂, Ti/SnO₂+Sb₂O₃/SnO₂+CeO₂. The XRD results show that CeO₂ in Ti/SnO₂+Sb₂O₃/SnO₂+CeO₂ displayed a good crystal structure, and there was no significant oxygen evolution reaction occurred after electrolytic oxidation. Compared with the other three electrodes, the Ce-doped …

Alumina Supported Iron Catalyst For Hydrogen Production: Calcination Study, Anis H. Fakeeha, Wasim Ullah Khan, Ahmed A. Ibrahim, Raja L. Al-Otaibi, Ahmed S. Al-Fatesh, Moustafa A. Soliman, Ahmed E. Abasaeed

Chemical Engineering

Production of clean hydrogen from thermal decomposition of methane was studied over impregnated 30%Fe/Al2O3 catalysts in a micro-activity fixed-bed reactor. The reactant gases comprising CH4 and N2 in the ratio of 1.5 to 1 were passed through reactor at a flow rate of 25 mL/min. Moreover, effect of calcination was investigated as well. The catalytic activity results indicated that calcination temperature had a significant impact on the performance of 30%Fe/Al2O3 catalyst. The catalyst calcined at 450°C, having CH4 conversion as well as H2 yield over 70%, showed better activity as compared to all other calcination temperatures.

Fe Supported Alumina Catalyst For Methane Decomposition: Effect Of Co Coupling, Anis H. Fakeeha, Ahmed A. Ibrahim, Ahmed S. Al-Fatesh, Wasim Ullah Khan, Yahya A. Mohammed, Ahmed E. Abasaeed, Moustafa A. Soliman, Raja L. Al-Otaibi

Chemical Engineering

In recent years hydrogen production received enormous attention, since it is an environmentally friendly, energy source. The aim of this research was to examine the hydrogen production with the help of methane’s catalytic decomposition. 30% Fe coupled with different % of Co over alumina support, were examined by catalytic decomposition of methane for the production of hydrogen. The catalysts were prepared by impregnation method. The catalytic activity results revealed that the catalysts, coupled 15%Co gave the highest conversion of 72.5% as depicted by the three hour time on stream profile. The fresh and spent catalysts were characterized using different techniques …

Designed Synthesis Of Nanoporous Organic Polymers For Selective Gas Uptake And Catalytic Applications, Pezhman Arab

Theses and Dissertations

Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO₂ capture.

Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 …

On The Catalytic Activity Of Palladium Nanoparticles-Based Anodes Towards Formic Acid Electro-Oxidation: Effect Of Electrodeposition Potential, Islam M. Al-Akraa Dr., Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

In this investigation, the catalytic activity of palladium nanoparticles (PdNPs)-modified glassy carbon (GC) (simply noted as PdNPs/GC) electrodes towards the formic acid electro-oxidation (FAO) was investigated. The deposition of PdNPs on the GC substrate was carried out by a potentiostatic technique at different potentials and the corresponding influence on the particles size and crystal structure of PdNPs as well as the catalytic activity towards FAO was studied. Scanning electron microscopy (SEM) demonstrated the deposition of PdNPs in spherical shapes and the average particle size of PdNPs deposited at a potential of 0 V vs. Ag/AgCl/KCl(sat.) was the smallest (ca. 8 …

Advances In Direct Formic Acid Fuel Cells: Fabrication Of Efficient Ir/Pd Nanocatalysts For Formic Acid Electro-Oxidation, Islam M. Al-Akraa, Ahmad M. Mohammad, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

No abstract provided.

Influence Of Support Type And Metal Loading In Methane Decomposition Over Iron Catalyst For Hydrogen Production, Ahmed A. Ibrahim, Ahmed S. Al-Fatesh, Wasim Ullah Khan, Moustafa A. Soliman, Raja L. Al-Otaibi, Anis H. Fakeeha

Chemical Engineering

Natural gas resources, stimulate the method of catalytic methane decomposition. Hydrogen is a superb energy carrier and integral component of the present energy systems, while carbon nanotubes exhibit remarkable chemical and physical properties. The reaction was run at 700 °C in a fixed bed reactor. Catalyst calcination and reduction were done at 500 °C. MgO, TiO2 and Al2O3 supported catalysts were prepared using a co-precipitation method. Catalysts of different iron loadings were characterized with BET, TGA, XRD, H2-TPR and TEM. The catalyst characterization revealed the formation of multi-walled nanotubes. Alternatively, time on stream tests of supported catalyst at 700 °C …

Thermo-Catalytic Methane Decomposition: A Review Of State Of The Art Of Catalysts, Ahmed A. Ibrahim, Ahmed S. Al-Fatesh, Wasim Ullah Khan, Moustafa A. Soliman, Raja L. Al-Otaibi, Anis H. Fakeeha

Chemical Engineering

The catalytic methane decomposition to produce carbon oxides–free hydrogen and carbon nanomaterial is a promising method feasible for larger production at a moderate cheap price. The produced hydrogen is refined and can be employed straight in fuel cell and in petrochemical industries to produce ammonia and methanol. Auto-thermal reforming of natural gas, partial oxidation, steam reforming are the conventional techniques for hydrogen production in industry, though these processes incur excessive costs for the purification of hydrogen from producing carbon oxides. Current research work on thermo-catalytic methane decomposition has concentrated on promoting the catalytic activity and stability for simultaneous production of …

Fundamental Studies Of Surfactant Templated Metal Oxide Materials Synthesis And Transformation For Adsorption And Energy Applications, Saikat Das

Theses and Dissertations--Chemical and Materials Engineering

This work addresses fundamental aspects of designing templates and curing conditions for the synthesis of mesoporous metal oxide thin films. The first section addresses selection of cationic-carbohydrate surfactant mixtures to synthesize templated silica thin films for selective adsorption of simple carbohydrates based on molecular imprinting. Nuclear magnetic resonance and fluorescence spectroscopy results suggest a novel structure for mixtures of alkyl glucopyranosides or xylopyranosides with cationic (trimethylammonium) surfactants. Despite thermodynamically favorable mixing, the carbohydrate headgroups in the mixed micelle adopt an inverted configuration with their headgroups in the micelle core, and therefore are inaccessible for molecular imprinting. This orientation occurs even …

The Synthesis Of Solid Supported Palladium Nanoparticles: Effective Catalysts For Batch And Continuous Cross Coupling Reactions, Kendra W. Brinkley

Theses and Dissertations

Catalysis is one of the pillars of the chemical industry. While the use of catalyst is typically recognized in the automobile industry, their impact is more widespread as; catalysts are used in the synthesis of 80% of the US commercial chemicals. Despite the improved selectivity provided by catalyst, process inefficiencies still threaten the sustainability of a number of synthesis methods, especially in the pharmaceutical industry. Recyclable solid supported catalysts offer a unique opportunity to address these inefficiencies. Such systems coupled with continuous synthesis techniques, have the potential to significantly reduce the waste to desired product ratio (E-factor) of the production …

Platinum Hollow Nanospheres With Different Sizes: Controllable Synthesis And Electrocatalytic Oxidation Toward Methanol, Xuan Lin, Mei-Qin Cheng, Zhong-Jin Shang, Ting Xiong, Xian-Tu Zhang, Wei Tian, Jian-Yun Lin, Qi-Ling Zhong, Bin Ren

Journal of Electrochemistry

The selenium (Se) templates and hollow platinum (Pthollow) nanospheres with different sizes were controllably synthesized by adjusting the concentration of sodium dodecyl sulphonate (SDSN) (CSDSN, μmol·L-1) which was used as a surfactant. Accordingly, the Pthollow nanospheres modified glassy carbon (GC) electrode (Pthollow/GC) was prepared. The morphology and composition of Pthollow nanospheres were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD) techniques. The electrocatalytic activities of Pthollow/GC and electrodeposited Pt nanoparticles modified glassy carbon electrode (Ptnano/GC) toward methanol oxidation …

Comparison In Factors Affecting Electrochemical Properties Of Thermal-Reduced Graphene Oxide For Supercapacitors, Peng Xiao, Da-Hui Wang, Jun-Wei Lang

Journal of Electrochemistry

In this paper, thermal-reduced graphene oxide (T-RGO) materials are synthesized by modified Hummer’s method, followed by thermal reduction under argon atmosphere at different temperatures. Electrochemical investigations show that, for T-RGO electrodes, good electrical conductivity is necessary and the surface functional groups play more significant role than the specific surface area in determining the electrochemical capacitance. The T-RGO obtained at 900 °C (T-RGO900) with a relatively high Brunauer-Emmett-Teller (BET) surface area (314 m²·g^-1) and a high electrical conductivity (2421 S·m^-1) shows a low specific capacitance of 56 F·g^-1. In comparison, the T-RGO obtained …

Synthesis Of Namnpo4 By Spraying Drying-High Temperature Sintering And Its Electrochemical Performance, Xiao-Chen Lin, Xiao-Biao Wu, Xu Hou, Yong Yang

Journal of Electrochemistry

As a cathode material for sodium ion batteries, NaMnPO₄/C nanocomposite is successfully synthesized by the combination of spraying drying and high temperature sintering methods. The crystal structure of the as-synthesized phosphate material is confirmed as the natrophilite NaMnPO₄, which possesses orthorhombic symmetry and Pmnb space group. It is shown that the precursors are hollow spherical particles and the obtained product consists of micro-scaled secondary particles, which are composed of NaMnPO₄ nanocrystallites (tens of nanometres) and amorphous carbon networks. The ionic and electronic conductivities of NaMnPO₄ are both effectively enhanced with the help of this …

One-Step Synthesis Of Pani/Nihcf Hybrid Film Using Unipolar Pulse Electrodeposition And Its Electrocatalytic Reduction Performance For H2O2 Detection, Sen-Liang Liao, Xiu-Min Li, Xiao-Gang Hao, Yan-Hong Wang, Chun-Feng Xue, Yong-Hong Wang

Journal of Electrochemistry

Organic–inorganic hybrid films composed of polyaniline/nickel hexacyanoferrate (PANI/NiHCF) were fabricated on platinum substrates using unipolar pulse one-step electrodeposition. The deposition mechanism of hybrid film was proposed: Due to high potential of unipolar pulse electrodeposition, which avoided the reduction of Fe(CN)₆^3-, the films with high electrocatalytic property and “insoluble” form of NiHCF were achieved. The morphology and composition of PANI/NiHCF hybrid film were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Fourier transform infrared spectroscopy (FT-IR). The effect of pulse potential on the electrochemical performance of hybrid film was investigated in detail. Results showed that …

Direct Electrochemistry And Glucose Biosensing Of Glucose Oxidase-Gold Nanoparticles Composite Synthesized By Enzyme Method, Fang He, Xiao-Li Qin, Ying-Chun Fu, Chao Chen, Qing-Ji Xie, Shou-Zhuo Yao

Journal of Electrochemistry

Glucose oxidase (GOx)-gold nanoparticles (AuNPs) composite was synthesized by the one-pot enzyme reaction in the mixture solution of NaAuCl₄, GOx and glucose, and a Nafion/GOx-AuNPs/glassy carbon electrode was fabricated by the cast-coating method to examine the direct electrochemistry of GOx and the biosensing performance on this electrode. Such a GOx-AuNPs composite showed good direct-electrochemistry activity and bioactivity of GOx, probably because the enzyme-mediated AuNPs are close to the redox active centers of GOx. This enzyme electrode exhibited a linear amperometric response to glucose concentration (0.54 mmol·L^-1) at -0.4 V (vs. SCE), and a detection limit of …

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

Journal of Electrochemistry

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