The Role of Microenvironment Reagent Solubility on Reaction Kinetics of 4-Nitrophenol Reduction

The Role of Microenvironment Reagent Solubility on Reaction Kinetics of 4-Nitrophenol Reduction Michael Zeevi1 with Andrew Harrison1 and Christina Tang, PhD1 1Department of Chemical and Life Science Engineering, VCU School of Engineering Introduction: Nanoparticles are of increasing interest due to their high surface area to volume ratio, as well as that they enable fine-tuning of the reaction microenvironment. Through flash nanoprecipitation, core-shell polymer nanoreactors were formed by directed self-assembly. Using the reduction of 4-nitrophenol as a model reduction reaction, we investigated the effect of reagent solubility in the nanoreactor microenvironment’s on nanoreactor kinetics. Methods: The standard reaction was conducted at room temperature, with a 1000-fold excess of sodium borohydride in a quartz cuvette for real-time in situ­ UV-Vis analysis. Reagent concentrations were varied to examine the resulting effect on the calculated reaction rate constant. Reagent solubility limits in the nanoreactor microenvironment were estimated from solubility measurements in solvents with similar Hansen solubility parameters. Ethanol was chosen to represent the hydrophilic poly(ethylene) glycol phase and chloroform was chosen to represent the hydrophobic polystyrene phase. The hydrophilic phase had a visual absorbance at nm, and thus UV-Vis spectrometry was used to determine the saturation concentration. 1H NMR analysis with chloroform-D containing an internal standard (v/v TMS 0.03%) was used to measure the reagent solubility in the hydrophobic phase. Results: 4-nitrophenol solubility in ethanol was determined by UV-Vis spectrometry to be . The solubility in chloroform-D was determined by 1H NMR to be . When 4-nitrophenol concentration is varied independently of sodium borohydride, an inverse relationship is observed with respect to the rate constant. However, when 4-nitrophenol and sodium borohydride concentrations are varied concurrently, no change is witnessed in the rate constant above the standard reaction concentration. Conclusions: This experiment demonstrated that the rate of reaction in polystyrene core nanoreactors is not dependent on the reagent concentrations above the standard concentration. Solubility in each phase was measured in an effort to explain this behavior. The differences in solubility observed between the hydrophobic and hydrophilic phases may serve to explain this behavior if the interior, hydrophobic phase is saturated by 4-nitrophenol at the standard concentration. Future work should include study of concentrations at lower values than the standard concentration to determine when a change in the observed rate constant occurs.https://scholarscompass.vcu.edu/uresposters/1287/thumbnail.jp

Research of kinetic characteristics of the process of decomposition of zinc concentrate with hydrochloric acid

The aim of the study was the theoretical justification of the kinetic characteristics of the process of producing zinc chloride from zinc concentrate of the Khandiza deposit. For this, the effect of temperature and duration of the process of autoclave zinc extraction in a 28% hydrochloric acid solution was studied at a ratio of Zn: HCI = 1:1.1. Variable parameters were the temperature of 70, 80 and 90 °C and the duration of the leaching process of 6, 8 and 10 hours. The optimal parameters for the production of zinc chloride were determined

Phenol Deoxygenation over Hydrotreating Catalysts

Phenol deoxygenation has been investigated as a model reaction for the deoxygenation of fatty acid methyl esters in biodiesel. Hydrodeoxygenated biodiesel is a drop-in fuel for petroleum diesel, and is a premium diesel with a high cetane number. As the first step in this research, two molybdenum catalysts were prepared, characterized and tested in a small-scale reactor. These catalysts were found to produce small amounts of benzene and cyclohexanol in the product stream, and confirmed the activity of the catalyst. A commercial cobalt molybdenum catalyst (Harshaw HT-400) was also tested and benzene, cyclohexanol, and cyclohexane were identified as products. Future work aims to synthesize catalysts to produce a high yield of cyclohexane. Once the conditions are optimized, we will do tests with biodiesel

Synthesis of Copper Oxide Nanoparticles in Droplet Flow Reactors

Synthesis of metal oxide nanoparticles within droplet flow reactors is advantageous over batch synthesis due to the elimination of concentration and temperature gradients inside the reactor and prevention of reactor fouling. We present results on the synthesis of copper oxide nanoparticles using aqueous droplets of copper acetate and acetic acid inside a bulk stream of sodium hydroxide in 1-octanol. Varying the copper acetate, acetic acid, and sodium hydroxide concentration resulted in needle-like and plate-like nanoparticles of varying sizes. The rate of mass transfer from the bulk to the droplet phase was found to increase with flow rate and addition of surfactants

Effect of Thiols for Nitrogen Reduction to Ammonia

Ammonia is an important chemical used for fertilizers and also a potential carbon-free hydrogen storage medium. The Haber-Bosch process is the main production process, which requires large energy- and capital-input. Therefore, it is crucial to develop an alternate scalable synthesis that provides a less energy intensive and more economical route for synthetic ammonia production. In this paper, a 1Fe1Ni film was functionalized with C3OH and C6OH for the electrochemical synthesis of ammonia. This work will provide some insight into how thiol ligands can increase the selectivity of the catalyst for nitrogen reduction reaction and can be improved on to provide a new synthesis for ammonia

Anodes for Direct Oxidation of Hydrocarbons in Solid Oxide Fuel Cells

In this paper we describe the development of Cu/CeO2/YSZ anodes for solid oxide fuel cells (SOFCs) that are active for the direct electrochemical oxidation of dry hydrocarbon fuels. A novel method for synthesizing thin-electrolyte, anode-supported cells is described. This method uses tape-casting of YSZ layers with graphite pore formers, followed by impregnation with aqueous solutions of Cu(NO3)2 and Ce(NO3)2. The performance of model SOFCs with Cu/CeO2/YSZ anodes while operating on a variety of dry hydrocarbon fuels, including methane, butane, decane, and synthetic diesel is reported

Photocatalytic Decomposition of Phenol under Visible and UV Light Utilizing Titanium Dioxide Based Catalysts

Pollution in wastewater effluvia from phenol and phenolic compounds is a common occurrence in many industrial manufacturing plants. Phenol is toxic to human beings as well as a contaminant to the environment, meanwhile, it is difficult to remove from wastewater due to its non-biodegradable nature. To boost the rate of decomposition, various catalytic approaches have been developed. With the interest of decreasing operation cost, titanium dioxide (TiO2) based catalysts have emerged as good candidates for the photocatalytic process. In this honors project, a series of TiO2 based catalysts, including TiO2, N-TiO2, Cu-TiO2, and Cu-N-TiO2, were utilized to study the decomposition of phenol. Each catalyst was studied under the visible light (589nm) and UV light (385nm) conditions. The UV-Vis spectrophotometer was used to evaluate the catalytic performance. The results revealed that the addition of nitrogen improved the decomposition rate of phenol compared with that of TiO2 itself. Copper did not show improved photocatalysis and requires further investigation