Hydrogenation of Carbon Dioxide to Dimethyl Ether on CuO-ZnO/ZSM-5 Catalysts: Comparison of Powder and Electrospun Structures.

The promising direct dimethyl ether (DME) production through CO2 hydrogenation was systematically analyzed in this research by synthesizing, characterizing, and testing several catalytic structures. In doing so, various combinations of precipitation and impregnation of copper- and zinc-oxides (CuO-ZnO) over a ZSM-5 zeolite structure were applied to synthesize the hybrid catalysts capable of hydrogenating carbon dioxide to methanol and dehydrating it to DME. The resulting catalytic structures, including the co-precipitated, sequentially precipitated, and sequentially impregnated CuO-ZnO/ZSM-5 catalysts, were prepared in the form of particle and electrospun fibers with distinguished chemical and structural features. They were then characterized using XRD, BET, XPS, ICP, TGA, SEM, and FIB-SEM/EDS analyses. Their catalytic performances were also tested and analyzed in light of their observed characteristics. It was observed that it is crucial to establish relatively small-size and well-distributed zeolite crystals across a hybrid catalytic structure to secure a distinguished DME selectivity and yield. This approach, along with other observed behaviors and the involved phenomena like catalyst particles and fibers, clusters of catalyst particles, or the whole catalytic bed, were analyzed and explained. In particular, the desired characteristics of a CuO-ZnO/ZSM-5 hybrid catalyst, synthesized in a single-pot processing of the precursors of all involved catalytically active elements, were found to be promising in guiding the future efforts in tailoring an efficient catalyst for this system.

Core-Sheath Pt-CeO2/Mesoporous SiO2 Electrospun Nanofibers as Catalysts for the Reverse Water Gas Shift Reaction.

One-dimensional (1D) core-sheath nanofibers, platinum (Pt)-loaded ceria (CeO2) sheath on mesoporous silica (SiO2) core were fabricated, characterized, and used as catalysts for the reverse water gas shift reaction (RWGS). CeO2 nanofibers (NFs) were first prepared by electrospinning (ES), and then Pt nanoparticles were loaded on the CeO2 NFs using two different deposition methods: wet impregnation and solvothermal. A mesoporous SiO2 sheath layer was then deposited by sol-gel process. The phase composition, structural, and morphological properties of synthesized materials were investigated by scanning electron microscope (SEM), scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), nitrogen adsorption/desorption method, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis, and CO2 temperature programmed desorption (CO2-TPD). The results of these characterization techniques revealed that the core-sheath NFs with a core diameter between 100 and 300 nm and a sheath thickness of about 40-100 nm with a Pt loading of around 0.5 wt.% were successfully obtained. The impregnated catalyst, Pt-CeO2 NF@mesoporous SiO2, showed the best catalytic performance with a CO2 conversion of 8.9% at 350 °C, as compared to the sample prepared by the Solvothermal method. More than 99% selectivity of CO was achieved for all core-sheath NF-catalysts.

Use of RSM for the multivariate, simultaneous multiobjective optimization of the operating conditions of aliphatic carboxylic acids ion-exclusion chromatography column: Quantitative study of hydrodynamic, isotherm, and thermodynamic behavior.

The present study evaluates the capability of ion exclusion chromatography (IEC) of short chain aliphatic carboxylic acids using a cation exchange column (8% sulfonated cross-linked styrene-divinylbenzene copolymer) in different experimental conditions. Since one of the prerequisites to the development of an efficient carboxylic acid separation process is to obtain the optimum operational conditions, response surface methodology (RSM) was used to develop an approach to evaluate carboxylic acids separation process in IEC columns. The effect of the operating conditions such as column temperature, sulfuric acid concentration as the mobile phase, and the flow rate was studied using Central Composite Face (CCF) design. The optimum operating conditions for the separate injection of lactic acid and acetic acid is temperature of 75 °C, sulfuric acid concentration of 0.003 N for both acids and flow rate of 0.916 (0.886) mL/min for acetic acid (lactic acid). Likewise, the optimum conditions for the simultaneous injection of acetic and lactic acid mixture are the column temperature of 68 °C, sulfuric acid concentration of 0.0003 N, and flow rate of 0.777 mL/min. In the next step, the adsorption equilibria of acetic acid and lactic acid on the stationary phase were investigated through a series of Frontal Analysis (FA), Frontal Analysis by Characteristic Points (FACP), and using Langmuir isotherm model. The results showed an excellent agreement between the model and experimental data. Finally, the results of thermodynamic studies proved that the IEC process for separation of acetic and lactic acid is a spontaneous, feasible, exothermic, and random process with a physical adsorption mechanism. The results of the current paper can be a valuable information in the stages of designing IEC columns for separation of aliphatic carboxylic acids.