ABSTRACT
This scientific review delves into the innovative realm of polyolefins/light alkanes valorization through their catalytic dehydrogenation employing pincer-ligated iridium organometallic complexes. These widely studied catalysts exhibit outstanding properties, although the intrinsic characteristics of homogeneous catalysis (such as challenging product-catalyst separation, poor applicability to continuous-flow processes and low recyclability) limit their activity and industrial application, as well as their thermal stability. Through the immobilization of complexes on inorganic supports, these downsides have been bypassed, harnessing the true potential of these catalysts, affording more selective and stable catalysts in addition to facilitating their implementation in industrial processes. The findings described herein contribute to the advancement in the understanding of catalytic processes in hydrocarbon transformations, offering promising avenues for sustainable and selective production of valuable chemical intermediates from readily available feedstocks.
ABSTRACT
Noble metal-free catalyst or catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid are proposed in this study as a proposal to solve one of the great disadvantages of this reaction of using preferably noble metal-based catalysts. The catalytic activity of six MnO2 crystal structures is studied as alternative. The obtained results showed a strong connection between catalytic activity the type of MnO2 structure organization and redox behavior. Among all tested catalysts, ϵ-MnO2 showed the best performance with an excellent yield of 74 % of 2,5-furandicarboxylic acid at full -hydroxymethylfurfural conversion.
ABSTRACT
Cotton stalks-based biochars were prepared and used to synthetize Ru-supported catalysts for selective production of γ-valerolactone from levulinic acid in aqueous media. Different biochars' pre-treatments (HNO3, ZnCl2, CO2 or a combination of them) were carried out to activate the final carbonaceous support. Nitric acid treatment resulted in microporous biochars with high surface area, whereas the chemical activation with ZnCl2 substantially increases the mesoporous surface. The combination of both treatments led to a support with exceptional textural properties allowing the preparation of Ru/C catalyst with 1422 m2/g surface area, 1210 m2/g of it being a mesoporous surface. The impact of the biochars' pre-treatments on the catalytic performance of Ru-based catalysts is fully discussed.
ABSTRACT
The CO2 methanation performance of Mg- and/or Ce-promoted Ni catalysts supported on cellulose-derived carbon (CDC) was investigated. The samples, prepared by biomorphic mineralization techniques, exhibit pore distributions correlated to the particle sizes, revealing a direct effect of the metal content in the textural properties of the samples. The catalytic performance, evaluated as CO2 conversion and CH4 selectivity, reveals that Ce is a better promoter than Mg, reaching higher conversion values in all of the studied temperature range (150-500 °C). In the interval of 350-400 °C, Ni-Mg-Ce/CDC attains the maximum yield to methane, 80%, reaching near 100% CH4 selectivity. Ce-promoted catalysts were highly active at low temperatures (175 °C), achieving 54% CO2 conversion with near 100% CH4 selectivity. Furthermore, the large potential stability of the Ni-Mg-Ce/CDC catalyst during consecutive cycles of reaction opens a promising route for the optimization of the Sabatier process using this type of catalyst.
ABSTRACT
A series of gold catalysts supported on pure CeO2, ZrO2, and two different Ce-Zr mixed oxides have been prepared and tested in the 5-hydroxymethyl-2-furfural oxidation reaction. All catalysts show high catalytic activity (100% conversion) and important selectivity (27-41%) to the desired product i.e., 2,5-furandicarboxylic acid at low base concentration. Products selectivity changes with the support nature as expected, however, the observed trend cannot be related neither to gold particle size, nor to catalyst reducibility and oxygen mobility. An important relation between the FDCA selectivity and the support textural properties is observed, conducing to the general requirement for optimal pore size for this reaction.
ABSTRACT
The understanding of major zeolite applications is partially based on diffusion of molecules inside or outside microporous networks. However, it is still a challenge to measure such phenomena. The diffusion ordered nuclear magnetic resonance spectroscopy (DOSY) technique has been reported to measure a probe molecule's diffusion inside porous solids. Pulsed-field gradient (PFG)-NMR has been used herein to measure the self-diffusivity of different probe molecules, such as neopentane, benzene, toluene and 1-dodecene with increasing dynamic diameter, respectively, on a series of H-ZSM-5 zeolites. The latter materials exhibit different crystal sizes, Si/Al ratios and the presence (or absence) of crystalline defects. In addition, shaped zeolite bodies representing industrial catalysts were compared with the afore-mentioned samples.
ABSTRACT
The development of technologies that allow us to reduce CO2 emissions is mandatory in today's society. In this regard, we present herein a comparative study of CO2 adsorption over three types of materials: zeolites, layered double hydroxides (LDH), and zeolites coated LDH composites. The influence of the zeolite Si/Al ratio on zeolites sorption capacity along with the presence of mesopores was investigated. By comparing these results with the well-known performance of LDHs, we aim to provide insights on the factors that may influence the CO2 capture capacity over zeolites, thus providing useful tools for tuning their properties upon post-treatments.
ABSTRACT
The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid-an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.
