Kinetic Modeling for the “One-Pot” Hydrogenolysis of Cellulose to Glycols over Ru@Fe3O4/Polymer Catalyst

Despite numerous works devoted to the cellulose hydrogenolysis process, only some of them describe reaction kinetics. This is explained by the complexity of the process and the simultaneous behavior of different reactions. In this work, we present the results of the kinetic study of glucose hydrogenolysis into ethylene- and propylene glycols in the presence of Ru@Fe3O4/HPS catalyst as a part of the process of catalytic conversion of cellulose into glycols. The structure of the Ru-containing magnetically separable Ru@Fe3O4/HPS catalysts supported on the polymeric matrix of hypercrosslinked polystyrene was studied to propose the reaction scheme. As a result of this study, a formal description of the glucose hydrogenolysis process into glycols was performed. Based on the data obtained, the mathematical model of the glucose hydrogenolysis kinetics in the presence of Ru@Fe3O4/HPS was developed and the parameter estimation was carried out. The synthesized catalyst was found to be characterized by the enhanced magnetic properties and higher catalytic activity in comparison with previously developed catalytic systems (i.e., on the base of SiO2). The summarized selectivity towards the glycols formation was found to be ca. 42% at 100% of the cellulose conversion in the presence of Ru@Fe3O4/HPS.

Effects of Ru catalyst changes by atmospheric exposure days on the interfacial and impact properties of glass fiber/p-DCPD composites

The ruthenium (Ru) catalyst is the most recently developed poly dicyclopentadiene (p-DCPD) polymer catalyst known to promote stable reactions, even upon contact with oxygen. However, the experimental results showed that exposure times exceeding three days can cause problems during curing due to reaction between oxygen and Ru catalyst. Consequently, 12 days of exposure degraded the mechanical and interfacial properties of p-DCPD or p-DCPD composites reinforced with 40 wt% 50-mm GF by 60%. The structural analysis simulation of the target product also showed noticeable changes in the catalyst that was exposed to air atmosphere for more than six days, which can deteriorate quality. This study demonstrated that when molding structures using p-DCPD, special care should be taken to control atmospheric exposure of the ruthenium catalyst.

Versatile Coordination Polymer Catalyst for Acid Reactions Involving Biobased Heterocyclic Chemicals

The chemical valorization/repurposing of biomass-derived chemicals contributes to a biobased economy. Furfural (Fur) is a recognized platform chemical produced from renewable lignocellulosic biomass, and furfuryl alcohol (FA) is its most important application. The aromatic aldehydes Fur and benzaldehyde (Bza) are commonly found in the slate of compounds produced via biomass pyrolysis. On the other hand, glycerol (Gly) is a by-product of the industrial production of biodiesel, derived from fatty acid components of biomass. This work focuses on acid catalyzed routes of Fur, Bza, Gly and FA, using a versatile crystalline lamellar coordination polymer catalyst, namely [Gd(H4nmp)(H2O)2]Cl·2H2O (1) [H6nmp=nitrilotris(methylenephosphonic acid)] synthesized via an ecofriendly, relatively fast, mild microwave-assisted approach (in water, 70 °C/40 min). This is the first among crystalline coordination polymers or metal-organic framework type materials studied for the Fur/Gly and Bza/Gly reactions, giving heterobicyclic products of the type dioxolane and dioxane, and was also effective for the FA/ethanol reaction. 1 was stable and promoted the target catalytic reactions, selectively leading to heterobicyclic dioxane and dioxolane type products in the Fur/Gly and Bza/Gly reactions (up to 91% and 95% total yields respectively, at 90 °C/4 h), and, on the other hand, 2-(ethoxymethyl)furan and ethyl levulinate from heterocyclic FA.

Electrochemical CO2 reduction: water/catalyst interface versus polymer/catalyst interface

Due to the low solubility and diffusion coefficients of carbon dioxide in aqueous solution, the carbon dioxide electrolytic cells with aqueous electrolytes are difficult to achieve high conversion current density....

Efficient synthesis of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural over sulfonated organic polymer catalyst

The sulfonic acid grafted porous organic nitrogen-containing polymer (PDVTA-SO3H) exhibited excellent catalytic activity in the synthesis of 5-ethoxymethylfurfural (EMF) from 5-hydroxymethylfurfural (HMF).

Redox-Mediated Polymer Catalyst for Lithium-Air Batteries with High Round-Trip Efficiency

Lithium-air batteries (LABs) continue to receive attention as a promising power source because they possess a high theoretical energy density of 3436 Wh L−1. However, the remaining Li2O2 resulting from the irreversible decomposition of Li2O2 during the charge process is one of the key challenges so as to address the deterioration of the cycling performance of LABs. In this study, we propose and report a redox-mediated polymer catalyst (RPC) as a cathode catalyst being composed of LiI and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with multi-wall carbon nanotubes (MWCNTs) as the cathode material. In the RPC, iodine molecules are chemically combined with the PVDF-HFP chain. The as-prepared RPC exhibits increased cycling performance by 194% and decreased overpotential by 21.1% at 0.1 mA cm−2 compared to the sample without LiI molecules. Furthermore, these results suggest that the RPC consisting of a polymer chain and redox mediators will be extensively utilized as highly efficient catalysts of LABs.