Manufacture of Carbon Materials with High Nitrogen Content

Nowadays one of the biggest challenges for carbon materials is their use in CO2 capture and their use as electrocatalysts in the oxygen reduction reaction (ORR). In both cases, it is necessary to dope the carbon with nitrogen species. Conventional methods to prepare nitrogen doped carbons such as melamine carbonization or NH3 treatment generate nitrogen doped carbons with insufficient nitrogen content. In the present research, a series of activated carbons derived from MOFs (ZIF-8, ZIF-67) are presented. Activated carbons have been prepared in a single step, by pyrolysis of the MOF in an inert atmosphere, between 600 and 1000 °C. The carbons have a nitrogen content up to 20 at.% and a surface area up to 1000 m2/g. The presence of this nitrogen as pyridine or pyrrolic groups, and as quaternary nitrogen are responsible for the great adsorption capacity of CO2, especially the first two. The presence of Zn and Co generates very different carbonaceous structures. Zn generates a greater porosity development, which makes the doped carbons ideal for CO2 capture. Co generates more graphitized doped carbons, which make them suitable for their use in electrochemistry.Authors acknowledge financial support by MINECO (Spain) through the project MAT2017-86992-R and “Ministerio de Ciencia e Innovación” (PID2020-116998RB-I00)

Valorization of CO2 through the Synthesis of Cyclic Carbonates Catalyzed by ZIFs

One way to exploit CO2 is to use it as a feedstock for the production of cyclic carbonates via its reaction with organic epoxides. As far as we know, there is still no heterogeneous catalyst that accelerates the reaction in a selective, efficient and industrially usable way. Cobalt and zinc-based zeolitic imidazole frameworks (ZIFs) have been explored as heterogeneous catalysts for this reaction. In particular, we have prepared ZIF-8 and ZIF-67 catalysts, which have been modified by partial replacement of 2-methylimidazole by 1,2,4-triazole, in order to introduce uncoordinated nitrogen groups with the metal. The catalysts have shown very good catalytic performance, within the best of the heterogeneous catalysts tested in the cycloaddition of CO2 with epichlorohydrin. The catalytic activity is due ultimately to defects on the outer surface of the crystal, and varies in the order of ZIF-67-m > ZIF-67 > ZiF-8-m = ZIF-8. Notably, reactions take place under mild reaction conditions and without the use of co-catalysts.The authors acknowledge financial support by MINECO (Spain) through the projects MAT2017-86992-R and CTQ2017-88171-P, “Ministerio de Ciencia e innovación” (PID2020-116998RB-I00), Ministerio de Educación y Formación Profesional (PRX21/00407), and Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022, MFA/2022/048)

Post-synthetic ligand exchange as a route to improve the affinity of ZIF-67 towards CO2

The Zeolitic Imidazolate Framework 67 (ZIF-67) is a highly promising material owing to its exceptional thermal stability, large specific surface area, cost-effectiveness, and versatile applications. One of the potential applications of ZIF-67 is gas separation processes, among which the separation of CO2/CH4 mixtures has attracted great interest nowadays in the biogas sector. However, when it comes to CO2/CH4 separation, ZIF-67 falls short as it lacks the desired selectivity despite its high adsorption capacity. This limitation arises from its relatively low affinity towards CO2. In this study, we have addressed this issue by partially exchanging the ligand of ZIF-67, specifically replacing 2-methylimidazole with 1,2,4 (1H) triazole, which introduces an additional nitrogen atom. This modification resulted in ZIF-67 showing significantly enhanced affinity towards CO2 and, as a result, greater selectivity towards CO2 over CH4. The modified materials underwent thorough characterization using various techniques, and their adsorption capacity was evaluated through high-pressure adsorption isotherms. Furthermore, their separation performance was assessed using the Ideal Solution Adsorption Theory, which provided valuable insights into their potential for efficient gas separation.Financial support from Ministerio de Ciencia e Innovación (Spain, PID2020-116998RB-I00) is gratefully acknowledged. Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana

Post-Synthetic Surface Modification of Metal–Organic Frameworks and Their Potential Applications

Metal–organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance. This article summarizes different types of post-synthetic modifications and possible applications of modified materials such as: catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids.The authors acknowledge financial support by Ministerio de Ciencia e Innovación (PID2020-116998RB-I00), Ministerio de Educación y Formación Profesional (PRX21/00407), Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022), and the King Abdullah University of Science and Technology (KAUST). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana

Reactive Infiltration: Effects of Different Parameters

Currently, the production of complex SiC and SiC/SiC parts through reactive infiltration is one of the most widely used technologies, due to its versatility and cost-effectiveness compared to more conventional technologies such as Hot Isostatic Pressing (HIP). This technology, while widely adopted, still faces some debate regarding the mechanisms of infiltration. Questions persist about what determines how infiltration occurs and whether the process is governed by physics (flow dynamics) or chemistry (reactions at the triple line (LT: (contact line between the solid, liquid and gas phases)). The present work provides new strong/consistent proof that reactive infiltration is mainly controlled by chemical reaction

Enhancing Trace Metal Extraction from Wastewater: Magnetic Activated Carbon as a High-Performance Sorbent for Inductively Coupled Plasma Optical Emission Spectrometry Analysis

A new fast, sensitive, and environmentally friendly analytical method has been developed for the simultaneous determination of Ba, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn in wastewater samples using inductively coupled plasma optical emission spectroscopy (ICP OES). A preconcentration step using a magnetic dispersive solid-phase extraction (MDSPE) technique with a new magnetic sorbent was performed. The new sorbent material was a carbon containing magnetic cobalt and nitrogen groups. This material was synthetized using controlled pyrolysis of a zeolitic imidazolate framework (i.e., ZIF-67). In order to optimize the experimental parameters that affect the MDSPE procedure, a multivariate optimization strategy, using Plackett–Burman and circumscribed central composite designs (CCD), was used. The method has been evaluated employing optimized experimental conditions (i.e., sample weight, 10 g; sample pH, 7.6; amount of sorbent, 10 mg; dispersive agent, vortex; complexing agent concentration, 0.5%; ionic concentration, 0%; eluent, HCl; eluent concentration, 0.5 M; eluent volume, 300 μL; elution time, 3 min and extraction time, 3 min) using external calibration. Limits of detection (LODs) in a range from 0.073 to 1.3 μg L−1 were obtained, and the repeatability was evaluated at two different levels, resulting in relative standard deviations below 8% for both levels (n = 5). An increase in the sensitivity was observed due to the high enrichment factors (i.e., 3.2 to 13) obtained compared with direct ICP OES analysis. The method was also validated through carrying out recovery studies that employed a real wastewater sample and through the analysis of a certified reference material (ERM®-CA713). The recovery values obtained with the real wastewater were between 94 and 108% and between 90 and 109% for the analysis of ERM®-CA713, showing negligible matrix effects

Metal–Organic Frameworks as Formose Reaction Catalysts with Enhanced Selectivity

The formose reaction is an autocatalytic series of aldol condensations that allows one to obtain monosaccharides from formaldehyde. The formose reaction suffers from a lack of selectivity, which hinders practical applications at the industrial level. Over the years, many attempts have been made to overcome this selectivity issue, with modest results. Heterogeneous porous catalysts with acid–base properties, such as Metal–Organic Frameworks (MOFs), can offer advantages compared to homogeneous strong bases (e.g., calcium hydroxide) for increasing the selectivity of this important reaction. For the very first time, four different Zeolite Imidazolate Frameworks are presented in this work as catalysts for the formose reaction in liquid phase, and their catalytic performances were compared with those of the typical homogeneous catalyst (i.e., calcium hydroxide). The heterogeneous nature of the catalysis, the possible contribution of leached metal or linkers to the solution, and the stability of the materials were investigated. The porous structure of these solids and their mild basicity make them suitable for obtaining enhanced selectivity at 30% formaldehyde conversion. Most of the MOFs tested showed low structural stability under reaction conditions, thereby indicating the need to search for new MOF families with higher robustness. However, this important result opens the path for future research on porous heterogeneous basic catalysts for the formose reaction.This research was funded by Junta de Andalucía through projects PY18-RE-0012 y “Carbocat” IE18_0047_FUNDACIÓN LOYOLA, Ministerio de Ciencia e Innovación (PID2020-116998RB-I00), and Consellería de Innovación, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana