Molecular Aspects in Porous Silicas Related to Adsorption and Catalytic Processes.

The aim of this special issue is to show the advances in the different applications that inorganic materials based on silica have had in recent years [...].

Nb-Based Catalysts for the Valorization of Furfural into Valuable Product through in One-Pot Reaction.

Nb-based catalysts supported on porous silica with different textural properties have been synthesized, characterized, and tested in the one-pot reaction of furfural to obtain valuable chemicals. The catalytic results reveal that the presence of fluoride in the synthesis, which limits the growing of the porous silica, limits diffusional problems of the porous silica, obtaining higher conversion values at shorter reaction times. On the other hand, the incorporation of NbOx species in the porous silica provides Lewis acid sites and a small proportion of Brönsted acid sites, in such a way that the main products are alkyl furfuryl ethers, which can be used as fuel additives.

The Role of Copper in the Hydrogenation of Furfural and Levulinic Acid.

Currently, there is a great interest in the development of sustainable and green technologies for production of biofuels and chemicals. In this sense, much attention is being paid to lignocellulosic biomass as feedstock, as alternative to fossil-based resources, inasmuch as its fractions can be transformed into value-added chemicals. Two important platform molecules derived from lignocellulosic sugars are furfural and levulinic acid, which can be transformed into a large spectrum of chemicals, by hydrogenation, oxidation, or condensation, with applications as solvents, agrochemicals, fragrances, pharmaceuticals, among others. However, in many cases, noble metal-based catalysts, scarce and expensive, are used. Therefore, an important effort is performed to search the most abundant, readily available, and cheap transition-metal-based catalysts. Among these, copper-based catalysts have been proposed, and the present review deals with the hydrogenation of furfural and levulinic acid, with Cu-based catalysts, into several relevant chemicals: furfuryl alcohol, 2-methylfuran, and cyclopentanone from FUR, and γ-valerolactone and 2-methyltetrahydrofuran from LA. Special emphasis has been placed on catalytic processes used (gas- and liquid-phase, catalytic transfer hydrogenation), under heterogeneous catalysis. Moreover, the effect of addition of other metal to Cu-based catalysts has been considered, as well as the issue related to catalyst stability in reusing studies.

Recent Advances in Mesoporous Materials and Their Biomedical Applications.

Since the beginning of civilization, porous materials have been used for medical purposes [...].

Influence of Structure-modifying Agents in the Synthesis of Zr-doped SBA-15 Silica and Their Use as Catalysts in the Furfural Hydrogenation to Obtain High Value-added Products through the Meerwein-Ponndorf-Verley Reduction.

Zr-doped mesoporous silicas with different textural parameters have been synthesized in the presence of structure-modifying agents, and then characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption-desorption at -196 °C, NH3 thermoprogrammed desorption (NH3⁻TPD), CO2 thermoprogrammed desorption (CO2⁻TPD), and X-ray photoelectron spectroscopy (XPS). These porous materials were evaluated in the furfural hydrogenation through the Meerwein-Ponndorf-Verley (MPV) reaction. The catalytic results indicate that the catalyst synthesized under hydrothermal conditions and adding a pore expander agent is more active and selective to furfuryl alcohol. However, the Zr-doped porous silica catalysts that were synthesized at room temperature, which possess narrow pore sizes, tend to form i-propyl furfuryl and difurfuryl ethers, coming from etherification between furfuryl alcohol (FOL) and isopropanol molecules (used as H-donor) by a SN2 mechanism.

Mesoporous Materials: From Synthesis to Applications.

Mesoporous silica are inorganic materials, which are formed by the condensation of sodium silicate or silicon alkoxides around an ordered surfactant used as template [...].

Porous SiO2 Nanospheres Modified with ZrO2 and Their Use in One-Pot Catalytic Processes to Obtain Value-Added Chemicals from Furfural.

Porous SiO2 nanospheres were modified with different loadings of ZrO2 to obtain catalysts with a Si/Zr molar ratio from 2.5 to 30. These materials were characterized by X-ray diffraction, transmission and scanning electron microscopies, N2 adsorption-desorption at -196 °C, X-ray photoelectron spectroscopy and pyridine and 2-6-dimethylpyridine thermoprogrammed desorption. The characterization of these catalysts has revealed that a high proportion of Zr favors the formation of Lewis acid sites, which are implied in catalytic transfer hydrogenation processes, whereas the low Brönsted acidity promotes a dehydration reaction, being possible to give rise to a large variety of products from furfural through consecutive reactions, such as furfuryl alcohol, i-propyl furfuryl ether, i-propyl levulinate, and γ-valerolactone, in a range of temperature of 110-170 °C and 1-6 h of reaction.

Evaluation of Cu-PPHs as active catalysts for the SCR process to control NOx emissions from heavy duty diesel vehicles.

Copper based catalysts supported on mesoporous materials, which were in turn based on a surfactant expanded zirconium phosphate for the formation of silica galleries in the interlayer space, were prepared by the impregnation method. They were then characterised and tested in the selective catalytic reduction of NO with ammonia as active catalysts for the control of the NOx emissions from heavy duty vehicles. Copper catalysts displayed a high catalytic performance, even in the presence of 14% (v/v) of H2O and 100 ppm of SO2. They also displayed improved catalytic behaviour when compared to a CuZSM5 catalyst.

Porous Silicon-Based Catalysts for the Dehydration of Glycerol to High Value-Added Products.

Increasing worldwide biodiesel production has led to the generation of an important glycerol surplus, which needs to be valorized in order to improve the economic and environmental sustainability of the biodiesel industry. In this context, glycerol dehydration to acrolein by acid catalysis appears to be a potential route of glycerol valorization, since acrolein is an important intermediate for many chemical industries. The main drawback of this catalytic process is catalyst deactivation. Different alternatives have been proposed for overcoming it, such as the use of mesoporous materials in order to facilitate the diffusion of glycerol and reaction products, thus minimizing deactivation. This review compiles the main achievements of the use of mesoporous silica-containing materials that have been deployed either as a catalyst or for support in glycerol dehydration to acrolein. Thus, the effect of mesoporosity on both catalytic performance and deactivation will be discussed, as well as the blocking of pores by coke deposition.

Selective Production of 2-Methylfuran by Gas-Phase Hydrogenation of Furfural on Copper Incorporated by Complexation in Mesoporous Silica Catalysts.

Copper species have been incorporated in mesoporous silica (MS) through complexation with the amine groups of dodecylamine, which was used as a structure-directing agent in the synthesis. A series of Cu/SiO2 catalysts (xCu-MS) with copper loadings (x) from 2.5 to 20 wt % was synthesized and evaluated in the gas-phase hydrogenation of furfural (FUR). The most suitable catalytic performance in terms of 2-methylfuran yield was obtained with an intermediate copper content (10 wt %). This 10Cu-MS catalyst exhibits a 2-methylfuran yield higher than 95 mol % after 5 h time-on-stream (TOS) at a reaction temperature of 210 °C with a H2 /FUR molar ratio of 11.5 and a weight hourly space velocity (WHSV) of 1.5 h-1 . After 14 h TOS, this catalyst still showed a yield of 80 mol %. In all cases, carbonaceous deposits on the external surface were the cause of the catalyst deactivation, although sintering of the copper particles was observed for higher copper loadings. This intermediate copper loading (10 wt %) offered a suitable balance between resistance to sintering and tendency to form carbonaceous deposits.

Dehydration of xylose to furfural over MCM-41-supported niobium-oxide catalysts.

A series of silica-based MCM-41-supported niobium-oxide catalysts are prepared, characterized by using XRD, N2 adsorption-desorption, X-ray photoelectron spectroscopy, Raman spectroscopy, and pyridine adsorption coupled to FTIR spectroscopy, and tested for the dehydration of D-xylose to furfural. Under the operating conditions used all materials are active in the dehydration of xylose to furfural (excluding the MCM-41 silica support). The xylose conversion increases with increasing Nb2 O5 content. At a loading of 16 wt % Nb2 O5 , 74.5 % conversion and a furfural yield of 36.5 % is achieved at 170 °C, after 180 min reaction time. Moreover, xylose conversion and furfural yield increase with the reaction time and temperature, attaining 82.8 and 46.2 %, respectively, at 190 °C and after 100 min reaction time. Notably, the presence of NaCl in the reaction medium further increases the furfural yield (59.9 % at 170 °C after 180 min reaction time). Moreover, catalyst reutilization is demonstrated by performing at least three runs with no loss of catalytic activity and without the requirement for an intermediate regeneration step. No significant niobium leaching is observed, and a relationship between the structure of the catalyst and the activity is proposed.