N. Mota

Catalysts for Hydrogen Production from Heavy Hydrocarbons

Sustainable hydrogen production is a key target in the development of future alternative energy systems for providing a clean and affordable energy supply. Nowadays, the lack of widely available sources of H2 dictates the use of logistic fuels, multicomponent mixtures containing a large number of hydrocarbons, in the near term as a way to facilitate the introduction of hydrogen in energy systems, as this option entails no extra capital cost for developing the infrastructure and so relieves the economic pressure on moving to a hydrogen economy. A further advantage is that developments in the field of hydrogen generation from conventional fuels could be applied to the extraction of hydrogen from other liquid fuels that contain heavy hydrocarbons produced from biomass, thereby providing a bridge for the transition of hydrogen production from fossil fuels to renewable production from biomass. Catalysts for hydrogen production from heavy hydrocarbons have made remarkable progress in recent years, but there are various technical challenges, mainly low activity and durability, that need to be addressed for future improvement. This Review provides an overview of the research progress on hydrogen production from logistic hydrocarbons. The challenges for catalysts applied to the reforming of logistic hydrocarbons are discussed in detail to reveal the specific needs for each of the main reforming processes used with such hydrocarbons: Steam reforming, partial oxidation, and autothermal reforming. The four challenges for each process are activity, sulfur poisoning, carbon formation, and sintering. An overview is provided of the research strategies and approaches adopted in search of catalysts that respond to the above challenges; that is, selection of active phase, promoters, and supports and control of the synthesis of materials for customizing the crystallinity, electronic structure and morphology of catalysts at the nanoscale.

CO Oxidation at 20 °C on Au Catalysts Supported on Mesoporous Silica: Effects of Support Structural Properties and Modifiers

In this work we report the effects of support structural properties and its modification with some metal oxides modifiers on the catalytic behavior of Au catalysts in the total CO oxidation at 20 °C. Au catalysts were supported on mesoporous silica materials (MSM) having different structural properties: Channel-like (SBA-15), cage-like (SBA-16), hexagonal (HMS), and disordered (DMS-1) structures. The effect of the modifier was evaluated by comparison of the catalytic response of the SBA-15-based catalysts modified with MgO, Fe2O3, TiO2, and CeO2. The chemical, structural, and electronic properties of the catalysts were investigated by a variety of techniques (metal content analysis by ICP-OES, N2 physisorption, XRD, UV-vis DRS, DRIFTS of adsorbed CO and OH regions, oxygen storage capacity (OSC), HR-TEM, and XPS). The activity of calcined catalysts in the CO oxidation reaction were evaluated at steady state conditions, at 20 °C, atmospheric pressure, and when using, as feed, a 1%CO/1%O2/98% gas mixture. The work clearly demonstrated that all Au catalysts supported on the mesoporous silicas modified with metal oxides were more active than the Au/SBA-15 and Au/MgO reference ones. The support structural properties and type of dopant were important factors influencing on the catalyst behavior. Concerning the support textural properties, it was found that the HMS substrate with the wormhole-structure offers better porosity and specific surface area than their silica counterparts having channel-like (SBA-15), cage-like (SBA-16), and disordered (DMS-1) mesoporous structures. Concerning the effect of modifier, the best catalytic response was achieved with the catalysts modified with MgO. After activation by calcination at 200 °C for 4 h, the Au/MgO/HMS catalyst exhibited the best catalytic performance, which was ascribed to the combined effects of the best structural properties, a large support oxygen storage capacity and homogeneous distribution of gold particles on the support (external and inner). Implications of the type of active sites (Au1+ or Au0), support structural properties and role of modifier on the catalytic activity are discussed.

Influence of the Reduction of Graphene Oxide with Hydroiodic Acid on the Structure and Photoactivity of CdS–rGO Hybrids

The temperature used in the chemical reduction of graphene oxide (GO) with hydroiodic acid has a significant influence on the removal of surface oxygenated functional groups, on the residual iodine species and on the rupture, stacking and graphitization of the graphene sheets in the reduced graphene oxides. The modification in the characteristics of the reduced graphene oxides induces changes in the surface area, the exposition of reduced graphene oxide entities and in the concentration of small CdS nanocrystals with strong confinement effect on the CdS-reduced graphene oxide hybrids. The hybridization of the reduced graphene oxide with CdS modifies in different way their photocatalytic behavior for hydrogen production from aqueous solutions of Na2S and Na2SO3 under simulated sunlight irradiation. Only the hybrid formed between the CdS and the reduced graphene oxide treated at higher temperature showed improved hydrogen production rate respect to the bare CdS reference associated with the better conductivity of the reduced graphene oxide and with the increase in the concentration of small CdS nanocrystals sith strong confinement effect observed in the hybrid.

Highly active Cu/ZnO–Al catalyst for methanol synthesis: effect of aging on its structure and activity

The influence of aging of precipitates on the physical and catalytic properties of a copper/zinc oxide-aluminium (Cu/ZnO–Al) catalyst with an optimized composition (low Al concentration, Cu/Zn/Al = 68/29/3) prepared using co-precipitation has been investigated in detail. The change in the structure of precipitates with aging (from amorphous zincian georgeite to crystalline zincian malachite) strongly influences the micro- and nano-structure (Cu and ZnO crystallite size, exposed copper surface area, Cu–ZnO interactions and stability of ZnO) of the final Cu/ZnO–Al catalysts obtained after calcination and reduction of the precipitates. The results of catalytic activity in methanol synthesis from syngas show the higher intrinsic activity of the catalysts derived from aged zincian malachite precipitates as consequence of the increase in the exposed copper surface area and the Cu–ZnO contacts. The stability of catalysts under the reaction conditions was also improved in the catalysts derived from precipitates aged after crystallization of malachite. The catalyst derived from the precipitate removed close to the point of crystallization of malachite shows very poor activity in the methanol synthesis as consequence of its segregated large Cu crystallites in low contact with ZnO derived from the absence of carbonate retention after calcination of the precipitate and the presence of sodium species after conventional washing which favour the strong sintering and crystallization of Cu during reduction.