The potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly.

Global warming issues and the medium-term depletion of fossil fuel reserves are stimulating researchers around the world to find alternative sources of energy and organic carbon. Biomass is considered by experts the only sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum in the production of chemicals and liquid transportation fuels. However, the transition from a petroleum-based economy to one based on biomass requires new strategies since the petrochemical technologies, well-developed over the last century, are not valid to process the biomass-derived compounds. Unlike petroleum feedstocks, biomass derived platform molecules possess a high oxygen content that gives them low volatility, high solubility in water, high reactivity and low thermal stability, properties that favour the processing of these resources by catalytic aqueous-phase technologies at moderate temperatures. This tutorial review is aimed at providing a general overview of processes, technologies and challenges that lie ahead for a range of different aqueous-phase transformations of some of the key biomass-derived platform molecules into liquid fuels for the transportation sector and related high added value chemicals.

A series of carbon molecular sieves (CMSs) has been prepared, either as powders or monoliths, from petroleum pitch using potassium hydroxide as the activating agent. The CMS monoliths are prepared without the use of a binder based on the self-sintering ability of the mesophase pitch. Characterization results show that these CMSs combine a large apparent surface area (up to ca. 3100 m(2) g(-1)) together with a well-developed narrow microporosity (V(n) up to ca. 1.4 cm(3) g(-1)). The materials exhibit high adsorption capacities for CO(2) at 1 bar and 273 K (up to ca. 380 mg CO(2) g sorbent(-1)). To our knowledge, this is the best result obtained for CO(2) adsorption using carbon-based materials. Furthermore, although the CO(2) adsorption capacity for activated carbons has usually been considered lower than that of zeolites, the reported values exceed the total amount adsorbed on traditional 13X and 5A zeolites (ca. 230 mg and 180 mg CO(2) g sorbent(-1), respectively), under identical experimental conditions. Additionally, the narrow pore openings found in the CMS samples (ca. 0.4 nm) allows for the selective adsorption of CO(2) from molecules of similar dimensions (e.g., CH(4) and N(2)).

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Catalytic hydrodeoxygenation (HDO) is a fundamental process for bio-resources upgrading to produce transportation fuels or added value chemicals. The bottleneck of this technology to be implemented at commercial scale is its dependence on high pressure hydrogen, an expensive resource which utilization also poses safety concerns. In this scenario, the development of hydrogen-free alternatives to facilitate oxygen removal in biomass derived compounds is a major challenge for catalysis science but at the same time it could revolutionize biomass processing technologies. In this review we have analysed several novel approaches, including catalytic transfer hydrogenation (CTH), combined reforming and hydrodeoxygenation, metal hydrolysis and subsequent hydrodeoxygenation along with non-thermal plasma (NTP) to avoid the supply of external H 2 . The knowledge accumulated from traditional HDO sets the grounds for catalysts and processes development among the hydrogen alternatives. In this sense, mechanistic aspects for HDO and the proposed alternatives are carefully analysed in this work. Biomass model compounds are selected aiming to provide an in-depth description of the different processes and stablish solid correlations catalysts composition-catalytic performance which can be further extrapolated to more complex biomass feedstocks. Moreover, the current challenges and research trends of novel hydrodeoxygenation strategies are also presented aiming to spark inspiration among the broad community of scientists working towards a low carbon society where bio-resources will play a major role. Figure 1. Three basic phenylpropane monomers: (1) p-coumaryl alcohol; (2) coniferyl alcohol; (3) sinapyl alcohol.

Although metal-organic framework (MOF) materials have been postulated as superior to any other sorbent for CO(2) adsorption at room temperature, here we prove that the appropriate selection of the raw material and the synthesis conditions allows the preparation of carbon molecular sieves (CMSs) with adsorption capacity, on a volumetric basis, highly exceeding those reported in the literature for MOFs. Furthermore, the excellent sorption properties of CMSs over the whole pressure range (up to 50 bar) are fully reversible after different adsorption/desorption cycles.

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