Three-dimensional graphene aerogels of controlled pore size have emerged as an important platform for several applications such as energy storage or oil-water separation. The aerogels of reduced graphene oxide are mouldable and light weight, with a porosity up to 99.9%, consisting mainly of macropores. Graphene aerogel preparation by self-assembly in the liquid phase is a promising strategy due to its tunability and sustainability. For graphene aerogels prepared by a hydrothermal method, it is known that the pH value has an impact on their properties but it is unclear how pH affects the auto-assembly process leading to the final properties. We have monitored the time evolution of the chemical and morphological properties of aerogels as a function of the initial pH value. In the hydrothermal treatment process, the hydrogel is precipitated earlier and with lower oxygen content for basic pH values (∼13 wt% O) than for acidic pH values (∼20 wt% O). Moreover, ∼7 wt% of nitrogen is incorporated on the graphene nanosheets at basic pH generated by NH addition. To our knowledge, there is no precedent showing that the pH value affects the microstructure of graphene nanosheets, which become more twisted and bent for the more intensive deoxygenation occurring at basic pH. The bent nanosheets attained at pH = 11 reduce the stacking by the basal planes and they connect via the borders, hence leading eventually to higher pore volumes. In contrast, the flatter graphene nanosheets attained under acidic pH entail more stacking and higher oxygen content after a long hydrothermal treatment. The gravimetric absorption capacity of non-polar solvents scales directly with the pore volume. The aerogels have proved to be highly selective, recyclable and robust for the absorption of nonpolar solvents in water. The control of the porous structure and surface chemistry by manipulation of pH and time will also pave the way for other applications such as supercapacitors or batteries.

Reduced graphene oxide (rGO) is widely seen as the most promising route for the low-cost mass production of graphene for many applications ranging from ultrathin electrodes to structural nanocomposites. The Hummers and Marcano methods are the two most successful approaches for producing high-performance rGO, but have been criticized for producing toxic emissions. We have applied life cycle assessment methodology to evaluate the environmental impacts of both production routes for GO and rGO in the context of applications requiring bulk materials or thin coatings. We find no current obstacle to the industrial scale production of graphene arising from its environmental impact. The cumulative energy demand is found to have a cap value between 20.7 and 68.5 GJ/Kg, a relatively high value; impact in other categories (such as human toxicity or resource depletion) is lower, and materials inventory does not include critical/strategic materials other than graphite itself. Our study proposes 1 kg of graphene as functional unit, and an application-specific functional unit normalized by conductivity which show that Hummers production method is far more suitable for bulk applications of graphene, with lower embedded energy per kg of graphene production, while Marcano's production method is better suited for thin film electronic applications.

Catalytic co-pyrolysis of grape seeds and waste tyres was performed in a fixed-bed reactor using calcined calcite as a catalyst. The organic phase obtained was analysed for its further application as a potential and stable drop-in fuel. Remarkable positive effects were achieved after the joint incorporation of both waste tyres and calcined calcite to grape seeds in the process. More specifically, the addition of considerable amounts of waste tyres (between 20 and 40 wt%) with a constant ratio of feedstock to calcined calcite of 1 were considered the optimal experimental conditions to promote positive synergistic effects on bio-oil yields and its characteristics as a fuel. Thus, when the proportion of waste tyres in the feed reached 40 wt%, the organic phase yield was considerable improved, reaching up values higher than 73 wt%, significantly greater than those obtained from conventional pyrolysis (61 wt%). Moreover, oxygen content was reduced to 4.2 wt%, minimizing any problems related to corrosivity and instability.HHV was enlarged from 15.3 up to 27.3 MJ/kg, significantly increasing the value of the resulting bio-oil. pH values and specially total acid number were also improved reaching values down to 1 mg KOH/g bio-oil in all cases. Additionally, a more valuable chemical composition was achieved since the production of aromatic and cyclic hydrocarbons was maximized, while a significant reduction in phenolic compounds was achieved. Moreover, bio-oil sulphur content was drastically reduced in comparison with the pyrolysis of waste tyres by itself from 0.6 down to 0.2 wt%. The role of calcined calcite was directly related to the promotion of dehydration reactions of acids and phenols in order to generate hydrocarbons. On the other hand, radical interactions between the biomass and waste tyres pyrolysis products played a fundamental role in the production of more valuable compounds. Finally, the CO 2 capture effect produced a more environmentally friendly gas while maintaining its calorific value.

Co-pyrolysis of grape seeds and polystyrene was conducted in a fixed-bed reactor, followed by an analysis of the organic phase for possible further application as a drop-in fuel. Significant positive synergistic effects were found with the addition of polystyrene (5-40 wt%) to the conventional pyrolysis of grape seeds. There was a considerable improvement in the organic phase yield, in particular, reaching values over 80 wt%, markedly higher than those obtained from conventional pyrolysis (61 wt%). Fuel properties of the bio-oil were also upgraded, with a decrease in oxygen content and an increase in the heating value. An organic bio-oil fraction with pH values ranging from 5.4 to 6.2 was obtained, reducing the issues associated with handling bio-oils obtained from common pyrolysis of lignocellulosic biomass, usually ranging between 2 and 3. Finally, an increment in the desired compounds, mainly aromatics, was also attained, while at the same time achieving a low content of undesired compounds, such as phenols. It was demonstrated that polystyrene can act as a H 2-donor, favoring oligomerization, cyclation and hydrodeoxygenation reactions into aromatic compounds.

The catalytic co-pyrolysis of grape seeds and waste tyres for the production of high-quality bio-oils was studied in a pilot-scale Auger reactor using different low-cost Ca-based catalysts. All the products of the process (solid, liquid, and gas) were comprehensively analysed. The results demonstrate that this upgrading strategy is suitable for the production of better-quality bio-oils with major potential for use as drop-in fuels. Although very good results were obtained regardless of the nature of the Ca-based catalyst, the best results were achieved using a high-purity CaO obtained from the calcination of natural limestone at 900 °C. Specifically, by adding 20 wt% waste tyres and using a feedstock to CaO mass ratio of 2:1, a practically deoxygenated bio-oil (0.5 wt% of oxygen content) was obtained with a significant heating value of 41.7 MJ/kg, confirming its potential for use in energy applications. The total basicity of the catalyst and the presence of a pure CaO crystalline phase with marginal impurities seem to be key parameters facilitating the prevalence of aromatisation and hydrodeoxygenation routes over the de-acidification and deoxygenation of the vapours through ketonisation and esterification reactions, leading to a highly aromatic biofuel. In addition, owing to the CO2-capture effect inherent to these catalysts, a more environmentally friendly gas product was produced, comprising H2 and CH4 as the main components.