The Small Unit Cell Reconstructions of SrTiO3 (111)

We analyze the basic structural units of simple reconstructions of the (111) surface of SrTiO3 using density functional calculations. The prime focus is to answer three questions: what is the most appropriate functional to use; how accurate are the energies; what are the dominant low-energy structures and where do they lie on the surface phase diagram. Using test calculations of representative small molecules we compare conventional GGA with higher-order methods such as the TPSS meta-GGA and on-site hybrid methods PBE0 and TPSSh, the later being the most accurate. There are large effects due to reduction of the metal d oxygen sp hybridization when using the hybrid methods which are equivalent to a dynamical GGA+U, which leads to rather substantial improvements in the atomization energies of simple calibration molecules, even though the d-electron density for titanium compounds is rather small. By comparing the errors of the different methods we are able to generate an estimate of the theoretical error, which is about 0.25eV per 1x1 unit cell, with changes of 0.5-1.0 eV per 1x1 cell with the more accurate method relative to conventional GGA. An analysis of the plausible structures reveals an unusual low-energy TiO2-rich configuration with an unexpected distorted trigonal biprismatic structure. This structure can act as a template for layers of either TiO or Ti2O3, consistent with experimental results as well as, in principle, Magnelli phases. The results also suggest that both the fracture surface and the stoichiometric SrTiO3 (111) surface should spontaneously disproportionate into SrO and TiO2 rich domains, and show that there are still surprises to be found for polar oxide surfaces.Comment: 14 pages, 4 Figure

Socio‐economic opportunities from Miscanthus cultivation in marginal land for bioenergy

Substantial areas of agricultural land in south European countries are becoming increasingly marginal and being abandoned due to arid climate with prolonged summers and low rainfall. Perennial, lignocellulosic crops, such as Miscanthus, offer an outlet that couples agriculture with energy, creates employment, and increases profits from feedstock production in rural areas. This research paper follows an Input Output methodology and uses an econometric model to investigate the impact of crop yielding performance and marginal land to jobs and profit from the cultivation and supply of Miscanthus in low quality, marginal land in Italy and Greece. Two value chain cases are analysed: small scale Combined Heat and Power (CHP) and Fast Pyrolysis Bio Oil (FPBO). The cultivation of Miscanthus in both reference value chains exhibits good employment prospects, with smaller scale value chains creating more labour‐intensive logistics operations. The activities can also generate substantial financial profit especially with higher crop yields. Results show a pronounced relationship between profitability and crop yield for both reference value chains ‐ cultivation and supply operations become more profitable with increasing yield. It is, therefore, important to achieve higher yields through good cropping practices, while maintaining high levels of environmental sustainability

Blending of Hydrothermal Liquefaction Biocrude with Residual Marine Fuel: An Experimental Assessment

As with all transport modes, the maritime sector is undergoing a drastic transition towards net zero, similar to the path in which Aviation is already engaged through global decarbonization programs such as CORSIA for the International Civil Aviation Organization, or the Emission trading Scheme of the European Union). Maritime indeed shares with Aviation a common element: the difficulty of shifting to electric in the short to medium term. Therefore, the use of sustainable fuels represents the main and only relevant option in this timeframe. As sustainable biofuels will be used as blend components in the case of large-scale deployment, it is necessary to investigate the behavior of bio-and fossil-based fuels when mixed in various percentages, in particular for low quality products such as HTL (HydroThermal Liquefaction) and fast pyrolysis oils from lignocellulosic biomass and waste. Biocrude from subcritical hydrothermal liquefaction of undigested sewage sludge, produced at reaction conditions of 350◦ C and 200 bar in a continuous HTL pilot scale unit, was manually mixed at 70◦ C with residual marine fuel (low-sulphur type F-RMG-380 per ISO 8217) at two different nominal biocrude shares, respectively 10 wt.% and 20 wt.% in the mixture. While the former blend resulted in the technically complete dissolution of biocrude in the fossil component, the latter sample formed biocrude agglomerates and only partial dissolution of the biocrude aliquot in marine fuel could be achieved (calculated between 14–16 wt.%). The blend with 10 wt.% of SS biocrude in the mixture resulted in compliance with limits of total acid number (TAN), inorganics (in particular vanadium, sodium, silicon and aluminum) and sulphur content, while only the ash content was slightly above the limit

The Potential Role of Ammonia for Hydrogen Storage and Transport: A Critical Review of Challenges and Opportunities

Hydrogen is being included in several decarbonization strategies as a potential contributor in some hard-to-abate applications. Among other challenges, hydrogen storage represents a critical aspect to be addressed, either for stationary storage or for transporting hydrogen over long distances. Ammonia is being proposed as a potential solution for hydrogen storage, as it allows storing hydrogen as a liquid chemical component at mild conditions. Nevertheless, the use of ammonia instead of pure hydrogen faces some challenges, including the health and environmental issues of handling ammonia and the competition with other markets, such as the fertilizer market. In addition, the technical and economic efficiency of single steps, such as ammonia production by means of the Haber–Bosch process, ammonia distribution and storage, and possibly the ammonia cracking process to hydrogen, affects the overall supply chain. The main purpose of this review paper is to shed light on the main aspects related to the use of ammonia as a hydrogen energy carrier, discussing technical, economic and environmental perspectives, with the aim of supporting the international debate on the potential role of ammonia in supporting the development of hydrogen pathways. The analysis also compares ammonia with alternative solutions for the long-distance transport of hydrogen, including liquefied hydrogen and other liquid organic carriers such as methanol

Production and characterization of co-composted biochar and digestate from biomass anaerobic digestion

Biochar, produced through pyrolysis of lignocellulosic biomass, is attracting increasing interest as soil amendment thanks to its potential numerous benefits to agriculture, as well as its ability to sequester carbon in soil. Solid fraction of digestate from anaerobic digestion is a well-known N-rich substrate, most often composted in large and small agro-industrial plants. Co- composting biochar and digestate has the potential to synergistically increase the agronomic value of both components: however, it needs further process and on-field research. The present research work reports on the experimental tests on producing biochar and co-composting various biochar amounts with digestate from biomass anaerobic digestion (product here named COMBI). Biochar was produced by feeding wood chips from chestnut to an innovative oxidative reactor. In order to evaluate the quality of the products obtained by composting and co-composting, correlating this with the final biochar rate in the material, the net organic matter yield, the humified organic matter, the compliance with the European Compost Network Quality Assurance Scheme (ECN-QAS) limits for inorganic pollutants, and the product stabilization and sanitization indexes were investigated. The 11.2% w/w d.b. biochar rate in the initial blend (19.8% w/w d.b final concentration in the co-composted products) offered the best performances and is recommended for further investigation. Additional benefits from co-composting were also assessed, as the reduced dust load that favors safety and health during logistics and use

Post covid-19 recovery and 2050 climate change targets: Changing the emphasis from promotion of renewables to mandated curtailment of fossil fuels in the eu policies

The present work considers the dramatic changes the COVID-19 pandemic has brought to the global economy, with particular emphasis on energy. Focusing on the European Union, the article discusses the opportunities policy makers can implement to reduce the climate impacts and achieve the Paris Agreement 2050 targets. The analysis specifically looks at the fossil fuels industry and the future of the fossil sector post COVID-19 pandemic. The analysis first revises the fossil fuel sector, and then considers the need for a shift of the global climate change policy from promoting the deployment of renewable energy sources to curtailing the use of fossil fuels. This will be a change to the current global approach, from a relative passive one to a strategically dynamic and proactive one. Such a curtailment should be based on actual volumes of fossil fuels used and not on percentages. Finally, conclusions are preliminary applied to the European Union policies for net zero by 2050 based on a two-fold strategy: continuing and reinforcing the implementation of the Renewable Energy Directive to 2035, while adopting a new directive for fixed and over time increasing curtailment of fossils as of 2025 until 2050

Thermochemical conversion of microalgae: challenges and opportunities

Research in Advanced Biofuels steadily developed during recent years. A number of highly innovative technologies have been explored at various scale: among these, lignocellulosic ethanol and CTO (Crude Tall Oil)-biofuel technologies already achieved the early-commercial status, while hydrotreating of vegetable oils (HVO, or HEFA) can be considered today fully commercial. However, despite the level of innovation in each specific technological process under consideration, the feedstock maintains a central role in making a biofuel chain really sustainable. In this context, microalgae grown in salt-water and arid areas offers a considerable opportunity for advanced biofuel production: at the same time, however, they also represent a considerable challenge. Processing microalgae in an economic way into a viable and sustainable liquid biofuel (a low-cost mass-produced product) is not trivial. So far, the main attention has been given to cultivating the microorganism, accumulating lipids, extracting the oil, valorising co-products, and treating the algae oil into biodiesel (through esterification) or HEFA (Hydrotreated Esthers and Fatty Acids), this second one representing a very high quality biofuels, almost a drop-in fuel (suitable either for road transport or for aviation), which production exceed 2 Mt y-1 today. However, extracting the algae oil at low cost and at industrial scale is not yet a full industrial mature process, and the still limited market size of algae-to-biofuels makes difficult the development of industrial-scale systems. Nevertheless, another option can be considered, i.e. processing the whole algae into dedicated thermochemical reactors, thus approaching the downstream processing of algae in a completely different way from separation. The present work examines the possible routes for thermochemical conversion of microalgae, distinguishing between dry-processes (namely pyrolysis and gasification) and wet-processes (near critical water hydrothermal liquefaction and hydrothermal gasification). Typical expected elementary composition of major products is given. Main peculiarities of batch versus continuous processing are also discussed from an engineering point of view. Major engineering advantages and challenges in thermochemically conversion of algae are identified and discussed, in view of the production of a transport biofuel. Finally, future perspectives for each route are given in terms of current and expected technological readiness level

The potential role of biomethane for the decarbonization of transport: An analysis of 2030 scenarios in Italy

This paper aims at evaluating the best allocation of potential biomethane generation for the decarbonization of the transport system, presenting a case study in Italy. The country has some peculiar features, such as several operating biogas plants, additional potential feedstock for biogas/biomethane generation, a well-developed natural gas network and established relevant natural gas uses in different final sectors, including transport. Based on current estimates for sustainable biomethane potential by 2030, ranging from 2.3 to 7.6 billion cubic meters depending on the scenario, the analysis compares technologies for the generation, distribution and final use of biomethane. The results of the analysis confirm the potential interesting contribution of biomethane in decarbonizing the Italian transport system: a billion cubic meters of biomethane can lead to 2.33–4.37 MtCO2e savings, depending on the feedstock mix and the application. On a national basis, annual climate emission savings in 2030 range from 10.0 to 26.7 MtCO2e, depending on the scenario. Additional 3.1–8.1 MtCO2e of emissions can be avoided if the CO2 captured during the biomethane upgrading can be stored or reused. The proposed methodology could be used to extend the analysis to other countries, and to the European context

Study on the effects of carbon dioxide atmosphere on the production of biochar derived from slow pyrolysis of organic agro-urban waste

Slow pyrolysis, a widely recognized thermochemical technique, is employed to produce biochar usually under inert atmospheres. Recently, there is a growing interest in utilizing CO2 as a carrier gas during pyrolysis as an alternative to inert atmospheres, aiming to modify the resulting pyrolytic products and make them suitable for different applications. This study investigated and compared the impact of CO2 atmosphere with N2 on pyrolysis of food waste, rice husk, and grape tree branches waste via slow pyrolysis at temperatures of 400, 500, and 600 degrees C at 5 and 15 degrees C/min for 1 h, to evaluate biochar production and its properties. The results demonstrate that CO2 atmosphere increased the biochar yield for all feedstocks and significantly influenced the physicochemical properties of biochar. Compared to N2, CO2-derived biochar exhibited less volatile matter, higher carbon content, lower O/H and O/C molar ratios and enhanced textural properties. This study highlighted the potential of utilizing CO2 for biochar production and tailoring biochar properties for specific applications and the findings contribute to the establishment of sustainable and efficient waste management systems and the production of value-added biochar products