An Agile Innovation Framework Supported through Business Incubators

Part 9: Innovation Networks

Ir supported over carbon materials for the selective hydrogenation of chloronitrobenzenes

In the present work we have studied the effect of carbon supports with different graphitic character (carbon nanotubes, mesoporous graphite and activated carbon) on the catalytic performance of iridium nanoparticles on the liquid phase chemoselective hydrogenation of para-chloronitrobenzene at room temperature. The effect of the oxygen groups was also evaluated by oxidizing a portion of the carbon nanotubes. The Raman and XRD spectra showed that the mesoporous graphite displayed the strongest graphitic character. The characterization of the catalysts by HR-TEM, XPS and TPR-H2, showed that the catalysts had similar particle size and that the catalysts prepared over the previously oxidized support, Ir/CNTox, was not fully reduced. The activity and selectivity achieved with the catalyst Ir/CNT was the best among the samples and the presence of irdium oxide on Ir/CNTox diminished the yield to p-chloroaniline, being the worse catalyst. The reactivity of different isomers was also studied over Ir/CNT and it followed the order m > o > p.

Selective hydrogenation by novel composite supported Pd egg-shell catalysts

Two organic–inorganic mixed phase supports were prepared, comprising an alumina filler and polymers of different chemical nature. Four low loaded Pd catalysts were prepared. Good activities and selectivities were obtained during the hydrogenations of styrene, 1-heptyne and 2,3-butanedione. The catalysts were found to have excellent mechanical properties and could be used in applications needing high attrition resistance and crushing strength. In this sense, processes for fine chemicals using slurry reactors or processes for commodities using long packed beds could advantageously use them.

Platinum supported on highly-dispersed ceria on activated carbon for the total oxidation of VOCs

Catalysts consisting in platinum supported on cerium oxide highly dispersed on activated carbon, with a Pt loading of 1 wt.% and ceria loadings of 5, 10 and 20 wt.% have been prepared by impregnation method and characterized by several techniques (N2 adsorption at 77 K, ICP, XRD, H2-TPR and XPS). Their catalytic behavior has been evaluated in the total oxidation of ethanol and toluene after reduction at 473 K. The obtained results show that the prepared catalysts have better performances than platinum supported on bulk CeO2. The best catalytic performance was obtained for 10 wt.% ceria loading, likely due to an optimum synergistic interaction between highly dispersed cerium oxide and platinum particles. Pt-10Ce/C achieves total conversion of ethanol and toluene to CO2 at 433 K and 453 K, respectively, and shows no deactivation during a test for 100 h. Under humid conditions (relative humidity, RH, of 40 and 80%), the activity was only slightly influenced due to the hydrophobic character of the activated carbon support, which prevents the adsorption of water.

Carbon-supported ionic liquids as innovative adsorbents for CO2 separation from synthetic flue-gas

Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.

Green synthesis of polypyrrole-supported metal catalysts: application to nitrate removal in water

Pt and Pt/Sn catalysts supported on polypyrrole (PPy) have been prepared using Ar plasma to reduce the metal precursors dispersed on the polymer. The PPy support was synthesized by chemical polymerization of pyrrole with FeCl3·6H2O, this leading to the conducting form of the polymer (conductimetric measurements). The Ar plasma treatment produced a partial reduction of platinum ions, anchored as platinum chloro-complexes to the PPy chain, into metallic platinum. A homogeneous distribution of Pt and Sn nanoparticles was observed by TEM. Activity of the PPy-supported catalysts was evaluated in the reduction of aqueous nitrate with H2 at room temperature. Nitrate concentration in water below the maximum acceptable level of 50 mg L−1 was achieved with all catalysts. However, considering not only efficiency in nitrate reduction, but also minimized concentrations of undesired nitrite and ammonium, the monometallic Pt catalyst seems to be the most promising one.

Earth-Abundant Zinc-IV-Nitride Semiconductors

This investigation is motivated by the need for new visible frequency direct bandgap semiconductor materials that are abundant and low-cost to meet the increasing demand for optoelectronic devices in applications such as solid state lighting and solar energy conversion. Proposed here is the utilization of zinc-IV-nitride materials, where group IV elements include silicon, germanium, and tin, as earth-abundant alternatives to the more common III-nitrides in optoelectronic devices. These compound semiconductors were synthesized under optimized conditions using reactive radio frequency magnetron sputter deposition. Single phase ZnSnN₂, having limited experimental accounts in literature, is validated by identification of the wurtzite-derived crystalline structure predicted by theory through X-ray and electron diffraction studies. With the addition of germanium, bandgap tunability of ZnSn_xGe_1-xN₂ alloys is demonstrated without observation of phase separation, giving these materials a distinct advantage over In_xGa_1-xN alloys. The accessible bandgaps range from 1.8 to 3.1 eV, which spans the majority of the visible spectrum. Electron densities, measured using the Hall effect, were found to be as high as 10²² cm⁻³ and indicate that the compounds are unintentionally degenerately doped. Given these high carrier concentrations, a Burstein-Moss shift is likely affecting the optical bandgap measurements. The discoveries made in this thesis suggest that with some improvements in material quality, zinc-IV-nitrides have the potential to enable cost-effective and scalable optoelectronic devices.

Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].

Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex

Materials that combine photoluminescence, optical transparency and facile processability are of high importance in many applications. This article reports on the development of photoluminescent poly(methyl methacrylate) materials based on novel highly emissive anionic molybdenum cluster complex [{Mo6I8}(OTs)6]2- (where OTs- is the p-toluenesulfonate ion). The materials were obtained by both solution and bulk copolymerisation of methyl methacrylate and (dMDAEMA)2[{Mo6I8}(OTs)6], where dMDAEMA+ is the polymerisable cation [2-(methacryloyloxy)ethyl]dimethyl-dodecylammonium. Evaluation of the resultant hybrid materials showed that one could combine the excellent photoluminescent properties of the cluster complex with the transparency and processability of PMMA.

Developmentof engineering projects supported by BIM technology: internship report

Building Information Modeling (BIM) concept is able to reshape each AEC project and the industry in general, offering a comprehensive collaboration process over a model of structure with regularly actualized and synchronized information. This report presents an overview of BIM with focus on its core concepts, applications in the project life cycle and benefits for project stakeholders through four case studies carried out during the internship in the engineering office NEWTON - Engineering Consultancy Company. The aim of the four cases studies was to cover multidisciplinary and varied projects. The first case study highlights the engineering project’s workflow and presents a comparison of traditional procedures and BIM concepts applied on the rehabilitation of an existing building. In the second and third case study, attention is focused on the goals achieved, particularly by structural engineer, due to the implementation of the mentioned technology on a full-lifecycle BIM project of a small residence and a complex project of residential building in Porto and on its architectural integration. In addition, through the fourth case study, the spatial coordination of Mechanical, Electrical and Plumbing (MEP) systems at a large-scale hotel project has been analyzed and accomplished, highlighting merits of BIM at this project stage. Through a reduction of the space used for facilities and infrastructures and the ability to identify conflicts and to nullify the related costs, its advantage for a complex building was proved.

Child-centred design supported by comprehensive child application use analysis

Since children already use and explore applications on smartphones, we use this as the starting point for design. Our monitoring and analysis framework, BaranC, enables us to discover and analyse which applications children uses and precisely how they interact with them. The monitoring happens unobtrusively in the background so children interact normally in their own natural environment without artificial constraints. Thus, we can discover to what extent a child of a particular age engages with, and how they physically interact with, existing applications. This information in turn provides the basis for design of new child-centred applications which can then be subject to the same comprehensive child use analysis using our framework. The work focuses on the first aspect, namely, the monitoring and analysis of current child use of smartphones. Experiments show the value of this approach and interesting results have been obtained from this precise monitoring of child smartphone usage.

The public interest of sports at non-profi t sports organizations that are supported by the government

This paper analyses the concept of public interest in sport and the criteria that must be taken into consideration in terms of Government support to clubs and sports associations. The data was collected through semi structured interviews that were applied to nine sports directors with board responsibilities: seven of them from sport clubs and sport associations, and two of them from public administration. The directors pointed out that sport is considered to be of public interest when: it is developed in the concept of “sport for all”, provides health benefi ts and serves as a means of education and social development. Regarding advantages used with public utility status, tax benefi ts and partnerships with the sports system organizations were the most mentioned aspects. Given a better use of fi nancial resources provided by public administration to clubs and associations, sport directors believe that the Government should have a strategy focused on setting priorities and ranking fi nancing criteria for sport. If the government had that strategy, the development of sports results would be much better. The participants also suggest that the Government should conduct an assessment of the social role of sport clubs and associations, according to the public and social interest of sport. In conclusion, sport and physical activity should be considered as public interest activities, provided that: are able to ensure positive effects on health plans and wellness, provide a qualitative and sustainable sport development, improve economic and social development of a population.

Dynamical modeling of biogas production supported by an experimental anaerobic digestion process

This paper presents the development of a combined experimental and numerical approach to study the anaerobic digestion of both the wastes produced in a biorefinery using yeast for biodiesel production and the wastes generated in the preceding microbial biomass production. The experimental results show that it is possible to valorise through anaerobic digestion all the tested residues. In the implementation of the numerical model for anaerobic digestion, a procedure for the identification of its parameters needs to be developed. A hybrid search Genetic Algorithm was used, followed by a direct search method. In order to test the procedure for estimation of parameters, first noise-free data was considered and a critical analysis of the results obtain so far was undertaken. As a demonstration of its application, the procedure was applied to experimental data.

Nanocarbon-Supported Electrocatalysts for the Alkaline Water Splitting and Fuel Cells

Electrocatalysts play a significant role in the processes of electrochemical energy conversion. This thesis focuses on the preparation of carbon-supported nanomaterials and their application as electrocatalysts for alkaline water electrocatalysis and fuel cell. A general synthetic route was developed, i.e., species intercalate into carbon layers of graphite forming graphite intercalation compound, followed by dispersion producing graphenide solution, which then as reduction agent reacts with different metal sources generating the final materials. The first metal precursor used was non-noble metal iron salt, which generated iron (oxide) nanoparticles finely dispersed on carbon layers in the final composite materials. Meanwhile, graphite starting materials differing in carbon layer size were utilized, which would diversify corresponding graphenide solutions, and further produce various nanomaterials. The characterization results showed that iron (oxide) nanoparticles varying in size were obtained, and the size was determined by the starting graphite material. It was found that they were electrocatalytically active for oxygen reactions. In particular, the one with small iron (oxide) nanoparticles showed excellent electrocatalytic activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Afterwards, the metal precursor was tuned from non-noble metal salt to noble metal salt. It was confirmed that carbon-supported Rh, Pt, and RhPt (oxide) nanoparticle composite materials were also successfully obtained from the reaction between graphenide solution and corresponding noble metal precursor. The electrochemical measurements showed that the prepared noble metal-based nanomaterials were quite effective for hydrogen evolution reaction (HER) electrocatalysis, and the Rh sample could also display excellent electrocatalytic property towards OER. Moreover, by this synthetic approach carbon-supported noble metal Pt and non-noble metal nickel (Ni) composite material was also prepared. Therefore, the utilization efficiency of noble metal could be improved. The prepared NiPt sample displayed a property close to benchmark HER electrocatalyst.

Development of predictive energy management strategies for hybrid electric vehicles supported by connectivity

Nowadays, the spreading of the air pollution crisis enhanced by greenhouse gases emission is leading to the worsening of the global warming. In this context, the transportation sector plays a vital role, since it is responsible for a large part of carbon dioxide production. In order to address these issues, the present thesis deals with the development of advanced control strategies for the energy efficiency optimization of plug-in hybrid electric vehicles (PHEVs), supported by the prediction of future working conditions of the powertrain. In particular, a Dynamic Programming algorithm has been developed for the combined optimization of vehicle energy and battery thermal management. At this aim, the battery temperature and the battery cooling circuit control signal have been considered as an additional state and control variables, respectively. Moreover, an adaptive equivalent consumption minimization strategy (A-ECMS) has been modified to handle zero-emission zones, where engine propulsion is not allowed. Navigation data represent an essential element in the achievement of these tasks. With this aim, a novel simulation and testing environment has been developed during the PhD research activity, as an effective tool to retrieve routing information from map service providers via vehicle-to-everything connectivity. Comparisons between the developed and the reference strategies are made, as well, in order to assess their impact on the vehicle energy consumption. All the activities presented in this doctoral dissertation have been carried out at the Green Mobility Research Lab} (GMRL), a research center resulting from the partnership between the University of Bologna and FEV Italia s.r.l., which represents the industrial partner of the research project.