In alphabetical order of the surname of the supervisor:
1. A Versatile Mechanochemical Route for Valorisation of Industrial Biodiesel Co-Products
The conversion of biomass into fuels and chemicals has attracted increasing interest from the academic to the industry, in order to develop effective alternatives to fossil-based carbon sources. A major route for lowering biodiesel cost is the valorisation of by-products in the transesterification industrial process, through clean and selective transformations to a wide variety of organic intermediates and high-value chemicals. This project aims the simple preparation of dispersed composites and their application and optimization as catalysts for the transformation of by-products into commodities, such as lactic acid, plastics, alcohols, and additives for biodiesel and diesel mixtures.
Supervisor: Elisabete C.B.A. Alegria (CQE/Técnico-ULisboa)
Co-supervisors: João Gomes (IBB), Jaime Puna (IBB)
Registration Institution: Técnico-ULisboa
2. Design of Magnetically Recoverable Nanocomposited Catalysts for Degradation of Antibiotics
This research proposal aims to design/develop new sustainable oxidative biomimetic catalytic processes for degradation of antibiotics, using magnetically recoverable nanocomposited catalysts based on metallo-tetrapyrrolic macrocycles. It encompasses 3 transversal parts: i) synthesis of conveniently functionalized porphyrins/phthalocyanines and their attachment to previously derivatized iron magnetic nanoparticles; ii) full spectroscopic and analytical characterization and structure-property evaluation of new catalytic systems; iii) evaluation of catalysts potential in the catalytic and photocatalytic degradation of antibiotics, using H2O2 or O2 as sustainable oxidants, nontoxic and earth-abundant first-row metal complexes organic moieties, in presence or absence of visible light, along with catalyst recoverability.
Supervisor: Mário Calvete (FCT-UCoimbra)
Co-supervisors: João Tomé (CQE/Técnico-ULisboa), M. Ermelinda Eusébio (FCT-UCoimbra)
Registration Institution: UCoimbra
3. Synthesis of High Added-Value Products Using Hybrid Catalysts and Microwave Irradiation
The development of sustainable catalytic processes for the activation of inexpensive and abundant small molecules (namely alcohols) to produce high added-value products is a great challenge. The use of hybrid catalysts and microwave irradiation presents additional advantages. In this work, functionalized complexes of several metals will be synthesized, characterized (namely by NMR, ESI-MS, X-ray measurements, etc.) and immobilized on carbon materials (e.g., carbon nanotubes, carbon nanohorns, nanodiamonds, graphenes), that allow easy functionalization. The hybrid catalysts will be used for the synthesis of high added value products of industrial significance using microwave irradiation.
Supervisor: Sónia Carabineiro (CQE/Técnico-ULisboa)
Co-supervisor: Carlos Geraldes (UCoimbra)
Registration Institution: UCoimbra
4. Oxidation of Hydrocarbons Catalyzed by Metal Complexes Supported on Silica-Based Porous Materials
The quest for efficient, stable and selective catalysts is a continuous task. The possibility to combine the advantages of homogeneous and heterogeneous catalysts by immobilizing metal complexes on solid supports is of great importance. The use of silica-based porous materials has additional advantages, since silica has flexible bonding properties and excellent stability. In this work, silica-based porous materials will be synthesized and used as supports for the immobilization of several (Mo, Au, Cu, V, Ni, among others) metal complexes. The obtained materials will be tested as catalysts in the oxidation of hydrocarbons (alkanes and alkenes) to yield important chemical products.
Supervisor Sónia Carabineiro (CQE/Técnico-ULisboa)
Co-supervisor: João Silva (Ciências-ULisboa)
Registration Institution: Ciências-ULisboa
5. Novel Materials as Catalyst Supports to Enhance Industrial Oxidations
The study to be development under this PhD work plan aims to prepare new catalysts for selective oxidation processes with industrial interest: oxidation of cyclohexane to cyclohexene/cyclohexanol, and of p-xylene to terephthalic acid. To achieve this goal the catalytic properties of immobilized V, Fe and Cu scorpionates onto carbon and zeolitic based supports will be explored. The initial phase of the studies will be centered on the supports which will be obtained exploring new and sustainable processes of synthesis or modification processes using, for example, renewable biomass as carbon materials precursor. The project follows Green Chemistry principles: the immobilization of the complexes in the solid matrices will allow catalysts reuse, and moderate temperature conditions and environmentally friendly oxidants (e.g. H2O2) will be tested.
Supervisor: Ana Paula Carvalho (Ciências-ULisboa)
Co-supervisors: Luísa Martins (CQE/Técnico-ULisboa), Angela Martins (Ciências-ULisboa and ISEL)
Registration Institution: Ciências-ULisboa
6. Development of New Methodologies for Biomass Valorization Using Mo and Re Complexes as Catalysts
Biomass conversion is currently one of the most challenging tasks for academics and industry due to the growing concerns about diminishing fossil resources, global warming and environmental pollution. Biomass, which is widespread, abundant and inexpensive, is regarded to be an ideal substitute for fossil resources. The main goal of this work is to develop new methodologies for the conversion of biomass resources into fuels, added value chemicals and biological compounds using homogeneous and heterogeneous molybdenum and rhenium catalysts.
Supervisior: Ana Cristina Fernandes (CQE/Técnico-ULisboa)
Co-supervisior: Carla Nunes (CQB/Ciências-ULisboa)
Registration Institution: Técnico-ULisboa
7. High-Value Chemicals from Small and Inexpensive Molecules: Activating N2, CO, and CO2 Using Transition Metals
The use of inexpensive and abundant feedstocks in the synthesis of high-value chemicals is a long standing goal in chemistry. In particular, the formation of N-C bonds from N2 and CO or CO2 is appealing since N2 is one of the most abundant molecules on Earth, CO2 is a greenhouse gas and CO is toxic. Using these sources of nitrogen and carbon is challenging, especially N2, one of the most stable molecules known. Success in the formation of these bonds will certainly attract the attention of both industry and academia. This project aims at the development of new group 4 metal catalysts, supported by monoanionic macrocyclic ligands, for N2 activation and subsequent functionalization with CO and CO2. The experimental work will be complemented by theoretical calculations in order to understand the reactivity and mechanisms of activation of these small molecules.
Supervisor: Maria João Ferreira (CQE/Técnico-ULisboa)
Co-supervisors: Maria José Calhorda (DQB/Ciências-ULisboa), Paulo Jorge Costa (DQB/Ciências-ULisboa)
Registration Institution: Técnico-ULisboa
8. Genesis of Novel Nitrogen Multifunctional Ligands: Synthesis, Reactivity and Catalytic Applications
Pioneering molecular systems, particularly derived from small heterocyclic azole rings, will be projected to be used as catalysts in relevant synthetic protocols. Multifunctional nitrogen ligands and their corresponding metal complexes, including chiral and achiral derivatives, should be able to alter their functionality and in particular stereoselectivity in situ via an external stimulus (e.g. radiation) in a repeatable/dynamic process. An integrated approach based on structural (X-ray), mechanistic (DFT calculations) and synthetic work will be considered during the development of synthetic methodologies for the preparation of target catalytic species.
Supervisor: Luís M. T. Frija (CQE/Técnico-ULisboa)
Co-supervisors: Teresa M.V.D. Pinho Melo (FCT-UCoimbra), Igor D. Reva (FCT-UCoimbra)
Registration Institution: Técnico-ULisboa
9. New Nickel, Cobalt and Iron complexes of Nitrenium Ligands: Catalytic Applications in Polymerisation, Hydrogenation and Coupling Reactions
N-heterocyclic carbenes are universal ligands in coordination/organometallic chemistry, since they not only bind to any transition metal, either in low or high oxidation states, but also stabilise and activate metal centres in quite different key catalytic steps of organic syntheses. The aim of this research project is the synthesis of new nickel, cobalt and iron complexes containing the newly proposed nitrenium chelating ligands, which are isostructural and isoelectronic analogues of N-heterocyclic carbenes. These novel bidentate or tridentate ligands are characterised by the possibility of structural modification and tuning, in order to transmit different electronic and/or steric features to the metal centre, allowing these complexes to behave as catalysts in selected reactions (polymerisation of olefins, alkene hydrogenation and Kumada coupling).
Supervisor: Clara S. B. Gomes (CQE/Técnico-ULisboa)
Co-supervisor: Teresa Avilés (UNova)
Registration Institution: Técnico-ULisboa
10. Photoactive Antimicrobial and Self-Cleaning Biofibers Through the Immobilization of Nanoparticles
Yellowing of natural fibers is one of the most widespread quality issues on several industrial sectors, particularly for textile business, associated to significant economic penalties. It is mainly caused by fiber damage due to chemical or biological degradation, exposure to excessive heat and/or intensive or long-term exposure to light radiation (photoyellowing). This project aims to overcome this biofibers burden through the immobilization of new nanophotocatalytic systems. New TiO2 based nanoparticles and/or TiO2-nanocomposite structures will be explored. The peculiarity of the new TiO2 based nano-systems is the ability to provide not only yellowing resistance to the fibers but also antimicrobial and self-cleaning properties, which are intrinsic to these NPs. The innovative nano-based biofibers composites will offer new functionalities and a higher life-cycle to the conventional biofibers.
Supervisor: João Gomes (IBB)
Co-supervisors: Maria Luísa Serralheiro (Ciencias-ULisboa), Elisabete Silva Geraldes (Ciências-ULisboa and IBB)
Registration Institution: Ciências-ULisboa or Técnico-ULisboa
11. New Metal Catalysts for the Production of Eco-friendly Recyclable Rubbers and Biocompatible/Biodegradable Plastics
Rubber and plastics recycling is an important current topic connected with environmental, waste and energy contemporary issues. Recently, we developed bulky N,N-bidentate 2-iminopyrrolyl ligand precursors (N^N). In this work the synthesis, characterization and reactivity studies (experimental and theoretical) of new early-transition metal complexes of the types [M(N^N)2Cl2] and [M(N^N)2(OR)2] (M= Ti, Zr; R= alkyl, aryl) will be carried out. The first type are potential promising precatalysts for the living polymerization of olefins to polymers and, especially, to block-copolymers that are recyclable thermoplastic elastomer (TPE) rubbers. The second type will be used as well-defined catalysts for the stereoselective living ring-opening polymerization (ROP) of lactides to biocompatible/biodegradable polylactide plastics.
Supervisor: Pedro T. Gomes (CQE/Técnico-ULisboa)
Co-supervisor: Maria José Calhorda (Ciências- ULisboa)
Registration Institution: Técnico-ULisboa
12. New Hydrogenation, Hydroboration and Hydroformylation Homogeneous Catalysts based on Earth Abundant Transition Metals
Homogeneous catalysis is going through a renaissance period owing to the efforts in the replacement of the classical expensive, rare and endangered (in the earth’s crust) metals used (e.g. Pd, Pt, Rh), by more sustainable, cheap and abundant first-row transition-metals such as Fe, Co, Ni. In line with these greener trends, we recently prepared bulky N,N-bidentate 2-iminopyrrolyl ligand precursors (N^N), and managed to synthesize the first cases of highly unsaturated complexes of the type [M(N^N)(L)Cl] (M= Fe, Co; L= neutral donor). In this work, we propose the extension of these synthetic and reactivity studies to obtain 2-iminopyrrolyl Fe and Co complexes in different oxidation states, containing N^N ligands modified by chiral groups, which will be studied as catalysts for the asymmetric hydrogenation, hydroboration and hydroformylation of alkenes.
Supervisor: Pedro T. Gomes (CQE/Técnico-ULisboa)
Co-supervisor: Mariette Pereira (FCT-UCoimbra)
Registration Institution: Técnico-ULisboa or FCT-UCoimbra
13. Catalysts for CO2 Activation: Sustainable Synthesis of Carboxylic Acid Pharmaceutical Synthons
Development of new approaches for carboxylic acids via metal-catalysed carboxylation of organic compounds, using CO2 as C1 source, is of high current interest since the carboxylic moiety is a most relevant functional group for biologically active molecules or pharmaceuticals. This project aims to develop catalytic carboxylation processes, under sustainable conditions, of hydrocarbons (including alkanes) and activated (hetero)-aromatics, contributing to a better utilization of alkanes (currently used as non-renewable fossil fuels) and CO2, a challenge in modern chemistry. It will include design/synthesis/characterization of metal catalysts, their immobilization onto solid supports and testing their activity for carboxylation reactions. Non-conventional conditions (organic solvent-free, microwave irradiation, scCO2 medium) will be applied. The biological activity of selected new compounds will also be investigated.
Supervisor: M. Fátima C. Guedes da Silva (CQE/Técnico-ULisboa)
Co-supervisors: Mariette Pereira (FCT-UCoimbra), Armando Pombeiro (CQE/Técnico-ULisboa)
Registration Institution: Técnico-ULisboa or FCT-UCoimbra
14. CO2 Methanation under DBD-plasma Assisted Catalysis
Plasma-assisted heterogeneous catalysis, were the catalytic process is complemented by the use of low-temperature plasmas, constitutes an alternative to thermal (conventional)–catalytic systems, aiming to improve reaction yields and energy efficiencies. The observed positive results are often interpreted as a synergetic effect between plasma and catalysis. Nevertheless, the basic mechanisms governing this synergy are far from being clarified, preventing the optimization of both catalysts and plasma characteristics, in a scientific base. CO2 methanation will be studied under a Dielectric Barrier Discharge (DBD) catalytic reactor. The evaluation of the synergies between the DBD plasma and the catalytic materials, as well as the modelling of CO2 methanation under this DBD plasma-catalyst system, will be performed.
Supervisor: Carlos Henriques (IBB)
Co-supervisors: Joaquim Badalo Branco (Técnico-ULisboa), Nuno Rombert Pinhão (CTN/Técnico-ULisboa)
Registration Institution: Técnico-ULisboa
15. Advanced Nanocatalysts for Sustainable Industrial Processes
The development of sustainable catalytic processes to produce high added-value products from inexpensive substrates remains a great challenge. Recently, there is a growing research interest in producing advanced nanomaterials with tailored chemical compositions from metal-organic-framework (MOF) precursors for energy storage, catalysis and electrochemistry. The main goal of this project is the design of MOF derived nanostructures using microwave based techniques and apply them as catalysts for reactions (e.g., carbonylation) present in synthetic processes with industrial significance.
Supervisor: Luísa Martins (CQE/Técnico-ULisboa)
Co-supervisor(s): Marta Piñeiro (FCT-UCoimbra), Ana Ribeiro (CQE/Técnico-ULisboa)
Registration Institution: Técnico-ULisboa or FCT-UCoimbra
16. New Bioelectrochemical System for Carbon Dioxide Mitigation and Formate Production
We aim to develop a new sustainable, green, biotechnology to use the abundant and low cost atmospheric carbon dioxide to produce chemical feedstocks and fuels. For that, we will characterise different formate dehydrogenases (FDH), enzymes that catalyse the reversible formate oxidation to carbon dioxide (HCOO ↔ CO2 + 2e- + H+), searching for the best carbon dioxide reducers. The best performers will be immobilised in suitable matrices and electrochemically and electrocatalytically characterised. The immobilised systems will integrate a prototype bioelectrochemical system that will be tested in real field conditions. Relevant bibliography: Mota, C. S., et al., J. Biol. Inorg. Chem. (2011) 16:1255-1268; Maia, L., et al., Inorg. Chim. Acta (2017) 455: 350-363; Maia, L., et al., J. Am. Chem. Soc. (2016) 138: 8834-8846.
Supervisor: José J. G. Moura (FCT-UNova)
Co-Supervisor: Luís Fonseca (IBB)
Registration Institution: UNova
17. New Process for the Direct Co-Polimerization of Bio-Based Diols with CO2
CO2 utilization as a C1 feedstock is a highly active field of research. In fact, CO2 is not only widely available, as it is non-flammable and less toxic than most of the chemicals used in industrial processes. In this context, one of the most promising large-scale applications is in the production of polycarbonates. This project aims at developing a continuous process to produce polycarbonates directly from CO2 and biomass-derived diols. The new process will significantly increase the number of bio-based substrates that can be used towards large-scale polymers production. As the reaction produces water, hydrophobic ionic liquids (with high CO2 up-take), will be explored as solvents for metal-based catalysts, in order to simultaneously increase CO2 concentration in the liquid phase and in-situ remove water from the reaction mixture.
Supervisor: Ana V.M. Nunes (FCT-UNova)
Co-Supervisors: M. Fátima C. Guedes da Silva (CQE/Técnico-ULisboa), Malgorzata Zakrzewska (FCT-UNova)
Registration Institution: UNova or Técnico-ULisboa
18. (Nano)Materials for Small Molecule Activation
Molecular activation is important not only in chemical systems but also in more complex biological systems. Small molecules such as CO2 and CO are extremely relevant both environmentally and biologically and their activation and subsequent conversion is a hot topic both in research and industry. However, research on this topic has been mainly carried out in homogeneous conditions with organic solvents. It is thus important to find catalysts that activate these molecules in aqueous medium and preferably in heterogeneous medium to facilitate catalyst recovery. This research project addresses the synthesis of homo- and hetero-binuclear Fe(II), Fe(III) and Co(II) complexes and their assembly into (nano)materials. The chemical and electrochemical activation of CO2 and CO will be explored and their conversion products analysed by current methods.
Supervisor: Carla Nunes (Ciencias-U Lisboa)
Co-supervisors: Maria João Ferreira (CQE/Técnico-ULisboa), Paulo Nuno Martinho (Ciências- ULisboa)
Registration Institution: Ciências-ULisboa
19. Green Approaches for the Synthesis of N-heterocyclic Ligands: Synthesis of Organometallic Complexes and Catalytic Evaluation
The pharmaceutical and fine chemical industries are under increasing economic and ecological pressure to develop greener chemical synthesis (with fewer steps, using non toxic reagents, creating minimal waste). N-Heterocyclic ligands like porphyrins, azo-compounds and carbenes are a class of molecules with great relevance for the synthesis of organometallic catalysts. Nevertheless, their synthesis still require pollutants chemical processes sometimes very difficult to implement its transposition to industrial scale. This project intends to develop new process for the synthesis of new N-heterocyclic based metal complexes using sustainable approaches based on solventless reactions with microwave irradiation or solid-solid mechanochemical methods. The new metal complexes will be used as catalysts for activation of H2 and CO2.
Supervisor: Marta Piñeiro (FCT-UCoimbra)
Co-supervisor: Beatriz Royo (ITQB-UNova)
Registration Institution: UNova
20. Synthesis of Chiral 2-(Tetrazol-5-yl)-2H-Azirines: an Approach to Molecules with Relevance in Medicinal Chemistry
We have recently described the synthesis of novel 2-(tetrazol-5-yl)-2H-azirines via the Neber reaction of β-ketoxime tetrazoles (J. Org. Chem. 2013, 78, 6983; Eur. J. Org. Chem. 2014, 5159. The main objective of this project is to develop an asymmetry version of this synthetic methodology by exploring organocatalysis. Preliminary studies have already demonstrated that the alkaloid-mediated reaction allows the asymmetric synthesis of 2-(tetrazol-5-yl)-2H-azirines.Development and screening of new organocatalysts will be carried in order to achieve highly enantioselective transformations. The methodology will be applied to the synthesis of the bioisosteres of naturally occurring biological active chiral 2H-azirine-2-carboxylates [azirinomycin and (-)-dysidazirine].
Supervisor: Teresa Pinho e Melo (FCT-UCoimbra)
Co-supervisors: João Costa Pessoa (CQE/Técnico-ULisboa), Anthony Burke (DQCQE-UÉvora)
Registration Institution: UCoimbra
21. Functionalization of Alkanes
Alkanes (main components of natural gas and oil) are the richest potential source of carbon which currently is being lost to the atmosphere since they are used mainly as non-renewable fossil fuels, what results also in environmental problems due to the formation and accumulation of CO2.
The project aims to shift such application of alkanes into their desired use as carbon feedstock for the syntheses of functionalized added-value organic compounds (alcohols, ketones, carboxylic acids, amides, etc), under sustainable conditions, a major challenge in modern Chemistry in view of their inert character. It will concern the design and synthesis of (bioinspired) homogeneous and supported metal catalysts and their application in mild oxidation, carbonylation and amidation reactions of alkanes. It should involve the collaboration of international groups in Russia, Austria and Italy.
Supervisor: Armando Pombeiro (CQE/Técnico-ULisboa)
Co-supervisors: Ana Paula Carvalho (Ciências-ULisboa), Dmytro Nesterov (CQE/Técnico-ULisboa)
Registration Institution: Técnico-ULisboa
22. Organometallic Manganese Complexes an Emerging Alternative for Catalysis
Manganese is a perfect candidate for catalysis, since it is an inexpensive, earth abundant, and biocompatible metal. Despite these features, Mn has remained relatively unexplored in catalysis. The aim of the project is the development of efficient catalytic systems using Mn complexes incorporating N-heterocyclic carbene ligands for the reduction and oxidation of organic functionalities. Special attention will be devoted to the asymmetric reduction of ketones and ketimines through hydrosilylation reactions, and to the oxidation of hydrocarbons, alcohols and other substrates to valuable products. Catalyst immobilization in different supports, including nano-particle systems will be explored. Computational studies will assist in disclosing the mechanistic details of the reactions. This project will allow the student to gain transdisciplinary training in synthesis, catalysis and theoretical chemistry.
Supervisor: Beatriz Royo (ITQB-UNova)
Co-supervisors: Maxim L. Kuznetsov (CQE/Técnico-ULisboa), Anthony J. Burke (DQCQE-UÉvora)
Registration Institution: UNova
23. New (Photo)active Catalytic Materials for Oxidation Reactions
This project aims the preparation of new (photo)active (multi)functional materials based on metallophthalocyanine dyes, which will be preferentially used as (photo)catalysts in different (photo)reactions. The use of these novel ligands and materials, with specific photo-physical and photo-chemical properties, combined with light opens new frontiers on the development of new (photo)catalytic reactions with industrial applications. The possibility of using sun light with a novel generation of sustainable heterogeneous photocatalysts, enables new Green processes for the transformation of various substrates, namely the inert and challenging alkanes, as well as alcohols and ketones of industrial significance.
Supervisor: João Tomé (CQE/Técnico-ULisboa)
Co-supervisors: Mário Calvete (FCT-UCoimbra), Elisabete Alegria (CQE/Técnico-ULisboa)
Registration Institution: Técnico-ULisboa
24. Development of New Catalysts for Asymmetric Reactions and their Application in the Total Synthesis of Biologically Active Compounds
New catalysts and ligands will be prepared from inexpensive chiral pool compounds, and tested in several asymmetric reactions. Different catalytic strategies will be explored, using organocatalysts and chiral ligands with different metals. A wide range of substrates, with more than one functional group, will be tested in the catalysed reactions. The possibility for cascade reactions with more than one catalytic mode of action will be explored.
After optimisation of the catalytic processes, one or more reactions will be chosen to be applied in the enantioselective synthesis of biologically active compounds.
Supervisor: Rita Ventura (ITQB-UNova)
Co-supervisor: Dina Murtinho (FCT-UCoimbra)
Registration Institution: UNova