CATSUS PhD Projects

  • MULTI-SUSCAT: SUSTAINABLE ASYMMETRIC CATALYTIC SYNTHESIS OF NOVEL OXINDOLE HYDRIDS WITH POTENTIAL BIOLOGICAL ACTIVITY

This project will involve the synthesis of bioactive single enantiomer oxindole-dihydropyrimid-2-ones and oxindole-peptides using sustainable stereoselective multi-catalytic reactions starting from biomass derived isatin precursors. The former will be accessed using a sustainable catalytic Biginelli-ketone arylation sequence using appropriate metal based and organocatalytic systems, whilst the latter using a sustainable catalytic Ugi-reaction-ketone arylation. The reactions will be carefully optimized, using enabling technologies such as micro-waves, mecano-chemistry and non-conventional solvents. The catalytic reaction mechanisms will be studies using computational methods.

Supervisor and co-supervisor(s):
Anthony J. BurkeDQCQE-UÉvora
Marta Pineiro Gomez – FCT-UC
Maxim L. Kuznetsov – CQE/IST

Registration Institution:FCT-UC

 

  • OXIDATION OF HYDROCARBONS CATALYZED BY METAL COMPLEXES SUPPORTED ON CHIRAL MESOPOROUS 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 mesoporous chiral materials has additional advantages since chirality plays a part in chemical reactions. In this work, Si-based MCM-41 chiral 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 and co-supervisor(s):
Sónia CarabineiroCQE/IST
Carla Nunes – FC-UL

Registration Institution: FC-UL

  

  • 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 and co-supervisor(s):
Sónia CarabineiroCQE/IST
Carlos Geraldes – FCT-UC

Registration Institution: FCT-UC

 

  • DEVELOPMENT OF NEW METHODOLOGIES FOR BIOMASS VALORIZATION USING Mo AND Re COMPLEXES AS CATALYSTS

Biomass has received considerable attention as a sustainable feedstock that can replace diminishing fossil fuels. The strategy in the production of hydrocarbon fuels from biomass involves (i) the reduction of substantial oxygen content of the parent feedstock and (ii) the formation of C–C bonds between biomass-derived intermediates. The aim of this project is to develop new methodologies for deoxygenation and for C-C bond formation from biomass compounds using Mo and Re complexes as catalysts.

Supervisor:
Ana Cristina FernandesCQE/IST

Registration Institution: IST-UL

 

  • HETEROGENIZATION OF OLEFIN METATHESIS CATALYSTS TOWARDS INDUSTRIAL APPLICATION: SYNTHESIS OF HIGH-VALUE PRODUCTS WITH RECYCLABLE CATALYSTS

Homogeneous OM catalysts are undeniably powerful tools in synthetic organic chemistry, Ru catalysts in particular, due to their higher tolerance to functional groups and thus its application to a broad range of substrates. Their separation from the reaction media is however problematic, hampering industrial application. The project intends to developed new supported catalysts that combine the versatility and activity of homogeneous catalysts with ease of separation and catalyst recyclability, making them more attractive to industry.

Supervisor and co-supervisor(s):
Maria João Gomes Ferreira CQE/IST
Auguste Fernandes – IBB

Registration Institution: IST-UL

 

  • HIGH-VALUE MOLECULES FROM SMALL 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 the number of applications of nitrogen containing organic and natural products. This project concerns the study of new group 4 metal catalysts supported by monoanionic macrocyclic ligands in N2 activation and subsequent functionalization by CO and CO2. The experimental work will be complemented by theoretical calculations aiming at understanding the reactivity and mechanisms of activation of these small molecules.

Supervisor and co-supervisor(s):
Maria João Gomes Ferreira CQE/IST
Paulo J. Costa – CQB/FC-UL

Registration Institution: IST-UL

 

  • MULTIFUNCTIONAL AND SWITCHABLE MOLECULAR SYSTEMS FOR DYNAMIC CATALYSIS: DESIGN, SYNTHESIS AND APPLICATIONS

Novel molecular systems, particularly derived from small heterocyclic azole rings, will be projected to be used as switchable catalysts in asymmetric synthesis. 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 and co-supervisor(s):
Luís M. T. FrijaCQE/IST
Igor D. Reva – FCT-UC

Registration Institution:IST-UL

  

  • MULTIFUNCTIONAL BIOACTIVE MOLYBDENUM CATALYSTS: A HYBRID APPROACH FOR WASTEWATER TREATMENT

Water contamination with persistent organic pollutants and microorganisms (biofouling) is a major public health concern, being also responsible for serious environmental and economic penalties. Novel synthesized molybdenum complexes evidenced promising structural and antimicrobial properties able to be tailored with other functionalities. This work aims to provide those bioactive complexes with antimicrobial and photocatalytic functionalities, suitable for organic pollutants degradation and biofouling prevention on water circuits. As ultimate goal, those bioactive complexes will be supported on mesoporous and/or zeolitic structures and further immobilization in polymeric matrices.

Supervisor and co-supervisor(s):
Elisabete Silva GeraldesCQB/FC-UL
João Gomes – IBB
Marta Saraiva – CQB/FC-UL

Registration Institution: FC-UL

 

  • PHOTOCATALYTIC BIOCIDAL-FOAM FILTERS FOR FLUIDS POLLUTANTS REMOVAL: A NON-TOXIC SELF-CLEANING STRATEGY

Fluids contamination with persistent organic pollutants and microorganisms cause serious environmental/economic penalties and healthy risks. This work aims to develop a new multifunctional non-toxic solution able to mitigate those pollutants in water/air circuits, through the: i. immobilization of TiO2 based-photocatalysts and biocides in polymeric coatings (WO2016/093719 A1) for foams surfaces protection; ii. development of as-formers foams with those immobilized agents. The high porous cellular foams structure and potential synergistic effects of the non-releasing agents can provide higher photocatalytic pollutants degradation efficiencies and biocidal efficacy (antifouling).

Supervisor and co-supervisor(s):
Elisabete Silva GeraldesCQB/FC-UL
João Gomes – IBB

Registration Institution: FC-UL

 

  • DEVELOPMENT OF NEW HETEROGENEOUS CATALYSTS, FROM NATURAL SOURCES, TO BE USED IN THE OBTENTION OF LIQUID FUELS FOR ROAD TRANSPORT

The production of biodiesel, used for road transportation, from vegetable and waste oils is still an interesting growing research area as newly and more efficient catalyzed processes are currently in need by industry. This research study aims to obtain newly heterogeneous catalysts, from waste sources of calcium (marine shells, etc.), to be tested both at laboratory and pilot plant scales, resulting in an improved biodiesel production process.

Supervisor and co-supervisor(s):
João GomesIBB
Rosa Quinta Ferreira – FCT-UC
Jaime Puna – IBB

Registration Institution: IST-UL

 

  • LIQUID FUELS FROM SYNTHESIS GAS ADDITIVES RESULTING FROM THE LIQUEFACTION OF BIOMASS

Recently, a process for obtaining synthesis gas (consisting of H2, CO, CO2 and O2) from water electrolysis without separation of produced gases by membranes and using graphite electrodes as carbon source was developed; as well as another process to convert wood biomass into liquid fuels. This research study aims to develop a process combining this latter source of carbon, and the use of newly developed catalysts to obtain liquid fuels (such as methanol and dimethyl ether) from synthesis gas.

Supervisor and co-supervisor(s):
João Gomes IBB
Rosa Quinta Ferreira – FCT-UC
Jaime Puna – IBB

Registration Institution: IST-UL

 

  • ENERGY-SAVING ECO-FRIENDLY CATALYTIC PROCESSES FOR METAL CATALYZED FUNCTIONALIZATION

The development of “greener” energy efficient processes is the main aim of the project, a highly challenging current research topic in catalysis. Catalysis plays a key role for greening of chemistry by replacing reagents or by enabling more efficient processes to reduce their environmental impact and costs. Reactions in green solvents like water, ionic liquids and supercritical fluids etc. will be promoted in this project, as well as the use of solar energy (for photolytic conversions) and microwave radiation to improve energy efficiency. This project will be based on such green and sustainable processes in fields of metal catalysed activation/functionalization of small molecules (e.g. olefins, alkanes, alcohols, carbon oxides, dihydrogen).

Supervisor and co-supervisor(s):
Marta Pineiro GomezFCT-UC
Manas Sutradhar – CQE/IST

Registration Institution:FCT-UC

 

  • OXIDATION OF HYDROCARBONS, ALCOHOLS AND OTHER SUBSTRATES BY PEROXIDES CATALYZED BY TRANSITION AND NON-TRANSITION METAL COMPLEXES

Oxidation (hydroxylation, epoxidation, halogenation, etc.) of hydrocarbons (alkanes, alkenes, arenes), alcohols and other substrates by peroxides (H2O2, ROOH, K2SO5, K2S2O8) catalyzed by various complexes of transition and non-transition metals should be investigated by both experimental and theoretical (DFT) methods. The project includes experimental realization of the titled reactions, optimization of reaction conditions, experimental and theoretical kinetic studies, elucidation of reaction mechanisms, principal driving forces and factors affecting these processes.

Supervisor and co-supervisor(s):
Maxim L. KuznetsovCQE/IST
Adrià Gil Mestres – FC-UL

Registration institution: IST-UL

 

  • RADICAL FUNCTIONALIZATION OF ALKANES CATALYSED BY TRANSITION METAL COMPLEXES

Atom and step economical methods of functionalization of cheap and inert alkanes are challenging. It is proposed to utilize alkyl radicals as reactive intermediates able to form C–X bonds (where X = C, N, O) upon reaction with suitable substrates. The project will be devoted to the (1) synthesis of transition metal complexes (catalysts), (2) study of catalytic formation of alkyl radicals upon reaction with oxidizer (peroxide), and (3) investigation of properties and optimization of the obtained radical catalytic systems towards products with industrial interest.

Supervisor and co-supervisor(s):
Dmytro S. Nesterov CQE/IST
Paulo N. Martinho – CQB/FC-UL

Registration institution: IST-UL

 

  • PRODUCTION OF CATALYSTS BY SUPERCRITICAL ANTISOLVENT PRECIPITATION (SAS)

The supercritical anti-solvent precipitation (SAS) process will be used to produce nano and microparticles of various metal catalysts, for example, of copper, iron and vanadium, with nitrogen- and/or oxygen- ligands, namely of the types of tetrazole derivatives, aza derivatives of beta-diketones, scorpionates, e.g., tris(pyrazol-1-yl)methane (HC(pz)3, pz = pyrazolyl),  and related ones, which will also be synthesized in this project and applied in various catalytic reactions of redox and Lewis acid characters, including modeling enzyme actions.

Supervisor and co-supervisors:
Maria Beatriz Pinto NobreCQE/IST
Carlos Alberto Nieto de Castro – FC-UL
Luís M.T. Frija – CQE/IST

Registration Institution: IST-UL

  

  • DEVELOPMENT OF NEW METAL CATALYSTS SUPPORTED ON MAGNETIC NANOMATERIALS FOR SUSTAINABLE, GREEN AND SELECTIVE CHEMICAL PROCESSES

In selective catalytic reactions using heterogeneous catalysts, nanomaterial’s based catalysts have recently attracted enormous attention due to their unique properties as catalysis compared with that of conventional catalysts. In view of the known advantages of immobilized complexes on heterogeneous supports such as mesoporous silica or silica-coated magnetic nanoparticles, in this work it is planned to support on selected materials some Fe, Co, Ni and Cu complexes. Further tasks will include testing them as potential catalysts in a number of reactions and compare their activity, selectivity, robustness and separation efficiency with those of the corresponding homogenous catalysts.

Supervisor and co-supervisor(s):
Carla D. NunesCQB/FC-UL
Clara S. B. Gomes – CQE/IST

Registration Institution: FC-UL

 

  • INNOVATION IN CATALYSIS FOR THE GLYCOSYLATION OF PAINS, PRODUCT BIOLOGICAL PROPERTIES AND BIOMEDICAL APPLICATIONS

The project covers research on homogeneous and heterogeneous catalysis for the synthesis of the O-/C-glycosyl polyphenols, in particular anticancer agents resveratrol and curcumin. Lewis acids will be investigated to evaluate the role of catalysts on the regio- and stereoselectivity. The studied aglycons include the so called Pan Assay INterference compoundS (PAINS), often used as ‘positive’ controls in a number of assays, but the searched specific enzyme inhibitory bioactivity is masked by their interference with the assay through cell membrane perturbation. Thus, biological evaluation of the new compounds will elucidate if this perturbation is prevented.

Supervisor and co-supervisor(s):
Amélia Pilar RauterCQB/FC-UL
Teresa Pinho e Melo – FCT-UC

Registration Institution:FC-UL

 

  • CO2 MITIGATION AND PRODUCTION OF METHANOL BY DRY REFORMING OF CH4

Carbon Capture and Utilization (CCU) offer important forward steps to mitigate greenhouse effect. Dry reforming of CH4 with CO2 offer a viable route for the production of CH3OH and mitigation of CO2. The development of this route could have significant repercussions in industry. Therefore, the main goal of this work is the development of a system able to capture CO2 and transform it into CH3OH. This system will be composed by an adsorbent to capture CO2 (Ca-based sorbents from cheap natural resources are being proposed to scrub CO2 from flue gas and syngas) and a heterogeneous catalyst able to transform CO2 and CH4 selectively into CH3OH in one step at low pressure.

Supervisor and co-supervisor(s):
Filipa RibeiroIBB
Joaquim Branco – IST-UL

Registration Institution: IST-UL

 

  • ASYMMETRIC CATALYSIS AND NANOCATALYSIS FOR BIOLOGICAL RELEVANT REACTIONS

Aziridines are very important compounds due to their uses as building blocks in synthesis, as well as antitumor agents, among biological applications. The search for better catalytic systems for their synthesis, under greener and cheaper conditions, has become one of the main focus of research in the last few years. This project addresses the development of new iron and manganese chiral complexes and nanomaterials, and their application as catalysts in aziridination reactions. Mechanistic studies will be performed to understand the catalytic pathways in enantioselective aziridination.

Supervisor and co-supervisor(s):
Marta Saraiva CQB/FC-UL
Paulo Nuno Martinho – CQB/FC-UL
Sónia Barroso – CQE/IST

Registration Institution: FC-UL

 

  • SYNTHESIS OF CHIRAL LIGANDS AND CATALYSTS FOR ASYMMETRIC TRANSFORMATIONS

This project will involve the design and synthesis of new chiral compounds using materials from the chiral pool. The newly synthesized catalysts will then be completely characterized using different techniques such as NMR and X-ray crystallography, among others. Subsequently, these compounds will be used to catalyze asymmetric processes for example alkylations, trimethylsilylcyanations and Henry reactions, among others. The organocatalyzed versions of some of these reactions may also be studied. DFT studies may be performed in order to complement the experimental work.

Supervisor and co-supervisor(s):
Maria Elisa da Silva SerraFCT-UC
Dina Maria Bairrada Murtinho – FCT-UC
Sónia Barroso – CQE/IST

Registration Institution:  FCT-UC

  

  • WASTE POLYOLEFINS VALORIZATION TO FUELS BY CATALYTIC TRANSFORMATION

Polyolefins (PE + PP) are the major plastic found in the municipal wastes. An important fraction (~40%) is not suitable to recycle as raw material due to some degree of contaminations. One way to achieve a valorization of this waste is the breaking down plastic polymers into their constituent monomers which in turn can be used to produce liquid fuels. Zeolite and mesoporous based materials of different acidity can be used as catalysts for this job. The objective of this study consist in evaluate the influence of the type catalysts, reaction conditions and presence of some contaminants in the yields and liquid product distribution.

Supervisor:
João Miguel Alves da SilvaIBB

Registration Institution: IST-UL

 

  • METAL-ORGANIC FRAMEWORKS (MOFS) FOR CATALYTIC REACTIONS IN WATER-ORGANIC REACTION MEDIA

It is known that some MOFs have low to moderate structural stability in aqueous media. However, water is an excellent choice as a solvent due to its low cost and lack of environmentalimpact. In this project it is aimed to improve the water-stability of selected MOFs to be used as catalysts in water-organic solvent mixtures reaction media.

Supervisor and co-supervisor(s):
João Pires da Silva FC-UL
Maria Eduarda Araújo – FC-UL

Registration Institution: FC-UL

 

  • IMMOBILIZED COMPLEXES ON CARBON NANOTUBES AND NANODIAMONDS IN MICROWAVE ASSISTED OXIDATION REACTIONS

The use ofMicrowave (MW) in the catalytic reactions received great attention in the last decade. MW heating is one of the simplest and energy efficient techniques compared to the conventional methods. Immobilization of complexes onto nanostructured ordered carbon materials could be significantly more active than their homogeneous counterparts, with the additional advantage of recyclability. Moreover, a variety of surface chemical groups can also be added to these materials: carboxylic acids, phenols, carbonyls, lactones, etc. Our goal is to find out the most promising catalysts in various oxidation processes (e.g. oxidation of alkanes, alcohols, epoxidation, carboxylation etc) by correlating their properties and activity/selectivity under optimized condition using microwave irradiation.

Supervisor and co-supervisor(s):
Manas SutradharCQE/IST
Tiago A. Fernandes – CQB/FC-UL

Registration Institution: IST-UL or FC-UL

 

  • RECYCLABLE EFFICIENT CATALYTIC OXIDATIONS BY ANCHORED VANADIUM COMPLEXES ONTO CARBON MATERIALS  

Vanadium complexes are potentially active catalyst towards the oxidation reaction of organic compounds under homogeneous conditions. Heterogenization of the complexes on solid support retains the homogeneous catalytic sites and has the advantages of easy separation and recycling. Several oxidation reactions, e.g. oxidation of alkanes, alcohols, epoxidation, oxidative C-C bond cleavage or sulfoxidation etc., by molecular oxygen or H2O2 will be examined by the vanadium complexes anchored onto carbon materials under mild conditions preferably at room temperature or under microwave condition. Thus, the proposed project will contribute to establish an energy efficient sustainable process.

Supervisor and co-supervisor(s):
Manas Sutradhar CQE/IST
Ana Paula Carvalho – FC-UL

Registration Institution: IST-UL or FC-UL

 

  • 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 and co-supervisor:
João Tomé – CQE/IST
Mário Calvete – FC-UL

Registration Institution: IST-UL or FC-UL