Group of Inorganic and Organometallic Chemistry
The research activities of the Inorganic and Organometallic Chemistry Group are centred on the study of several aspects of f-element chemistry (lanthanides and actinides), both at a fundamental level and directed at applications in nuclear, catalysis and new materials areas. These activities are associated to projects financed by the Fundação para a Ciência e a Tecnologia and the European Commission – FP7, and are organised under five major subjects:
1. Main Activities
1.1. Coordination and organometallic chemistry of lanthanides and actinides
The main purpose of this research topic is the creation of new coordination environments for the f-elements (lanthanides, thorium and uranium) that can lead to unusual reactivity patterns, enabling the study of the organometallic chemistry of these elements at a fundamental level and of potential applications in organic synthesis and catalysis. The work has mainly involved the use of scorpionate, functionalised aza-macrocyclic and diamine-bisphenolate ligands. In addition to the structural and chemical properties of the obtained compounds, their magnetic properties are also studied, particularly for the case of uranium, in collaboration with the Solid State Group of UCQR-IST/ITN. The actinide chemistry studies also involve a collaboration with the Laboratoire de Reconnaissance Ionique et Chimie de Coordination of CEA-Grenoble and the lanthanide chemistry studies a collaboration with the Centro de Química Estrutural of IST.
1.2. Catalytic applications of inorganic compounds with f-block elements
The main objectives of this research theme are: (i) the study of the behaviour of f-elements (lanthanides, thorium and uranium) as catalysts or catalyst precursors in heterogeneous phase; (ii) the development of new methods of preparation of nanostructured materials with 4f and 5f elements to be used in catalytic applications; (iii) the contribution to a solution for relevant environmental problems. The catalysts used are mainly bimetallic oxides obtained from d-f intermetallic compounds or by sol-gel processes, and also K-Ln molten salts. Special attention is given to the activation of methane and carbon dioxide as key C1 feedstock. Other examined applications are the elimination of primary gaseous pollutants and urban waste. The use of non-thermal plasma for methane activation has also been studied, in collaboration with the Nuclear Instruments and Methods Group of UFA-IST/ITN.
1.3. Functional hybrid materials with f-elements
Within this research topic, new materials containing f-elements (lanthanides, thorium and uranium) have been studied namely Metal-Organic Frameworks (MOFs) and Layered Lanthanide Hydroxides (LLHs). The structural, photophysical and photochemical properties of these materials (MOFs and LLHs) have been examined in collaboration with CICECO-U. Aveiro, while the magnetic properties (LLHs) have been surveyed in collaboration with the Solid State Group of UCQR-IST/ITN.
1.4. Gas-phase chemistry/mass spectrometry of lanthanides and actinides
In this research theme, gas-phase chemistry studies of the f-elements (lanthanides, thorium, protactinium, uranium, neptunium, plutonium, americium and curium) are performed by means of advanced mass-spectrometry techniques (LDI-FTICR/MS and ESI-QIT/MS), accompanied by computational studies of selected systems. The main purpose of the work is the identification of new species and reactions involving these elements and the study of their physicochemical properties. Several aspects of the coordination chemistry of the lanthanides and actinides are also investigated using the ESI-QIT/MS technique which allows the correlation between solution and gas-phase chemistry. These studies are relevant for nuclear science, in subjects like the thermodynamic properties of elementary actinide species, lanthanide/actinide separations and the bioinorganic chemistry of the f-elements. The work involves a close collaboration with the Glenn T. Seaborg Center of the Lawrence Berkeley National Laboratory.
1.5. Molecular energetics of organic, inorganic and organometallic compounds
This research topic has as main purpose the collection of energetics data of organic and inorganic compounds, their systematisation and the investigation of correlations between the energetics and the molecular structure of the compounds. The experimental techniques used are calorimetry, thermal analysis and mass spectrometry (FTICR/MS e QIT/MS), while databases of thermochemical properties and models for prediction of such properties have been also developed. Special attention is given to compounds of the f-elements and the physicochemical properties of ionic liquids have also been studied in detail. The work is performed in collaboration with the Molecular Energetics Group of the Chemistry and Biochemistry Centre of FCUL.
1.6. Other activities
The Inorganic and Organometallic Chemistry Group also carries out:
- (i) Research activities in other scientific areas, namely:
- Studies of the selective electrochemical conversion of carbon dioxide, in collaboration OMNIDEA - AeroSpace Technology and Energy Systems;
- Studies of the gas-phase chemistry of d-transition metals, in collaboration with CQE-IST;
- Studies of the degradation of bio-recalcitrant compounds, in collaboration with the Radiation Technologies-Processes and Products Group of UFA-IST/ITN;
- Studies of hybrid materials for biomedical applications, in collaboration with the Condensed Matter Physics Group of UFA-IST/ITN and the U. Aveiro;
- Studies in glass science, in collaboration with VICARTE – Vidro e Cerâmica para as Artes of FCT-UNL.
- (ii) Analytical support activities to the research at UCQR-IST/ITN and external services,
- CHNS elemental analysis;
- Chemical analysis by mass spectrometry.
- (iii) Education activities, in particular of research students, with several dozens of PhD, MSc and Graduation theses having been accomplished in the Group since its creation in 1980. Some members of the Group are involved in graduation and post-graduation courses at the universities, and one of them is responsible for the theme Chemistry for Education in the Chemistry and Biochemistry Department of FCUL.
2. Equipment and Infrastructures
Main equipment and infra-structures implemented and/or maintained by the Group:
- Organometallic Synthesis Laboratories (lanthanide, thorium and uranium)
- Actinide Laboratory (protactinium and transuranics)
- Catalysis Laboratory
- Mass Spectrometry Laboratories (EI+LDI-FTICR and ESI+nESI+APCI-QIT / Member of RNEM-National Mass Spectrometry Network)
- Calorimetry and Thermal Analysis Laboratories (DSC, Solution-Reaction Calorimetry)
- Analytical Laboratories (UV/Vis and FTIR spectroscopies; CHNS elemental analysis)
3. Technical Services
- Molecular analysis by ESI and APCI mass spectrometry
- Molecular analysis by FTICR mass spectrometry (High resolution)
- Gas analysis (H2, CO, CO2, CH4, N2O, etc.)
- Manipulation of CO in a controlled laboratory
- Thermal analysis (DSC)
- Solution-reaction calorimetry
- CHNS elemental analysis