Martyn Pillinger

Qualificacões académicas

1994: PhD Química no grupo do Professor John Evans, Universidade de Southampton, Inglaterra - "EXAFS studies of polyoxometalates and polyoxometalate-anion-pillared layered double hydroxides"
1990: BSc Química (Classe 1), Universidade de Southampton, Inglaterra

Actividades anteriores

2008-2015: Investigador Auxiliar no CICECO
2007-2008: Investigador Auxiliar no Instituto de Engenharia Electrónica e Telemática de Aveiro, Aveiro, Portugal
2002-2007: Investigador Auxiliar no CICECO
1999-2002: Investigador pós-doutoramento no grupo do Prof. Dr. João Rocha, Departamento de Química, Universidade de Aveiro (UA), Portugal (bolsas da UA e FCT)
1996-1999: Investigador pós-doutoramento no grupo do Prof. Alan Dyer, Chemistry Division, Science Research Institute, Universidade de Salford, Inglaterra (EU Framework 4 Nuclear Fission Safety Program - Partitioning Experiments and Waste Minimisation - "Waste Volume Minimisation Using Highly Selective Inorganic Ion Exchange Materials")
1994-1995: Investigador pós-doutoramento no grupo do Prof. Dr. Carlos C. Romão, Instituto de Tecnologia Química e Biológica, Oeiras, Portugal (TMR Programme - Selective Processes and Catalysis Involving Small Molecules - "Syntheses and Chemistry of Organotransition Metal Oxides")

Martyn’s research mainly involves the synthesis and chemistry of inorganic/organometallic hybrid and composite materials with interesting photofunctional, biofunctional and/or catalytic properties. A recurring theme has been organometallic inclusion and intercalation chemistry employing, for example, ordered mesoporous materials, cyclodextrins and layered double hydroxides as hosts (some examples are given on this page). To fully understand these systems it has been crucial to use multiple analysis techniques, e.g. X-ray absorption spectroscopy and powder X-ray diffraction. These studies have been and continue to be performed in close collaboration with colleagues at CICECO and other Portuguese institutions. Other collaborative research interests include the synthesis and characterization of molecular and hybrid molybdenum oxide-based catalysts for oxidation reactions, and solid acid catalysts for biomass conversion.

Present

Estudantes de Doutoramento: Isabel Margarida Bento Calhau (bolsa FCT; co-orientação com a Dr.ª Isabel S. Gonçalves), Rodrigo Pinto Monteiro (bolsa FCT; co-orientação com a Dr.ª Isabel S. Gonçalves), Martinique da Silva Nunes (bolsa FCT; co-orientação com a Dr.ª Isabel S. Gonçalves e a Dr.ª Anabela A. Valente).

Previous

Estudantes de Doutoramento: Ana Sofia Vagueiro de Sousa Dias (2007, co-orientação com a Dr.ª Anabela A. Valente), Bernardo Ramos Batista Monteiro (2009, co-orientação com a Dr.ª Isabel S. Gonçalves), Maria Margarida Feitor Pintão Moreno Antunes (2012, co-orientação com a Dr.ª Anabela A. Valente).
Estudantes de Mestrado: Joana Leão Candeias (2012, co-orientação com a Dr.ª Anabela A. Valente), Joana Helena Aguiar de Almeida Pinho Abrantes (2014, co-orientação com a Dr.ª Anabela A. Valente), Clara Isabel Ribeiro Magalhães (2015, co-orientação com a Dr.ª Isabel S. Gonçalves).
Investigadores de pós-doutoramento: Ana Sofia Madureira Bruno (2009-2015, co-orientação com a Dr.ª Anabela A. Valente), Sérgio Nuno Martins Lima (2005-2012, co-orientação com a Dr.ª Anabela A. Valente), Sandra Maria Nunes Gago (2006-2010), Ana Catarina Costa Gomes (2010-2019, co-orientação com a Dr.ª Isabel S. Gonçalves), Carlos Granadeiro (2016-2018, co-orientação com a Dr.ª Salete S. Balula (Universidade de Porto)), Margarida Antunes (2013-2019, co-orientação com a Dr.ª Anabela A. Valente).

Aveiro (CICECO): Isabel S. Gonçalves, Anabela A. Valente, Ana C. Gomes, Patrícia Neves, Sofia M. Bruno, Margarida M. Antunes, Filipe A. Almeida Paz.
Portugal: Carlos C. Romão (ITQB), André D. Lopes (Universidade do Algarve), Prof. Sérgio Seixas de Melo (Universidade de Coimbra), Salete Balula and Luís Cunha Silva (Universidade de Porto).

Investigador responsável do projeto SASCOT "Sistemas ativados por estímulos para a terapia com monóxido de carbono" (CENTRO-01-0145-FEDER-028031; 1/5/2018-30/4/2022).

Participante no projeto HyLight "Desenvolvimento Inteligente de Emissores de Luz Branca Energeticamente Eficientes Baseados em Híbridos Orgânicos-Inorgânicos" (Instituição Proponente = Universidade de Coimbra; POCI-01-0145-FEDER-031625; 1/7/2018-30/6/2022).
Participante no projeto BiOle_AcidOxCat "Conversao catalitica de olefinas derivadas da biomassa" (Instituição Proponente = Universidade de Aveiro; POCI-01-0145-FEDER-030075; 26/7/2018-25/3/2022).

PTDC/QEQ-SUP/1906/2012 (participante; instituição proponente = Universidade de Aveiro): Catalisadores de metaloceno modificados por contentores moleculares.
PTDC/EQU-EQU/121677/2010 (participante; instituição proponente = Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares - Porto): Dessulfurização do gasóleo por processos heterogéneos de oxidação catalítica sustentáveis
CICECO-funded project (1/3/10-28/2/11, investigador responsável): Metal carbonyl intercalated anion exchangers as drug delivery systems
PTDC/QUI/71198/2006 (participante): Ansa-bridged Organorhenium(VII) oxides and their application as homogeneous and heterogeneous catalysts
POCI/CTM/58507/2004 (investigador responsável): Argilas aniónicas multifuncionais
POCI/QUI/56109/2004 (participante): New oxometal compounds with tailored catalytic properties
POCI/QUI/56112/2004 (participante): Conversão catalítica de sacarídeos em aldeídos furânicos
POCTI/QUI/37990/2001 (participante): Tailored oxomolybdenum catalysts
POCTI/QUI/32889/99 (participante): Heterogenisation of photochemically and catalytically active transition metal complexes on mesoporous oxides

260 publicações em revistas internacionais com arbitragem científica, w-index 11, h-index 53

Top three cited papers (dezembro 2023):
(233 citações) Octahedral Bipyridine and Bipyrimidine Dioxomolybdenum(VI) Complexes: Characterization, Application in Catalytic Epoxidation, and Density Functional Mechanistic Study, F. E. Kühn, M. Groarke, É. Bencze, E. Herdtweck, A. Prazeres, A. M. Santos, M. J. Calhorda, C. C. Romão, I. S. Gonçalves, A. D. Lopes, M. Pillinger, Chem. Eur. J., 2002, 8, 2370. Link
(284 citações) Dehydration of xylose into furfural over micro-mesoporous sulfonic acid catalysts, A.S. Dias, M. Pillinger, A.A. Valente, J. Catal., 2005, 229, 414. Link
(206 citações) Conversion of mono/di/polysaccharides into furan compounds using 1-alkyl-3-methylimidazolium ionic liquids, S. Lima, P. Neves, M. M. Antunes, M. Pillinger, N. Ignatyev, A. A. Valente, Appl. Catal. A: Gen., 2009, 363, 93-99. Link

Reviews
1) Group 6 carbonyl complexes of N,O,P-ligands as precursors of high-valent metal-oxo catalysts for olefin epoxidation, S.M. Bruno, A.A. Valente, I.S. Gonçalves, M. Pillinger, Coord. Chem. Rev., 2023, 478, 214983. Link
2) Reaction induced self-separating metal catalysts – Wonder systems in 21st century catalysis, P. Neves, D.M. Gomes, I.S. Gonçalves, M. Pillinger, A.A. Valente, Coord. Chem. Rev., 2023, 491, 215229. Link

Carbon monoxide-releasing materials
This research theme comprises the design of metal carbonyl complexes as prodrugs for carbon monoxide (CO) delivery for therapeutic applications in human medicine (e.g., as antimicrobial agents to fight drug-resistant bacteria). We aim to develop pharmaceutically acceptable CO-releasing materials based on macromolecular (e.g., cyclodextrins, cucurbiturils) and metal-organic nanomaterial scaffolds.
1) A.F. Silva, I.B. Calhau, A.C. Gomes, A.A. Valente, I.S. Gonçalves, M. Pillinger, A hafnium-based metal-organic framework for the entrapment of molybdenum hexacarbonyl and the light-responsive release of the gasotransmitter carbon monoxide, Mater. Sci. Eng. C, 2021, 124, 112053. Link
2) A. F. Silva, I. B. Calhau, A. C. Gomes, A. A. Valente, I S. Gonçalves, M. Pillinger, Tricarbonyl-Pyrazine-Molybdenum(0) Metal−Organic Frameworks for the Storage and Delivery of Biologically Active Carbon Monoxide, ACS Biomater. Sci. Eng., 2023, 9, 1909−1918. Link

1) An Indigo Carmine-Based Hybrid Nanocomposite with Supramolecular Control of Dye Aggregation and Photobehavior, A.L. Costa, A.C. Gomes, M. Pillinger, I.S. Gonçalves, J.S. Seixas de Melo, Chem. Eur. J., 2015, DOI: 10.1002/chem.201501344. Link

Tune into the blues: Zn-Al layered double hydroxides (LDHs) containing solely indigo carmine (IC) or 1-hexanesulfonate (HS) anions, or a mixture of the two with different HS/IC molar ratios, were prepared by the direct synthesis method. For the LDH containing solely IC anions, the dye molecules assembled within the interlayer galleries to form a J-type stacking arrangement. Through a comprehensive electronic spectral and photophysical study it was shown that incorporation of IC within the LDH decreased the level of aggregation, and that further addition of HS induced the appearance of isolated IC units within the LDH galleries. The indigo carmine-based nanocomposites constitute a step-forward in the design of hybrid materials with tunable properties.

2) Controlling the Fluorescence Behavior of 1-Pyrenesulfonate by Cointercalation with a Surfactant in a Layered Double Hydroxide, A.L. Costa, A.C. Gomes, M. Pillinger, I.S. Gonçalves, J.S. Seixas de Melo, Langmuir, 2015, 31, 4769. Link

3) Intercalation of a Molybdenum η³-Allyl Dicarbonyl Complex in a Layered Double Hydroxide and Catalytic Performance in Olefin Epoxidation, A. C. Gomes, S. M. Bruno, C. A. Gamelas, A. A. Valente, M. Abrantes, I. S. Gonçalves, C. C. Romão, M. Pillinger, Dalton Trans, 2013, 42, 8231. Link

4) Intercalation of a Molybdenum(0)-Tetracarbonyl-Bipyridine Complex in a Layered Double Hydroxide, A. C. Gomes, S. M. Bruno, A. A. Valente, I. S. Gonçalves, M. Pillinger, J. Organomet. Chem., 2013, 744, 53. Link
5) Preparation and photophysical characterisation of Zn-Al layered double hydroxides intercalated by anionic pyrene derivatives, S. Gago, T. Costa, J. Seixas de Melo, I. S. Gonçalves, M. Pillinger, J. Mater. Chem., 2008, 18, 894. Link

6) Investigation of layered double hydroxides intercalated by oxomolybdenum catecholate complexes, B. Monteiro, S. Gago, F. A. Almeida Paz, R. Bilsborrow, I. S. Gonçalves, M. Pillinger, Inorg. Chem., 2008, 47, 8674. Link
7) Immobilization of Oxomolybdenum Species in a Layered Double Hydroxide Pillared by 2,2'-Bipyridine-5,5'-Dicarboxylate Anions, S. Gago, M. Pillinger, A. A. Valente, T. M. Santos, J. Rocha, I. S. Gonçalves, Inorg. Chem., 2004, 43, 5422. Link

8) Immobilization of Lanthanide Ions in a Pillared Layered Double Hydroxide, S. Gago, M. Pillinger, R. A. Sá Ferreira, L. D. Carlos, T. M. Santos, I. S. Gonçalves, Chem. Mater., 2005, 17, 5803. Link
Outras publicações

1) Desulfurization of model diesel by extraction/oxidation using a zinc-substituted polyoxometalate as catalyst under homogeneous and heterogeneous (MIL-101(Cr) encapsulated) conditions, D. Julião, A.C. Gomes, M. Pillinger, L. Cunha-Silva, B. de Castro, I.S. Gonçalves, S.S. Balula, Fuel Processing Technology, 2015, 131, 78. Link

2) Investigation of a dichlorodioxomolybdenum(VI)-pyrazolylpyridine complex and a hybrid derivative as catalysts in olefin epoxidation, T.R. Amarante, P. Neves, F.A.A. Paz, A.A. Valente, M. Pillinger, I.S. Gonçalves, Dalton Trans., 2014, 43, 6059. Link

3) Hydrothermal Synthesis, Crystal Structure and Catalytic Potential of a One-Dimensional Molybdenum Oxide/Bipyridinedicarboxylate Hybrid, T. R. Amarante, P. Neves, A. A. Valente, F. A. A. Paz, A. N. Fitch, M. Pillinger, I. S. Gonçalves, Inorg. Chem., 2013, 52, 4618. Link

4) Catalytic Cyclodehydration of Xylose to Furfural in the Presence of Zeolite H-Beta and a Micro/Mesoporous Beta/TUD-1 Composite Material, S. Lima, M. M. Antunes, A. Fernandes, M. Pillinger, M. F. Ribeiro, A. A. Valente, Appl. Catal. A: Gen., 2010, 388, 141. Link

5) Grafting of molecularly ordered mesoporous phenylene-silica with molybdenum carbonyl complexes: Efficient heterogeneous catalysts for the epoxidation of olefins, A. C. Coelho, S. S. Balula, S. M. Bruno, J. C. Alonso, N. Bion, P. Ferreira, M. Pillinger, A. A. Valente, J. Rocha, I. S. Gonçalves, Adv. Synth. Catal., 2010, 352, 1759. Link

6) Investigation of molybdenum tetracarbonyl complexes as precursors to Mo^VI catalysts for the epoxidation of olefins, T. R. Amarante, P. Neves, A. C. Coelho, S. Gago, A. A. Valente, F. A. A. Paz, M. Pillinger, I. S. Gonçalves, Organometallics, 2010, 29, 883. Link

7) Influence of Cyclodextrins on Catalytic Olefin Epoxidation with Metal Carbonyl Compounds. Crystal Structure of the TRIMEB Complex with CpFe(CO)₂Cl, S. S. Balula, A. C. Coelho, S. S. Braga, A. Hazell, A. A. Valente, M. Pillinger, J. D. Seixas, C. C. Romão, I. S. Gonçalves, Organometallics, 2007, 26, 6857. Link

8) Immobilisation of rhodium acetonitrile complexes in ordered mesoporous silica, M. Pillinger, C. D. Nunes, P. D. Vaz, A. A. Valente, I. S. Gonçalves, P. J. A. Ribeiro-Claro, J. Rocha, L. D. Carlos, F. E. Kühn, Phys. Chem. Chem. Phys., 2002, 4, 3098. Link

9) Sorption behaviour of radionuclides on crystalline synthetic tunnel manganese oxides, A. Dyer, M. Pillinger, J. A. Newton, R. Harjula, T. Möller, S. Amin, Chem. Mater., 2000, 12, 3798. Link

10) Ion exchange of caesium and strontium on a titanosilicate analogue of the mineral pharmacosiderite, A. Dyer, M. Pillinger, S. Amin, J. Mater. Chem., 1999, 9, 2481. Link