Project title: ”Graphenes as eco-heterogeneous catalysts for the eco-production of C4-dicarboxylic acids”

Nr. 121/2017

Project code: PN-III-P4-ID-PCE-2016-0146


Project objectives:

The GrafEco project challenges two very ambitious objectives: i) synthesis and investigation of Graphenes as eco-heterogeneous catalysts, and ii) the eco-production of C4-dicarboxylic acids. It envisages the production of graphene-based supports and catalysts for the selective direct production of three C4 di-acids ie fumaric, malic and itaconic acid derivatives from cellulose/glucose. Acids with additional keto- or hydroxyl-groups (like malic acid) are desirable building blocks for polyesters, while di-carboxylic acids (like fumaric acid) are used for the production of polyamides with advanced material properties. Fumaric acid is also used as a raw material for pharmaceutics. Itaconic acid is another C4 unsaturated dicarboxylic acid with a high potential as a platform for chemicals derived from sugars. As specific segments, the synthetic strategy of these acids will consider the in-situ transformation of the tartaric acid produced from cellulose/glucose: i) to fumaric acid via the didehydroxylation of vicinal diols; ii) the Wacker oxidation of fumaric double bond to a ketone followed by the in-situ enzymatic reduction of the C=O double bond to the asymmetric malic acid, and iii) the Sonogashira reaction of fumaric acid with acetylene and acetylene derivatives. For such a purposes Re, Cu, and Pd are envisaged as active species. The engineering of producing oriented nano-alloys will be as well investigated in these syntheses. Functionalization of graphenes with basic active components able to facilitate desorption of the carboxylic acids, the catalysts recycling and the transfer of the production of the targeted molecules from batch reactions to flow reactor conditions constitute additional challenging objectives. The present proposal is well fitting the Romanian National Plan for research, development and innovation for the period of 2015-2020.


Desired results:

The project envisages the production of graphene-based supports and catalysts for the selective direct production of three C4 di-acids ie fumaric, malic and itaconic acid derivatives from cellulose/glucose.

Time: 12.07.2017-31.12.2019

The total amount of the project: 850.000,00 RON


2017

Oral presentations:

1. M. Florea, F. Neatu, S. Nicolae, G. Culica, V.I. Parvulescu, F. Cavani, An unprecedented synthesis of terephthalic acid by p­cymene oxidation, 13th EUROPACAT, Florence, Italy, August 27-31, 2017.

2. I. Podolean, N. Candu, M. Tudorache, V.I. Parvulescu, S.M. Coman, Successful development of benign catalytic oxidation methodologies for the synthesis of bio­succinic acid, 13th EUROPACAT, Florence, Italy, August 27-31, 2017.


2018

Research articles:

1. P. Granger, S. Troncea, J.P. Dacquin, M. Trentesaux, V.I. Parvulescu, Support-induced effect on the catalytic properties of Pd particles in water denitrification: Impact of surface and structural features of mesoporous ceria-zirconia support, Appl. Catal. B: Environ. 224 (2018) 648–659.

2. O.D. Pavel, I. Podolean, V.I. Parvulescu, S.F.R. Taylor, H. Manyar, K. Ralphs, P. Goodrich, C. Hardacre, Impact of SCILL catalysts for the S-S coupling of thiols to disulfides, Faraday Discuss. 206 (2018) 535 – 547.

3. M. El Fergani, N. Candu, S.M. Coman, V.I. Parvulescu, Nb-Based Zeolites: Efficient bi-Functional Catalysts for the One-Pot Synthesis of Succinic Acid from Glucose, Molecules, 22 (2018) 2218; doi:10.3390

4. P. Sazama, J. Pastvova, C. Rizescu, A. Tirsoaga, V.I. Parvulescu, H. Garcia, L. Kobera, J. Seidel, J. Rathousky, P. Klein, I. Jirka, J. Moravkova, V. Blechta, Catalytic Properties of 3D Graphene-Like Microporous Carbons Synthesized in a Zeolite Template, ACS Catal., 8 (2018) 1779-1789.

5. M. Magureanu, N.B. Mandache, C. Bradu, V.I. Parvulescu, High efficiency plasma treatment of water contaminated with organic compounds. Study of the degradation of ibuprofen, Plasma Process. Polym.15 (2018)1700201.

6. M. Florea, F. Matei-Rutkovska, G. Postole, A. Urda, F. Neatu, V.I. Pârvulescu, P. Gelin, Doped ceria prepared by precipitation route for steam reforming of methane, Catal. Today 306 (2018) 166-171.

7. N. Candu, D. Paul, I.-C. Marcu, V. I. Parvulescu, S.M. Coman, Levulinate-intercalated LDH: a potential heterogeneous organocatalyst for the green epoxidation of a,b-unsaturated esters, Catal. Today 306 (2018) 154-165.

8. A. Negoi, V.I. Parvulescu, M. Tudorache, Peroxidase-based biocatalysis in a two-phase system for allylic oxidation of a-pinene, Catal. Today 306 (2018) 199-206.

9. M. Verziu, M. Serano, B. Jurca, V.I. Parvulescu, S.M. Coman, G. Scholz, E. Kemnitz, Catalytic features of Nb-based nanoscopic inorganic fluorides for anefficient one-pot conversion of cellulose to lactic acid,Catal. Today 306 (2018) 102-110

10. P.T. Huyen, L.T. H. Nam, T.Q. Vinh, C. Martínez, V.I. Parvulescu, ZSM-5/SBA-15 versus Al-SBA-15 as supports for the hydrocracking/hydroisomerization of alkanes, Catal. Today 306 (2018) 121-127.

11. I. Man, S.G. Soriga, V.I. Parvulescu, Effect of Ca and Sr in MgO(100) on the activation of methanol and methyl acetate, Catal. Today 306 (2018) 207-214.

12. C. Opris, N. Amanov, V.I. Parvulescu, M. Tudorache, Peroxidase-based oxidative polymerization of monolignols, Compt. Rend. Chim. 21 (2018) 362-368.

13. N. Candu, D. Paul, I.-C. Marcu, M. Tudorache, V.I. Parvulescu, S.M. Coman, New organic-inorganic LDH composites: synthesis, characterization and catalytic behavior in the green epoxidation of α, β-unsaturated esters, Inorg. Chim. Acta. 475 (2018) 127-132.

14. S. Ion, C. Opris, B. Cojocaru, M. Tudorache, I. Zgura, A. Galca, A. Bodescu, M. Enache, G. Maria, V.I Parvulescu, Front. Chem., section Green and Sustainable Chemistry, 6 (2018) 124.

15. A. Primo, A. Franconetti, M. Magureanu, N.B. Mandache, C. Bucur, C. Rizescu, B. Cojocaru, V.I. Parvulescu, H. Garcia, Engineering active sites on reduced graphene oxide by hydrogen plasma irradiation: Mimicking bifunctional metal/supported catalysts in hydrogenation reactions, Green Chem. 20 (2018) 2611-2623.

16. N. Candu, A. Simion, S.M. Coman, A. Primo, I. Esteve-Adell, V.I. Parvulescu, H. Garcia, Graphene film-supported oriented 1.1.1 gold (0) versus 2.0.0 copper (I) nanoplatelets as very efficient catalysts for coupling reactions, Top. Catal. (2018).

17. I. Podolean, B. Cojocaru, H. Garcia, C. Teodorescu, V.I. Parvulescu, S.M. Coman, From glucose direct to succinic acid: an optimized recyclable bi-functional Ru@MNP-MWCNT catalyst, Top. Catal. (2018).

18. M. Tudorache, C. Opris, B. Cojocaru, N. Apostol, A. Tirsoaga, S. Coman, V.I. Parvulescu, B. Duraki, F. Krumeich, J. van Bokhoven, Highly efficient, easily recoverable and recyclable Re-SiO2-Fe3O4 catalyst for the fragmentation of lignin, ACS Sustain. Chem. Eng., 8 (2018) 9606-9618.

19. I. Podolean O.D. Pavel H.G.Manyar S.F.R.Taylor K. Ralphs P. GoodrichV.I.PârvulescuC Hardacre, SCILLs as selective catalysts for the oxidation of aromatic alcohols, Catal. Today(2018).

20. N. Candu, M. El Fergani, M. Verziu, B. Cojocaru, B. Jurca, N. Apostol, C. Teodorescu, V.I. Parvulescu, S.M. Coman, Efficient glucose dehydration to HMF onto Nb-BEA catalysts, Catal. Today(2018).

21. M. Trandafir, L. Pop, N.D. Hӑdade, I. Hristea, C.M. Teodorescu, F. Krumeich, J.A. van Bokhoven, I. Grosu, V.I. Parvulescu Spirobifluorene-based porous organic polymers as efficient porous support for Pd and Pt for the selective hydrogenations, ChemCatChem (2018).


Reviews:

1. M. Magureanu, C. Bradu, V.I. Parvulescu, Plasma processes for the treatment of water contaminated with harmful organic compounds, J. Phys. D: Appl. Phys. 51 (2018) 313002.

2. P. Sudarsanam, R. Zhong, S. Van den Bosch, S. Coman, V.I. Parvulescu, B. Sels, Functionalised heterogeneous catalysts for sustainable biomass valorisation, Chem. Soc. Rev. (2018)

3. V.I. Parvulescu, H. Garcia, Heterogeneous catalysis based on the supramolecular association, Catal. Sci. & Technol., (2018)


Invited lectures:

1. V.I. Pârvulescu, Modified Graphenes as support and catalysts for organic reactions, a great challenge!, 1st International Conference on Reaction Kinetics, Mechanisms and Catalysis, RKMC 2018, June 6-9, 2018 / Budapest, Hungary.

2. V.I. Pârvulescu, N. Candu, S.M. Coman, C. Teodorescu, A. Primo, H. Garcia, Oriented Au(111)/Graphene: an efficient catalyst for coupling reactions, The 8th Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT), August 5-10, 2018; Yokohama, Japan.

3. P. Sazama, J. Pastvova, C. Rizescu, A. Tarsoaga, V.I. Pârvulescu, H. Garcia, L. Kobera, J. Seidel, J. Rathovsky, P. Klein, I. Jirka, J. Morarkova, Catalytic Properties of 3D Graphene-like Microporous Carbons Synthesized in a Zeolite Template, Pre-symposium of ZMPC2018, "International Symposium on Advanced Zeolite Science & Technology", August 3, 2018, Tokyo, Japan.

4. V.I. Pârvulescu, Graphenes: a great challenge as support and catalysts for organic reactions, Twelfth International Symposium on Heterogeneous Catalysis: Catalysis a motor of economy, August 26-29, 2018, Sofia, Bulgaria.

5. E. Kemnitz, V.I. Pârvulescu, S.M. Coman, Nanoscaled metal fluorides: A new class of heterogeneous catalysts, 14th Pannonian International Symposium on Catalysis, 3–7 September, 2018, Starý Smokovec, Slovakia.


Oral presentations:

1. N. Candu, A. Simion, S.M. Coman, A. Primo, I. Esteve-Adell, H. Garcia, V.I. Parvulescu, Graphene film-supported oriented 1.1.1 gold (0) versus 2.0.0 copper (I) nanoplatelets as very efficient catalysts for Michael reactions, 5th Challenging organic syntheses inspired by nature - from natural products chemistry to drug discovery Workshop, March 1-2, 2018, Malta (ORAL PRESENTATION).

2. C. Opris, B. Cojocaru, N. Gheorghe, M. Tudorache, S.M. Coman, B. Duraki, J.A. van Bokhoven, V.I. Parvulescu, Lignin fragmentation onto multifunctional Fe3O4@Nb2O5@Co@Re catalysts: the role of composition and deposition route of rhenium, 4th Workshop: Valorisation of lignocellulosic biomass side streams for sustainable production of chemicals, materials & fuels using low environmental impact technologies, March 12-14th 2018, Thessaloniki, Greece. (ORAL PRESENTATION)

4. N. Candu, A. Primo, S.M. Coman, H. Garcia, V.I. Parvulescu, Graphene Film-Supported Oriented 1.1.1 Gold (0) Versus 2.0.0 Copper (I) Nanoplatelets As Substitute Catalysts for Michael Additions, CHAOS (C-H Activation in Organic Synthesis) 4th Workshop, March 22-23, 2018, Alcala de Henares, Spain (ORAL PRESENTATION).

5. M. Tudorache, S. Ion, C. Opris, B. Cojocaru, I. Zgura, A.C. Galca, A. Bodescu, M. Enache, G.-M. Maria, V.I Parvulescu, One-pot system based on enzyme oxi-copolymerization of monolignols for designing the lignin-composites, 4th Multistep Enzyme Catalyzed Processes Congress, March 19-22, 2018, Trondheim, Norway (ORAL PRESENTATION).

6. P. Sazama, R. Pilar, V.I. Parvulescu, G. Sadovska, J. Moravkova, D. Kaucky, J. Pastvova, S. Sklenak, A. Vondrova, Enhanced functionality of Al-rich zeolite beta catalysts in industrially relevant acid- and redox-catalysed reactions, The 8th Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT), August 5-10, 2018; Yokohama, Japan (ORAL PRESENTATION).

7. S.M. Coman, M. El Fergani, N. Candu, V.I. Parvulescu, Nb-Beta zeolite catalysts for the efficient transformation of glucose to multiple platform molecules, The 8th Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT), August 5-10, 2018; Yokohama, Japan.


2019

Research articles:

  1. V.I. Parvulescu, S.M. Coman, Core-Magnetic Composites Catalysts for the Valorization and Up-grading of the Renewable Feedstocks. A Minireview, Curr. Catal. 8 (2019) 2-19

  2. P. Sudarsanam, E. Peeters, E.V. Makshina, V.I. Parvulescu, B.F. Sels, Advances in porous and nanoscale catalysts for viable biomass conversion, Chem. Soc. Rev. 48 (2019) 2366-2421.


Invited lectures:

  1. V.I. Pârvulescu, Graphenes: A great challenge as support and catalysts for organic reactions, environment remediation and energy production, 5th Indo-French  Symposium on Functionalized Materials for Sustainable Catalytic and Related Applications, MATSUCAT-2019, 26 February – 1 March, 2019, Pune, India.

  2. V.I. Pârvulescu, Engineering Active Sites on Reduced Graphene Oxide by Hydrogen Plasma Irradiation: Mimcking Bifunctional Metal/Supported Catalysts in Hydrogenation Reactions, 19th International Balkan Workshop on Applied Physics, July 16-19, 2019, Constanta, Romania.


Oral presentations:

  1. V.I. Pârvulescu, Graphene film-supported oriented antimonium nanoplatelets as very efficient catalysts for Michael and Henry additions, CHAOS (C-H Activation in Organic Synthesis) 6th Workshop,, 3-5 April, 2019, Ayia Napa, Cyprus, (ORAL PRESENTATION).

  2. N. Candu, M. El Fergani, V.I. Parvulescu, S.M. Coman, Recent advances in production of succinic acid from glucose using Nb-based zeolites nanocomposites, ISGC-2019, The International Symposium on Green Chemistry, La Rochelle, France, May 13-17, 2019 (ORAL PRESENTATION).

  3. S. Ion, M. Tudorache, C. Sora, V.I. Parvulescu, Flavors and fragrances produced from the biocatalytic oxidation of -pinene, ISGC-2019, The International Symposium on Green Chemistry, La Rochelle, France, May 13-17, 2019 (ORAL PRESENTATION).

  4. N. Candu, A. Simion, S. Coman, V.I. Parvulescu, A. Primo, H. Garcia, Bimetallic oriented (Au/Cu2O) vs monometallic 1.1.1. Au(0) or 2.0.0 Cu2O Graphene-Supported Nanoplatelets as very efficient Catalysts for Henry addition, 14th EUROPACAT, Germany, August 18-23, 2019.

  5. M. Tudorache, C. Opris, B. Cojocaru, S. Coman, N. Gheorghe, B. Duraki, J. van Bokhoven, V.I. Parvulescu, Multifunctional Fe3O4@Nb2O5@Co@Re catalysts for lignin fragmentation, 14th EUROPACAT, Germany, August 18-23, 2019.

  6. M. El Fergani, A. Tirsoaga, V.I. Parvulescu, S. Coman, Catalytic oxidation of 5-hydroxymethyl furfural (HMF) to valuable dicarboxylic acids, 14th EUROPACAT, Germany, August 18-23, 2019.

  7. M. Tudorache, S. Ion, C. Lite, I.Zgura, A. Galca, A. Bodescu, M. Enache, G. Maria, V.I. Parvulescu, O. Pavel, Designing artificial lignin-based composites using enzyme catalysis for monoglicols oxi-(co)polymerization, 14th EUROPACAT, Germany, August 18-23, 2019.

  8. I. Podolean, V.I. Parvulescu, M. Andruh, Graphene-immobilized binuclear [Cu(II)La(III)] complexes as non-precious metals catalysts for oxidative coupling, 14th EUROPACAT, Germany, August 18-23, 2019.

  9. A. Primo, A.Franconetti, H. Garcia, M. Magureanu, N. Mandache, C. Bucur, C. Rizescu, B. Cojocaru, V.I. Parvulescu, Engineering active sites by hydrogen plasma irradiation: Mimicking bifunctional metal/supported catalysts in hydrogenation reactions, 14th EUROPACAT, Germany, August 18-23, 2019, (ORAL PRESENTATION).

  10. N. Candu, M. El Fergani, A. Tirsoaga, V. I. Parvulescu, S. M. Coman, The direct catalytic synthesis of dicarboxylic acids from glucose, 8th Asia Pacific Congress in Catalysis (APCAT-8), 4–7th August 2019, Bangkok, Thailand , (ORAL PRESENTATION).

  11. I. Podolean, V.I. Parvulescu, M. Andruh, Transition-metal binuclear complexes as new graphene-supported heterogeneous catalysts, 8th Asia Pacific Congress in Catalysis (APCAT8), 4–7th August 2019, Bangkok, Thailand , (ORAL PRESENTATION).

  12. O.D. Pavel, R. Zavoianu, R. Birjega, E.-A. Stamate, V.I. Parvulescu, Mechanochemical versus co-precipitation evaluated for LDH for the production of fine chemicals, Workshop on Layered Materials, September 2-4, 2019, Liblice Castle, Czech Republic (ORAL PRESENTATION).

  13. I. Podolean, B. Cojocaru, S. Coman, E. Ioannou, S. Kikionis,V. Roussis, A. Primo, H. Garcia, V.I. Parvulescu, Marine ulvan polysaccharide as a valuable pool of rare sugars, 5th International Congress on Catalysis in Biorefineries – CATBIOR 2019, 23-27 September 2019, Turku, Finland (ORAL PRESENTATION).