Solid State NMR Group

Photo of the Group: (from left to right): Back Seats: Mr Orfanidis Savvas, Mr Subrati Ahmed, Mr Subrati Mohammed, Ms Gkoura Lydia, Mr Anastasiou Athanasios Front Seats: Dr. Fardis Michalis, Dr. Papavassiliou George, Dr. Karagianni Marina, Dr. Panopoulos Nikolaos

 

NMR Facility

4 Superconductive Magnets 100 MHz, 200 MHz (2), and 400 MHz Measurements 1.2K-
1000K, unique High Temperature NMR facility in Greece

 

Bruker 100 MHz NMR Spectrometer

 

Bruker 200 MHz NMR Spectrometer

Bruker 400 MHz NMR Spectrometer

 

Fabrication of State-of-the-Art Benchtop NMR Spectrometers for Outdoor Applications

 

  • Benchtop Broadband Solid State NMR operating in the frequency Range 2MHz-800MHz.
  • Portable Halbach Magnets for in-field applications
  • Full NMR Data Acquisition and Analysis software development

  • Dynamic 2D NMR measurements (T1 – T2, D – T2, T2 – Τ2) of fluids as a function of temperature
  • Self-diffusion coefficient measurements in:
  1. the Stray field of Superconductive Magnets
  2. Pulsed Field Gradient
  • Implementation of 1D and 2D Inversion Algorithms to acquire Relaxation Times/Diffusion Distribution

Research Activities

Research activities are mainly focused in the study of functionalized nanostructured materials in five different areas: (i) Two Dimensional Materials with Exotic Electronic Properties, such as Topological Insulators (ultrathin Bi2Se3 and Bi2Te3 nanoplateletes), single layer MoS2 on Graphene and CNTs, and Germanane (GeH). (ii) Complex transition metal oxides (magnetic and superconductive materials – strong electron correlations), (iii) Functionalized magnetic and photoactivated Transition Metal Oxide nanoparticles such as Fe2O3, Fe3O4, TiO2, etc. (iv) Contemporary Nanocatalysts for HER/OER, and HDS (such as MoS2, Ni2P, nanozeolites, etc.), (v) NMR studies of nanofluidity in porous systems with emphasis in carbon nanotubes, nanozeolites, as well as cement-based materials, industrial porous structures and oil-reservoir rock samples.

In addition:

(i) Development and application of solid state NMR methodologies in condensed matter systems. Measurements are performed in the temperature range 2K-1000K. The NMR studies are combined with other experimental techniques, such as XRD, Magnetic Measurements (PPMS, SQUID), Transmission Electron Microscopy (TEM), and Scanning Electron Microscopy (SEM).

(ii) Development of NMR Nanocrystallography: Combination of Density Functional Theory (DFT) calculations with NMR experiments in order to acquire the crystal and electronic structure of ultrafine nanoparticles. The method is implemented on Nanoscaled Materials which are at the forefront of Science and Technology (e.g. Topological Insulators and Topological Catalysts).

In the last five years there is very successful collaboration with excellent results among the ssNMR group of INN, the Chemical Engineering Department of Khalifa University at Abu Dhabi (UAE), Vanderbilt university (USA), the Korea Basic Science Institute at Daejeon (Korea) and the University of Ioannina (Greece). Work concerns (i) development and application of nanocatalysts in the Petroleum Industry (MoS2, Ni2P, and novel substrates), (ii) Implementation of Magnetic Nanoparticles for Reservoir Characterization (iii) Development of NMR methodologies for login oil reservoir applications.

Selected Publications

 

  •  “Polaron freezing and the quantum liquid-crystal phase in the ferromagnetic metallic La0.67Ca0.33MnO3”, N. Panopoulos, M. Pissas, H. J. Kim, Jin-Gyu Kim, S. J. Yoo, J. Hassan, Y. AlWahed, S. Alhassan, M. Fardis, N. Boukos, G. Papavassiliou, npj Quantum Materials Nature 3, 20 (2018)
  •  “NMR and EPR Structural Analysis and Stability Study of Inverse Vulcanized Sulfur Copolymers”, Vijay Kumar Shankarayya Wadi,Kishore K. Jena,Shahrukh Z. Khawaja, Konstantina Yannakopoulou, Michael Fardis,George Mitrikas, Marina Karagianni, Georgios Papavassiliou,and Saeed M. Alhassan*, ACS Omega 3, 3330−3339 (2018)
  • “Ultrafast Stratified Diffusion of Water Inside Carbon Nanotubes; Direct Experimental Evidence with 2D D–T2 NMR Spectroscopy”, J. Hassan, G. Diamantopoulos, L. Gkoura, M. Karagianni, S. Alhassan, S. V. Kumar, M. S. Katsiotis, T. Karagiannis, M. Fardis, N. Panopoulos, H. J. Kim, M. Beazi-Katsioti, and G. Papavassiliou, The Journal of Physical Chemistry C, ACS Publications  10.1021/acs.jpcc.8b01377 (2018)
  • “Facile MoS2 growth on reduced graphene-oxide via liquid phase method”, Vasileios Tzitzios, Konstantinos Dimos, Saeed M. Alhassan, Rohan Mishra, Antonios Kouloumpis, Dimitrios Gournis, Nikolaos Boukos, Manuel Roldan, Juan-Carlos Idrobo, Michael A. Karakassides, Georgia Basina, Yasser Alwahedi, Hae Jin Kim, Michael Fardis, Sokrates Pantelides and George Papavassiliou, Front. Mater. doi:10.3389/fmats.2018.00029 (2018)
  • “Iron-substituted cubic silsesquioxane pillared clays: Synthesis, characterization and acid catalytic activity”, Georgia Potsi, Athanasios K. Ladavos, Dimitrios Petrakis, Alexios P. Douvalis, Yiannis Sanakis, Marios S. Katsiotis, Georgios Papavassiliou, Saeed Alhassan, Dimitrios Gournis, and Petra Rudolf, Journal of Colloid and Interface Science 510, 395–406 (2018)
  •  “Iron-substituted cubic silsesquioxane pillared clays: Synthesis, characterization and acid catalytic activity”, Georgia Potsi, Athanasios K. Ladavos, Dimitrios Petrakis, Alexios P. Douvalis, Yiannis Sanakis, Marios S. Katsiotis, Georgios Papavassiliou, Saeed Alhassan, Dimitrios Gournis, and Petra Rudolf. Journal of Colloid and Interface Science 510, 395–406 (2018).
  • Unexpected orbital magnetism in Bi-rich Bi2Se3 nanoplatelets”.  H. J. Kim*, M. S.  Katsiotis, S. M. Alhassan, I. Zafiropoulou, M. Pissas, Y. Sanakis, G. Mitrikas, N. Panopoulos, N. Boukos, V. Tzitzios, M. Fardis, J-G. Kim, S-G. Lee, Y-M. Kim, S.J. Yoo, J.-H. Lee, A. Kouloumpis, D. Gournis, M.  Karakassides, G. Papavassiliou, Nature Publishing Group, Asia Materials 8, e271; am.2016.56 (2016).
  • “Water coordination, proton mobility and Lewis acidity in HY nanozeolites: A high temperature 1H and 27Al NMR study”, M.S. Katsiotis, M. Fardis, Y. AlWahedi, S. Stephen, V. Tzitzios, N. Boukos, H. J. Kim, S. Alhassan, and G. Papavassiliou. Journal of Physical Chemistry C 119(6), 3428-3438 (2015).
  • “Pore structure evolution and strength development of G-type elastic oil well cement. A combined 1H NMR and ultrasonic study”, E. Karakosta, L. Lagkaditi, S. ElHardalo, A. Biotaki c, V.C. Kelessidis, M. Fardis, G. Papavassiliou, Cement and Concrete Research 72, pp90–97 (2015).
  • “Attachment of Pseudomonas putida onto differently structured kaolinite minerals: A combined ATR-FTIR and 1H NMR study”,  I. A. Vasiliadou, D. Papoulis, C. V. Chrysikopoulos, D. Panagiotaras, E. Karakosta, M. Fardis, G. Papavassiliou. Colloids and Surfaces B: Biointerfaces 84, 354-9 (2011).
  • 139La NMR evidence for phase solitons in the ground state of overdoped manganites”, D. Koumoulis, N. Panopoulos, A. Reyes, M. Fardis, M. Pissas, A. Douvalis, T. Bakas, D. Argyriou and G. Papavassiliou. Phys. Rev. Letters 104, 077204 (2010).
  • “Spin order and lattice frustration in optimally doped manganites. A high temperature NMR study”, N. Panopoulos, D. Koumoulis, G. Diamantopoulos, M. Belesi, M. Fardis, M. Pissas, and G. Papavassiliou. Phys. Rev. B 82 (Editor’s suggestion), 235102 (2010).
  • “Photo-induced carbonation of lime-TiO2 mortars”, I. Karatasios, M. S. Katsiotis, V. Likodimos, A. Kontos, G. Papavassiliou, P. Falaras, V. Kilikoglou. Applied Catalysis B:  Environmental 95, 78-86 (2010).
  • “In situ monitoring of cement gel growth dynamics. Use of a miniaturized permanent Halbach magnet for precise 1H NMR studies”, E. Karakosta, G. Diamantopoulos, M. S. Katsiotis, M. Fardis, G. Papavassiliou, P. Pipilikaki, M. Protopapas, and D. Panagiotaras, Industrial and Engineering Chemistry Research 49, 613-622 (2010).

Optimizing hydrocarbon recovery is a high priority target globally. Key milestone for this goal is full and in depth characterization of oil reservoirs. In this perception, improving Laboratory and Logging (field) methods for oil reservoir characterization is an issue of critical importance. Currently, important logging methods are based on utilizing earth’s gravitational, magnetic, and electrical fields. Searching for local perturbations in these naturally occurring fields may be of high economic interest due to the concealed geological features, which are related with efficient and cost-benefit planning of oil production projects. A major disadvantage of a great number of state of the art logging technologies is the fact that they penetrate and provide information only a few inches from the wellbore, while others lack the required resolution and the capacity to deeply penetrate reservoir lithology, especially in tight formations. Besides, in harsh environment, like high temperature and high pressure, many of the logging tools become unreliable.

mnp1

By introducing sensors and techniques combined with imaging-contrast agents, altering optical, magnetic, and electrical properties, one can illuminate the geophysical properties of reservoir fluids and rocks far beyond the wellbore, and acquire three-dimensional distribution of reservoir fluids and rocks, and dynamic fluid paths in distance of several hundred meters. In this context, nanotechnology derived imaging contrast agents, such as magnetic nanoparticles, have the potential to unveil long distance reservoir architecture, establishing fluid-flow trends, and identify reserve growth potential. The high magnetic susceptibilities of these particles (compared to most reservoir rocks and fluids) make them ideal potential magnetic contrast agents to mix with proppant and help to monitor the progress of hydraulic fracturing jobs downhole.

mnp2

This project aims to the development of novel Magnetic Nano-Particles (MNPs) with controlled size, shape, and surface coating, acquiring long-term aqueous stability and long-distance transportability into the harsh oil reservoir environment. MNPs will be flooded with water into oil reservoirs, and their flow paths will be tracked with logging Electromagnetic Methods (magnetic permeability alteration maps), providing thus a novel methodology for 3D mapping of fracture architecture and fluids distribution in the Middle-East Carbonate Reservoirs.

The project will last three (3) years and will be realized by:

the Abu Dhabi Marine Operating Company (ADMA-OPCO) (United Arabic Emirates)

and a Consortium of Academic partners comprising of:

  • The Petroleum Institute – PI (United Arabic Emirates) Lead Principal Investigator,
  • National Center for Scientific Research Demokritos – NCSRD (Greece) Co-lead Principal Investigator,
  • Korea Basic Science Institute – KBSI (Rep. of Korea),
  • University of Ioannina – UoI (Greece),
  • Vanderbilt University – VU (USA).

The project includes two phases:

1st Phase. Laboratory and small-scale pilot implementation (current phase).

2nd Phase. Development phase, i.e. field implementation in ADMA’s Oil reservoir.

mnp3