Nanoconfinement for Energy Storage in Metal Organic Frameworks


Project Director: Dr. Cezar COMANESCU

Project Code: PN-III-P1-1.1-TE-2021-1657 (TE 84 / 2022)

Project Title: Nanoconfinement for Energy Storage in Metal Organic Frameworks

Project Director: Dr. Cezar Comanescu

Project type: National

Project category: Research projects to stimulate young independent teams (TE)

Financed by: Executive Unit for the Financing of Higher Education, Research, Development and Innovation (UEFISCDI)

Contractor: National Institute of Materials Physics, Bucharest-Magurele, Romania

Status: In progress

Start date: 15.05.2022

Closing date: 14.05.2024

 

SUMMARY: The aim of this project is to synthesize new amine-substituted, mesoporous MOF-NH2 (MOF: metal organic framework), with tunable pore sizes, as supports for complex metal borohydrides (M(BH4)2, M=Mg, Ca, Zn, etc.), leading to new nanocomposite materials of general formula M(BH4)x@MOF-NH2.  The hydrogen storage capacity will be enhanced by functionalities grafted on synthesized MOFs, and/or active metals decoration (such as Pd2+ etc.). Complex hydride nanoconfinement in MOF pores will alter the kinetics and thermodynamics of hydrogen storage. It is expected that hydrogen release will be fast and have an onset at or below 100 °C, and rehydrogenation to be enhanced. The maximum hydrogen storage capacity of such catalyzed composites M(BH4)x@MOF-NH2 will be assessed in a Sievert-type volumetric apparatus, and is expected to be close or meet DOE standards of 4.5 wt.% H2, while behaving reversibly.

OBJECTIVES: The main objectives of the NESMOF project are focused on nanoconfinement of reactive metal hydrides in MOFs, and designing a composite material to fulfill the DOE requirements for a viable, state-of-the-art energy storage material. The goal of this project is to synthesize, characterize and evaluate its hydrogen uptake capacity of a series of nanoconfined complex metal borohydrides in custom-made, substituted metal organic frameworks (MOFs) with tailored architectures, pore sizes and functionalities.

ESTIMATED RESULTS: Achieving the proposed objectives considers two main stages: (i) fundamental research related to MOF, MOF-NH2 and M(BH4)2 syntheses and characterization of the hybrid M(BH4)2@MOF obtained by borohydride nanoconfinement; (ii) the FLP concept will be formulated and introduced to M(BH4)2@MOF-NH2 (Frustrated Lewis Pair). These results could be further optimized and demonstrated at a sub-gram lab scale.

The main deliverables of the project are: (i) publication of 2 articles in top ISI journals (IF>3); (ii) at least 3 presentations at international conferences (1 conference/ year); (iii) 1 patent application registered at OSIM; (iv) the feasibility of composite M(BH4)x@MOF-NH2 will be demonstrated at laboratory scale.

  1. Cezar Comanescu, Dr.; Director proiect; UEFISCDI ID (UEF-iD): U-1700-031X-8033. https://www.brainmap.ro/cezar-comanescu.
  2. Simona-Gabriela Greculeasa, Dr.;  UEFISCDI ID (UEF-iD): U-1700-039S-4308; https://www.brainmap.ro/simona-gabriela-greculeasa.
  3. Claudiu Locovei, Drd.; UEFISCDI ID (UEF-iD):U-1900-061W-8993; https://www.brainmap.ro/claudiu-locovei.
  4. Anda Elena Stanciu, Dr.; UEFISCDI ID (UEF-iD):U-1800-046A-7559; https://www.brainmap.ro/anda-elena-stanciu.
  5. Ioana Dorina Vlaicu, Dr.; UEFISCDI ID (UEF-iD):U-1700-037A-2366; https://www.brainmap.ro/ioana-dorina-vlaicu.

Patent application, May 2024 :

Procedeu de obținere a unor nanocompozite de tip hidrura complexa metalica si compuși cadre metal-organice si tipuri de sisteme obținute, Comanescu Cezar, Greculeasa Simona-Gabriela, Stanciu Anda, Vlaicu Ioana Dorina, Locovei Claudiu-Iulian, depus OSIM mai 2024.

 

October 15th  2023

Comanescu, C., Recent Advances in Surface Functionalization of Magnetic Nanoparticles. Coatings2023, 13, 1772. https://doi.org/10.3390/coatings13101772  (IF=3.4; AIS=0.439)

 

May 27th 2023

Graphene Supports for Metal Hydride and Energy Storage Applications. Comanescu, C., Crystals 2023, 13, 878. https://doi.org/10.3390/cryst13060878 (IF=2.7; AIS=0.424)

 

June 5th 2023

Calcium Borohydride Ca(BH4)2: Fundamentals, Prediction and Probing for High-Capacity Energy Storage Applications, Organic Synthesis and Catalysis. Comanescu, C., Energies2023, 16, 4536. https://doi.org/10.3390/en16114536 (IF=3.2; AIS=0.439)

January 2nd, 2023: Our new paper was just published:

Palade P.;Comanescu, C.; Radu, C. Nickel and Cobalt ferrite – doped graphene as efficient catalysts for improving the hydrogen storage kinetics of lithium borohydride,  Materials 2023, 16(1), 427; https://doi.org/10.3390/ma16010427. (IF=3.748, AIS=0.541)

 

January 2023

Comanescu, C. Paving the Way to the Fuel of the Future - Nanostructured Complex Hydrides,  Int. J. Mol. Sci.2023, 24(1), 143; https://doi.org/10.3390/ijms24010143. (IF=6.208, AIS=1.064)

 

May 27th, 2023:

Comanescu, C.  Graphene Supports for Metal Hydride and Energy Storage Applications. Crystals 2023, 13, 878. https://doi.org/10.3390/cryst13060878 (IF=2.7; AIS=0.424)

 

June 5th, 2023:

Comanescu, C. Calcium Borohydride Ca(BH4)2: Fundamentals, Prediction and Probing for High-Capacity Energy Storage Applications, Organic Synthesis and Catalysis. Energies 2023, 16, 4536. https://doi.org/10.3390/en16114536 (IF=3.2; AIS=0.439)

 

October 15th, 2023

Comanescu, C. Recent Advances in Surface Functionalization of Magnetic Nanoparticles. Coatings 2023, 13, 1772. https://doi.org/10.3390/coatings13101772  (IF=4.4; AIS=0.439)

Results (Stage 1)

Within Stage 1 (Fundamental research of metal borohydrides in MOFs), a series of over 10 MOFs was obtained from dicarboxylic ligands and different metal salts (of Cr, Fe, Co, Mn, Ni, etc.) (Activity 1.1). Preliminary studies were carried out regarding the optimal methods of infiltration of complex metal borohydrides into MOFs and melt impregnation was chosen in a two-step process for maximum confinement in the pores using as an example a LiBH4–Ca(BH4)2 eutectic mixture in Cr-MOF (Activity 1.2., Activity 1.3.). The synthesized MOFs and LiBH4-Ca(BH4)2@Cr-MOF type nanocomposites were morphologically and structurally studied (Activities 1.1, 1.2 and 1.3). Preliminary studies were carried out regarding H2 storage in the as-synthesized M(BH4)x@M-MOF nanocomposites, revealing a H2 storage capacity of 4.0 wt% (first desorption cycle) and ~2.5 wt% (the second desorption cycle) in the particular case of the LiBH4-Ca(BH4)2@Cr-MOF composite. New MOF type compounds will be synthesized, including organic functionalities (amino type, e.g.) that will be investigated in the desorption/absorption processes of H2 in borohydride @ MOF composites. The nature of intermediate products generated in the cycling of the material during hydrogenation will be investigated.

 

Results (Stage 2)

Within Stage 2 (Formulation of the FLP concept and its technological applicability), the anticipated results were 1 scientific research report; 1 ISI article in magazines with IF>3; creation and management of project website and dissemination through social media; participation in a national / international conference. In short, an optimal model for M(BH4)2 – MOF composites was proposed, followed by the optimized synthesis of M(BH4)2 – MOF composites. The metal-organic composites M(BH4)x-MOF were produced by incipient wetness, melt infiltration and/or mechano-chemistry (milling in a ball mill), and the weight loading of M(BH4)x borohydride was optimized, as well as the reaction parameters (T, p). The hydrogenation properties of said composites M(BH4)2 – MOFwere measured in a Sievert-type apparatus.

 

Results (Stage 3)

Within Stage 3, loading tests were performed with complex hydride (borohydrides LiBH4, Ca(BH4)2 or eutectic LiBH4+Ca(BH4)2) or RHC (2LiNH2+MgH2) in the porosity of MOF and MOF-NH2 type nanosupports, using loading levels between 40 and 80 wt% (weight percentages of reactive hydride compound). An attempt was also made to obtain additional catalyzed composites, in this case using oxide compounds of the SrFe12O19 hexaferrite type. Ferrite-type compounds can catalyze a faster decomposition of the borohydride mixture, releasing H2 simultaneously with the formation of the corresponding borates. The amount of storage composite used was scaled up to 250 mg, with results comparable to the situation where 100 mg of nanocomposite was used. Two types of hydride@MOF materials were obtained, with a reversible storage capacity of 3 wt% and 4.2 wt%, respectively, results that were the subject of a patent submitted to OSIM.

 

Outcome indicators

Regarding the fulfillment of indicators, it is worth noting the publication of 8 open access articles in ISI scientific journals most of them with IF>3 where the project director (C.C.) is the principal author (first author / corresponding author).

Regarding the participation at conferences, C.C. participated as author at 7 international conferences in 2022-2023 (6 of them having the author as main lead).

 

Articles:

  1. Complex Metal Borohydrides: from Laboratory Oddities to Prime Candidates in Energy Storage Applications, Comanescu, C. Materials 2022, 15(6), 2286. https://doi.org/10.3390/ma15062286 (IF=3.748, AIS=0.541)
  2. Recent Development in Nanoconfined Hydrides for Energy Storage, Comanescu, C. Int. J. Mol. Sci. 2022, 23(13), 7111; https://doi.org/10.3390/ijms23137111 (IF=6.208, AIS=1.064)
  3. Magnetic Nanoparticles: Current Advances in Nanomedicine, Drug Delivery and MRI. Comanescu, C., Chemistry 2022, 4, 872-930. https://doi.org/10.3390/chemistry4030063 (AIS=0.303)
  4. Paving the Way to the Fuel of the Future - Nanostructured Complex Hydrides, Comanescu, C. Int. J. Mol. Sci. 2023, 24(1), 143; https://doi.org/10.3390/ijms24010143. (IF=6.208, AIS=1.064)
  5. Nickel and Cobalt ferrite – doped graphene as efficient catalysts for improving the hydrogen storage kinetics of lithium borohydride, Palade P.; Comanescu, C.*; Radu, C. Materials 2023, 16(1), 427; https://doi.org/10.3390/ma16010427. (IF=3.748, AIS=0.541)
  6. Comanescu, C. Recent Advances in Surface Functionalization of Magnetic Nanoparticles. Coatings 2023, 13, 1772. https://doi.org/10.3390/coatings13101772  (IF=4.4; AIS=0.439)
  7. Comanescu, C. Calcium Borohydride Ca(BH4)2: Fundamentals, Prediction and Probing for High-Capacity Energy Storage Applications, Organic Synthesis and Catalysis. Energies 2023, 16, 4536. https://doi.org/10.3390/en16114536 (IF=3.2; AIS=0.439)
  8. Comanescu, C.  Graphene Supports for Metal Hydride and Energy Storage Applications. Crystals 2023, 13, 878. https://doi.org/10.3390/cryst13060878 (IF=2.7; AIS=0.424)

 

Conferences:

1. Cezar Comanescu,Petru Palade, Nicusor Iacob, Gabriel Schinteie, Victor Kuncser. Exploring the journey of ferrites from biomedical to energy storage applications, 22ndRomanian International Conference on Chemistry and Chemical Engineering (RICCCE 2022), 7-9 September 2022, Sinaia, Romania. (oral presentation)

2. Cezar COMANESCU, Petru PALADE, Nicusor IACOB, Victor KUNCSER. Transition metal ferrites – efficient tools for energy storage, environment remediation and biomedical applications. 5thInternational Conference on Emerging Technologies in Materials Engineering (EmergeMAT), 27-28 October 2022, Bucharest, Romania. (oral presentation)

3. Cezar COMANESCU, Petru PALADE, Victor KUNCSER. Versatility of iron oxides and ferrites: from biomedical applications to hydrogen storage hosts and catalysts. 20thInternational Balkan Workshop on Applied Physics and Materials Science (IBWAP 2022), 12-15 July 2022. (oral presentation)

4. Cezar COMANESCU, Petru PALADE, Gabriel SCHINTEIE, Nicusor IACOB, Andrei KUNCSER, Victor KUNCSER, Functionalized MOFs for energy storage and environment remediation, 21st International Balkan Workshop on Applied Physics and Materials Science (IBWAP 2023), 11-14 July 2023. (oral presentation)

5.  Cezar COMANESCU, P. Palade, N. IACOB, G. SCHINTEIE, V. KUNCSER Transformative prospects of metal-organic framework (MOF)-based nanomaterials for advanced energy storage applications, 6th INTERNATIONAL CONFERENCE PROGRAMME Emerging Technologies in Materials Engineering – EmergeMAT, 9-10 Nov. 2023, Bucharest, Romania)

6.  Cezar COMANESCU, Petru PALADE, Nicusor IACOB, Andrei KUNCSER, Gabriel SCHINTEIE, Victor KUNCSER, Development of novel catalysts for enhanced hydrogen storage properties of complex hydrides, 8th International Workshop of Materials Physics IWMP - Advanced Materials and Methods for Heterogeneous Catalysis, 17-19 May 2023, Magurele, Romania.

7. Cristina Bartha, Cezar Comanescu, Mihai Grigoroscuta, Claudiu Locovei, Andrei Alexandru-Dinu, Nicusor Iacob, Aurel Leca, Petre Badica, Victor Kuncser, Structural, Mössbauer spectroscopy and magnetic investigatins of Gd3Fe5O12 garnets obtained by different routes, 37th International Conference on the Applications of the Mössbauer Effect, ICAME 2023, will be held in Cartagena de Indias, Colombia, from September 3 to 8 in 2023.

Patent Application

  1. Procedeu de obținere a unor nanocompozite de tip hidrura complexa metalica si compuși cadre metal-organice si tipuri de sisteme obținute, Comanescu Cezar, Greculeasa Simona-Gabriela, Stanciu Anda, Vlaicu Ioana Dorina, Locovei Claudiu-Iulian, depus OSIM mai 2024.

 

  1. Complex Metal Borohydrides: from Laboratory Oddities to Prime Candidates in Energy Storage Applications, Comanescu, C. Materials 2022, 15(6), 2286. https://doi.org/10.3390/ma15062286 (IF=3.748, AIS=0.541)
  2. Recent Development in Nanoconfined Hydrides for Energy Storage, Comanescu, C. Int. J. Mol. Sci. 2022, 23(13), 7111; https://doi.org/10.3390/ijms23137111 (IF=6.208, AIS=1.064)
  3. Magnetic Nanoparticles: Current Advances in Nanomedicine, Drug Delivery and MRI. Comanescu, C., Chemistry 2022, 4, 872-930. https://doi.org/10.3390/chemistry4030063 (AIS=0.303)
  4. Paving the Way to the Fuel of the Future - Nanostructured Complex Hydrides, Comanescu, C. Int. J. Mol. Sci.2023, 24(1), 143; https://doi.org/10.3390/ijms24010143. (IF=6.208, AIS=1.064)
  5. Nickel and Cobalt ferrite – doped graphene as efficient catalysts for improving the hydrogen storage kinetics of lithium borohydride, Palade P.;Comanescu, C.; Radu, C. Materials 2023, 16(1), 427; https://doi.org/10.3390/ma16010427. (IF=3.748, AIS=0.541)
  6. Comanescu, C. Recent Advances in Surface Functionalization of Magnetic Nanoparticles. Coatings 2023, 13, 1772. https://doi.org/10.3390/coatings13101772  (IF=4.4; AIS=0.439)
  7. Comanescu, C. Calcium Borohydride Ca(BH4)2: Fundamentals, Prediction and Probing for High-Capacity Energy Storage Applications, Organic Synthesis and Catalysis. Energies 2023, 16, 4536. https://doi.org/10.3390/en16114536 (IF=3.2; AIS=0.439)
  8. Comanescu, C.  Graphene Supports for Metal Hydride and Energy Storage Applications. Crystals 2023, 13, 878. https://doi.org/10.3390/cryst13060878 (IF=2.7; AIS=0.424)

cezar.comanescu@infim.ro

PROJECTS/ NATIONAL PROJECTS

Back to top

Copyright © 2024 National Institute of Materials Physics. All Rights Reserved