Center for Molecular Modeling - C. Serre

Unraveling the Mechanisms of Zirconium Metal–Organic Frameworks-Based Mixed-Matrix Membranes Preventing Polysulfide Shuttling

leen — Mon, 02 Oct 2023 08:37:13 +0000

W. Lu, Z. Pang, A. Lamaire, F. Liu, S.Dai, M. L. Pinto, R. Demir-Cakan, K. O. Tan, V. Van Speybroeck, V. Pimenta, C. Serre

Small Science

4, 2300339

2024

Abstract

Lithium-sulfur batteries are considered as promising candidates for next-generation energy storage devices for grid applications due to their high theoretical energy density. However, the inevitable shuttle effect of lithium polysulfides and/or dendrite growth of Li metal anodes hinder their commercial viability. Here, the microporous Zr fumarate MOF-801(Zr) was considered to produce thin (~15.6 µm, ~1mg cm²) mixed matrix membranes (MMM) as a novel interlayer for Li-S batteries. It was found that the MOF-801(Zr)/C/PVDF-HFP composite interlayer facilitates Li⁺ ions diffusion, and anchors polysulfides while promoting their redox conversion effectively. We demonstrated that MOF-801 effectively trapped polysulfides at the cathode side, and confirmed for the first time the nature of the interaction between the adsorbed polysulfides and the host framework, through a combination of solid-state NMR and molecular dynamics simulations. The incorporation of MOF-801(Zr)/C/PVDF-HFP MMM interlayer resulted in a notable enhancement in the initial capacity of Li-S batteries up to 1110 mA h g^-1. Moreover, even after 50 cycles, a specific capacity of 880 mA h g^-1 was delivered.

DOI

http://dx.doi.org/10.1002/smsc.202300339

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Published.pdf

How Reproducible are Surface Areas Calculated from the BET Equation?

sven — Mon, 23 May 2022 11:10:33 +0000

J.W.M. Osterrieth, J. Rampersad, D. Madden, N. Rampal, L. Skoric, B. Connolly, M.D. Allendorf, V. Stavila, J.L Snider, R. Ameloot, J. Marreiros, C. Ania, D. Azevedo, E. Vilarrasa-Garcia, B.F. Santos, X.-H. Bu, Z. Chang, H. Bunzen, N.R. Champness, S.L. Griffin, B. Cheng, R.-B. Lin, B. Coasne, S. Cohen, J.C. Moreton, Y.J. Colón, L. Chen, R. Clowes, F.-X. Coudert, Y. Cui, B. Hou, D.M. D'Alessandro, P.W. Doheny, M. Dincă, C. Sun, C. Doonan, M.T. Huxley, J.D. Evans, P. Falcaro, R. Ricco, O. Farha, K.B. Idrees, T. Islamoglu, P. Feng, H. Yang, R.S. Forgan, D. Bara, S. Furukawa, E. Sanchez, J. Gascon, S. Telalović, S.K. Ghosh, S. Mukherjee, M.R. Hill, M.M. Sadiq, P. Horcajada, P. Salcedo-Abraira, K. Kaneko, R. Kukobat, J. Kenvin, S. Keskin, S. Kitagawa, K.-i. Otake, R.P. Lively, S.J.A. DeWitt, P.L. Llewellyn, B.V. Lotsch, S.T. Emmerling, A.M. Pütz, C. Martí-Gastaldo, N.M. Padial, J. García-Martínez, N. Linares, D. Maspoch, J.A. Suárez del Pino, P.Z. Moghadam, R. Oktavian, R.E. Morris, P.S. Wheatley, J. Navarro, C. Petit, D. Danaci, M.J. Rosseinsky, A.P. Katsoulidis, M. Schroeder, X. Han, S. Yang, C. Serre, G. Mouchaham, D.S. Sholl, R. Thyagarajan, D. Siderius, R.Q. Snurr, R.B. Goncalves, S. Telfer, S.J. Lee, V.P. Ting, J.L. Rowlandson, T. Uemura, T. Iiyuka, M.A. van der Veen, D. Rega, V. Van Speybroeck, S.M.J. Rogge, A. Lamaire, K.S. Walton, L.W. Bingel, S. Wuttke, J. Andreo, O. Yaghi, B. Zhang, C.T. Yavuz, T.S. Nguyen, F. Zamora, C. Montoro, H. Zhou, A. Kirchon, D. Fairen-Jimenez

Advanced Materials

34, 27, 2201502

2022

Abstract

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible.

Gold Open Access

DOI

http://dx.doi.org/10.1002/adma.202201502

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main.pdf

Mechanical properties of a gallium fumarate metal-organic framework: a joint experimental-modelling exploration

jelle — Mon, 15 May 2017 07:14:56 +0000

P. Ramaswamy, J. Wieme, E. Alvarez, L. Vanduyfhuys, J.-P. Itié, P. Fabry, V. Van Speybroeck, C. Serre, P.G. Yot, G. Maurin

Journal of Materials Chemistry A

5 (22), 11047-11054

2017

Abstract

A gallium analogue of the commercially available Al-fumarate MOF A520 - recently identified as isotypic to MIL-53(Al)-BDC - has been synthesized and further characterized in its hydrated and dehydrated forms. The structural response under applied mechanical pressure of this MIL-53(Ga)-FA solid was investigated using advanced experimental techniques coupled with computational tools. Hg porosimetry and high-pressure X-Ray Powder Diffraction (XRPD) experiments evidenced that the pristine dehydrated large pore form undergoes an irreversible structure contraction upon an applied pressure of 85 MPa with an associated volume change of ca. 14% which makes this material promising for mechanical energy storage applications, in particular as a shock absorber. The breathing behavior was further rationalized performing a series of periodic Density Functional Theory (DFT) calculations with the construction of an energy profile as a function of volume for both MIL-53(Ga)-FA and its Aluminum analogue. As such we could fully unravel the microscopic origin of the difference in pressure-induced behavior for the aluminum and gallium fumarate based materials.

DOI

http://dx.doi.org/10.1039/C7TA01559C

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Ramaswamy2017.pdf

Mechanical energy storage performance of an aluminum fumarate metal-organic framework

louis — Mon, 14 Sep 2015 07:56:46 +0000

P.G. Yot, L. Vanduyfhuys, E. Alvarez, J. Rodriguez, J.-P. Itié, P. Fabry, N. Guillou, T. Devic, P.L. Llewellyn, V. Van Speybroeck, C. Serre, G. Maurin

Chemical Science

7, 446-450

2016

Abstract

The aluminum fumarate MOF A520 or MIL-53-FA is revealed to be a promising material for mechanical energy-related applications with performances in terms of work and heat energies which surpass those of any porous solids reported so far. Complementary experimental and computational tools are deployed to finely characterize and understand the pressure-induced structural transition at the origin of these unprecedented levels of performance.

Open Access version available at UGent repository

DOI

http://dx.doi.org/10.1039/C5SC02794B

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16-ChemSience-7(2016)446-Yot.pdf

ACL Chem Sci Al-Fum.pdf

Metal-organic frameworks as potential shock absorbers: the case of the highly flexible MIL-53(Al)

michel — Thu, 22 May 2014 12:44:21 +0000

P.G. Yot, Z. Boudene, J. Macia, D. Granier, L. Vanduyfhuys, T. Verstraelen, V. Van Speybroeck, T. Devic, C. Serre, G. Ferey, N. Stock, G. Maurin

Chemical Communications

50, 9462-9464

2014

Abstract

The mechanical energy absorption ability of the highly flexible; MIL-53(Al) MOF material was explored using a combination of; experiments and molecular simulations. A pressure-induced transition; between the large pore and the closed pore forms of this solid; was revealed to be irreversible and associated with a relatively large; energy absorption capacity. Both features make MIL-53(Al) the first; potential MOF candidate for further use as a shock absorber.

Open Access version available at UGent repository

DOI

http://dx.doi.org/10.1039/c4cc03853c

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14_chemcomm_50,9462_Yot.pdf

Impact of the mechanical pressure under various conditions on the flexibility of various metal-organic frameworks

jelle — Mon, 25 Sep 2017 14:08:51 +0000

P.G. Yot, P. Ramaswamy, J. Wieme, L. Vanduyfhuys, C. Serre, V. Van Speybroeck, G. Maurin

ISBN/ISSN:

Talk

Conference / event / venue

EUROMAT 2017

Thessaloniki, Greece

Sunday, 17 September, 2017 to Friday, 22 September, 2017