Quest for an optimal methane hydrates formation in the pores of hydrolytically stable MOFs
Daemen, Luke L.
Ramirez-Cuesta, Anibal J.
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Chemical Science Program
Functional Materials Design, Discovery and Development (FMD3)
Physical Science and Engineering (PSE) Division
Online Publication Date2020-07-11
Print Publication Date2020-08-05
Embargo End Date2021-07-11
Permanent link to this recordhttp://hdl.handle.net/10754/664293
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AbstractPorous MOFs capable of storing relatively high amount of dry methane (CH4) in adsorbed phase are largely explored, however solid CH4 storage in confined pores of MOFs in the form of hydrates is yet to be discovered. Here we report a rational approach to form CH4 hydrates by taking advantage of the optimal pore confinement in relatively narrow cavities of hydrolytically stable MOFs. Unprecedentedly, we were able to isolate methane hydrate (MH) nanocrystals with a sI structure encapsulated inside MOF pores with an optimal cavity dimension. It was found, that confined nanocrystals require cavities slightly larger than the unit cell crystal size of MHs (1.2 nm), as exemplified in the experimental case study performed on Cr-soc-MOF-1 vs smaller cavities of Y-shp-MOF-5. Under these conditions, the excess amount of methane stored in the pores of Cr-soc-MOF-1 in the form of MH was found to be 50% larger than the corresponding dry adsorbed amount at 10 MPa. More importantly, the pressure gradient driving the CH4 storage/delivery process could be drastically reduced compared to the conventional CH4 adsorbed phase storage on the dry Cr-soc-MOF-1 (≤3 MPa vs. 10 MPa)
CitationCuadrado-Collados, C., Mouchaham, G., Daemen, L. L., Cheng, Y., Ramirez-Cuesta, A. J., Aggarwal, H., … Silvestre-Albero, J. (2020). Quest for an optimal methane hydrates formation in the pores of hydrolytically stable MOFs. Journal of the American Chemical Society. doi:10.1021/jacs.0c01459
SponsorsG.M, M.E and Y.B thank Aramco sponsored research fund (contract. 66600024505). We would like also to acknowledge the support by King Abdullah University of Science and Technology. J.S.A would like to acknowledge financial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), Oak Ridge beam time availability (Project IPTS-20859.1) and Spanish ALBA synchrotron (Project 2020014008).
PublisherAmerican Chemical Society (ACS)