2021 Annual Meeting

(90f) ZIF-8 Membrane Performance Modification Via Facile Vapor-Phase Metal-Organic Treatment

Authors

Dorneles de Mello, M., UNIVERSITY OF MINNESOTA
Hayashi, M., Tokyo Institute of Technology
Boscoboinik, J., Brookhaven National Laboratory
Tsapatsis, M., Johns Hopkins University
Zeolitic imidazole frameworks (ZIFs), constructed from tetrahedral single transition metal nodes linked by imidazole-based linkers, have great potential in membrane separation due to their uniform and fine-tunable pore size and structural diversity.[1] Since the first promising H2 purification by solvothermally grown ZIF-8 membranes,[2] a wide range of reports regarding ZIF membranes have emerged, demonstrating enhancements in propylene/propane separation properties by structural and chemical features of porous supports as well as membrane synthesis methods.[3–5] Furthermore, precise tuning of gas permeation properties of ZIF-8 membranes for smaller gas molecule separations has been facilitated by postsynthetic treatments including rapid heat treatment[6] and vapor phase ligand treatment.[7]

This presentation will describe remarkable enhancements in both propylene/propane and H2/CH4 selectivity of ZIF-8 membranes by a new facile vapor phase treatment with manganese(II) acetylacetonate (Mn(acac)2) at different temperatures (i.e., 165 °C and 175 °C, respectively).[8] Systematic characterizations of the microstructure and compositional analysis of ZIF-8 membrane surface upon Mn(acac)2 ­treatment (Mn-ZIF-8) will be discussed. Of particular interest is the observed ideal selectivity of 242 for H2/CH4 with 1.210-7 mol m-2 Pa-1 s-1 H2 permeance at room temperature, which is facilitated by the presence of a few nanometer-thick Mn(acac)2 deposit on the membrane surface.

Vapor-phase metal-organic treatment, employed in this work, is a facile and effective approach to tuning the gas separation properties of as-formed membranes and has great potential to be applicable with ease to other porous membranes which could display anomalous membrane performance modifications for other gas pair separations.

References

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[3] S. Zhou, Y. Wei, L. Li, Y. Duan, Q. Hou, L. Zhang, L. X. Ding, J. Xue, H. Wang, J. Caro, Sci. Adv. 2018, 4, 1–9.

[4] X. Ma, P. Kumar, N. Mittal, A. Khlyustova, P. Daoutidis, K. A. Mkhoyan, M. Tsapatsis, Science (80-. ). 2018, 361, 1008 LP – 1011.

[5] M. N. Shah, M. A. Gonzalez, M. C. McCarthy, H. K. Jeong, Langmuir 2013, 29, 7896–7902.

[6] D. J. Babu, G. He, J. Hao, M. T. Vahdat, P. A. Schouwink, M. Mensi, K. V. Agrawal, Adv. Mater. 2019, 31, 6–11.

[7] K. Eum, M. Hayashi, M. D. De Mello, F. Xue, H. T. Kwon, M. Tsapatsis, Angew. Chemie - Int. Ed. 2019, 58, 16390–16394.

[8] M. Hayashi, D. T. Lee, M. Dorneles de Mello, A. Boscoboinik, M. Tsapatsis, Angew. Chemie Int. Ed. 2021, n/a, DOI https://doi.org/10.1002/anie.202100173.