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Title: Incorporation of free halide ions stabilizes metal–organic frameworks (MOFs) against pore collapse and renders large-pore Zr-MOFs functional for water harvesting

Journal Article · · Journal of Materials Chemistry. A
DOI: https://doi.org/10.1039/d1ta10217f · OSTI ID:1978846

Chemically and hydrolytically stable MOFs have shown promising water-vapor adsorption properties. However, MOFs that can simultaneously satisfy the following three requirements for effective water harvesting from low-humidity air are quite rare: (1) high water-uptake capacity; (2) hydrolytic and mechanical stability; (3) complete uptake at ~20–30% relative humidity (RH). Here we show that incorporating free halide ions is effective for enabling a representative Zr-MOF to meet these requirements for water harvesting. As-synthesized MOF-808 initially exhibits very good capacity at RH ≥ 30%, but quickly suffers large capacity losses due to water-evacuation-induced pore collapse. Via a framework-charging and free counter-ion inclusion approach, we were able to replace node-ligated formate anions with charge-neutral aqua ligands and site desired water-sorbing free-halide ions within the large pores of MOF-808. In this study, altered samples show increased gravimetric water uptake, show beneficial shifts of water sorption isotherms toward lower water-vapor partial pressure, eliminate undesirable sorption/desorption isotherm hysteresis, and render MOF-808-Br indefinitely recyclable for ambient-temperature uptake of water vapor and lower-temperature liquid-water release.

Research Organization:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE
Grant/Contract Number:
FG02-08ER15967; DMR-1121262
OSTI ID:
1978846
Alternate ID(s):
OSTI ID: 1846998
Journal Information:
Journal of Materials Chemistry. A, Vol. 10, Issue 12; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (4)