TY - JOUR
T1 - Water Promotes Melting of a Metal-Organic Framework
AU - Sørensen, Søren Strandskov
AU - Christensen, Anders K. R.
AU - Bouros-Bandrabur, Elena A
AU - Andersen, Emil S.
AU - Christiansen, Heidi F.
AU - Lang, Sofie
AU - Cao, Fengming
AU - Jalaludeen, M Faizal Ussama
AU - Christensen, Johan F. S.
AU - Winters, Wessel M. W.
AU - Andersen, Bettina P.
AU - Nielsen, Anders B.
AU - Nielsen, Niels Chr.
AU - Bomholdt Ravnsbæk, Dorthe
AU - Kristensen, Peter K.
AU - Yue, Yuanzheng
AU - Smedskjær, Morten Mattrup
PY - 2024/3
Y1 - 2024/3
N2 - Water is one of the most reactive and abundant molecules on Earth, and it is thus crucial to understand its reactivity with various material families. One of the big unknown questions is how water in liquid and vapor forms impact the fast-emerging class of metal-organic frameworks (MOFs). Here, we discover that high-pressure water vapor drastically modifies the structure and hence the dynamic, thermodynamic, and mechanical properties of MOF glasses. In detail, we find that an archetypical MOF (ZIF-62) is extremely sensitive to heat treatments performed at 460 °C and water vapor pressures up to ∼110 bar. Both the melting and glass transition temperatures decrease remarkably (by >100 °C), and simultaneously, hardness and Young's modulus increase by up to 100% under very mild treatment conditions (<20 bar of hydrothermal pressure). Structural analyses suggest water to partially coordinate to Zn in the form of a hydroxide ion by replacing a bridging imidazolate-based linker. The work provides insight into the role of hot-compressed water in influencing the structure and properties of MOF glasses and opens a new route for systematically changing the thermodynamics and kinetics of MOF liquids and thus altering the thermal and mechanical properties of the resulting MOF glasses.
AB - Water is one of the most reactive and abundant molecules on Earth, and it is thus crucial to understand its reactivity with various material families. One of the big unknown questions is how water in liquid and vapor forms impact the fast-emerging class of metal-organic frameworks (MOFs). Here, we discover that high-pressure water vapor drastically modifies the structure and hence the dynamic, thermodynamic, and mechanical properties of MOF glasses. In detail, we find that an archetypical MOF (ZIF-62) is extremely sensitive to heat treatments performed at 460 °C and water vapor pressures up to ∼110 bar. Both the melting and glass transition temperatures decrease remarkably (by >100 °C), and simultaneously, hardness and Young's modulus increase by up to 100% under very mild treatment conditions (<20 bar of hydrothermal pressure). Structural analyses suggest water to partially coordinate to Zn in the form of a hydroxide ion by replacing a bridging imidazolate-based linker. The work provides insight into the role of hot-compressed water in influencing the structure and properties of MOF glasses and opens a new route for systematically changing the thermodynamics and kinetics of MOF liquids and thus altering the thermal and mechanical properties of the resulting MOF glasses.
UR - http://www.scopus.com/inward/record.url?scp=85187111757&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.3c02873
DO - 10.1021/acs.chemmater.3c02873
M3 - Journal article
C2 - 38558915
SN - 0897-4756
VL - 36
SP - 2756
EP - 2766
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 6
ER -