Counterintuitive Trend of Intrusion Pressure with Temperature in the Hydrophobic Cu 2 (tebpz) MOF
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- Department of Chemical Pharmaceutical and Agricultural Sciences University of Ferrara Ferrara 44121 Italy
- College of Chemistry and Chemical Engineering Chemistry and Chemical Engineering Guangdong Laboratory Shantou University Guangdong 515063 China
- College of Chemistry and Materials Science Jinan University Guangzhou 510632 China
- Institute of Physics University of Silesia Chorzów 41‐500 Poland
- Institute of Chemistry University of Silesia Szkolna 9 Katowice 40‐006 Poland
- NIST Center for Neutron Research National Institute of Standards and Technology Gaithersburg MD 20899 USA
- X‐Ray Science Division Advanced Photon Source Argonne National Laboratory Argonne IL 60439 USA
- Institute of Chemistry University of Silesia Szkolna 9 Katowice 40‐006 Poland, Centre for Cooperative Research on Alternative Energies (CIC energiGUNE) Basque Research and Technology Alliance (BRTA) Vitoria‐Gasteiz 01510 Spain
Abstract Liquid porosimetry experiments reveal a peculiar trend of the intrusion pressure of water in hydrophobic Cu 2 (3,3′,5,5′‐tetraethyl‐4,4′‐bipyrazolate) MOF. At lower temperature ( T ) range, the intrusion pressure ( P i ) increases with T . For higher T values, P i first reaches a maximum and then decreases. This is at odds with the Young–Laplace law, which for systems showing a continuous decrease of contact angle with T predicts a corresponding reduction of the intrusion pressure. Though the Young–Laplace law is not expected to provide quantitative predictions at the subnanoscale of Cu 2 (tebpz) pores, the physical intuition suggests that to a reduction of their hydrophobicity corresponds a reduction of the P i . Molecular dynamics simulations and sychrothron experiments allowed to clarify the mechanism of the peculiar trend of P i with T . At increasing temperatures the vapor density within the MOF’ pores grows significantly, bringing the corresponding partial pressure to ≈5 MPa. This pressure, which is consistent with the shift of P i observed in liquid porosimetry, represents a threshold to be overcame before intrusion takes place. Beyond some value of temperature, the phenomenon of reduction of hydrophobicity (and water surface tension) dominated over the opposite effect of increase of vapor pressure and P i inverts its trend with T .
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 2427418
- Journal Information:
- Small, Journal Name: Small Journal Issue: 42 Vol. 20; ISSN 1613-6810
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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