Details
| Original language | English |
|---|---|
| Pages (from-to) | 8413-8423 |
| Number of pages | 11 |
| Journal | Chemistry of materials |
| Volume | 31 |
| Issue number | 20 |
| Early online date | 18 Sept 2019 |
| Publication status | Published - 22 Oct 2019 |
Abstract
An effective separation of propylene/propane mixtures is one of the most important processes in the petrochemical industry. Incidentally, this separation is challenging due to the extensive similarities between both gases in terms of physicochemical properties such as, but not only limited to, boiling point, kinetic diameter, and molecular weight. A drive to switch to energy efficient processes, like adsorption or membrane separation, has highlighted several microporous metal organic frameworks as promising materials. In this work, we present a combined numerical and experimental investigation on propane and propylene adsorption in Zr-fumarate-MOF (also known as MOF-801), a small pore isoreticular analogue of UiO-66. Here, we demonstrate how the presence of structural defects can completely change the sorptive properties and separation performance of the Zr-fumarate-MOF, with the loss of sieving effects and a reversal of selectivity toward propane, as well as enhanced capacity and diffusion rates for C3-sized hydrocarbons. Extensive GCMC simulations performed on mixed defective supercells show that a ratio of missing-cluster defects of around 1/8 can best account for the experimental results. Furthermore, analysis of low-frequency phonon spectra is used to explain gaseous diffusion in the original pristine material. Finally, the thermodynamic preference for propane over propylene is confirmed through column breakthrough experiments, suggesting the potential applicability of the Zr-fumarate-MOF in this challenging separation.
ASJC Scopus subject areas
- Chemistry(all)
- General Chemistry
- Chemical Engineering(all)
- General Chemical Engineering
- Materials Science(all)
- Materials Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Chemistry of materials, Vol. 31, No. 20, 22.10.2019, p. 8413-8423.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Role of Structural Defects in the Adsorption and Separation of C3 Hydrocarbons in Zr-Fumarate-MOF (MOF-801)
AU - Iacomi, Paul
AU - Formalik, Filip
AU - Marreiros, Joao
AU - Shang, Jin
AU - Rogacka, Justyna
AU - Mohmeyer, Alexander
AU - Behrens, Peter
AU - Ameloot, Rob
AU - Kuchta, Bogdan
AU - Llewellyn, Philip L.
N1 - Funding information: P.I., P.L.L., J.M., and R.A. have received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Grant Agreement No. 641887 (project acronym: DEFNET). F.F., J.R., and B.K. are supported by the Polish National Science Centre (NCN, Grant No. 2015/17/B/ST8/00099). J.S. acknowledges the financial support from the Research Grants Council of Hong Kong (CityU 21301817). This research was supported in part by PL-Grid Infrastructure. F.F. thanks Dr. Halina Maniak for insightful discussions on coordinational chemistry.
PY - 2019/10/22
Y1 - 2019/10/22
N2 - An effective separation of propylene/propane mixtures is one of the most important processes in the petrochemical industry. Incidentally, this separation is challenging due to the extensive similarities between both gases in terms of physicochemical properties such as, but not only limited to, boiling point, kinetic diameter, and molecular weight. A drive to switch to energy efficient processes, like adsorption or membrane separation, has highlighted several microporous metal organic frameworks as promising materials. In this work, we present a combined numerical and experimental investigation on propane and propylene adsorption in Zr-fumarate-MOF (also known as MOF-801), a small pore isoreticular analogue of UiO-66. Here, we demonstrate how the presence of structural defects can completely change the sorptive properties and separation performance of the Zr-fumarate-MOF, with the loss of sieving effects and a reversal of selectivity toward propane, as well as enhanced capacity and diffusion rates for C3-sized hydrocarbons. Extensive GCMC simulations performed on mixed defective supercells show that a ratio of missing-cluster defects of around 1/8 can best account for the experimental results. Furthermore, analysis of low-frequency phonon spectra is used to explain gaseous diffusion in the original pristine material. Finally, the thermodynamic preference for propane over propylene is confirmed through column breakthrough experiments, suggesting the potential applicability of the Zr-fumarate-MOF in this challenging separation.
AB - An effective separation of propylene/propane mixtures is one of the most important processes in the petrochemical industry. Incidentally, this separation is challenging due to the extensive similarities between both gases in terms of physicochemical properties such as, but not only limited to, boiling point, kinetic diameter, and molecular weight. A drive to switch to energy efficient processes, like adsorption or membrane separation, has highlighted several microporous metal organic frameworks as promising materials. In this work, we present a combined numerical and experimental investigation on propane and propylene adsorption in Zr-fumarate-MOF (also known as MOF-801), a small pore isoreticular analogue of UiO-66. Here, we demonstrate how the presence of structural defects can completely change the sorptive properties and separation performance of the Zr-fumarate-MOF, with the loss of sieving effects and a reversal of selectivity toward propane, as well as enhanced capacity and diffusion rates for C3-sized hydrocarbons. Extensive GCMC simulations performed on mixed defective supercells show that a ratio of missing-cluster defects of around 1/8 can best account for the experimental results. Furthermore, analysis of low-frequency phonon spectra is used to explain gaseous diffusion in the original pristine material. Finally, the thermodynamic preference for propane over propylene is confirmed through column breakthrough experiments, suggesting the potential applicability of the Zr-fumarate-MOF in this challenging separation.
UR - http://www.scopus.com/inward/record.url?scp=85073257457&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.9b02322
DO - 10.1021/acs.chemmater.9b02322
M3 - Article
AN - SCOPUS:85073257457
VL - 31
SP - 8413
EP - 8423
JO - Chemistry of materials
JF - Chemistry of materials
SN - 0897-4756
IS - 20
ER -