Probing Metal–Organic Framework Design for Adsorptive Natural Gas Purification
Abstract
Parent and amine-functionalized analogues of metal–organic frameworks (MOFs), UiO-66(Zr), MIL-125(Ti), and MIL-101(Cr), were evaluated for their hydrogen sulfide (H2S) adsorption efficacy and post-exposure acid gas stability. Adsorption experiments were conducted through fixed-bed breakthrough studies utilizing multicomponent 1% H2S/99% CH4 and 1% H2S/10% CO2/89% CH4 natural gas simulant mixtures. Instability of MIL-101(Cr) materials after H2S exposure was discovered through powder X-ray diffraction and porosity measurements following adsorbent pelletization, whereas other materials retained their characteristic properties. Linker-based amine functionalities increased H2S breakthrough times and saturation capacities from their parent MOF analogues. Competitive CO2 adsorption effects were mitigated in mesoporous MIL-101(Cr) and MIL-101–NH2(Cr), in comparison to microporous UiO-66(Zr) and MIL-125(Ti) frameworks. This result suggests that the installation of H2S binding sites in large-pore MOFs could potentially enhance H2S selectivity. In situ Fourier transform infrared measurements in 10% CO2 and 5000 ppm H2S environments suggest that framework hydroxyl and amine moieties serve as H2S physisorption sites. In conclusion, results from this study elucidate design strategies and stability considerations for engineering MOFs in sour gas purification applications.
- Authors:
-
- Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1470678
- Grant/Contract Number:
- SC0012577
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Langmuir
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 29; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 0743-7463
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)
Citation Formats
Joshi, Jayraj N., Zhu, Guanghui, Lee, Jason J., Carter, Eli A., Jones, Christopher W., Lively, Ryan P., and Walton, Krista S. Probing Metal–Organic Framework Design for Adsorptive Natural Gas Purification. United States: N. p., 2016.
Web. doi:10.1021/acs.langmuir.8b00889.
Joshi, Jayraj N., Zhu, Guanghui, Lee, Jason J., Carter, Eli A., Jones, Christopher W., Lively, Ryan P., & Walton, Krista S. Probing Metal–Organic Framework Design for Adsorptive Natural Gas Purification. United States. https://doi.org/10.1021/acs.langmuir.8b00889
Joshi, Jayraj N., Zhu, Guanghui, Lee, Jason J., Carter, Eli A., Jones, Christopher W., Lively, Ryan P., and Walton, Krista S. Sun .
"Probing Metal–Organic Framework Design for Adsorptive Natural Gas Purification". United States. https://doi.org/10.1021/acs.langmuir.8b00889. https://www.osti.gov/servlets/purl/1470678.
@article{osti_1470678,
title = {Probing Metal–Organic Framework Design for Adsorptive Natural Gas Purification},
author = {Joshi, Jayraj N. and Zhu, Guanghui and Lee, Jason J. and Carter, Eli A. and Jones, Christopher W. and Lively, Ryan P. and Walton, Krista S.},
abstractNote = {Parent and amine-functionalized analogues of metal–organic frameworks (MOFs), UiO-66(Zr), MIL-125(Ti), and MIL-101(Cr), were evaluated for their hydrogen sulfide (H2S) adsorption efficacy and post-exposure acid gas stability. Adsorption experiments were conducted through fixed-bed breakthrough studies utilizing multicomponent 1% H2S/99% CH4 and 1% H2S/10% CO2/89% CH4 natural gas simulant mixtures. Instability of MIL-101(Cr) materials after H2S exposure was discovered through powder X-ray diffraction and porosity measurements following adsorbent pelletization, whereas other materials retained their characteristic properties. Linker-based amine functionalities increased H2S breakthrough times and saturation capacities from their parent MOF analogues. Competitive CO2 adsorption effects were mitigated in mesoporous MIL-101(Cr) and MIL-101–NH2(Cr), in comparison to microporous UiO-66(Zr) and MIL-125(Ti) frameworks. This result suggests that the installation of H2S binding sites in large-pore MOFs could potentially enhance H2S selectivity. In situ Fourier transform infrared measurements in 10% CO2 and 5000 ppm H2S environments suggest that framework hydroxyl and amine moieties serve as H2S physisorption sites. In conclusion, results from this study elucidate design strategies and stability considerations for engineering MOFs in sour gas purification applications.},
doi = {10.1021/acs.langmuir.8b00889},
journal = {Langmuir},
number = 29,
volume = 34,
place = {United States},
year = {Sun Jun 26 00:00:00 EDT 2016},
month = {Sun Jun 26 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Worldwide development potential for sour gas
journal, January 2011
- Burgers, W. F. J.; Northrop, P. S.; Kheshgi, H. S.
- Energy Procedia, Vol. 4
Hydrogen Sulfide—Mechanisms of Toxicity and Development of an Antidote
journal, February 2016
- Jiang, Jingjing; Chan, Adriano; Ali, Sameh
- Scientific Reports, Vol. 6, Issue 1
Air Filters For The Face
journal, December 2014
- Jacoby, Mitch
- Chemical & Engineering News Archive, Vol. 92, Issue 49, p. 34-38
Mesoporous-molecular-sieve-supported Polymer Sorbents for Removing H2S from Hydrogen Gas Streams
journal, April 2008
- Wang, Xiaoxing; Ma, Xiaoliang; Xu, Xiaochun
- Topics in Catalysis, Vol. 49, Issue 1-2
Natural gas removal of hydrogen sulphide and mercaptans
journal, February 2012
- de Angelis, A.
- Applied Catalysis B: Environmental, Vol. 113-114
Natural Gas Processing with Membranes: An Overview
journal, April 2008
- Baker, Richard W.; Lokhandwala, Kaaeid
- Industrial & Engineering Chemistry Research, Vol. 47, Issue 7
Monte Carlo Simulation of Adsorption of Polar and Nonpolar Gases in (FP)YEu Metal–Organic Framework
journal, October 2016
- Al-Jadir, Thaer M.; Siperstein, Flor R.
- Journal of Chemical & Engineering Data, Vol. 61, Issue 12
Adsorption of hydrogen sulphide on Metal-Organic Frameworks
journal, January 2013
- Gutiérrez-Sevillano, Juan José; Martín-Calvo, Ana; Dubbeldam, David
- RSC Advances, Vol. 3, Issue 34
Capture of H2S and SO2 from trace sulfur containing gas mixture by functionalized UiO-66(Zr) materials: A molecular simulation study
journal, November 2016
- Li, Zhi; Liao, Feiyang; Jiang, Fei
- Fluid Phase Equilibria, Vol. 427
Molecular Insight into the Adsorption of H 2 S in the Flexible MIL-53(Cr) and Rigid MIL-47(V) MOFs: Infrared Spectroscopy Combined to Molecular Simulations
journal, December 2010
- Hamon, Lomig; Leclerc, Hervé; Ghoufi, Aziz
- The Journal of Physical Chemistry C, Vol. 115, Issue 5
Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) Metal−Organic Frameworks at Room Temperature
journal, July 2009
- Hamon, Lomig; Serre, Christian; Devic, Thomas
- Journal of the American Chemical Society, Vol. 131, Issue 25
A robust amino-functionalized titanium(iv) based MOF for improved separation of acid gases
journal, January 2013
- Vaesen, Sébastien; Guillerm, Vincent; Yang, Qingyuan
- Chemical Communications, Vol. 49, Issue 86
A Multiunit Catalyst with Synergistic Stability and Reactivity: A Polyoxometalate–Metal Organic Framework for Aerobic Decontamination
journal, October 2011
- Song, Jie; Luo, Zhen; Britt, David K.
- Journal of the American Chemical Society, Vol. 133, Issue 42, p. 16839-16846
Molecular dynamics investigation of separation of hydrogen sulfide from acidic gas mixtures inside metal-doped graphite micropores
journal, January 2015
- Huang, Pei-Hsing
- Physical Chemistry Chemical Physics, Vol. 17, Issue 35
Molecular chemisorption on open metal sites in Cu3(benzenetricarboxylate)2: A spatially periodic density functional theory study
journal, September 2010
- Watanabe, Taku; Sholl, David S.
- The Journal of Chemical Physics, Vol. 133, Issue 9
Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions
journal, October 2015
- Nijem, Nour; Fürsich, Katrin; Bluhm, Hendrik
- The Journal of Physical Chemistry C, Vol. 119, Issue 44
Isoreticular rare earth fcu -MOFs for the selective removal of H 2 S from CO 2 containing gases
journal, September 2017
- Bhatt, Prashant M.; Belmabkhout, Youssef; Assen, Ayalew H.
- Chemical Engineering Journal, Vol. 324
Selective H 2 S/CO 2 Separation by Metal–Organic Frameworks Based on Chemical-Physical Adsorption
journal, June 2017
- Liu, Jia; Wei, Yajuan; Li, Peizhou
- The Journal of Physical Chemistry C, Vol. 121, Issue 24
Fundamental Aspects of H 2 S Adsorption on CPO-27-Ni
journal, July 2013
- Chavan, Sachin; Bonino, Francesca; Valenzano, Loredana
- The Journal of Physical Chemistry C, Vol. 117, Issue 30
Hydrogen Sulfide Adsorption on MOFs and MOF/Graphite Oxide Composites
journal, October 2010
- Petit, Camille; Mendoza, Barbara; Bandosz, Teresa J.
- ChemPhysChem, Vol. 11, Issue 17
Metal-organic frameworks with high capacity and selectivity for harmful gases
journal, August 2008
- Britt, D.; Tranchemontagne, D.; Yaghi, O. M.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11623-11627
Acid-functionalized UiO-66(Zr) MOFs and their evolution after intra-framework cross-linking: structural features and sorption properties
journal, January 2015
- Ragon, Florence; Campo, Betiana; Yang, Qingyuan
- Journal of Materials Chemistry A, Vol. 3, Issue 7
Computational exploration of H2S/CH4 mixture separation using acid-functionalized UiO-66(Zr) membrane and composites
journal, August 2015
- Wang, Shumeng; Wu, Dong; Huang, Hongliang
- Chinese Journal of Chemical Engineering, Vol. 23, Issue 8
Evaluation of MOFs for air purification and air quality control applications: Ammonia removal from air
journal, March 2015
- Jasuja, Himanshu; Peterson, Gregory W.; Decoste, Jared B.
- Chemical Engineering Science, Vol. 124
Tuning the Adsorption Properties of UiO-66 via Ligand Functionalization
journal, October 2012
- Cmarik, Gregory E.; Kim, Min; Cohen, Seth M.
- Langmuir, Vol. 28, Issue 44
Experimental Study of CO 2 , CH 4 , and Water Vapor Adsorption on a Dimethyl-Functionalized UiO-66 Framework
journal, March 2013
- Jasuja, Himanshu; Walton, Krista S.
- The Journal of Physical Chemistry C, Vol. 117, Issue 14
Alkylamine-Tethered Stable Metal-Organic Framework for CO 2 Capture from Flue Gas
journal, January 2014
- Hu, Yingli; Verdegaal, Wolfgang M.; Yu, Shu-Hong
- ChemSusChem, Vol. 7, Issue 3
Polar Group and Defect Engineering in a Metal-Organic Framework: Synergistic Promotion of Carbon Dioxide Sorption and Conversion
journal, February 2015
- Jiang, Zhuo-Rui; Wang, Hengwei; Hu, Yingli
- ChemSusChem, Vol. 8, Issue 5
Engineering UiO-66-NH 2 for Toxic Gas Removal
journal, January 2014
- Peterson, Gregory W.; DeCoste, Jared B.; Fatollahi-Fard, Farzin
- Industrial & Engineering Chemistry Research, Vol. 53, Issue 2
Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks
journal, April 2012
- Schoenecker, Paul M.; Carson, Cantwell G.; Jasuja, Himanshu
- Industrial & Engineering Chemistry Research, Vol. 51, Issue 18
Synthesis and post-synthetic modification of MIL-101(Cr)-NH2via a tandem diazotisation process
journal, January 2012
- Jiang, Dongmei; Keenan, Luke L.; Burrows, Andrew D.
- Chemical Communications, Vol. 48, Issue 99
Effect of NH2 and CF3 functionalization on the hydrogen sorption properties of MOFs
journal, January 2011
- Zlotea, Claudia; Phanon, Delphine; Mazaj, Matjaz
- Dalton Transactions, Vol. 40, Issue 18
Effects of pelletization pressure on the physical and chemical properties of the metal–organic frameworks Cu3(BTC)2 and UiO-66
journal, September 2013
- Peterson, Gregory W.; DeCoste, Jared B.; Glover, T. Grant
- Microporous and Mesoporous Materials, Vol. 179, p. 48-53
Structuring adsorbents and catalysts by processing of porous powders
journal, July 2014
- Akhtar, Farid; Andersson, Linnéa; Ogunwumi, Steven
- Journal of the European Ceramic Society, Vol. 34, Issue 7
Shaping amine-based solid CO2 adsorbents: Effects of pelletization pressure on the physical and chemical properties
journal, March 2015
- Rezaei, Fateme; Sakwa-Novak, Miles A.; Bali, Sumit
- Microporous and Mesoporous Materials, Vol. 204
Research Challenges in Avoiding “Showstoppers” in Developing Materials for Large-Scale Energy Applications
journal, October 2017
- Walton, Krista S.; Sholl, David S.
- Joule, Vol. 1, Issue 2
Heat-Treatment of Defective UiO-66 from Modulated Synthesis: Adsorption and Stability Studies
journal, October 2017
- Jiao, Yang; Liu, Yang; Zhu, Guanghui
- The Journal of Physical Chemistry C, Vol. 121, Issue 42
A Modulated Hydrothermal (MHT) Approach for the Facile Synthesis of UiO-66-Type MOFs
journal, April 2015
- Hu, Zhigang; Peng, Yongwu; Kang, Zixi
- Inorganic Chemistry, Vol. 54, Issue 10
Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis
journal, May 2016
- Shearer, Greig C.; Chavan, Sachin; Bordiga, Silvia
- Chemistry of Materials, Vol. 28, Issue 11
How Reproducible Are Isotherm Measurements in Metal–Organic Frameworks?
journal, November 2017
- Park, Jongwoo; Howe, Joshua D.; Sholl, David S.
- Chemistry of Materials, Vol. 29, Issue 24
A facile synthesis of UiO-66, UiO-67 and their derivatives
journal, January 2013
- Katz, Michael J.; Brown, Zachary J.; Colón, Yamil J.
- Chemical Communications, Vol. 49, Issue 82
Porous Chromium Terephthalate MIL-101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and Catalysis
journal, May 2009
- Hong, Do-Young; Hwang, Young Kyu; Serre, Christian
- Advanced Functional Materials, Vol. 19, Issue 10
Roll-up in fixed-bed, multicomponent adsorption under pore-diffusion limitation
journal, July 1987
- Kapoor, A.; Yang, R. T.
- AIChE Journal, Vol. 33, Issue 7
Direct Air Capture of CO 2 Using Amine Functionalized MIL-101(Cr)
journal, August 2016
- Darunte, Lalit A.; Oetomo, Aloysius D.; Walton, Krista S.
- ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 10
Carbon Dioxide Capture from the Air Using a Polyamine Based Regenerable Solid Adsorbent
journal, December 2011
- Goeppert, Alain; Czaun, Miklos; May, Robert B.
- Journal of the American Chemical Society, Vol. 133, Issue 50, p. 20164-20167
Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO 2 Capture Applications: A Quasielastic Neutron Scattering Study
journal, June 2017
- Holewinski, Adam; Sakwa-Novak, Miles A.; Carrillo, Jan-Michael Y.
- The Journal of Physical Chemistry B, Vol. 121, Issue 27
Role of Additives in Composite PEI/Oxide CO 2 Adsorbents: Enhancement in the Amine Efficiency of Supported PEI by PEG in CO 2 Capture from Simulated Ambient Air
journal, November 2015
- Sakwa-Novak, Miles A.; Tan, Shuai; Jones, Christopher W.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 44
In Situ Fourier Transform Infrared (FTIR) Investigation of CO 2 Adsorption onto Zeolite Materials
journal, September 2008
- Stevens, Robert W.; Siriwardane, Ranjani V.; Logan, Jennifer
- Energy & Fuels, Vol. 22, Issue 5
Effect of Humidity on the CO 2 Adsorption of Tertiary Amine Grafted SBA-15
journal, October 2017
- Lee, Jason J.; Chen, Chia-Hsin; Shimon, Daphna
- The Journal of Physical Chemistry C, Vol. 121, Issue 42
Catalytic properties of MIL-101
journal, January 2008
- Henschel, Antje; Gedrich, Kristina; Kraehnert, Ralph
- Chemical Communications, Issue 35
Defect-Engineered Metal-Organic Frameworks
journal, June 2015
- Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E.
- Angewandte Chemie International Edition, Vol. 54, Issue 25
Brønsted Acidity in Metal–Organic Frameworks
journal, June 2015
- Jiang, Juncong; Yaghi, Omar M.
- Chemical Reviews, Vol. 115, Issue 14
Carbon Dioxide Adsorption in Amine-Functionalized Mixed-Ligand Metal-Organic Frameworks of UiO-66 Topology
journal, October 2014
- Ethiraj, Jayashree; Albanese, Elisa; Civalleri, Bartolomeo
- ChemSusChem, Vol. 7, Issue 12
Works referencing / citing this record:
The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials
journal, February 2020
- Ploetz, Evelyn; Engelke, Hanna; Lächelt, Ulrich
- Advanced Functional Materials, Vol. 30, Issue 41
Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture
journal, September 2019
- Rieth, Adam J.; Wright, Ashley M.; Dincă, Mircea
- Nature Reviews Materials, Vol. 4, Issue 11