Point Defects Control Guest Molecule Diffusion in the 1D Pores of Zn(tbip)

Cai, Xuqing; Sholl, David S.

doi:10.1021/acs.jpcc.2c04175

Title: Point Defects Control Guest Molecule Diffusion in the 1D Pores of Zn(tbip)

Journal Article · 11 August 2022 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.2c04175 · OSTI ID:1885333

Cai, Xuqing ^[1];

^[2]

Georgia Institute of Technology, Atlanta, GA (United States)
Georgia Institute of Technology, Atlanta, GA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Molecular diffusion plays a critical role in metal-organic frameworks (MOFs) within the application of kinetic chemical separations. We carefully study in this work the unexpected role of point defects for short-chain alkanes diffusing in Zn(tbip), an MOF with rigid one-dimensional (1D) channels. Inside a defect-free Zn(tbip), guest molecules are expected to follow single-file diffusion along 1D channels. It has been found previously by Heinke et al. that these parallel 1D channels are connected for molecular diffusion. Our density functional theory (DFT) calculations suggest that linker vacancy defects could arise under experimentally relevant conditions by removing a pair of linkers. Further climbing-image nudged elastic band (cNEB) DFT calculations indicate that hopping of short-chain alkanes between adjacent 1D channels over defect windows can occur at moderate temperatures. In addition to providing insights into connected adjacent 1D channels in Zn(tbip), Heinke et al. also inferred that most 1D pores are blocked from a microkinetic model. Additionally, we explored the influence of hydrolyzed linker created by the formation of linker removal inside 1D pores. Our DFT calculations show that the linkers can effectively block the pores and the linker diffusion in 1D channels is slow. Our results, for the first time, offer a mechanistic explanation of the unexpected molecular diffusion behavior in this MOF with 1D channels.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: Dow Chemical Company; USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1885333

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 33 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Surface‐Mounted Metal–Organic Frameworks: Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications (Adv. Mater. 26/2019) Heinke, Lars; Wöll, Christof Advanced Materials, Vol. 31, Issue 26 https://doi.org/10.1002/adma.201970184	journal	June 2019
Three-Dimensional Visualization of Defects Formed during the Synthesis of Metal-Organic Frameworks: A Fluorescence Microscopy Study Ameloot, Rob; Vermoortele, Frederik; Hofkens, Johan Angewandte Chemie International Edition, Vol. 52, Issue 1 https://doi.org/10.1002/anie.201205627	journal	November 2012
Defect-Engineered Metal-Organic Frameworks Fang, Zhenlan; Bueken, Bart; De Vos, Dirk E. Angewandte Chemie International Edition, Vol. 54, Issue 25 https://doi.org/10.1002/anie.201411540	journal	June 2015
Tuning the Properties of MOF‐808 via Defect Engineering and Metal Nanoparticle Encapsulation Hardian, Rifan; Dissegna, Stefano; Ullrich, Aladin Chemistry – A European Journal, Vol. 27, Issue 22 https://doi.org/10.1002/chem.202005050	journal	March 2021
Defects in MOFs: A Thorough Characterization St. Petkov, Petko; Vayssilov, Georgi N.; Liu, Jinxuan ChemPhysChem, Vol. 13, Issue 8 https://doi.org/10.1002/cphc.201200222	journal	April 2012
Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions Pang, Qingqing; Yang, Lingyi; Li, Qiaowei Small Structures, Vol. 3, Issue 5 https://doi.org/10.1002/sstr.202100203	journal	February 2022
Evidence for single file diffusion of ethane in the molecular sieve AlPO4-5 Gupta, Vishwas; Nivarthi, Sriram S.; McCormick, Alon V. Chemical Physics Letters, Vol. 247, Issue 4-6 https://doi.org/10.1016/S0009-2614(95)01246-X	journal	December 1995
Defect engineering of Mn-based MOFs with rod-shaped building units by organic linker fragmentation Wu, Doufeng; Yan, Wenqing; Xu, Huoshu Inorganica Chimica Acta, Vol. 460 https://doi.org/10.1016/j.ica.2016.07.022	journal	April 2017
Towards modeling spatiotemporal processes in metal–organic frameworks Van Speybroeck, Veronique; Vandenhaute, Sander; Hoffman, Alexander E. J. Trends in Chemistry, Vol. 3, Issue 8 https://doi.org/10.1016/j.trechm.2021.04.003	journal	August 2021
What Are the Best Materials To Separate a Xenon/Krypton Mixture? Simon, Cory M.; Mercado, Rocio; Schnell, Sondre K. Chemistry of Materials, Vol. 27, Issue 12 https://doi.org/10.1021/acs.chemmater.5b01475	journal	June 2015
Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis Shearer, Greig C.; Chavan, Sachin; Bordiga, Silvia Chemistry of Materials, Vol. 28, Issue 11 https://doi.org/10.1021/acs.chemmater.6b00602	journal	May 2016
Role of Structural Defects in the Adsorption and Separation of C3 Hydrocarbons in Zr-Fumarate-MOF (MOF-801) Iacomi, Paul; Formalik, Filip; Marreiros, Joao Chemistry of Materials, Vol. 31, Issue 20 https://doi.org/10.1021/acs.chemmater.9b02322	journal	September 2019
Metal–Organic Framework (MOF) Defects under Control: Insights into the Missing Linker Sites and Their Implication in the Reactivity of Zirconium-Based Frameworks Gutov, Oleksii V.; Hevia, Miguel González; Escudero-Adán, Eduardo C. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01053	journal	August 2015
Molecular Dynamics Investigation of Surface Resistances in Zeolite Nanosheets Knio, Omar; Fang, Hanjun; Boulfelfel, Salah Eddine The Journal of Physical Chemistry C, Vol. 124, Issue 28 https://doi.org/10.1021/acs.jpcc.0c03572	journal	June 2020
Computational Model and Characterization of Stacking Faults in ZIF-8 Polymorphs Han, Rebecca; Sholl, David S. The Journal of Physical Chemistry C, Vol. 120, Issue 48 https://doi.org/10.1021/acs.jpcc.6b09317	journal	November 2016
Competitive Binding of Ethylene, Water, and Carbon Monoxide in Metal–Organic Framework Materials with Open Cu Sites You, Wenqin; Liu, Yang; Howe, Joshua D. The Journal of Physical Chemistry C, Vol. 122, Issue 16 https://doi.org/10.1021/acs.jpcc.8b00909	journal	April 2018
Stability of Zeolitic Imidazolate Frameworks in NO ₂ Bhattacharyya, Souryadeep; Han, Rebecca; Joshi, Jayraj N. The Journal of Physical Chemistry C, Vol. 123, Issue 4 https://doi.org/10.1021/acs.jpcc.8b11377	journal	January 2019
Propagation of Degradation-Induced Defects in Zeolitic Imidazolate Frameworks Han, Rebecca; Tymińska, Nina; Schmidt, J. R. The Journal of Physical Chemistry C, Vol. 123, Issue 11 https://doi.org/10.1021/acs.jpcc.9b00304	journal	February 2019
Kinetic Model of Acid Gas Induced Defect Propagation in Zeolitic Imidazolate Frameworks Cui, Kai; Nair, Sankar; Sholl, David S. The Journal of Physical Chemistry Letters, Vol. 13, Issue 28 https://doi.org/10.1021/acs.jpclett.2c01516	journal	July 2022
Defects in Metal–Organic Frameworks: Challenge or Opportunity? Sholl, David S.; Lively, Ryan P. The Journal of Physical Chemistry Letters, Vol. 6, Issue 17 https://doi.org/10.1021/acs.jpclett.5b01135	journal	August 2015
Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8 Zhang, Chenyang; Han, Chu; Sholl, David S. The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02683	journal	January 2016
Assessing the Impact of Point Defects on Molecular Diffusion in ZIF-8 Using Molecular Simulations Han, Chu; Verploegh, Ross J.; Sholl, David S. The Journal of Physical Chemistry Letters, Vol. 9, Issue 14 https://doi.org/10.1021/acs.jpclett.8b01749	journal	June 2018
Using Site Heterogeneity in Metal–Organic Frameworks with Bimetallic Open Metal Sites for Olefin/Paraffin Separations You, Wenqin; Sen, Trisha; Kawajiri, Yoshiaki ACS Applied Nano Materials, Vol. 3, Issue 6 https://doi.org/10.1021/acsanm.0c00693	journal	May 2020
Hydrocarbon Separations in Metal–Organic Frameworks Herm, Zoey R.; Bloch, Eric D.; Long, Jeffrey R. Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm402897c	journal	September 2013
Zn(tbip) (H ₂ tbip= 5- tert -Butyl Isophthalic Acid): A Highly Stable Guest-Free Microporous Metal Organic Framework with Unique Gas Separation Capability Pan, Long; Parker, Brett; Huang, Xiaoying Journal of the American Chemical Society, Vol. 128, Issue 13 https://doi.org/10.1021/ja057667b	journal	April 2006
The Nature of Surface Barriers on Nanoporous Solids Explored by Microimaging of Transient Guest Distributions Hibbe, Florian; Chmelik, Christian; Heinke, Lars Journal of the American Chemical Society, Vol. 133, Issue 9 https://doi.org/10.1021/ja108625z	journal	March 2011
Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr) Vermoortele, Frederik; Bueken, Bart; Le Bars, Gaëlle Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja405078u	journal	July 2013
Ordered Vacancies and Their Chemistry in Metal–Organic Frameworks Tu, Binbin; Pang, Qingqing; Wu, Doufeng Journal of the American Chemical Society, Vol. 136, Issue 41 https://doi.org/10.1021/ja5063423	journal	September 2014
Temperature and Loading-Dependent Diffusion of Light Hydrocarbons in ZIF-8 as Predicted Through Fully Flexible Molecular Simulations Verploegh, Ross J.; Nair, Sankar; Sholl, David S. Journal of the American Chemical Society, Vol. 137, Issue 50 https://doi.org/10.1021/jacs.5b08746	journal	December 2015
Engineering a Highly Defective Stable UiO-66 with Tunable Lewis- Brønsted Acidity: The Role of the Hemilabile Linker Feng, Xiao; Hajek, Julianna; Jena, Himanshu Sekhar Journal of the American Chemical Society, Vol. 142, Issue 6 https://doi.org/10.1021/jacs.9b13070	journal	January 2020
Predicting Local Transport Coefficients at Solid–Gas Interfaces Zimmermann, Nils E. R.; Smit, Berend; Keil, Frerich J. The Journal of Physical Chemistry C, Vol. 116, Issue 35 https://doi.org/10.1021/jp3059855	journal	August 2012
Transport into Nanosheets: Diffusion Equations Put to Test Zimmermann, Nils E. R.; Zabel, Timm J.; Keil, Frerich J. The Journal of Physical Chemistry C, Vol. 117, Issue 14 https://doi.org/10.1021/jp400152q	journal	April 2013
A porous maze Sholl, David S. Nature Chemistry, Vol. 3, Issue 6 https://doi.org/10.1038/nchem.1054	journal	May 2011
Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography Willhammar, Tom; Sun, Junliang; Wan, Wei Nature Chemistry, Vol. 4, Issue 3 https://doi.org/10.1038/nchem.1253	journal	January 2012
Correlated defect nanoregions in a metal–organic framework Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5176	journal	June 2014
Excavating hidden adsorption sites in metal-organic frameworks using rational defect engineering Chong, Sanggyu; Thiele, Günther; Kim, Jihan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01478-4	journal	November 2017
Defects and disorder in metal organic frameworks Cheetham, Anthony K.; Bennett, Thomas D.; Coudert, François-Xavier Dalton Transactions, Vol. 45, Issue 10 https://doi.org/10.1039/C5DT04392A	journal	January 2016
Characterization and properties of Zn/Co zeolitic imidazolate frameworks vs. ZIF-8 and ZIF-67 Zhou, Kui; Mousavi, Bibimaryam; Luo, Zhixiong Journal of Materials Chemistry A, Vol. 5, Issue 3 https://doi.org/10.1039/C6TA07860E	journal	January 2017
Defect engineering in metal–organic frameworks: a new strategy to develop applicable actinide sorbents Yuan, Liyong; Tian, Ming; Lan, Jianhui Chemical Communications, Vol. 54, Issue 4 https://doi.org/10.1039/C7CC07527H	journal	January 2018
Band gap modulation in zirconium-based metal–organic frameworks by defect engineering Taddei, Marco; Schukraft, Giulia M.; Warwick, Michael E. A. Journal of Materials Chemistry A, Vol. 7, Issue 41 https://doi.org/10.1039/C9TA05216J	journal	January 2019
Nanoconfinement and mass transport in metal–organic frameworks Sharp, Conor H.; Bukowski, Brandon C.; Li, Hongyu Chemical Society Reviews, Vol. 50, Issue 20 https://doi.org/10.1039/D1CS00558H	journal	January 2021
A systematic examination of the impacts of MOF flexibility on intracrystalline molecular diffusivities Yang, Yuhan; Sholl, David S. Journal of Materials Chemistry A, Vol. 10, Issue 8 https://doi.org/10.1039/D1TA09267G	journal	January 2022
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Optimization methods for finding minimum energy paths Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme The Journal of Chemical Physics, Vol. 128, Issue 13 https://doi.org/10.1063/1.2841941	journal	April 2008
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Assessing Guest Diffusivities in Porous Hosts from Transient Concentration Profiles Heinke, Lars; Tzoulaki, Despina; Chmelik, Christian Physical Review Letters, Vol. 102, Issue 6 https://doi.org/10.1103/PhysRevLett.102.065901	journal	February 2009
Correlating Surface Permeability with Intracrystalline Diffusivity in Nanoporous Solids Heinke, Lars; Kärger, Jörg Physical Review Letters, Vol. 106, Issue 7 https://doi.org/10.1103/PhysRevLett.106.074501	journal	February 2011
Single-File Diffusion Observation Hahn, K.; Kärger, J.; Kukla, V. Physical Review Letters, Vol. 76, Issue 15 https://doi.org/10.1103/PhysRevLett.76.2762	journal	April 1996
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013

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