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Research Article

Controlled growth and composition of multivariate metal-organic frameworks-199 via a reaction-diffusion process

Razan Issa1,§, Fayrouz Abou Ibrahim1,§, Mazen Al-Ghoul1,2,( ), Mohamad Hmadeh1,( )
Department of Chemistry, American University of Beirut, P.O.Box 11-0236, Riad El-Solh 1107 2020, Beirut, Lebanon
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal H2A 0B8, Canada

§ Razan Issa and Fayrouz Abou Ibrahim contributed equally to this work.

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Abstract

In this paper, we exploit our prior successful synthesis of MOF-199 single crystals using the reaction-diffusion framework (RDF), to synthesize multivariate metal-organic frameworks (MTV-MOFs) version with enhanced properties. The MTV-MOFs are synthesized by creating defects within the MOF-199 crystal structure by integrating organic linkers entailing different functional groups. Accordingly, 5-aminoisophthalic acid (NH2-BDC) and 5-hydroxyisophthalic acid (OH-BDC) are separately mixed with 1,3,5-benzenetricarboxylic acid (BTC) in three different starting ratios of X-BDC:BTC (1:3, 1:1) and 3:1). The effects of this linker on the morphology of the synthesized MTV-MOFs, their thermal stability, and their surface area are investigated. The extent of the incorporation of the linkers in the framework is elucidated via 1H-NMR spectroscopy and it is shown that the incorporation varies as a function of the location along the tubular reactor, a characteristic of RDF. The enhanced properties of the synthesized MTV-MOFs are further demonstrated by measuring its adsorptive capability for methylene blue (MB) and rhodamine B (Rh B) in aqueous solution, and compared with that of the as-synthesized MOF-199. The kinetic and thermodynamic studies reveal that MTV-MOFs with the ratio of X-BDC:BTC (1:1) exhibit the best uptakes of MB (263 mg/g) for X = OH and Rh B (156 mg/g) for X = NH2. The adsorbents are also easily regenerated for three consecutive cycles without losing their efficiency. We finally demonstrate that MTV-MOFs can be designed to tune the dye removal selectivity and enhance the removal capacity of both MB and RhB in a binary aqueous solution of these dyes.

Keywords

adsorptionreaction-diffusion framework (RDF)multivariate metal-organic frameworks (MTV-MOFs)methylene blue (MB)rhodamine B (Rh B)

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References

[1]
H. C. Zhou,; J. R. Long,; O. M. Yaghi, Introduction to metal-organic frameworks. Chem. Rev. 2012, 112, 673-674.
Crossref Google Scholar
[2]
C. V. McGuire,; R. S. Forgan, The surface chemistry of metal-organic frameworks. Chem. Commun. 2015, 51, 5199-217.
Crossref Google Scholar
[3]
O. M. Yaghi,; M. O’Keeffe,; N. W. Ockwig,; H. K. Chae,; M. Eddaoudi,; J. Kim, Reticular synthesis and the design of new materials. Nature 2003, 423, 705-714.
Crossref Google Scholar
[4]
H. Furukawa,; K. E. Cordova,; M. O’Keeffe,; O. M. Yaghi, The chemistry and applications of metal-organic frameworks. Science 2013, 341, 1230444.
Crossref Google Scholar
[5]
H. Furukawa,; N. Ko,; Y. B. Go,; N. Aratani,; S. B. Choi,; E. Choi,; A. Ö. Yazaydin,; R. Q. Snurr,; M. O’Keeffe,; J. Kim, et al. Ultrahigh porosity in metal-organic frameworks. Science 2010, 329, 424-428.
Crossref Google Scholar
[6]
S. Rojas,; F. J. Carmona,; C. R. Maldonado,; P. Horcajada,; T. Hidalgo,; C. Serre,; J. A. R. Navarro,; E. Barea, Nanoscaled zinc pyrazolate metal-organic frameworks as drug-delivery systems. Inorg. Chem. 2016, 55, 2650-2663.
Crossref Google Scholar
[7]
D. Zhao,; Y. J. Cui,; Y. Yang,; G. D. Qian, Sensing-functional luminescent metal-organic frameworks. CrystEngComm 2016, 18, 3746-3759.
Crossref Google Scholar
[8]
X. C. Yang,; Q. Xu, Bimetallic metal-organic frameworks for gas storage and separation. Ryst. Growth Des. 2017, 17, 1450-1455.
Crossref Google Scholar
[9]
G. Xiong,; B. Yu,; J. Dong,; Y. Shi,; B. Zhao,; L. N. He, Cluster-based MOFs with accelerated chemical conversion of CO2 through C-C bond formation. Chem. Commun. 2017, 53, 6013-6016.
Crossref Google Scholar
[10]
N. Stock,; S. Biswas, Synthesis of metal-organic frameworks(MOFs): Routes to various MOF topologies, morphologies, and composites. Chem. Rev. 2012, 112, 933-969.
Crossref Google Scholar
[11]
L. E. Kreno,; K. Leong,; O. K. Farha,; M. Allendorf,; R. P. Van Duyne,; J. T. Hupp, Metal-organic framework materials as chemical sensors. Chem. Rev. 2012, 112, 1105-1125.
Crossref Google Scholar
[12]
Y. Belmabkhout,; V. Guillerm,; M. Eddaoudi, Low concentration CO2 capture using physical adsorbents: Are metal-organic frameworks becoming the new benchmark materials? Chem. Eng. J. 2016, 296, 386-397.
Crossref Google Scholar
[13]
R. Issa,; M. Hmadeh,; M. Al-Ghoul, Control of particle size and morphology of MOF-199 crystals via a reaction-diffusion framework. Defect Diffus. Forum 2017, 380, 39-47.
Crossref Google Scholar
[14]
H. L. Zhu,; D. X. Liu, The synthetic strategies of metal-organic framework membranes, films and 2D MOFs and their applications in devices. J. Mater. Chem. A 2019, 7, 21004-21035.
Crossref Google Scholar
[15]
D. R. Sun,; F. X. Sun,; X. Y. Deng,; Z. H. Li, Mixed-metal strategy on metal-organic frameworks (MOFs) for functionalities expansion: Co substitution induces aerobic oxidation of cyclohexene over inactive Ni-MOF-74. Inorg. Chem. 2015, 54, 8639-8643.
Crossref Google Scholar
[16]
J. A. Villajos,; G. Orcajo,; C. Martos,; J. Á. Botas,; J. Villacañas,; G. Calleja, Co/Ni mixed-metal sited MOF-74 material as hydrogen adsorbent. Int. J. Hydrogen Energy 2015, 40, 5346-5352.
Crossref Google Scholar
[17]
A. Naeem,; V. P. Ting,; U. Hintermair,; M. Tian,; R. Telford,; S. Halim,; H. Nowell,; M. Hołyńska,; S. J. Teat,; I. J. Scowen, et al. Mixed-linker approach in designing porous zirconium-based metal-organic frameworks with high hydrogen storage capacity. Chem. Commun. 2016, 52, 7826-7829.
Crossref Google Scholar
[18]
R. Haldar,; T. K. Maji, Metal-organic frameworks (MOFs) based on mixed linker systems: Structural diversities towards functional materials. CrystEngComm 2013, 15, 9276-9295.
Crossref Google Scholar
[19]
H. X. Deng,; C. J. Doonan,; H. Furukawa,; R. B. Ferreira,; J. Towne,; C. B. Knobler,; B. Wang,; O. M. Yaghi, Multiple functional groups of varying ratios in metal-organic frameworks. Science 2010, 327, 846-850.
Crossref Google Scholar
[20]
X. Q. Kong,; H. X. Deng,; F. Y. Yan,; J. Kim,; J. A. Swisher,; B. Smit,; O. M. Yaghi,; J. A. Reimer, Mapping of functional groups in metal-organic frameworks. Science 2013, 341, 882-885.
Crossref Google Scholar
[21]
J. S. Qin,; S. Yuan,; Q. Wang,; A. Alsalme,; H. C. Zhou, Mixed-linker strategy for the construction of multifunctional metal-organic frameworks. J. Mater. Chem. A 2017, 5, 4280-4291.
Crossref Google Scholar
[22]
T. M. Osborn Popp,; O. M. Yaghi, Sequence-dependent materials. Acc. Chem. Res. 2017, 50, 532-534.
Crossref Google Scholar
[23]
Y. Lee,; S. Kim,; J. K. Kang,; S. M. Cohen, Photocatalytic CO2 reduction by a mixed metal (Zr/Ti), mixed ligand metal-organic framework under visible light irradiation. Chem. Commun. 2015, 51, 5735-5738.
Crossref Google Scholar
[24]
C. Z. Duan,; F. E. Li,; H. Zhang,; J. Q. Li,; X. J. Wang,; H. X. Xi, Template synthesis of hierarchical porous metal-organic frameworks with tunable porosity. RSC Adv. 2017, 7, 52245-52251.
Crossref Google Scholar
[25]
Z. N. Shi,; L. Li,; Y. X. Xiao,; Y. X. Wang,; K. K. Sun,; H. X. Wang,; L. Liu, Synthesis of mixed-ligand Cu-MOFs and their adsorption of malachite green. RSC Adv. 2017, 7, 30904-30910.
Crossref Google Scholar
[26]
G. W. Peterson,; K. Au,; T. M. Tovar,; T. H. Epps, Multivariate CuBTC metal-organic framework with enhanced selectivity, stability, compatibility, and processability. Chem. Mater. 2019, 31, 8459-8465.
Crossref Google Scholar
[27]
S. Yuan,; J. S. Qin,; J. L. Li,; L. Huang,; L. Feng,; Y. Fang,; C. Lollar,; J. D. Pang,; L. L. Zhang,; D. Sun, et al. Retrosynthesis of multi-component metal-organic frameworks. Nat. Commun. 2018, 9, 808.
Crossref Google Scholar
[28]
H. Furukawa,; U. Müller,; O. M. Yaghi, “Heterogeneity within order” in metal-organic frameworks. Angew. Chem., Int. Ed. 2015, 54, 3417-3430.
Crossref Google Scholar
[29]
A. D. Burrows, Mixed-component metal-organic frameworks (MC-MOFs): Enhancing functionality through solid solution formation and surface modifications. CrystEngComm 2011, 13, 3623-3642.
Crossref Google Scholar
[30]
L. J. Wang,; H. X. Deng,; H. Furukawa,; F. Gándara,; K. E. Cordova,; D. Peri,; O. M. Yaghi, Synthesis and characterization of metal-organic framework-74 containing 2, 4, 6, 8, and 10 different metals. Inorg. Chem. 2014, 53, 5881-5883.
Crossref Google Scholar
[31]
G. Ayoub,; B. Karadeniz,; A. J. Howarth,; O. K. Farha,; I. Đilović,; L. S. Germann,; R. E. Dinnebier,; K. Užarević,; T. Friscic, Rational synthesis of mixed-metal microporous metal-organic frameworks with controlled composition using mechanochemistry. Chem. Mater. 2019, 31, 5494-5501.
Crossref Google Scholar
[32]
O. Karagiaridi,; W. Bury,; J. E. Mondloch,; J. T. Hupp,; O. K. Farha, Solvent-assisted linker exchange: An alternative to the de novo synthesis of unattainable metal-organic frameworks. Angew. Chem., Int. Ed. 2014, 53, 4530-4540.
Crossref Google Scholar
[33]
W. Q. Xi,; Y. Liu,; Q. C. Xia,; Z. J. Li,; Y. Cui, Direct and post-synthesis incorporation of chiral metallosalen catalysts into metal-organic frameworks for asymmetric organic transformations. Chem.—Eur. J. 2015, 21, 12581-12585.
Crossref Google Scholar
[34]
S. Yuan,; W. G. Lu,; Y. P. Chen,; Q. Zhang,; T. F. Liu,; D. W. Feng,; X. Wang,; J. S. Qin,; H. C. Zhou, Sequential linker installation: Precise placement of functional groups in multivariate metal-organic frameworks. J. Am. Chem. Soc. 2015, 137, 3177-3180.
Crossref Google Scholar
[35]
C. X. Chen,; Z. W. Wei,; J. J. Jiang,; Y. Z. Fan,; S. P. Zheng,; C. C. Cao,; Y. H. Li,; D. Fenske,; C. Y. Su, Precise modulation of the breathing behavior and pore surface in Zr-MOFs by reversible post-synthetic variable-spacer installation to fine-tune the expansion magnitude and sorption properties. Angew. Chem., Int. Ed. 2016, 55, 9932-9936.
Crossref Google Scholar
[36]
T. Li,; J. E. Sullivan,; N. L. Rosi, Design and preparation of a core-shell metal-organic framework for selective CO2 capture. J. Am. Chem. Soc. 2013, 135, 9984-9987.
Crossref Google Scholar
[37]
L. C. He,; Y. Liu,; J. Z. Liu,; Y. S. Xiong,; J. Z. Zheng,; Y. L. Liu,; Z. Y. Tang, Core-shell noble-metal@metal-organic-framework nanoparticles with highly selective sensing property. Angew. Chem., Int. Ed. 2013, 125, 3829-3833.
Crossref Google Scholar
[38]
D. J. Tranchemontagne,; J. R. Hunt,; O. M. Yaghi, Room temperature synthesis of metal-organic frameworks: MOF-5, MOF-74, MOF-177, MOF-199, and IRMOF-0. Tetrahedron 2008, 64, 8553-8557.
Crossref Google Scholar
[39]
M. Al-Ghoul,; R. Issa,; M. Hmadeh, Synthesis, size and structural evolution of metal-organic framework-199 via a reaction-diffusion process at room temperature. CrystEngComm 2017, 19, 608-612.
Crossref Google Scholar
[40]
J. L. Zhuang,; D. Ceglarek,; S. Pethuraj,; A. Terfort, Rapid room-temperature synthesis of metal-organic framework HKUST-1 crystals in bulk and as oriented and patterned thin films. Adv. Funct. Mater. 2011, 21, 1442-1447.
Crossref Google Scholar
[41]
G. A. Al Akhrass,; M. Ammar,; H. El-Rassy,; M. Al-Ghoul, Self-assembled lanthanum hydroxide microspheres within a reaction-diffusion framework: Synthesis, characterization, control and application. RSC Adv. 2016, 6, 3433-3439.
Crossref Google Scholar
[42]
D. Saliba,; A. Ezzeddine,; A. H. Emwas,; N. M. Khashab,; M. Al-Ghoul, Dynamics and mechanism of intercalation/de-intercalation of rhodamine B during the polymorphic transformation of the CdAl layered double hydroxide to the brucite-like cadmium hydroxide. Ryst. Growth Des. 2016, 16, 4327-4335.
Crossref Google Scholar
[43]
D. Saliba,; A. Ezzeddine,; R. Sougrat,; N. M. Khashab,; M. Hmadeh,; M. Al-Ghoul, Cadmium-aluminum layered double hydroxide microspheres for photocatalytic CO2 reduction. ChemSusChem 2016, 9, 800-805.
Crossref Google Scholar
[44]
J. Rahbani,; M. Ammar,; M. Al-Ghoul, Reaction-diffusion framework: The mechanism of the polymorphic transition of α- to β-cobalt hydroxide. J. Phys. Chem. A 2013, 117, 1685-1691.
Crossref Google Scholar
[45]
D. Saliba,; M. Al-Ghoul, Stability and particle size control of self-assembled cadmium-aluminum layered double hydroxide. CrystEngComm 2016, 18, 8445-8453.
Crossref Google Scholar
[46]
D. Saliba,; M. Ammar,; M. Rammal,; M. Al-Ghoul,; M. Hmadeh, Crystal growth of ZIF-8, ZIF-67, and their mixed-metal derivatives. J. Am. Chem. Soc. 2018, 140, 1812-1823.
Crossref Google Scholar
[47]
P. Redfield, Fluid technologies: The Bush Pump, the LifeStraw® and microworlds of humanitarian design. Soc. Stud. Sci. 2016, 46, 159-183.
Crossref Google Scholar
[48]
M. Eddaoudi,; J. Kim,; J. Wachter,; H. K. Chae,; M. O'keeffe,; O. M. Yaghi, Porous metal-organic polyhedra: 25 Å cuboctahedron constructed from 12 Cu2(CO2)4 paddle-wheel building blocks. J. Am. Chem. Soc. 2001, 123, 4368-4369.
Crossref Google Scholar
[49]
S. R. Venna,; J. B. Jasinski,; M. A. Carreon, Structural evolution of zeolitic imidazolate framework-8. J. Am. Chem. Soc. 2010, 132, 18030-18033.
Crossref Google Scholar
[50]
Z. L. Fang,; J. P. Dürholt,; M. Kauer,; W. H. Zhang,; C. Lochenie,; B. Jee,; B. Albada,; N. Metzler-Nolte,; A. Pöppl,; B. Weber, et al. Structural complexity in metal-organic frameworks: Simultaneous modification of open metal sites and hierarchical porosity by systematic doping with defective linkers. J. Am. Chem. Soc. 2014, 136, 9627-9636.
Crossref Google Scholar
[51]
J. Park,; Z. U. Wang,; L. B. Sun,; Y. P. Chen,; H. C. Zhou, Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly. J. Am. Chem. Soc. 2012, 134, 20110-20116.
Crossref Google Scholar
[52]
L. Xiong,; Y. Yang,; J. X. Mai,; W. L. Sun,; C. Y. Zhang,; D. P. Wei,; Q. Chen,; J. R. Ni, Adsorption behavior of methylene blue onto titanate nanotubes. Chem. Eng. J. 2010, 156, 313-320.
Crossref Google Scholar
[53]
F. Raposo,; M. A. De La Rubia,; R. Borja, Methylene blue number as useful indicator to evaluate the adsorptive capacity of granular activated carbon in batch mode: Influence of adsorbate/adsorbent mass ratio and particle size. J. Hazard. Mater. 2009, 165, 291-299.
Crossref Google Scholar
[54]
L. Li,; X. L. Liu,; H. Y. Geng,; B. Hu,; G. W. Song,; Z. S. Xu, A MOF/graphite oxide hybrid (MOF: HKUST-1) material for the adsorption of methylene blue from aqueous solution. J. Mater. Chem. A 2013, 1, 10292-10299.
Crossref Google Scholar
[55]
P. P. Selvam,; S. Preethi,; P. Basakaralingam,; N. Thinakaran,; A. Sivasamy,; S. Sivanesan, Removal of rhodamine B from aqueous solution by adsorption onto sodium montmorillonite. J. Hazard. Mater. 2008, 155, 39-44.
Crossref Google Scholar
[56]
K. Kadirvelu,; C. Karthika,; N. Vennilamani,; S. Pattabhi, Activated carbon from industrial solid waste as an adsorbent for the removal of rhodamine-B from aqueous solution: Kinetic and equilibrium studies. Chemosphere 2005, 60, 1009-1017.
Crossref Google Scholar
[57]
H. X. Guo,; F. Lin,; J. H. Chen,; F. M. Li,; W. Weng, Metal-organic framework MIL-125(Ti) for efficient adsorptive removal of rhodamine B from aqueous solution. Appl. Org. Chem. 2015, 29, 12-19.
Crossref Google Scholar
[58]
S. Eftekhari,; A. Habibi-Yangjeh,; S. Sohrabnezhad, Application of AlMCM-41 for competitive adsorption of methylene blue and rhodamine B: Thermodynamic and kinetic studies. J. Hazard. Mater. 2010, 178, 349-355.
Crossref Google Scholar
[59]
S. J. Dukhin, (Ed.). Fundamentals of Interface and Colloid Science, vol. IV, Academic Press, New York-Toronto (2005). Adv. Colloid Interface Sci. 2006, 119, 69-70.
Crossref Google Scholar
[60]
M. A. Fontecha-Cámara,; M. V. López-Ramón,; M. A. Álvarez-Merino,; C. Moreno-Castilla, Effect of surface chemistry, solution pH, and ionic strength on the removal of herbicides diuron and amitrole from water by an activated carbon fiber. Langmuir 2007, 23, 1242-1247.
Crossref Google Scholar
[61]
G. Blanco-Brieva,; J. M. Campos-Martin,; S. M. Al-Zahrani,; J. L. G. Fierro, Removal of refractory organic sulfur compounds in fossil fuels using MOF sorbents. Global NEST J. 2010, 12, 296-304.
Crossref Google Scholar
[62]
A. Banerjee,; R. Gokhale,; S. Bhatnagar,; J. Jog,; M. Bhardwaj,; B. Lefez,; B. Hannoyer,; S. Ogale, MOF derived porous carbon-Fe3O4 nanocomposite as a high performance, recyclable environmental superadsorbent. J. Mater. Chem. 2012, 22, 19694-19699.
Crossref Google Scholar
Nano Research
Volume 14 Issue 2,
February 2021
Pages 423-431
DOI: 10.1007/s12274-020-2870-1
Cite this article:
Issa R, Ibrahim FA, Al-Ghoul M, et al. Controlled growth and composition of multivariate metal-organic frameworks-199 via a reaction-diffusion process. Nano Research, 2021, 14(2): 423-431. https://doi.org/10.1007/s12274-020-2870-1
Topics:
MetalsMorphologyNuclear magnetic resonance spectroscopyOrganic frameworks Organic polymersOrganometallics

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Received: 04 February 2020
Revised: 17 April 2020
Accepted: 09 May 2020
Published: 25 June 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
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