Discovery of Novel Highly Functional Materials

MANAR Center is currently developing the next generation of porous, crystalline materials. The principles of reticular chemistry are employed, whereby inorganic clusters (and/or metals) are linked with organic struts through strong bonds in a geometrically controlled fashion. Furthermore, the flexibility  in choosing these building units, affords the resulting materials with unique opportunities for fine-tuning their pore metrics and environment, surface area, and overall topology.

MANAR's primary focus, with respect to research conducted, is the discovery of new extended, porous metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs). These classes of crystals have received a great deal of attention owing to their applications in clean energy storage, fuel cells, heterogeneous catalysis, thin films, chemical sensors and biomedicine among many others. 

Recent representative publications:

(1) Zeolitic Imidazolate Framework-Coupled Resonators for Enhanced Gas Detection, Y. Hwang, A. Phan, K. Galatsis, O. M Yaghi, and R. N. Candler, J. Micromech. Microeng. 201323, 125027.

(2) Dielectrophoresis-Assembled Zeolitic Imidazolate Framework Nanoparticle-Coupled Resonators for Highly Sensitive and Selective Gas Detection, Y. Hwang, H. Sohn, A. Phan, O. M. Yaghi, and R. N. Candler, Nano Lett. 201313, 5271.

(3) Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks, N. T. T. Nguyen, H. Furukawa, F. Gandara, H. T. Nguyen, K. E. Cordova, O. M. Yaghi, Angew. Chem. Int. Ed. 2014, 53, 10645.

(4) Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal-Organic Framework-177, Y.-B. Zhang, H. Furukawa, N. Ko, W. Nie, H. J. Park, S. Okajima, K. E. Cordova, H. Deng, J. Kim, O. M. Yaghi, J. Am. Chem. Soc. 2015, 137, 2641.

Gas Storage and Separation

Some of the most pressing concerns for the world today is the need for cleaner energy technology and to rid the atmosphere of toxic pollutants and greenhouse gases. At MANAR, researchers find a feasible and practical solution to these two issues. The composition of MOFs, ZIFs, and COFs provide us with a viable platform to accomplish these feats. The constituent building units of these materials can be systematically varied in order to perform certain applications. This has led to the design of novel structures that are highly functional in gas adsorption and separation.
MANAR is currently exploring the synthesis of MOFs and COFs that have a high capacity for hydrogen and methane storage, which in the future will lead to cleaner automobile fueling. Furthermore, focus is on discovering new water-stable ZIFs that are capable of capturing carbon dioxide and separating it from automobile and factory exhaust. The adsorption of toxic gases and volatile organic compounds (i.e. carbon monoxide, ammonia, hydrogen sulfide, alcohols, etc.) is also being studied.

  

Recent representative publications:

(1) Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks, N. T. T. Nguyen, H. Furukawa, F. Gandara, H. T. Nguyen, K. E. Cordova, O. M. Yaghi, Angew. Chem. Int. Ed. 201453, 10645.

(2) Tailoring the Water Adsorption Properties of MIL-101 Metal-Organic Frameworks by Partial Functionalization, N. Ko, P. G. Choi, J. Hong, M. Yeo, S. Sung, K. E. Cordova, H. J. Park, J. K. Yang, J. Kim, J. Mat. Chem. A 20153, 2057.

(3) Significant Enhancement of Water Vapour Uptake at Low Pressure by Amine-Functionalization of UiO-67, N. Ko, J. Hong, S. Sung, K. E. Cordova, H. J. Park, J. K. Yang, J. Kim, Dalton Trans. 201544, 2047.

(4) Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal-Organic Framework-177, Y.-B. Zhang, H. Furukawa, N. Ko, W. Nie, H. J. Park, S. Okajima, K. E. Cordova, H. Deng, J. Kim, O. M. Yaghi, J. Am. Chem. Soc. 2015, 137, 2641.

Catalysis and Conductivity

Though MOF materials have been traditionally used for adsorption and separation of gases, MANAR is also concentrating on developing new MOFs, ZIFs, and COFs for applications in heterogeneous catalysis. MOF materials' large surface areas and structured internal pore environments facilitate reactivity and selectivity in the catalysis of organic transformations, similar to what is observed in nature. MANAR seeks to exploit all constituents of the framework to discover collaborative, highly active catalysts that may not be synthesized otherwise. MANAR views catalytic MOF materials as enzyme analogues.

MANAR has recently expanded their attention to synthesizing thermally robust, chemically stable structures that serve as promising candidates for ion conduction. Furthermore, with MOF materials, MANAR is seeking to systematically functionalize specific sites throughout the architecture in order to define a direct ion pathway and observe exceptional conductivity values.

Recent representative publications:

(1) Propargylamine Synthesis via Direct Oxidative C-C Coupling Reaction between N,N-dimethylanilines and Terminal Alkynes under Metal-Organic Framework Catalysis G. H. Dang, D. T. Nguyen, D. T. Le, T. Truong, N. T. S. Phan, J. Mol. Catal. A: Chem. 2014395, 300.

(2) Tailoring the Optical Adsorption of Water Stable Zr(IV)- and Hf(IV)-Based Metal-Organic Framework Photocatalysts T. L. Doan, H. L. Nguyen, H. Q. Pham, N.-N. Pham-Tran, T. N. Le, K. E. Cordova, Chem. Asian J. 201510, 2660.

(3) Azobenzene-Containing Metal-Organic Framework as an Efficient Heterogeneous Catalyst for Direct Amidation of Benzoic Acids: Synthesis of Bioactive Compounds, L. T. M. Hoang, L. H. Ngo, H. L. Nguyen, C. K. Nguyen, B. T. Nguyen, Q. T. Ton, H. K. D. Nguyen, K. E. Cordova, T. Truong, Chem. Commun201551, 17132.

(4) New Topological Co2(BDC)2(DABCO) as Highly Active Heterogeneous Catalyst for Amination of Oxazoles via Oxidative C-H/N-H Couplings, T. N. Tu, K. D. Nguyen, T. N. Nguyen, T. Truong, N. T. S. Phan, Catal. Sci. Technol20166, 1384.

Structural Analysis Characterization

Due to their highly crystalline structure, MOFs and ZIFs  are routinely characterized through X-ray diffraction (XRD) analysis. Here at MANAR, an in-house single crystal XRD and powder XRD is used to solve the crystal structures of the materials that are synthesized. MANAR prides theirselves on the fact that every student has the opportunity to operate the instruments and hone their expertise in crystallography.
In order to check for thermal stability and architectural robustness, thermal gravimetric analysis and conventional porosity (nitrogen and argon) tests, respectively, are frequently performed. Furthermore, gas adsorption isotherms are carried out to quantify the uptake capacity of various gases. The materials are also analyzed for the ability to selectively adsorb gases from mixtures by performing kinetic breakthrough experiments. Throughout the course of a project, other characterization techniques including, but not limited to: solution and solid-state NMR, microscopy (optical, transmission electron microscopy, scanning electron microscopy, and scanning tunneling microscopy), UV-Vis, FT-IR, and mass spectrometry may be encountered.

Recent representative publications:

(1) Engineering of Band Gap in Metal-Organic Frameworks by Functionalizing Organic Linker: A Systematic Density Functional Theory Investigation, H. Pham, T. Mai, N. N. Pham-Tran, Y. Kawazoe, H. Mizuseki, D. Nguyen-Manh, J. Phys. Chem. C 2014, 118, 4567.

(2) Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks, N. T. T. Nguyen, H. Furukawa, F. Gandara, H. T. Nguyen, K. E. Cordova, O. M. Yaghi, Angew. Chem. Int. Ed. 2014, 53, 10645.

(3) Significant Enhancement of Water Vapour Uptake at Low Pressure by Amine-Functionalization of UiO-67, N. Ko, J. Hong, S. Sung, K. E. Cordova, H. J. Park, J. K. Yang, J. Kim, Dalton Trans. 2015, 44, 2047.

(4) Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal-Organic Framework-177, Y.-B. Zhang, H. Furukawa, N. Ko, W. Nie, H. J. Park, S. Okajima, K. E. Cordova, H. Deng, J. Kim, O. M. Yaghi, J. Am. Chem. Soc. 2015, 137, 2641.

(5) Three-Dimensional Metal-Catecholate Frameworks and their Ultrahigh Proton Conductivity, N. T. T. Nguyen, H. Furukawa, F. Gándara, C. A. Trickett, H. M. Jeong, K. E. Cordova, O. M. Yaghi, J. Am. Chem. Soc., 2016137, 15394.