Effective and stable catalysts are important to a wide variety of processes important to research and industry. An emerging technology is to support catalysts on materials known as metal-organic frameworks (MOFs). A MOF contains organic linkers and inorganic (metal-containing) nodes; they improve the efficiency of the catalysts they support by isolating catalytic sites one from another and are potentially useful in a wide variety of applications. The Energy Frontier Research Center (EFRC) called the Inorganometallic Catalyst Design Center (ICDC), based at the University of Minnesota and funded by the Department of Energy, has made enormous progress in the development of these materials.
In a recent paper in the Journal of the American Chemical Society, two MSI PIs in the Department of Chemistry, Professors Chris Cramer and Laura Gagliardi, along with members of their research groups and experimental colleagues from ICDC, published a study in which nickel ions were precisely placed on a zirconium-based MOF called NU-1000 by using a method called atomic layer deposition in MOFs (AIM). The resulting material, which contains distributed Ni ions in high density and large quantity, is designated Ni-AIM. The material is valuable as a stable, active catalyst based on an earth-abundant, and therefore cheap, metal that can be used to generate bulk commodity chemicals from industrial feedstocks. Exploitation of the AIM method to generate a number of new catalytic systems is expected to be extremely promising. Professors Cramer and Gagliardi modeled the AIM process and the catalytic properties of the final material for ethylene dimerization and hydrogenation by performing high-level quantum chemical calculations on the MSI supercomputers.
The paper can be found on the JACS website: Li, Zhanyong, Neil M. Schweitzer, Aaron B. League, Varinia Bernales, Aaron W. Peters, Andrew Bean Getsoian, Timothy C. Wang, Jeffrey T. Miller, Aleksei Vjunov, John L. Fulton, Johannes A. Lercher, Christopher J. Cramer, Laura Gagliardi, Joseph T. Hupp, Omar K. Farha. 2016. Sintering-resistant single-site nickel catalyst supported by metal-organic framework. Journal of the American Chemical Society 138 (6) (FEB 17): 1977-82.
Professor Cramer’s MSI research involves developing, coding, and applying novel and/or established classical and quantum mechanical methodologies to model chemical structures, properties, and reactivities. He is a member of the Chemical Theory Center, the Center for Sustainable Polymers, the Inorganic Catalyst Design Center, and the Nanoporous Materials Genome Center.
Professor Gagliardi uses MSI resources for a number of projects that develop novel quantum chemical methods and applies them to study phenomena related to sustainable energies, with special focus on chemical systems relevant to catalysis, spectroscopy, photochemistry, and gas separation. Professor Gagliardi and her group model molecular species, materials, and interfaces. They explore actinide and transactinide chemistry, with the aim of understanding the chemical bonding in molecular species and the processes that govern the formation of actinide-based materials relevant to the spent nuclear fuel reprocessing. They also explore phenomena related to gas separation. Professor Gagliardi is the director of the Inorganic Catalyst Design Center, director of the Chemical Theory Center, associate director of the Nanoporous Materials Genome Center, and a member of the Materials Research Science and Engineering Center.
Other recent publications by the Cramer and Gagliardi groups concerning MOFs are shown below:
- Klet, Rachel C., Samat Tussupbayev, Joshua Borycz, James R. Gallagher, Madelyn M. Stalzer, Jeffrey T. Miller, Laura Gagliardi, Joseph T. Hupp, Tobin J. Marks, Christopher J. Cramer, Alex B.F. Martinson. 2015. Single-site organozirconium catalyst embedded in a metal-organic framework. Journal of the American Chemical Society 137 (50) (DEC 23): 15680-3.
- McDonald, Thomas M., Jarad A. Mason, Xueqian Kong, Eric D. Bloch, David Gygi, Alessandro Dani, Valentina Crocella, Filippo Odoh, Walter S. Drisdell, Bess Blalsavljevic, Allison L. Dzubak, Roberta Poloni, Sondre K. Schnell, Nora Planas, Kyuho Lee, Tod Pascal, Liwen F. Wan, David Prendergast, Jeffrey B. Neaton, Berend Smit, Jeffrey B. Kortright, Laura Gagliardi, Silvia Bordiga, Jeffrey A. Reimer, Jeffrey A. Long. 2015. Cooperative insertion of CO2 in diamine-appended metal-organic frameworks. Nature 519, (7543) (MAR 19), 10.1038/nature14327.
- Dianne J. Xiao, Miguel I. Gonzalez, Lucy E. Darago, Konstantinos D. Vogiatzis, Emmanuel Haldoupis, Laura Gagliardi, and Jeffrey R. Long. 2016. Selective, tunable O2 binding in cobalt(II)-Triazolate/Pyrazolate metal-organic frameworks. Journal of the American Chemical Society 138, (22) (JUN 8): 7161-70.
- Yang, Dong, Samuel O. Odoh, Timothy C. Wang, Omar K. Farha, Joseph T. Hupp, Christopher J. Cramer, Laura Gagliardi, and Bruce C. Gates. 2015. Metal-organic framework nodes as nearly ideal supports for molecular catalysts. Journal of the American Chemical Society 137 (23) (JUN 17): 7391-6.
Image description: Structural representation of NU-1000, highlighting its organic linker, mesoporous channel, and Zr6-containing node and a schematic depiction of the process used to anchor Ni to the Zr6 node of NU-1000 via AIM. Color code: Zr (green), O (red), C (gray), H (white), Ni (purple). Li et al., JACS, 2016, 138(6), 1977-82, DOI: 10.102/jacs.5b12515. © American Chemical Society.
posted on October 5, 2016