title: Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework.
abstract: Developing supported single-site catalysts is an important goal in heterogeneous catalysis since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based metal-organic framework (MOF), NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a MOF (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.
authors.affiliation: Department of Chemistry and Chemical and Biological Engineering, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Zhanyong
authors.initials: Z
authors.lastname: Li
authors.affiliation: Department of Chemistry and Chemical and Biological Engineering, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Neil M
authors.initials: NM
authors.lastname: Schweitzer
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Aaron B
authors.initials: AB
authors.lastname: League
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Varinia
authors.initials: V
authors.lastname: Bernales
authors.affiliation: Department of Chemistry and Chemical and Biological Engineering, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Aaron W
authors.initials: AW
authors.lastname: Peters
authors.affiliation: Chemical Science and Engineering Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Andrew Bean
authors.initials: AB
authors.lastname: Getsoian
authors.affiliation: Department of Chemistry and Chemical and Biological Engineering, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Timothy C
authors.initials: TC
authors.lastname: Wang
authors.affiliation: Chemical Science and Engineering Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.|School of Chemical Engineering, Purdue University , 480 Stadium Mall Drive, West Lafayette, Indiana 47907-2100, United States.
authors.forename: Jeffrey T
authors.initials: JT
authors.lastname: Miller
authors.affiliation: Institute for Integrated Catalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
authors.forename: Aleksei
authors.initials: A
authors.lastname: Vjunov
authors.affiliation: Institute for Integrated Catalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
authors.forename: John L
authors.initials: JL
authors.lastname: Fulton
authors.affiliation: Institute for Integrated Catalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.|Department of Chemistry and Catalysis Research Institute, Technische Universität München , Lichtenbergstrasse 4, 85748 Garching, Germany.
authors.forename: Johannes A
authors.initials: JA
authors.lastname: Lercher
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: Department of Chemistry and Chemical and Biological Engineering, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Joseph T
authors.initials: JT
authors.lastname: Hupp
authors.affiliation: Department of Chemistry and Chemical and Biological Engineering, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.|Department of Chemistry, Faculty of Science, King Abdulaziz University , Jeddah 21589, Saudi Arabia.
authors.forename: Omar K
authors.initials: OK
authors.lastname: Farha
mesh_terms: D002384:Catalysis; D006865:Hydrogenation; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D009930:Organic Chemicals; D009532:Nickel