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.
Original language | English (US) |
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Pages (from-to) | 1977-1982 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 138 |
Issue number | 6 |
DOIs | |
State | Published - Feb 17 2016 |
Funding
O.K.F., J.T.H., C.J.C., and L.G. gratefully acknowledge the financial support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). A.V., J.L.F. and J.A.L gratefully acknowledge the financial support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). The work was performed at the Pacific Northwest National Laboratory operated by Battelle for the U.S. Department of Energy. A.W.P was supported by the Department of Defense (DoD) through the National Defense Science and Engineering Fellowship (NDSEG) program. JTM and AG Getsoian were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences under Contract DE-AC- 02-06CH11357. This work made use of the J.B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of Northwestern University. This work made use of the EPIC facility (NUANCE Center-Northwestern University), which has received support from the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); and the State of Illinois, through the IIN. This work made use of IMSERC facilities at Northwestern University supported by the National Institutes of Health under NIH (1S10OD012016- 01/1S10RR019071-01A1). Use of the Advanced Photon Source is supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. Materials Research Collaborative Access Team (MRCAT, Sectors 10 μ<sub>B</sub> and 10ID) operations are supported by the Department of Energy and the MRCAT member institutions.
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry