Insights into the structure−activity relationships in metal−Organic framework-supported nickel catalysts for ethylene hydrogenation

Xingjie Wang, Xuan Zhang, Riddhish Pandharkar, Jiafei Lyu, Debmalya Ray, Ying Yang, Satoshi Kato, Jian Liu, Megan C. Wasson, Timur Islamoglu, Zhong Li, Joseph T. Hupp, Christopher J. Cramer, Laura Gagliardi, Omar K. Farha

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Abstract

Solid supports play an indispensable role in heterogeneous catalysis, as they can directly affect the catalytic activity and selectivity of supported catalysts. However, the specific roles of such supports remain to be demystified owing to the difficulties in obtaining precise structural information on supported catalysts. To understand the effects of MOF topology, pore environment, and metal identity of node supports on the catalytic activity, a Ni catalyst was supported on eight Zr- or Hf-MOFs based on 8-connected nodes: namely M-NU-1200, M-NU-1000, M-NU-1008, and M-NU-1010 (M = Zr, Hf). Single-crystal X-ray diffraction (SCXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the supported catalyst structures. To investigate the support effects on their activities, the supported Ni catalysts were evaluated by using ethylene hydrogenation as a model reaction. The results revealed that all Hf-based-MOF-supported Ni catalysts exhibited higher catalytic reactivity with TOF (turnover frequency) values at least double of those isostructural Zr counterparts. Additionally, MOFs with less congested metal anchoring sites, as a result of the topology and surrounding pore environment, yielded higher TOFs, suggesting the importance of supports in dictating both the catalyst accessibility and activity. Computational analysis complemented the experimental observations and provided insights into reaction barrier differences and their performance variation. This study demonstrates the essential role of the supports and provides a thought for selecting/designing suitable supports in heterogeneous catalysis.

Original languageEnglish (US)
Pages (from-to)8995-9005
Number of pages11
JournalACS Catalysis
Volume10
Issue number16
DOIs
StatePublished - Aug 21 2020
Externally publishedYes

Bibliographical note

Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0012702). X.W. gratefully acknowledges support from the China Scholarship Council (CSC) during his visit to Northwestern University (201706150062). M.C.W. is supported by an NSF Graduate Research Fellowship under grant DGE-1842165. This work made use of the J. B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. This work made use of Keck-II facilities of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267), SHyNE Resource (NSF NNCI-1542205), the State of Illinois, and IIN.

Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0012702). X.W. gratefully acknowledges support from the China Scholarship Council (CSC) during his visit to Northwestern University (201706150062). M.C.W. is supported by an NSF Graduate Research Fellowship under grant DGE-1842165. This work made use of the J. B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. This work made use of Keck-II facilities of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267), SHyNE Resource (NSF NNCI-1542205), the State of Illinois, and IIN.

Keywords

  • Computational analysis
  • Ethylene hydrogenation
  • Nickel catalyst
  • Support effect
  • Zr- and Hf-based MOFs

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