Beyond the Active Site: Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization

Journal of the American Chemical Society
Jian LiuJoseph T Hupp

Abstract

To modify its steric and electronic properties as a support for heterogeneous catalysts, electron-withdrawing and electron-donating ligands, hexafluoroacetylacetonate (Facac-) and acetylacetonate (Acac-), were introduced to the metal-organic framework (MOF), NU-1000, via a process akin to atomic layer deposition (ALD). In the absence of Facac- or Acac-, NU-1000-supported, AIM-installed Ni(II) sites yield a mixture of C4, C6, C8, and polymeric products in ethylene oligomerization. (AIM = ALD-like deposition in MOFs). In contrast, both Ni-Facac-AIM-NU-1000 and Ni-Acac-AIM-NU-1000 exhibit quantitative catalytic selectivity for C4 species. Experimental findings are supported by density functional theory calculations, which show increases in the activation barrier for the C-C coupling step, due mainly to rearrangement of the siting of Facac- or Acac- to partially ligate added nickel. The results illustrate the important role of structure-tuning support modifiers in controlling the activity of MOF-sited heterogeneous catalysts and in engendering catalytic selectivity. The results also illustrate the ease with which crystallographically well-defined modifications of the catalyst support can be introduced when the node-coordinating mol...Continue Reading

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Citations

Nov 8, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Hiroyasu TabeYusuke Yamada
Jun 5, 2020·Science Advances·Wufeng WuWanbin Li
May 8, 2019·Nature Communications·Iker Agirrezabal-TelleriaMustapha Soukri
Feb 6, 2020·Topics in Current Chemistry·Alexander Schoedel, Sahar Rajeh
Jan 22, 2021·Chemical Society Reviews·F Pelin KinikBerend Smit
Apr 23, 2021·ACS Applied Materials & Interfaces·Jian LiuJoseph T Hupp
Dec 4, 2019·ACS Applied Materials & Interfaces·Jian LiuJoseph T Hupp
Dec 19, 2019·Journal of the American Chemical Society·In Soo KimAlex B F Martinson
Jul 3, 2019·Journal of the American Chemical Society·Ping LiuGabor A Somorjai
Dec 1, 2018·Journal of the American Chemical Society·Chenyue SunMircea Dincă
Jun 18, 2019·ACS Catalysis·Rasmus Yding BrogaardKristof De Wispelaere
May 2, 2020·Chemical Reviews·Yong-Sheng WeiQiang Xu
Jul 16, 2020·Langmuir : the ACS Journal of Surfaces and Colloids·Amy J BrandtDonna A Chen
Jul 17, 2020·Chemical Reviews·Jenna L MancusoChristopher H Hendon
May 24, 2019·Journal of the American Chemical Society·Bin HanJianzhuang Jiang
Nov 25, 2021·Journal of the American Chemical Society·Benjamin YehAditya Bhan
Nov 27, 2021·Journal of the American Chemical Society·Ana E Platero-PratsKarena W Chapman

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