4.6 Article

Chemoselective Hydrogenation of Crotonaldehyde Catalyzed by an Au@ZIF-8 Composite

Journal

CHEMCATCHEM
Volume 8, Issue 4, Pages 855-860

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201501171

Keywords

aldehydes; chemoselectivity; gold; hydrogenation; metal-organic frameworks

Funding

  1. National Science Foundation [DMR-1334928, CHE-0923236]
  2. Northwestern University
  3. MRSEC program at the Materials Research Center [NSF DMR-1121262]
  4. Nanoscale Science and Engineering Center at the International Institute for Nanotechnology [NSF EEC-0647560]
  5. State of Illinois, through the International Institute for Nanotechnology
  6. Division Of Materials Research
  7. Direct For Mathematical & Physical Scien [1334928] Funding Source: National Science Foundation

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Au nanoparticles of size 2.2nm were encapsulated in a zeolitic imidazolate framework ZIF-8 framework (Au@ZIF-8). The composite was used as a catalyst for the selective hydrogenation of crotonaldehyde to crotyl alcohol with 90-95% selectivity. Hydrogenation of 1-hexene yielded n-hexane in approximately the same conversion as crotonaldehyde, whereas cis-cyclohexene did not detectably react. To account for the confined environment of the ZIF, we supported Au nanoparticles on the outside of ZIF-8 (Au/ZIF-8). Using Au/ZIF-8 as a catalyst, 1-hexene and cis-cyclohexene were hydrogenated in low conversion whereas crotonaldehyde would only react at higher pressures in 70% selectivity towards crotyl alcohol. Post-experiment TEM analysis of Au/ZIF-8 showed significant sintering whereas the median particle size of Au@ZIF-8 remained almost unchanged. Au@ZIF-8 was recycled as a catalyst for the hydrogenation of crotonaldehyde three times without significant loss of activity or selectivity.

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