Abstract
Four-carbon olefins, such as 1-butene and 1,3-butadiene, are important chemical feedstocks for the production of adhesives and synthetic rubber. These compounds are found in the C4 fraction of "green oil"products that can arise during the hydrogenation of acetylene. Here, we demonstrate that control of the catalyst structure increases the yield and productivity of these important olefins with a family of catalyst materials comprising Cu nanoparticles (CuNPs) bound within the pores of Zr-based metal-organic frameworks. Using carbon monoxide as a probe molecule, we characterize the surfaces of these catalytic CuNPs with diffuse reflectance infrared Fourier transform spectroscopy, revealing that the electronic structure of the CuNP surfaces is size-dependent. Furthermore, we find that as the CuNP diameter decreases, the selectivity for C4 products increases and that lowering the stoichiometric ratio of H2/acetylene improves the selectivity and productivity of the catalyst.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 31496-31502 |
| Number of pages | 7 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 12 |
| Issue number | 28 |
| DOIs | |
| State | Published - Jul 15 2020 |
Funding
O.K.F. gratefully acknowledges the financial support from the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (DE-SC0012702). C.-K.T. acknowledges the financial support from the National Science Foundation (CHE-1566445) and Boston College. This material is based upon work supported by the National Science Foundation (NSF) under grant number EEC-1757618. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. L.R.R. gratefully acknowledges the support of the U.S. Department of Energy (DOE), Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. The ORISE is managed by ORAU under Contract DE-SC0014664. Use was made of the IMSERC X-ray Facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center.
Keywords
- acetylene dimerization
- green oil
- heterogeneous catalysis
- metal-organic framework
- nanoparticle
ASJC Scopus subject areas
- General Materials Science