TY - JOUR
T1 - Tuning the Product Distribution of Acetylene Dimerization through Bimetallic Metal-Organic Framework-Supported Nanoporous Systems
AU - Goetjen, Timothy A.
AU - Kropf, A. Jeremy
AU - Alayoglu, Selim
AU - Delferro, Massimiliano
AU - Hupp, Joseph T.
AU - Farha, Omar K.
N1 - Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontiers Research Center (EFRC) funded by the Department of Energy (DOE), Office of Science, Basic Energy Sciences under award number DE-SC0012702. This work made use of the IMSERC Crystallography facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University. This work made use of the Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center (QBIC). The REACT Facility of the Northwestern University Center for Catalysis and Surface Science is supported by a grant from the DOE (DE-SC0001329). MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. T.A.G. acknowledges the support of the US 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, and ORISE is managed by ORAU under contract DE-SC0014664.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022
Y1 - 2022
N2 - Metal-organic frameworks (MOFs) are receiving increased attention due to their well-defined structures that allow the determination of structure-property relationships. MOFs have been used as heterogeneous catalyst supports in a variety of fashions including for confinement of metal nanoparticles, which have demonstrated enhanced resistance to aggregation, a common issue in amorphous metal oxide supports. Cu and In catalysts were installed in the Zr-based MOF NU-907, being confined within the nanoporous structure. The Cu catalyst is known to, under various conditions, either selectively hydrogenate acetylene to ethylene or generate C4 products such as butenes and 1,3-butadiene, an important feedstock for rubber and adhesives. The addition of indium to the Cu catalyst is intended to serve as a promoter to produce C4 products by decreasing the surface coverage of copper while still allowing for C-C coupling. When employed for acetylene dimerization, InCu-NU-907 shows slightly decreased C4 production overall but enhanced 1,3-butadiene production compared to all other catalysts studied herein. These catalysts were thoroughly characterized by a range of techniques to confirm structural integrity and porosity and probe the nature of the interactions of indium with the Cu nanoparticle active site.
AB - Metal-organic frameworks (MOFs) are receiving increased attention due to their well-defined structures that allow the determination of structure-property relationships. MOFs have been used as heterogeneous catalyst supports in a variety of fashions including for confinement of metal nanoparticles, which have demonstrated enhanced resistance to aggregation, a common issue in amorphous metal oxide supports. Cu and In catalysts were installed in the Zr-based MOF NU-907, being confined within the nanoporous structure. The Cu catalyst is known to, under various conditions, either selectively hydrogenate acetylene to ethylene or generate C4 products such as butenes and 1,3-butadiene, an important feedstock for rubber and adhesives. The addition of indium to the Cu catalyst is intended to serve as a promoter to produce C4 products by decreasing the surface coverage of copper while still allowing for C-C coupling. When employed for acetylene dimerization, InCu-NU-907 shows slightly decreased C4 production overall but enhanced 1,3-butadiene production compared to all other catalysts studied herein. These catalysts were thoroughly characterized by a range of techniques to confirm structural integrity and porosity and probe the nature of the interactions of indium with the Cu nanoparticle active site.
KW - acetylene dimerization
KW - heterogeneous catalysis
KW - metal-organic frameworks
KW - nanoparticle
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U2 - 10.1021/acsanm.2c03201
DO - 10.1021/acsanm.2c03201
M3 - Article
AN - SCOPUS:85139316772
SN - 2574-0970
JO - ACS Applied Nano Materials
JF - ACS Applied Nano Materials
ER -