Journal
ACS APPLIED NANO MATERIALS
Volume 2, Issue 9, Pages 6040-6056Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsanm.9b01555
Keywords
MOF-74; MOF-derived catalysts; core shell nanoparticles; furfural hydrogenation; furfural hydrogenolysis; CoCu; structure-property relationship
Funding
- Catalysis Center for Energy Innovation, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science [DE-SC0001004]
- DOE Office of Science [DE-AC02-06CH11357]
- National Science Foundation [ECCS-1542174]
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The transformation of Co, Cu, and mixed Co/Cu MOF-74 crystals into bimetallic, carbon-supported Co-Cu catalysts is investigated via high-temperature pyrolysis. Mixed-metal MOFs prepared via a one-step solvothermal synthesis of MOF-74 are transformed into high metal content (48-63 wt %) catalysts by pyrolysis in N-2 at atmospheric pressure and elevated temperatures (300-900 degrees C). Comprehensive catalysis and structural characterization studies (temperature-programmed reduction, N-2 physisorption, transmission electron microscopy, scanning transmission electron microscopy, X-ray photoelectron spectroscopy, and in situ X-ray absorption spectroscopy) are reported using a range of CoxCu1-x (0.33 < x < 0.95) catalyst compositions. The data suggest MOF precursor restructuring occurs to increasingly favor, at higher pyrolysis temperatures, formation of bimetallic nanoparticles with a Co-rich core and Cu-rich shell (Co@Cu core-shell) and suggest a metallic active site in furfural hydrogenation. For differential furfural conversion reactions of the bimetallic catalysts, furfuryl alcohol selectivities between 66 and 89% and 2-methylfuran selectivities of 10-25% are obtained at 180 degrees C and a W/F of 3.6 g(cat)/(mol.h) (specific rates of 50-530 mu mol/(g(cat).min)). Higher Co:Cu ratios tend to increase activity and shift selectivity toward production of 2-methylfuran. Catalysts formed at elevated pyrolysis temperatures (>= 600 degrees C) display more complete Cu-shells, while at lower pyrolysis temperatures some Co atoms are still present on the nanoparticle surface, resulting in lower furfuryl alcohol selectivity and higher conversion.
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