title: Copper Nanocrystals Encapsulated in Zr-based Metal-Organic Frameworks for Highly Selective CO2Hydrogenation to Methanol.
abstract: We show that the activity and selectivity of Cu catalyst can be promoted by a Zr-based metal-organic framework (MOF), Zr6O4(OH)4(BDC)6(BDC = 1,4-benzenedicarboxylate), UiO-66, to have a strong interaction with Zr oxide [Zr6O4(OH)4(-CO2)12] secondary building units (SBUs) of the MOF for CO2hydrogenation to methanol. These interesting features are achieved by a catalyst composed of 18 nm single Cu nanocrystal (NC) encapsulated within single crystal UiO-66 (Cu⊂UiO-66). The performance of this catalyst construct exceeds the benchmark Cu/ZnO/Al2O3catalyst and gives a steady 8-fold enhanced yield and 100% selectivity for methanol. The X-ray photoelectron spectroscopy data obtained on the surface of the catalyst show that Zr 3d binding energy is shifted toward lower oxidation state in the presence of Cu NC, suggesting that there is a strong interaction between Cu NC and Zr oxide SBUs of the MOF to make a highly active Cu catalyst.
authors.affiliation: Department of Chemistry, University of California-Berkeley, Kavli Energy NanoSciences Institute , Berkeley, California 94720, United States.
authors.forename: Bunyarat
authors.initials: B
authors.lastname: Rungtaweevoranit
authors.affiliation: Department of Chemistry, University of California-Berkeley, Kavli Energy NanoSciences Institute , Berkeley, California 94720, United States.
authors.forename: Jayeon
authors.initials: J
authors.lastname: Baek
authors.affiliation: Department of Chemistry, University of California-Berkeley, Kavli Energy NanoSciences Institute , Berkeley, California 94720, United States.|Materials Metrology Division, National Institute of Metrology, Quality, and Technology , Duque de Caxias, Rio de Janeiro 25250-020, Brazil.
authors.forename: Joyce R
authors.initials: JR
authors.lastname: Araujo
authors.affiliation: Materials Metrology Division, National Institute of Metrology, Quality, and Technology , Duque de Caxias, Rio de Janeiro 25250-020, Brazil.
authors.forename: Braulio S
authors.initials: BS
authors.lastname: Archanjo
authors.affiliation: Department of Chemistry, University of California-Berkeley, Kavli Energy NanoSciences Institute , Berkeley, California 94720, United States.
authors.forename: Kyung Min
authors.initials: KM
authors.lastname: Choi
authors.affiliation: Department of Chemistry, University of California-Berkeley, Kavli Energy NanoSciences Institute , Berkeley, California 94720, United States.|King Abdulaziz City for Science and Technology , Riyadh 11442, Saudi Arabia.
authors.forename: Omar M
authors.initials: OM
authors.lastname: Yaghi
authors.affiliation: Department of Chemistry, University of California-Berkeley, Kavli Energy NanoSciences Institute , Berkeley, California 94720, United States.
authors.forename: Gabor A
authors.initials: GA
authors.lastname: Somorjai
keywords: CO2 hydrogenation; Metal−organic framework; heterogeneous catalyst; metal nanocrystal; methanol; strong metal−support interaction