title: Fundamental Role of Oxygen Stoichiometry in Controlling the Band Gap and Reactivity of Cupric Oxide Nanosheets.
abstract: CuO is a nonhazardous, earth-abundant material that has exciting potential for use in solar cells, photocatalysis, and other optoelectronic applications. While progress has been made on the characterization of properties and reactivity of CuO, there remains significant controversy on how to control the precise band gap by tuning conditions of synthetic methods. Here, we combine experimental and theoretical methods to address the origin of the wide distribution of reported band gaps for CuO nanosheets. We establish reaction conditions to control the band gap and reactivity via a high-temperature treatment in an oxygen-rich environment. SEM, TEM, XRD, and BET physisorption reveals little to no change in nanostructure, crystal structure, or surface area. In contrast, UV-vis spectroscopy shows a modulation in the material band gap over a range of 330 meV. A similar trend is found in H2 temperature-programmed reduction where peak H2 consumption temperature decreases with treatment. Calculations of the density of states show that increasing the oxygen to copper coverage ratio of the surface accounts for most of the observed changes in the band gap. An oxygen exchange mechanism, supported by (18)O2 temperature-programmed oxidation, is proposed to be responsible for changes in the CuO nanosheet oxygen to copper stoichiometry. The changes induced by oxygen depletion/deposition serve to explain discrepancies in the band gap of CuO, as reported in the literature, as well as dramatic differences in catalytic performance.
authors.affiliation: Department of Chemical and Environmental Engineering, Yale University , New Haven, Connecticut 06520-8286, United States.
authors.forename: Zachary S
authors.initials: ZS
authors.lastname: Fishman
authors.affiliation: Department of Chemistry and Energy Sciences Institute, Yale University , New Haven, Connecticut 06520-8107, United States.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Rudshteyn
authors.affiliation: Department of Chemistry, Nankai University , Tianjin 300071, China.
authors.forename: Yulian
authors.initials: Y
authors.lastname: He
authors.affiliation: Department of Mechanical Engineering, Yale University , New Haven, Connecticut 06520-8286, United States.
authors.forename: Bolun
authors.initials: B
authors.lastname: Liu
authors.affiliation: Department of Chemistry and Energy Sciences Institute, Yale University , New Haven, Connecticut 06520-8107, United States.
authors.forename: Subhajyoti
authors.initials: S
authors.lastname: Chaudhuri
authors.affiliation: Department of Chemistry and Energy Sciences Institute, Yale University , New Haven, Connecticut 06520-8107, United States.
authors.forename: Mikhail
authors.initials: M
authors.lastname: Askerka
authors.affiliation: Department of Chemical and Environmental Engineering, Yale University , New Haven, Connecticut 06520-8286, United States.|Department of Chemistry and Energy Sciences Institute, Yale University , New Haven, Connecticut 06520-8107, United States.
authors.forename: Gary L
authors.initials: GL
authors.lastname: Haller
authors.affiliation: Department of Chemistry and Energy Sciences Institute, Yale University , New Haven, Connecticut 06520-8107, United States.
authors.forename: Victor S
authors.initials: VS
authors.lastname: Batista
authors.affiliation: Department of Chemical and Environmental Engineering, Yale University , New Haven, Connecticut 06520-8286, United States.
authors.forename: Lisa D
authors.initials: LD
authors.lastname: Pfefferle