How to stabilize highly active Cu+ cations in a mixed-oxide catalyst

Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You; Yang, Xiaofang; Baber, Ashleigh E.; Hoffmann, Friedrich M.; Senanayake, Sananayake; Rodriguez, Jose A.; Chen, Jingguang G.; Liu, Ping; Stacchiola, Dario J.

doi:10.1016/j.cattod.2015.08.025

Title: How to stabilize highly active Cu⁺ cations in a mixed-oxide catalyst

Journal Article · Sat Sep 12 00:00:00 EDT 2015 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2015.08.025· OSTI ID:1246791

Mudiyanselage, Kumudu ^[1]; Luo, Si ^[2]; Kim, Hyun You ^[3]; Yang, Xiaofang ^[1]; Baber, Ashleigh E. ^[4]; Hoffmann, Friedrich M. ^[5]; Senanayake, Sananayake ^[1]; Rodriguez, Jose A. ^[1]; Chen, Jingguang G. ^[6]; Liu, Ping ^[1]; Stacchiola, Dario J. ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
State Univ. of New York (SUNY), Stony Brook, NY (United States)
Chungnam National Univ., Daejeon (Korea)
James Madison Univ., Harrisonburg, VA (United States)
BMCC-CUNY, New York, NY (United States)
Columbia Univ., New York, NY (United States)

Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuO_x) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu₂O-like phase coexists with TiCuO_x and TiO_x domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuO_x film occurs. Stepwise oxidation of TiCuO_x shows that the formation of the mixed-oxide is faster than that of pure Cu₂O. As the Ti coverage increases, Ti-rich islands (TiO_x) form. The adsorption of CO has been used to probe the exposed surface sites on the TiO_x–CuO_x system, indicating the existence of a new Cu⁺ adsorption site that is not present on Cu₂O/Cu(111). Adsorption of CO on Cu⁺ sites of TiCuO_x is thermally more stable than on Cu(111), Cu₂O/Cu(111) or TiO₂(110). The Cu⁺ sites in TiCuO_x domains are stable under both reducing and oxidizing conditions whereas the Cu₂O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuO_x films, which are not present on Cu(111), Cu₂O/Cu(111), or TiO₂(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704; SC0012704

OSTI ID:: 1246791

Alternate ID(s):: OSTI ID: 1389103

Report Number(s):: BNL-111953-2016-JA; R&D Project: CO009; KC0302010

Journal Information:: Catalysis Today, Vol. 263, Issue C; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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Title: How to stabilize highly active Cu+ cations in a mixed-oxide catalyst

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Title: How to stabilize highly active Cu⁺ cations in a mixed-oxide catalyst