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. 2017 Jan 10:7:39695.
doi: 10.1038/srep39695.

Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

Zhao Jin  1 , Chang Liu  1 , Kun Qi  1 , Xiaoqiang Cui  1
Affiliations

Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

Zhao Jin et al. Sci Rep. .

Abstract

Non-noble metal nanoparticles are becoming more and more important in catalysis recently. Cu/CuO nanoclusters on highly ordered TiO2 nanotube arrays are successfully developed by a surfactant-free photoreduction method. This non-noble metal Cu/CuO-TiO2 catalyst exhibits excellent catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with the presence of sodium borohydride (NaBH4). The rate constant of this low-cost Cu/CuO based catalyst is even higher than that of the noble metal nanoparticles decorated on the same TiO2 substrate. The conversion efficiency remains almost unchanged after 7 cycles of recycling. The recycle process of this Cu/CuO-TiO2 catalyst supported by Ti foil is very simple and convenient compared with that of the common powder catalysts. This catalyst also exhibited great catalytic activity to other organic dyes, such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). This highly efficient, low-cost and easily reusable Cu/CuO-TiO2 catalyst is expected to be of great potential in catalysis in the future.

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Figures

Figure 1
Figure 1. Fabrication and reusability schematic of Cu/CuO-TiO2 catalyst for the 4-NP reduction with NaBH4.
Figure 2
Figure 2. SEM images of the fabricated catalysts.
(a) C-0.02; (b) C-0.1; (c) C-0.5 and (d) their corresponding XRD patterns compared with TiO2 nanotube arrays. Insets show the high magnification images of the catalysts.
Figure 3
Figure 3
(a) TEM image of Cu/CuO nanoparticle obtained from C-0.1; (b) High resolution TEM image of the marked region.
Figure 4
Figure 4. XPS spectra of catalyst C-0.1.
(a) XPS survey spectrum; (b) Cu 2p spectrum; (c) O 1 s spectrum and (d) Ti 2p spectrum.
Figure 5
Figure 5
Time-dependent UV-vis absorption spectra for the reduction of 4-NP with (a) C-0.02; (b) C-0.1; (c) C-0.5; and (d) the corresponding plots of ln (Ct/C0) versus reaction time.
Figure 6
Figure 6. Time-dependent UV-vis absorption spectra for the reduction of 4-NP with different catalysts.
(a) Au-TiO2; (b) Ag-TiO2; (c) Pd-TiO2. (d) The corresponding plots of ln (Ct/C0) of different catalysts versus reaction time.
Figure 7
Figure 7. Reusability of the C-0.1 catalyst for the reduction of 4-NP.
(a) Plots of Ct/C0 versus reaction time for 7 reaction cycles and (b) the corresponding conversions of 4-NP.
Figure 8
Figure 8
Time-dependent UV-vis absorption spectra for the degradation of (a) MB; (b) RhB and (c) MO with catalyst C-0.1. The corresponding plots of ln (Ct/C0) versus reaction time for (d) MB; (e) RhB and (f) MO.
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