Evidence for Metal-Support Interactions in Au-modified. TiOx/SBA-15 materials prepared by photo-deposition. Bastian Meiâ ,â¡, Christian Wiktor#,+,â¡, Stuart ...
Supporting Information
Evidence for Metal-Support Interactions in Au-modified TiOx/SBA-15 materials prepared by photo-deposition Bastian Mei†,‡, Christian Wiktor#,+,‡, Stuart Turner+, Gustaaf van Tendeloo+, Roland A. Fischer#, Martin Muhler†, and Jennifer Strunk*,† Department of Chemistry and Biochemistry, Laboratory of Industrial Chemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum, Germany. # Department of Chemistry and Biochemistry, Chair of Anorganische Chemie II, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum, Germany. + Electron Microscopy for Materials Science (EMAT), Antwerp University, Groenenborgerlaan, 171, 2020 Antwerpen, Belgium †
Table 1: Au content after photo-deposition determined by ICP-OES measurements for Ti(x)/SBA-15 and for ZnOxcontaining SBA-15 materials. Sample
Au/SBA-15
Au loading (wt%) 0.02
Au/Ti0.3/SBA
Au/Ti1.0/SBA
Au/Ti2.0/SBA
Au/Ti2.7/SBA
0.25
0.29
0.27
0.28
Sample
Au/Zn0.3/SBA
Au/Ti1.2/Zn0.3/SBA
Au/Zn0.3/Ti1.2/SBA
Au loading (wt%)
0.05
0.1
0.14
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Fig. S1. a) BFTEM image of Ti1.0/SBA. b) EFTEM Ti map of the piece of material shown in a). In both images the intact channels of SBA-15 can be seen. The Ti distribution is homogeneous and free of particle-like enrichments as they are found in Au/Ti1.0/SBA. c) EELS spectrum of T1.5/SBA showing the Ti-L2,3 and the O-K edge.
Fig. S2. The H2 evolution during the stepwise photo-deposition of Au nanoparticles on Ti2.0/SBA is shown. The overall amount of deposited Au is indicated.
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Fig. S3. A) Diffuse reflectance UV-Vis spectra of Au-modified materials with varying Ti loading a) Au/SBA-15, b) Au/Ti0.3/SBA, c) Au/Ti1.0/SBA, d) Au/Ti2.0/SBA, e) Au/Ti2.7/SBA, f) Au/Ti1.0/SBA (0.55 wt% Au), g) Au/Ti2.0/SBA (0.55 wt% Au). b) Diffuse reflectance UV-Vis spectra of the Au-modified materials containing ZnOx in the SBA-15 matrix a) Au/Zn0.3/SBA, b) Au/Zn0.3/Ti1.2/SBA, c) Au/Ti1.2/Zn0.3/SBA, and d) Au/Ti1.0/SBA.
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Fig. S4. a) HAADF-STEM images of Au/Ti1.0/SBA. Numbered white frames label the areas where STEM-EDX spectra were recorded. b) and c) show magnified HAADF-STEM images of the areas where spectrum 2 and 3 were recorded. d) EDX spectra of the material in the areas 1 (black), 2 (red) and 3 (blue), only 3 shows an Au signal.
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Fig. S5. Tomographic reconstruction of a typical Au/Ti1.0/SBA crystal. In the 3D representation (left top) the Au nanoparticles are displayed in yellow, the SBA framework in soft-red. The arrangement of the channels is visible as well as the Au particles. The orthoslices through the reconstruction show that the SBA framework pores are resolved. The Au nanoparticles are found within the SBA-15 crystal as well as at the surface.
Fig. S6. EELS spectrum of Au/Zn0.3/Ti1.2/SBA showing the Ti-L2,3 and the O-K edge.
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Fig. S7. HAADF-STEM image of Au/Zn0.3/Ti1.2/SBA. The monodispersed Au particles are visible as bright dots.
N orm alized Frequency
1,0 0,8 0,6 0,4 0,2 0,0 2
3
4
5
6
7 8 9 10 11 12 13 14 15 16 D iam eter[nm ]
Fig. S8. Size distribution of Au particles in the Au/Zn0.3/Ti1.2/SBA material. The size of the particles was determined from HAADF-STEM images. The diameter was calculated by assuming a spherical shape for the particles.
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Fig. S9. EDX spectrum of a typical Au/Zn0.3/Ti1.2/SBA crystal. The inset table shows the composition of the crystal in wt.%, its error, and the composition in at.%.
Fig. S10. Tomographic reconstruction of a typical Au/Zn0.3/Ti1.2/SBA crystal, reconstruction size = 622x738x817 nm (boundaries indicated by the orange box). In the 3D representation (left top) the Au nanoparticles are displayed in yellow, the SBA framework in soft-red. The arrangement of the channels is clearly visible as well as the Au particles. The orthoslices through the reconstruction show that the SBA framework pores are resolved. The Au nanoparticles are found within the SBA15 crystal as well as at the surface.
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Fig. S11. a): BF-TEM image of Au/Ti1.2/Zn0.3/SBA. The crystal in the center of the image has been imaged along its channel direction. FT analysis of the area highlighted by the white frame (inset) shows a spacing of approximately 9.5 nm of the hexagonally packed pores for the imaged crystal. b) HR-TEM of a gold particle in Au/Ti1.2/Zn0.3/SBA. The particle is imaged along its [110] zone axis orientation as it can be seen in the FT analysis (inset). c) HAADF-STEM image of a Au/Ti1.2/Zn0.3/SBA crystal along its pore direction. d) FT analysis of the area highlighted by the white frame (inset) shows a spacing of 10 nm for the imaged crystal. The imaged gold particles are relatively monodispersed. BF-TEM (e), magnification the Au/Ti1.2/Zn0.3/SBA material (f) and Ti EFTEM map of the Au/Ti1.2/Zn0.3/SBA crystal (g). The titanium distribution is homogeneous except for small enrichments.h) EELS spectrum of Au/Ti1.2/Zn0.3/SBA showing the Ti-L2,3 and the O-K edge.
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