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Mesoporous silica films as hard templates for electrodeposition of nanostructured gold
Published in Nanoscale Advances, DOI:10.1039/D2NA00512C
Dataset DOI:10.5258/SOTON/D2407

Tauqir Nasir, Li Shao, Yisong Han, Richard Beanland, Philip N. Bartlett and Andrew L. Hector

School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, U.K.
Department of Physics, University of Warwick, Coventry CV4 7AL, U.K.

Micrographs are provided in the manuscript and supplementary information. Original data used to produce other figures is provided in the provided text format files. These contain small angle X-ray scattering, electrochemical and X-ray diffraction results.

Figure 1. The GISAXS patterns of (a) the mesoporous silica film template 1 synthesised by evaporation- induced self-assembly, (b) template 2 synthesised by electrochemically assisted self-assembly, and (c) and (d) the vertical and horizonal integration of (a) and (b) respectively. The incident angle was 0.3° and scan time set for 20 mins. The peak information was calculated using GIXSGUI.31

Figure 2. (a) Top-view FE-SEM images of template 1; (b) A cross section FE-SEM image of template 1; (c) The size distribution histogram of the pores in (a); and (d) TEM of template 2. Software “Image J” was used to analyse the pore size distribution and “Origin” was used to draw the histogram. A Gaussian distribution in “Origin” was conducted to fit the histogram and calculate pore size.

Figure 3. (a) Cyclic voltammograms obtained from an electrolyte of 0.5 mmol dm-3 K[AuCl4] and 0.1 mol dm-3 KCl aqueous solution on a bare TiN substrate (black) and on a mesoporous silica film dip- coated on a TiN substrate (blue). (b) Cyclic voltammograms obtained from an electrolyte containing 1 mmol dm-3 K[AuCl4] and 0.1 mol dm-3 KCl aqueous solution on a bare ITO (black) and on a mesoporous silica film coated on an ITO working electrode (blue). Scan rate 50 mV/s.

Figure 4. Current transients during pulsed potential deposition (a) in 0.5 mmol dm-3 K[AuCl4]: nucleation at -1.5 V for 1 s, followed by growth at -0.1 V for 1 s for 100 cycles (template 1), first 20 cycles are shown. (b) in 1.0 mmol dm-3 K[AuCl4]: nucleation at -1.0 V for 5 s, followed by growth at 0 V for 25 cycles (template 2).

Figure 5. In-plane GISAXS patterns of template 1 (a) and template 2 (b), mesoporous silica film template 1 and 2 (black), template 1 and 2 with surfactant F127 and C20TAB (red) and gold- electrodeposited template 1 and 2 (blue). The incident angles for templates 1 and 2 were 0.25° and 0.30°, respectively.

Figure 6. The grazing incidence XRD patterns of gold electrodeposited into templates 1 (TiN substrate) and 2 (ITO substrate), with substrate patterns and the standard intensities for gold shown for comparison.43 The incident angle was 1°.

Figure 7. Top-view (a) and cross-view (b) FE-SEM images of gold electrodeposited in Template 1; (c) A cross-view FE-SEM image of gold electrodeposited in Template 2; (d) the size distribution histogram of the particles in (c). These images were obtained by Zeiss Gemini FE-gun SEM.

Figure 8. Top-view FE-SEM images of gold nanoparticles arrangements at the surface after etching Template 1 (a) and Template 2 (c). (b) and (d) are the size distribution histograms of the particles in (a) and (c) respectively.

Figure S1. Cyclic voltammograms of 5 mM [Ru(NH3)6Cl3] in 0.1 M NaNO3 (a) at template 1 and (b) template 2 (red) with surfactant inside pores, (blue) open pores without surfactant and (black) bare electrode substrates. Scan rate 50 mv/s.

Figure S2. (a) Cyclic voltammograms obtained from an electrolyte of 0.5 mmol dm-3 K[AuCl4] and 0.1 mol dm-3 KCl aqueous solution on a mesoporous silica film (template 1) on TiN substrate. (b) Cyclic voltammograms obtained from an electrolyte containing 1 mmol dm-3 K[AuCl4] and 0.1 mol dm-3 KCl aqueous solution on a mesoporous silica film (template 2) coated on an ITO working electrode. Scan rate 50 mV/s.

Figure S3. Top-view SEM images of Au electrodeposited in Template 1 under different conditions. Nucleation was at -1.0 or -1.5 V for 0.1 or 1.0 s, as shown, followed in all cases by electrodepositing at -0.1 V for 1 s for 100 cycles.

Figure S4. (a, b) Top view TEM images of template 2 after Au electrodeposition. (c, d) The sample is tilted using a high tilt holder to achieve an edge-on condition (looking down the cross section of a piece of the film). The Au particles only appear on bottom side of the silica film.

Figure S5. Top-view SEM images after removal of template 1 from Au electrodeposited sample. The electrodeposition conditions were the same as those used in Fig S2.

Figure S6. (a) In plane XRD spectra of (black) mesoporous silica, (red) Au electrodeposited into mesoporous silica and (blue) after mesoporous silica removal by HF of Au electrodeposited sample. (b) Wide angle XRD spectra of (black) mesoporous silica and Au (red) after mesoporous silica removal by HF etching of Au electrodeposited sample. (* Au peaks and remainder ITO).

Geographic location of data collection: University of Southampton, U.K.

Dataset available under a CC BY 4.0 licence

Publisher: University of Southampton, U.K.

Date: October 2022