Hollow Mesoporous Plasmonic Nanoshells for Enhanced Solar Vapor ...
Supporting Information
Hollow Mesoporous Plasmonic Nanoshells for Enhanced Solar Vapor Generation Marcin S. Zielinski,1 Jae-Woo Choi,1 Thomas La Grange,2 Miguel Modestino,1 Seyyed Mohammad Hosseini Hashemi,1 Ye Pu,1* Susanne Birkhold,1 Jeffrey A. Hubbell,3,4 and Demetri Psaltis1
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Laboratory of Optics (LO), School of Engineering (STI), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 2
Interdisciplinary Center for Electron Microscopy (CIME), School of Basic Sciences (SB), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 3
Institute of Bioengineering (IBI) and Institute of Chemical Sciences and Engineering (ISIC), School of Life Sciences, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 4
Institute for Molecular Engineering, University of Chicago, Chicago, IL, 60637 USA
*corresponding author: (Y.P.) E-mail: [email protected]
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Figure S1. Maximum Pixel Spectrum of the HyperMap data generated by the Bruker’s Espirit software package. Particular element peaks are described with color markers: Ag – green, Au – purple, visible Cu peaks (orange) appear as a signal originating from the TEM grid.
Figure S2. (A) Normalized VIS-NIR spectra showing change in extinction for: Ag core NPs (black), Ag/Au core/5nm shell NPs (blue), Ag/Au core/shell NPs (green), 10-nm-thick HMPNSs (orange) and 5-nm-thick HMP-NSs (red). Absorption peak values are given in nm. (B) DLS data (NanoSight NS300, Malvern Instruments) recorded for the 10-nm-thick hollow NSs. All the samples (inset picture, from the left: Ag/Au core/shell, 10 nm HMP-NSs, 5 nm HMP-NSs) were diluted to the same NP concentration of 2.0×109 NPs ml-1. The graph shows also small diameter peaks representing residue of free 20-nm silica mask beads remaining in the solution.
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A )
B )
E )
C )
D
F )
Figure S3. Chemical analysis of Ag/Au alloy fibril-like semi-hollow NS scaffold (corresponding to the inset in Figure 2B in the main text): A) HAADF STEM image of the analyzed region, B) Ag EDS X-ray map displaying the deconvoluted net counts, C) Au EDS Xray map displaying the deconvoluted net counts, D) EDS X-ray map showing line-scan region. E) Change in the deconvoluted net X-ray counts of Ag and Au across the line-scan region marked in Figure S3C. F) Variation in the quantified normalized mass percentage across the linescan region.
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Figure S4. HAADF and EDS X-ray structural composition analysis of 5 nm and 10 nm thick hollow NSs. (A) and (E) show HAADF images with marked line-scan regions across the 5 and 10 nm hollow NSs, respectively. Corresponding EDS X-ray maps of: Ag (B, F) and Au (C, G) display the deconvoluted net counts of atomic surface distribution. Plots: (D) and (H) demonstrate variations in the quantified normalized mass percentage of Ag (red) and Au (blue) across the line scan regions. Scale bars correspond to 50 nm. A ) B )
Figure S5. (A) Scheme of the solar experimental setup: sun symbol is a solar simulator source with an output light focused by the lens “L” into 7 mm focal spot passing through a transparent PMMA cuvette (1.0/1.0 cm wide, 2.0 cm high) containing NP sample. The cuvette is placed on a laboratory scale for the mass loss control. Local increase in temperature is controlled by a thermocouple sensor placed in a corner of the cuvette (next to the irradiated volume, but not irradiated directly). Setup is thermally insulated by a 3 cm thick polystyrene (PS) box with a 4
small window cut for the optical path. Air humidity inside the PS chamber is kept below 20 % with the help of low and constant flow of pure N2. (B) Picture of irradiated HMP-NSs solution (taken outside the experimental chamber), showing focused solar light into a 0.785 cm3 volume and its absorption/scattering interaction with NPs.
Figure S6. Spectral irradiance (black curve, vendor-supplied) of the solar simulator used in our experiment. Pink-gray area enclosed in the white curve shows NREL AM 1.5 solar irradiance as a reference.
Figure S7. Unsubtracted solar vapor generation data obtained over 70 min of irradiation. (A) Mass loss caused by PEG6k-coated NPs. (B) Mass loss caused by PEG12-coated NPs. (C)
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Temperature change caused by PEG6k-coated NPs. (D) Temperature change caused by PEG12coated NPs. Error bars indicate standard deviation.
Figure S8. Scheme representing mechanism of solar vapor generation at single hollow mesoporous thermal cavity NS.
Figure S9. Mie-theoretic calculation of the extinction, absorption, and scattering spectra of the 5-nm-thick HMP-NS showing the tunability by varying the size of the initial Ag core. The blue, green, red, and black curves show the spectra of HMP-NS with core diameter of 20 nm, 50 nm, 100 nm, and 200 nm, respectively. The solid, dashed, and dotted curves indicate the extinction, absorption, and absorption spectra, respectively. Each set of extinction, absorption, and scattering spectra is normalized with the maximum extinction. The gray area with white curve shows AM 1.5 solar irradiation spectrum as a reference.
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Hollow Mesoporous Plasmonic Nanoshells for Enhanced Solar Vapor Generation Marcin S. Zielinski,1 Jae-Woo Choi,1 Thomas La Grange,2 Miguel Modestino,1 Seyyed Mohammad Hosseini Hashemi,1 Ye Pu,1* Susanne Birkhold,1 Jeffrey A. Hubbell,3,4 and Demetri Psaltis1
1
Laboratory of Optics (LO), School of Engineering (STI), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 2
Interdisciplinary Center for Electron Microscopy (CIME), School of Basic Sciences (SB), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 3
Institute of Bioengineering (IBI) and Institute of Chemical Sciences and Engineering (ISIC), School of Life Sciences, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 4
Institute for Molecular Engineering, University of Chicago, Chicago, IL, 60637 USA
*corresponding author: (Y.P.) E-mail: [email protected]
1
Figure S1. Maximum Pixel Spectrum of the HyperMap data generated by the Bruker’s Espirit software package. Particular element peaks are described with color markers: Ag – green, Au – purple, visible Cu peaks (orange) appear as a signal originating from the TEM grid.
Figure S2. (A) Normalized VIS-NIR spectra showing change in extinction for: Ag core NPs (black), Ag/Au core/5nm shell NPs (blue), Ag/Au core/shell NPs (green), 10-nm-thick HMPNSs (orange) and 5-nm-thick HMP-NSs (red). Absorption peak values are given in nm. (B) DLS data (NanoSight NS300, Malvern Instruments) recorded for the 10-nm-thick hollow NSs. All the samples (inset picture, from the left: Ag/Au core/shell, 10 nm HMP-NSs, 5 nm HMP-NSs) were diluted to the same NP concentration of 2.0×109 NPs ml-1. The graph shows also small diameter peaks representing residue of free 20-nm silica mask beads remaining in the solution.
2
A )
B )
E )
C )
D
F )
Figure S3. Chemical analysis of Ag/Au alloy fibril-like semi-hollow NS scaffold (corresponding to the inset in Figure 2B in the main text): A) HAADF STEM image of the analyzed region, B) Ag EDS X-ray map displaying the deconvoluted net counts, C) Au EDS Xray map displaying the deconvoluted net counts, D) EDS X-ray map showing line-scan region. E) Change in the deconvoluted net X-ray counts of Ag and Au across the line-scan region marked in Figure S3C. F) Variation in the quantified normalized mass percentage across the linescan region.
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Figure S4. HAADF and EDS X-ray structural composition analysis of 5 nm and 10 nm thick hollow NSs. (A) and (E) show HAADF images with marked line-scan regions across the 5 and 10 nm hollow NSs, respectively. Corresponding EDS X-ray maps of: Ag (B, F) and Au (C, G) display the deconvoluted net counts of atomic surface distribution. Plots: (D) and (H) demonstrate variations in the quantified normalized mass percentage of Ag (red) and Au (blue) across the line scan regions. Scale bars correspond to 50 nm. A ) B )
Figure S5. (A) Scheme of the solar experimental setup: sun symbol is a solar simulator source with an output light focused by the lens “L” into 7 mm focal spot passing through a transparent PMMA cuvette (1.0/1.0 cm wide, 2.0 cm high) containing NP sample. The cuvette is placed on a laboratory scale for the mass loss control. Local increase in temperature is controlled by a thermocouple sensor placed in a corner of the cuvette (next to the irradiated volume, but not irradiated directly). Setup is thermally insulated by a 3 cm thick polystyrene (PS) box with a 4
small window cut for the optical path. Air humidity inside the PS chamber is kept below 20 % with the help of low and constant flow of pure N2. (B) Picture of irradiated HMP-NSs solution (taken outside the experimental chamber), showing focused solar light into a 0.785 cm3 volume and its absorption/scattering interaction with NPs.
Figure S6. Spectral irradiance (black curve, vendor-supplied) of the solar simulator used in our experiment. Pink-gray area enclosed in the white curve shows NREL AM 1.5 solar irradiance as a reference.
Figure S7. Unsubtracted solar vapor generation data obtained over 70 min of irradiation. (A) Mass loss caused by PEG6k-coated NPs. (B) Mass loss caused by PEG12-coated NPs. (C)
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Temperature change caused by PEG6k-coated NPs. (D) Temperature change caused by PEG12coated NPs. Error bars indicate standard deviation.
Figure S8. Scheme representing mechanism of solar vapor generation at single hollow mesoporous thermal cavity NS.
Figure S9. Mie-theoretic calculation of the extinction, absorption, and scattering spectra of the 5-nm-thick HMP-NS showing the tunability by varying the size of the initial Ag core. The blue, green, red, and black curves show the spectra of HMP-NS with core diameter of 20 nm, 50 nm, 100 nm, and 200 nm, respectively. The solid, dashed, and dotted curves indicate the extinction, absorption, and absorption spectra, respectively. Each set of extinction, absorption, and scattering spectra is normalized with the maximum extinction. The gray area with white curve shows AM 1.5 solar irradiation spectrum as a reference.
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