SUPPLEMENTARY INFORMATION (17 Pages)

Combining Photocatalysis and Optical Fibre Technology towards improved Microreactor Design for
Hydrogen Generation with Metallic Nanoparticles

Matthew E. Pottera*, Daniel J. Stewarta, Alice E. Oakleya, Richard P. Boardmanb, Tom Bradleyc, Pier J.
A. Sazioc and Robert Rajaa

a) Department of Chemistry, University of Southampton, Highfield Campus, Southampton, SO17 1BJ,

UK.

b) Mu-Vis X-ray Imaging Centre, University of Southampton, Highfield Campus, Southampton, SO17
1BJ, UK.

c) Optoelectronics Research Centre, University of Southampton, Highfield Campus, Southampton,

SO17 1BJ, UK.

*M.E.Potter@soton.ac.uk

Contents
Title Page
Experimental S2
Fibre Synthesis S2
Synthesis of Analogous Powder Samples S2
Catalysis S2
UV/Vis Spectroscopy S4
Transmission Electron Microscopy S4
X-ray Absorption Spectroscopy S5
Fluorescence Spectroscopy S5
ICP Data S6
UV/Vis Data S6
Ex situ EXAFS S6
Pellets and Standards S6
MOFC Systems S8
TEM Findings S10
Photocatalytic Data S16
Efficiency Calculation S17
References S17

Page S1
Experimental
Fibre Synthesis

Since their inception in the mid 1990s(S1) the microstructured optical fibre, or the Photonic Crystal
Fibre (PCF), has given rise to substantial global research effort within the academic and industrial
photonics community. This is due to the numerous degrees of freedom that the glass microstructuring
affords for precisely tailoring the waveguiding properties of the fibre, resulting in some unique optical
properties. PCFs comprised of air and fused silica are typically manufactured using a macroscopic fibre
preform up to one metre in length that incorporates the desired transverse glass lattice pattern, which
are then drawn on the fibre drawing tower into the microscopic scale fibres that, due to the
remarkable thermomechanical properties of pure silica, preserve the intended cross-sectional lattice
design. The stack and draw techniques first devised by Knight et al.(S1) begins with fabricating
capillaries of the required dimensions with specific aspect ratio. These are then stacked in the desired
lattice arrangement. The PCF preform is finally drawn into canes or fibres by adjusting drawing
parameters such as feed rate, draw speed and furnace temperature. The cane or fibre dimensions are
set according to a simplified mass conservation law, Apvp = Afvf where Ap and Af are the cross-sectional
area of the preform and cane/fibre respectively while vp is the preform feed rate and vf the fibre
drawing speed. The tower furnace temperature is maintained between the glass softening and melting
temperature of around 2100 oC. The very wide viscosity range of pure silica is exploited to ensure
precise control of the PCF dimensions and uniformity, with online measurement tools such as laser
interferometry of the outside diameter.

Synthesis of Analogous Powder Samples

Analogous powder samples were synthesised for spectroscopic comparisons with the Pd/TiO2/MOFC
samples. As per above three different concentrations were made. For the standard synthesis (as
above) 0.38 mL of an aqueous 10.6 mg/mL K2PdCl4 solution and 0.20 mL of an aqueous 6.50 mg/mL
polyvinylpyrollidone (PVP) solution were added together in 80 mL of methanol. The system was stirred
for 10 minutes when 0.51 mL of an aqueous 0.1 M NaBH4 solution was added dropwise. This gave a
final Pd concentration of 0.05 mg/mL. After stirring for 2 hours 0.1 g of P25 TiO2 was added and the
system was left to stir for 18 hours. After which the suspension was filtered to yield a grey powder,
which was then dried at 70 oC overnight. Two other samples were prepared where the concentrations
of K2PdCl4, NaBH4 and PVP were increased by factors of 3 and 9, this gave three powdered samples
labelled Z-Pd/TiO2/Pellet, where Z is either 0.05, 0.15 or 0.45 mg/mL representing the concentration
of the Pd nanoparticle solution.

Catalysis

The catalytic set-up consisted of a Oriel 150 W Xe short arc lamp, equipped with a AMG1.5G solar
simulator filter, giving a power output of roughly 800 mW/cm2 (placed 6 cm away from the coated
MOFC), a peristaltic pump, a “50 mL” 3-neck round bottom flask (RBF), a mass-flow controller and a
four-way valve, constructed as below. The coated MOFC was approximately 6 cm away from the
output of the solar simulator and positioned at the focal point of a reflective parabolic trough. Once
assembled 60 mL of deionised water was put into the 3-neck RBF, with the outlet (to the coated MOFC)
solely in the liquid phase, and the inlet (from the four-way valve) was in the gaseous headspace.
Initially the system (degassing mode) was degassed for one hour at a flow rate of 50 mL/min of

Page S2
nitrogen to ensure all residual oxygen was removed from the system, and the deionised water. After
degassing the four-way valve was switched (catalysis mode) to isolate the system, and the nitrogen
flow stopped. 0.6 mL of methanol was then injected into the 3-neck RBF through a rubber septum,
and then the aqueous methanol solution was pumped at 0.17 mL/min through the system. Once the
coated MOFC was filled with the solution, a gas-phase sample was taken through the septum (as the
zero point), and the solar simulator was turned on, and the reaction started. The 3-neck RBF containing
the methanolic solution was covered to shield it from the light. The system was maintained at 25 oC,
and 1 atm of pressure.
Peristaltic pump
DEGASSING MODE

Solar simulator Coated MOF

Four-way valve
Vent

Mass-flow controller

3-neck RBF Nitrogen cylinder

Figure S1: Photocatalytic set up for degassing the system prior to reaction.

Peristaltic pump
CATALYSIS MODE

Solar simulator Coated MOF

Four-way valve
Vent

Mass-flow controller

3-neck RBF Nitrogen cylinder

Figure S2: Photocatalytic set up for reaction.

Gas-phase samples were then taken as a function of reactor time as the reaction progressed. All
samples were 1 mL and were analysed on a Perkin-Elmer Clarus 400 gas-chromatogram with a Thermal
Conductivity Detector (TCD) and a Carboxen 1010 PLOT column (30 m x 0.53 mm). The GC method
used held the temperature at 35 oC for 25 minutes, with an injector temperature of 200 oC, a detector

Page S3
temperature of 230 oC and 4.0 psi of Argon flowed at 14 mL/min was used as the reference. The make-
up flow was set to maximise the signal intensity. Prior to analysis a calibration was performed using
known quantities of hydrogen and nitrogen, which found that an area of 72515 (mV.ssec)
corresponded to 1 μL of hydrogen injected.

Figure S3: GC calibration plot to obtain the relative response factor from hydrogen on a TCD detector.

The total volume of hydrogen was calculated by dividing the area of the hydrogen peak area by 72515
to calculate the μL of hydrogen injected. This was then multiplied by the gaseous dead volume of the
system (measured as 26.36 mL for our system), and finally divided by the volume of the syringe (1000
μL) to give the total volume of hydrogen produced in mL.
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑃𝑒𝑎𝑘 𝐴𝑟𝑒𝑎 × 26.36 𝑚𝐿
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑉𝑜𝑙𝑢𝑚𝑒 =
72515 × 1000 𝜇𝐿

UV/Vis Spectroscopy

UV/Vis was performed on a Perkin Elmer 750 S spectrometer in diffuse reflectance mode. Data was
collected from 800 – 200 nm, with a step size of 1 nm and a scan speed of 0.225 seconds per step, and
the data was normalised for 100 % reflectance using a BaSO4 standard. A black beam-stop disk was
used as the background, with the canes placed in between the source and the black beam-stop disk.

Transmission Electron Microscopy

Transmission electron microscopy (TEM) was performed at the Biomedical Imaging Unit at the
University of Southampton. The cane was crushed into a fine powder prior to use. TEM images were
obtained using a Hitachi HT7700 with a LaB6 filament installed and operated at an accelerating voltage
of 100 kV. Nanoparticle size distributions were performed on 50-100 nanoparticles for each system,
measuring the average dimensions of each particle from the TEM images, using three independent
images to calculate mean and standard deviations, expressed represented as both histograms and

Page S4
Gaussian curves. Mean values and standard deviations for the distributions were used to calculate the
polydisperstiy index (PdI):(S2)
2
𝑃𝑑𝐼 =
𝜎
𝑑()
where σ is the standard deviation of the particle diameters and d is the average particle diameter.(S2)

The shape factor (SF) was also calculated to explore the shape of the nanoparticle systems, for each
particle the largest and smallest measurable distances were measured from the TEM images using
ImageJ analysis software.(S3) The largest dimension was divided by the smallest, and then averaged for
each particle in a given system to provide insight into the shapes of the particle. A sample of perfectly
circular nanoparticles will give a SF value of 1.

X-ray Absorption Spectroscopy

X-ray absorption spectroscopy (XAS) data was collected at B18 at the Diamond Light Source, Didcot,
UK via rapid access proposal SP21199. Measurements were performed using a QEXAFS set-up with a
fast scanning Si(311) double crystal monochromator. 5 cane samples were run ex situ in fluorescence
mode. 3 powdered Pd/TiO2 samples were made into an 8 mm disc, with cellulose as a binding agent,
and run in transmission mode. All spectra were acquired simultaneously with a Pd reference foil placed
between the It and Iref chambers to align the energy values of the sample. 6 scans were collected for
each sample, at a resolution of 0.5 eV at 5 minutes per spectrum. XAFS data processing and EXAFS
analysis were performed using IFEFFIT with the Horae package (Athena and Artemis).(S4) The amplitude
factor; S02 was determined from the Pd reference foil as 0.812, and the data was fit within the ranges
of 3 < k < 12, and 1 < R < 3 to give 11.2 independent points. All spectra were fit using both a Pd-C and
a Pd-Pd path to give 7 variables.

Fluorescence Spectroscopy

Page S5
Figure S4: Stacked fluorescence spectra from site 1 (bare cane) and site 2 (TiO2 rich).

ICP Data
Table S1: Pd content of different MOFC samples.

Sample Pd/ppm
0.05-Pd-3/TiO2/MOFC 53
0.15-Pd-1/TiO2/MOFC 48
0.15-Pd-3/TiO2/MOFC 58
0.15-Pd-18/TiO2/MOFC 120
0.45-Pd-3/TiO2/MOFC 77

UV/Vis Data

Figure S5: UV/Vis spectra comparing the bare cane with TiO2 and Pd/TiO2 coating.

Ex situ EXAFS
Pellets and standards

Page S6
Figure S6: k3 weighted EXAFS analysis of pelletised samples and Pd foil. Spectra stacked by 25 Å-3 for
clarity.

Figure S7: |χ(R)| data for the Pd foil reference standard, showing the goodness of fit. Spectra
stacked for clarity.

Figure S8: |χ(R)| data for the Pd pellet systems showing the goodness of fit. Spectra stacked for
clarity.

Page S7
MOFC Systems

Figure S9: Normalised μ(E) XAS spectra of MOFC systems, varying with deposition time. Spectra
stacked by 0.5 in μ(E) for clarity.

Figure S10: k3 weighted EXAFS analysis of MOFC systems varying with the Pd precursor
concentration. Spectra stacked by 25 Å-3 for clarity.

Page S8
Figure S11: k3 weighted EXAFS analysis of MOFC systems varying with the deposition time. Spectra
stacked by 25 Å-3 for clarity.

Figure S12: |χ(R)| data for the MOFC systems, varying as a function of deposition time, showing the
goodness of fit. Spectra stacked for clarity.

Page S9
Figure S13: |χ(R)| data for the MOFC systems, varying as a function of Pd precursor concentration,
showing the goodness of fit. Spectra stacked for clarity.

TEM Findings

Page S10
Page S11
Figure S14: TEM images showing the influence of palladium concentration (A, C and F), deposition
time (B, C and D) and comparing before and after reaction (D and E).

20 A) 0.05-Pd-3/TiO2/MOFC
18 3.6  0.7 nm
16

14

12
Counts

10

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle size (nm)

Page S12
 25
B) 0.15-Pd-1/TiO2/MOFC
4.9  0.9 nm
20

15
Counts

10

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle Size (nm

14 C) 0.15-Pd-3/TiO2/MOFC
4.7  1.0 nm
12

10
Counts

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle size (nm)

Page S13
 14 D) 0.15-Pd-18/TiO2/MOFC

12 4.7  1.0 nm

10
Counts

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle size (nm)

20 E) 0.15-Pd-18/TiO2/MOFC Used
18
4.8  1.0 nm
16

14

12
Counts

10

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle size (nm)

Page S14
 12
F) 0.45-Pd-3/TiO2/MOFC
10
5.6  1.4 nm

8
Counts

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle size (nm)

Figure S15: Nanoparticle size distributions showing the influence of palladium concentration (A, C
and F), deposition time (B, C and D) and comparing before and after reaction (D and E).

Table S2: Geometric parameters for Pd nanoparticles found from analysis of TEM images:

Sample Mean particle size Standard deviation PdIa Shape

(nm) (nm) factor
0.05-Pd-3/TiO2/MOFC 3.6 0.7 0.038 1.30
0.15-Pd-1/TiO2/MOFC 4.9 0.9 0.034 1.22
0.15-Pd-3/TiO2/MOFC 4.7 1.0 0.045 1.30
0.15-Pd-18/TiO2/MOFC 4.7 1.0 0.045 1.38
0.15-Pd-18/TiO2/MOFC Used 4.8 1.0 0.043 1.32
0.45-Pd-3/TiO2/MOFC 5.6 1.4 0.063 1.33
a) Calculated as per reference S2.

Page S15
Photocatalytic Data

Figure S16: Variations in hydrogen production with the MOFC systems varying as a function of
deposition time, with a Pd precursor concentration of 0.05 mg/mL.

Figure S17: Variations in hydrogen production with the MOFC systems varying as a function of
deposition time, with a Pd precursor concentration of 0.45 mg/mL.

Page S16
Efficiency calculation

0.15-Pd-3/TiO2/MOFC achieved a hydrogen yield of 0.15 mL in 3 hours, thus produced 0.05 mL

hydrogen/hr.

The system contains 861 ppm of TiO2 and 58 ppm of Pd, corresponding to 919 ppm or 0.0919 wt%.

10 cm of cane was used, which weighs 0.773 g, therefore the mass of catalyst is 0.00071 g. 0.05
mL/hr divided by 0.00071 g is a production rate of 70.4 mL hydrogen/hr/g catalyst.

Previous powder systems(S5) have used 0.2 g of catalyst, producing hydrogen at a rate of 2.8 mL/hr,
therefore a production rate of 14 mL hydrogen/hr/g catalyst.

References
S1. Knight, J. C.; Birks, T. A.; Russell, P. St. J.; Atkin, D. M. All-silica single-mode optical fiber with
photonic crystal cladding. Optics Lett. 1996, 21, 1547-1549.

S2. Clayton, K. N.; Salameh, J. W.; Wereley, S. W.; Kinzer-Ursem, T. L. Physical characterization of
nanoparticle size and surface modification using particle scattering diffusometry. Biomicrofluidics
2016, 10, 0547107.

S3. Schneider, C. A.; Rasband, W. S.; Eliceiri, K. W. NIH Image to ImageJ: 25 years of image analysis.
Nature Methods 2012, 9, 671-675.

S4. Ravel, B.; Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption
spectroscopy using IFEFFIT. J. Synchrotron Rad. 2005, 12, 537-541.

S5. Bahruji, H.; Bowker, M.; Davies, P. R.; Morgan, D. J.; Morton, C. A.; Egerton, T. A.; Kennedy, J.;
Jones, W. Rutile TiO2–Pd Photocatalysts for Hydrogen Gas Production from Methanol Reforming.
Top. Catal. 2015, 58, 70-76.

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