Characterization and Structure Management of Mesoporous Bismuth

Vanadate/Tungsten Trioxide Thin Films

Marion Hope

May 9th – August 5th

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Abstract

Experiments were conducted to create a tungsten trioxide/bismuth vanadate (WO3/BiVO4)

photoelectrode that could efficiently hydrolyze water for the creation of hydrogen fuel.

WO3/BiVO4 alloys were created across a range of weight ratios to determine which film(s) had the

best structure and water splitting abilities. BiVO4 is currently the best performing photoelectrode

due to its bandgap that is well suited for absorbance of visible light, however it has poor charge

carrying capacity. WO3 has a bandgap that is better suited for absorbance of UV light and has a

better charge carrying capacity than BiVO4. Ideally, the creation of a WO3/BiVO4 photoelectrode

would solve the conductance issues of BiVO4 and produce an alloy with a large range of

absorbance. This metal oxide would be superior to either pure material. The films with the greatest

structure had the highest WO3 percentage, 60/40-80/20. Optimal performance in IPCE and APCE

was held by the 90/10 film which had a max IPCE of 1.45% at 360 nm and a max APCE of 3.4%

at 400nm.

Experimental

Bismuth chloride (BiCl3) and vanadyl acetylacetonate (VO(acac)2) were used as precursors for

BiVO4. Tungsten chloride (WCl6) was used as the precursor for WO3. 50 mg of PS-b-PEO was

dissolved in 2 mL THF and vortexed for 5 min to create a polymer solution. 0.06 mL of fuming

HCl was added to the polymer solution and vortexed for 5 min to induce persistent micelle

templating (PMT)1. The polymer solution was separated evenly into 1.5 mL aliquots which were

added to vials of WCl6 ranging from 12.83 mg to 115.41 mg to create WO3. BiVO4 precursors

were dissolved in ~6:1:1 AcHE (EtOH, Acetic Acid and fuming HCl) solution and 5 min of

vortexing. The BiVO4 solution was added to the WO3 vials in appropriate amounts to create 10/90

(0.0323 mol WO3/0.208 mol BiVO4) to 90/10 (0.291 mol WO3/0.0232 mol BiVO4) mol ratios of

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WO3/BiVO4 in increments of 20/80, 30/70, 40/60 etc. WO3/BiVO4 solution was deposited by spin

coating with a dwell time of 15 s and 1500 rpm onto mica (plasma-cleaned in ozone for 10 min)

for structural characterization. Kapton tape was used to mount the WO3/BiVO4 samples to the

SAXS machine holder. Structure control of the mesoporous and crystalline structure of the samples

were quantified using SAXS, MAXS, and WAXS. Samples that appeared to be well ordered were

selected for PEC characterization. WO3/BiVO4 solution was deposited on cleansed fluorine doped

tin oxide (FTO) by spin coating with a dwell time of 15s at 1500 rpm. FTO samples were calcined

at 450 °C for 1 hr. PEC measurements were performed using an electrolyte, 0.5 M potassium

borate (KB(OH)4), a hole scavenger, 0.2 M sodium sulfite (Na2SO4), and at a pH of 9.35.

Photoelectrochemical (PEC) characterization was performed to obtain data on incident photon-to-

current efficiency (IPCE), absorbance photon-to-current efficiency (APCE) and the photocurrent

response and is described in more detail elsewhere2

Results

Figure 1. SAXS characterization results across ratio of calcined WO3/BiVO4

films. Weight ratio of WO3 to BiVO4 is indicated by the legend.

Figure 1 displays the SAXS data from samples across the WO3/BiVO4 weight ratio. Samples

with higher ratios of WO3, 60/40, 70/30 and 90/10 WO3/BiVO4 , produced peaks under SAXS

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measurements while none of the samples with high BiVO4 content produced peaks. Peaks

represent order within the structure of the sample.

Figure 2. Photocurrent response for a calcined 80:20

WO3/BiVO4 film. The Dotted line is dark current, the dashed
line is backside illumination and the solid line is front side
illumination. A voltage, 1.23 V, is marked as the
thermodynamic potential to split water.

Figure 2 displays the absorbance of an 80/20 WO3/BiVO4 film for front side illumination, dark

current, and back side illumination photocurrent. The film had a maximum front-side illumination

photocurrent of 0.44 mA cm-2, dark current photocurrent of 0.28 mA cm-2 and back-side

illumination photocurrent of 0.36 mA cm-2 at a voltage of 1.23 V vs. RHE. Results were as

expected, the front-side illumination photocurrent was the highest due to the light having the

shortest distance and no obstructions to travel though to get to the film.

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 Figure 3. Absorbance profile across varying weight ratios of
WO3/BiVO4. Dotted line used to show plateau of 60/40
sample. Weight ratio of WO3 to BiVO4 is indicated in the
legend.

Figure 3 displays the absorption profile for the films at varying WO3/BiVO4 weight ratios. The

higher the WO3 percentage the higher the absorbance in the UV range and the lower the absorbance

in the visible light range. A plateau for 60/40 ratio occurred at 430 nm at 45% absorption.

Figure 4. Intrinsic photon-to-current across varying

weight ratios of WO3/BiVO4. Weight ratio of WO3 to
BiVO4 is indicated in the legend.

Figure 4 depicts IPCE across varying weight ratios of WO3/BiVO4. Maximum IPCE occurred

at 360 nm with 1.45% efficiency for the 90/10 WO3/BiVO4 film. WO3 rich films had higher

efficiencies at short wavelengths. A small increase in efficiency was observed in the 60/40

WO3/BiVO4 film at 480 nm due to the moderate presence of BiVO4.

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 Figure 5. Absorbance photon-to-current across varying
weight ratios of WO3/BiVO4. Weight ratio of WO3 to
BiVO4 is indicated in the legend.

Figure 5 depicts the APCE across varying weight ratios of WO3/BiVO4. Maximum APCE

occurred at 400nm with 3.4% efficiency for the 90/10 WO3/BiVO4 film. WO3 rich films had higher

efficiencies for shorter wavelengths. Small increase in efficiency was observed starting at 480 nm

for 90/10 and 60/40 WO3/BiVO4 films and at 500 nm for 80/20 WO3/BiVO4 due to BiVO4

absorbing light in the visible range.

Discussion

The purpose of these experiments was to create a mixed metal oxide photoelectrode that had

superior properties than that of the pure substances it was comprised of. In order to accomplish

this, a sol-gel recipe was developed so the mixed metal oxide system could be deposited onto mica

for structure characterization and FTO for PEC characterization.

PMT was an integral part of designing the mixed metal oxide system. According to the Steiner

group, even poorly structured macroporous films have superior photocatalytic properties to that of

their control group.3 Macroporous films are expected to have superior photocatalytic properties

than films without pores because the pores shorten the distance the electrons need to travel to

escape the film when they are excited. This rational was the basis of designing the mixed metal

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oxide as a mesoporous material. While other groups have looked at doping and homojunctions of

BiVO4,4 the experiments listed in this report were aimed at creating a mixed metal oxide. The

purpose of making a mixed metal oxide as opposed to doping or homojunctions is to create a film

that combines the qualities of and surpasses the qualities of the pure substances that were used to

create the mixed metal oxide.

Structure of the films were determined through the use of SAXS. According to Figure 1 the

only ratios that showed mesoporous morphology were the 60/40-90/10 WO3/BiVO4 films. Solvent

compatibility issues were the main reason for the BiVO4 rich films not performing as well as the

WO3 rich films. BiVO4 precursors require many polar solvents and are dissolved into a solution

that is more complex than the WO3 precursor. Compatibility between the precursors and polymer

are another issue plaguing the structure of the BiVO4 rich films. Finally, humidity control over the

reaction should be tested. After characterization of structure the films underwent PEC

characterization.

PEC testing showed that the films do split water, but rather poorly. All of the WO3 rich films

absorb more UV light than visible light. This is due to the large bandgap in WO3 which only allows

it to absorb in the UV range. Figure 3 shows that even 90/10 WO3/BiVO4 had some absorbance in

the visible light range due to its BiVO4 content. It is evident in the 60/40 WO3/BiVO4 that BiVO4

plays a large role in absorbing in the visible light range as a plateau occurs in the visible light range

at 430 nm. Figures 4 and 5 show how many photons at a certain wavelength are absorbed and are

converted into electrons. Figure 4 shows that 1.45% of all photons absorbed at 360 nm are

converted into electrons and Figure 5 shows that of the photons absorbed at 400 nm, only 3.4%

are converted into electrons. These low absorbance rates could be caused due to poor structure

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control, however the more likely cause is the WO3/BiVO4 solution failing to properly deposit onto

the FTO.

Control over the sol-gel recipe, structure and PEC characterization are integral parameters in

the creation of a mixed metal oxide photoelectrode. The experiments detailed in this report found

that WO3 rich samples had the best structure of the WO3/BiVO4 mixed metal oxide films and that

the WO3/BiVO4 photoelectrode produces photocurrent. Structure quality can be enhanced through

tighter control over the sol-gel recipe, specifically in finding a suitable polymer to use with the

polar solvents that BiVO4 precursors are added to. Improvements to the deposition method in terms

of spin coater speed, dwell time and application of additional layers of solution should be looked

into. Another consideration for improved film quality should be in the form of film treatments such

as aging. Ultimately, for the experiments listen in this report to be truly successful, order of the

BiVO4 rich samples must be improved for PEC characterization as they would have the ability to

absorb light at a greater wavelength range than the WO3 samples.

References

(1) Sarkar, A.; Stefik, M. J. Mater. Chem. A 2017.

(2) Lamm, B.; Sarkar, A.; Stefik, M. J. Mater. Chem. A 2017, Accepted (13).

(3) Li, L.; Krissanasaeranee, M.; Pattinson, S. W.; Stefik, M.; Wiesner, U.; Steiner, U.; Eder,

D. Chem. Commun. (Camb). 2010, 46 (40), 7620–7622.

(4) Abdi, F. F.; Han, L.; Smets, A. H. M.; Zeman, M.; Dam, B.; van de Krol, R. Nat.

Commun. 2013, 4, 2195.

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