Influence of anodic oxidation and post-processing

conditions on the morphology and photocatalytic

properties of nanostructured WO3 layers

Original article by: Yulia Nazarkina, Vladislav

Rusakov, Anton Salnikov, Alexey Dronov and
Daria Dronova
Presentation by: Vladislav Rusakov

Moscow, 2019
 Environmentally-friendly water
and air purification from organic Self-cleaning and self-sterilizing surfaces
pollutants

Photocatalysis applications

Organic synthesis Alternative fuel manufacturing:

conversion of water to hydrogen
gas

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 Photocatalytic materials

TiO2: energy gap of 3.2 eV : requires UV WO3: energy gap of 2.8 eV : works
under visible light

Improvement of photocatalytic
properties of WO3
component in composite photocatalytic
materials like WO3/ZnO and WO3/TiO2

improvement of the effective surface area of

the photocatalyst

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 Sample preparation

• W foils (99.93% purity, 20 micrometer thickness)

• ultrasonic cleaning (acetone, 10 minutes)

• washing (here and further) in deionized water
• drying in air stream
• electrochemical polishing (2.5 M NaOH, 40 seconds; potentiostatic
mode, U=20 V)
• anodization in potentiostatic and galvanostatic modes (depending
on the electrolyte used), with thermostabilization and stirring
• thermal treatment in air (temperature: 500 °С, duration: 2 hours)

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 Aqueous fluorine-containing electrolyte

Tungsten foil anodization process variables in fluorine-containing electrolytes.

Electrolyte Anodization time t, Voltage U, V Temperature T,
min °С
0,5% NH4F (aq) 30 60 20
40 20
20 20
1 M Na2SO4, 0.7 wt% 15 40 7-8
NH4F (aq)
0.15 м NaF (aq) 120 60 4-5

Digital images of anodized W samples, obtained in aqueous electrolytes, containing: a)

0,5 wt% NH4F (aq), b) 0,15 M NaF, c) 1 M Na2SO4, 0.7 wt% NH4F (aq). 5
.
Fluorine-containing ethylene glycol-based electrolyte

Process variables of tungsten foil anodization in

fluorine-containing ethylene glycol-based electrolytes.

Electrolyte Anodization Voltage Temperature

time t, min U, V T, °С
0,5% NH4F (EG) 30 60 7-8
40
20
0,5% NH4F (EG) 15 60 7-8
40
0,5% NH4F (EG) 5 60 7-8
40

Cross section FESEM images of the WO3 samples surfaces,

formed in solution 0,5% NH4F:EG: a) T=5 °С, U=20V, t=30
min; b) T=7-8 °С, U=60V, t=5 min; c)T=7-8 °С, U=60V, t=15
min. Insets: top view of the islets of nanostructured
tungsten oxide. 6
Ethylene glycol-based fluoride-free electrolyte

Process variables of tungsten foil anodization in

NH4NO3: EG: 1% H2O.
Electrolyte
Anodization Voltage U, Temperature
time t, min V T, °С
NH4NO3:EG: 360 20 40
1% H2O

FESEM images of the WO3 samples surfaces, formed in

solution NH4NO3: EG:1% H2O, a) T = 40̊С, U = 20V, t = 360
min, without annealing; b) after annealing for 1 h at
500C.

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 Phosphoric acid electrolyte
Process variables of tungsten foil anodization in H3PO4.
Temperature Current density j, Anodization time
T, °С mA/cm2 t, min
20 15 30
100 1 60, 80, 90, 240
100 6 5,6,15,20,23
100 7 45, 60

FESEM images of the WO3 samples surfaces, formed in H3PO4 at 100° С:

c) j = 1 mA/cm2, t= 90 min, d) j = 1 mA/cm2, t= 240 min.
Insets: chronopotentiometric curves of anodic oxidation.
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 Photocatalytic properties

Kinetics of MB decomposition at 20⁰C.

Rate constants of MB decomposition.

Photocatalyst Rate constant
Barrier layer 0,00499
H3PO4 0,00603
NH4NO3:EG: 1% H2O 0,00690
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 Summary

• Samples with homogeneous nanostructured tungsten oxide layers with a high

effective surface area were obtained in two types of electrolytes, with the following
process variables:

1. 85wt% H3PO4 at T=100°C, j = 1 mA/cm2, t= 90 min;

2. NH4NO3:EG: 1% H2O at T = 40°С, U = 20V, t = 360 min.

• The morphology of samples prepared in phosphoric acid strongly depends on the

process temperature and the accuracy of its control, making it a less technologically
versatile process than preparation in ammonium nitrate ethylene glycol-based
electrolyte.

• The nanostructured sample formed in NH4NO3:EG: 1% H2O is 1.14 times more

efficient photocatalyst than that one formed in H3PO4 and 1.38 times more efficient
than barrier layer of WO3.

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Thank you for your attention.

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