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Improved photoelectrocatalytic activity of anodic TiO2 nanotubes by boron in situ doping coupled with geometrical optimization: Application of a potent photoanode in the purification of dye wastewater

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Abstract

A comparative study on the photoelectrocatalytic activity of anodic TiO2 nanotubes (TNTs) and boron-doped TiO2 nanotubes (BTNTs) was performed through fabricating them in two distinguished fluoride-containing electrolytes, namely NH4F and NH4BF4. Furthermore, by applying anodization voltage (in the range of 40–60 V) as a regulating factor, an analogy was drawn between morphologies, optical properties, photoelectrochemical features, and photoelectrocatalytic activities of both TNTs and BTNTs. The results revealed that using NH4BF4 not only led to the introduction of boron into TiO2 lattices but also resulted in shorter nanotubes owing to their less corrosive effect compared with NH4F. Furthermore, anodization voltage had a significant impact on the optical properties; with increasing the voltage to 60 V, a red shift occurred in the band edge of both TNTs (from 3.05 to 2.8 eV) and BTNTs (from 2.9 to 2.6 eV). Particularly, via anodization at 60 V in NH4BF4 instead of NH4F, the photocurrent density and photoconversion efficiency increased from 0.19 to 0.67 Ma cm−2 and from 0.12 to 0.270%, respectively. Moreover, methylene blue degradation tests showed that BTNTs had an outstanding photoelectrocatalytic activity in comparison to TNTs; in this regard, the sample synthesized at 60 V in NH4BF4 rather than NH4F enhanced PEC degradation efficiency from 79 to 100% under UV irradiation. Finally, the kinetics investigation confirmed that all photoelectrocatalytic reactions in both groups followed the first-order kinetics.

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Acknowledgments

The authors would gracefully like to acknowledge Iran National Science Foundation (INSF) with Grant No: 97025674 for their unspeakable financial support.

Nomencalture

ERHE Reversible hydrogen electrode potential (V).

EAg/AgCl Ag/AgCl electrode potential (V).

E°Ag/AgCl Ag/AgCl standard electrode potential (V).

Dint Nanotubes’ inner diameter (nm).

L Nanotubes’ length (μm).

w Nanotubes’ wall thickness (nm).

Dext Nanotubes’ outer diameter (nm).

SA Nanotubes’ surface area (m2 m−2).

α Light absorption constant.

ϑ Radiation frequency.

A Planck constant.

Eg Band gap energy (eV).

ε Photoconversion efficiency.

jp Photocurrent density (mA cm−2).

E°rev Reversible standard potential (V).

Eapp Absolute potential applied to the photoanode (V).

I0 Intensity of light radiation.

Emeas Photoanode potential (V).

Eoc Open–circuit potential of photoanode (V).

C0 Initial concentration of methylene blue (ppm).

C Concentration of methylene blue at time “t” (ppm).

r Photoelectrocatalytic reaction rate (ppm min−1).

K Adsorption constant.

k Rate constant (min−1).

t Photoelectrocatalytic degradation time (min).

kapp Apparent rate constant (min−1).

UV Ultra-violet radiation.

Funding

The authors has financial support from the Iran National Science Foundation (INSF) with Grant No: 97025674.

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Authors and Affiliations

  1. Fouman Faculty of Engineering, College of Engineering, University of Tehran, P. O. Box 43515-1155, Fouman, 43516-66456, Iran

    Rezgar Habibi, Javad Vahabzadeh Pasikhani & Azadeh Ebrahimian Pirbazari

  2. Department of Chemical Engineering, University of Guilan, Rasht, 41996-13776, Iran

    Neda Gilani

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  1. Rezgar Habibi
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Correspondence to Neda Gilani.

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Habibi, R., Gilani, N., Pasikhani, J.V. et al. Improved photoelectrocatalytic activity of anodic TiO2 nanotubes by boron in situ doping coupled with geometrical optimization: Application of a potent photoanode in the purification of dye wastewater. J Solid State Electrochem 25, 545–560 (2021). https://doi.org/10.1007/s10008-020-04825-6

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