Electrochemical Phase Engineering of Anatase/Rutile/Brookite TiO<sub>2</sub> Nanopowders via Pulsed Alternating Current for Photocatalytic Water Remediation

Ulyankina, Anna; Kravchenko, Daria; Belichenko, Tatyana; Gorshenkov, Mikhail; Leontyev, Igor; Faddeev, Nikita; Yatsenko, Aleksey; Ponomarev, Denis; Rakhmatullin, Aydar; Zhigunov, Denis; Smirnova, Nina

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J. Electrochem. Sci. Technol > Accepted Articles

Research Article

DOI: https://doi.org/10.33961/jecst.2026.00059 [Accepted]
Published online May 4, 2026.

Electrochemical Phase Engineering of Anatase/Rutile/Brookite TiO₂ Nanopowders via Pulsed Alternating Current for Photocatalytic Water Remediation

Anna Ulyankina¹, Daria Kravchenko¹, Tatyana Belichenko¹, Mikhail Gorshenkov², Igor Leontyev³, Nikita Faddeev¹, Aleksey Yatsenko¹, Denis Ponomarev¹, Aydar Rakhmatullin⁴, Denis Zhigunov⁵, Nina Smirnova¹

¹Platov South-Russian State Polytechnic University (NPI), Novocherkassk 346428, Russia
²Department of Physical Materials Science, National University of Science and Technology (MISIS), Moscow 119049, Russia
³Department of Physics, Southern Federal University, 344090 Rostov-on-Don, Russia
⁴Conditions Extrêmes et Matériaux: Haute Température et Irradiation, CEMHTI, UPR 3079–CNRS Univ. Orléans, 45071 Orléans, France
⁵Center for Photonics and Quantum Materials, Skolkovo Institute of Science and Technology, Moscow 143026, Russian Federation

Correspondence: Anna Ulyankina,
Email: anya-barbashova@yandex.ru

Received: 28 January 2026 • Accepted: 25 April 2026

Abstract

Phase engineering of TiO₂ photocatalyst via high-throughput and sustainable approaches remains an intriguing challenge. This study presents a novel electrochemical strategy for the phase engineering of TiO₂ nanopowders derived from bulk Ti through pulsed alternating current (PAC) synthesis using aqueous NH4Cl electrolyte without any organic surfactants and solvents. The implementation of PAC significantly enhances the Ti dispersion rate and plays a critical role in the crystallization pathway of TiO₂ during the subsequent thermal annealing facilitating the formation of mixed phase anatase/rutile/brookite TiO₂ compared to unidirectional pulsed current. By modulating the pulse voltage (U_pulse) from 30 V to 55 V, followed by thermal annealing, the rutile content was tuned from 18.6% to 49.2%. The TiO₂ produced at U_pulse of 45 V and annealed at 500 ºC exhibited superior photocatalytic activity for 2,4-Dinitrophenol (DNP) degradation, attributed to an optimized anatase/rutile/brookite ratio (61.7/31.5/6.8%), along with enhanced surface acidity and specific surface area. The degradation of ciprofloxacin (CIP) was optimized in a flow UV photoreactor by varying a flow rate, TiO₂ loading, pH solution, and a low-power UV intensity. The solar-driven potential of electrochemically synthesized TiO₂ was validated using natural light irradiation. These findings provide valuable insights into the electrochemically driven phase engineering of TiO₂ and establish a scalable framework for the design of high-performance, multi-phase photocatalysts via PAC synthesis.

Keywords: TiO₂ nanopowders, Phase Engineering, Electrosynthesis, Pulsed alternating current, Photocatalysis