Ni-Fe Oxides/TiO2 Heterojunction Anodes for Reactive Chlorine Generation and Mediated Water Treatment

Evandi Rahman; Sukhwa Hong; Jaesang Lee; Seok Won Hong; Kangwoo Cho

doi:10.1021/acsami.3c00581

Ni-Fe Oxides/TiO₂ Heterojunction Anodes for Reactive Chlorine Generation and Mediated Water Treatment

ACS Appl Mater Interfaces. 2023 Apr 12;15(14):17867-17878. doi: 10.1021/acsami.3c00581. Epub 2023 Mar 29.

Authors

Evandi Rahman^{1

2}, Sukhwa Hong³, Jaesang Lee⁴, Seok Won Hong^{1

2}, Kangwoo Cho^{3

5}

Affiliations

¹ Division of Energy and Environment Technology, KIST-School, University of Science and Technology, Seoul 02792, Republic of Korea.
² Water Cycle Research Center, Korea Institute of Science and Technology, Hwarangro 14 gil, Seongbuk-gu, Seoul 136-791, Republic of Korea.
³ Division of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 790-784, Korea.
⁴ Civil, Environmental, and Architectural Engineering, Korea University, Seoul 136-701, Korea.
⁵ Institute for Convergence Research and Education in Advanced Technology (I-CREATE), Yonsei University International Campus, Incheon 21983, Republic of Korea.

PMID: 36988213
DOI: 10.1021/acsami.3c00581

Abstract

Reactive chlorine-mediated electrochemical water treatment necessitates selective chlorine evolution reaction (ClER) versus parallel oxygen evolution reaction (OER) in mild pH (7-10), with minimal deployments of precious electrocatalysts. This study reports Ni_0.33Fe_0.67O_y/TiO₂ heterojunction anode prepared by a straightforward sol-gel coating with thermal decomposition at 425 °C. The ClER current efficiency (CE, 70%) and energy efficiency (2.3 mmol W h^-1) were comparable to benchmarking Ir₇Ta₃O_y/TiO₂ at 30 mA cm^-2 in 50 mM NaCl solutions with near-neutral pH. Correlations of ClER CE of variable Ni_xFe_1-xO_y/TiO₂ (x: 0.33, 0.8-1) with the flat-band potential and p-band center, as experimental descriptors for surface charge density, nominated the outer TiO₂ to be the active ClER center. The underlying Ni_0.33Fe_0.67O_y, characterized as biphasic NiFe₂O₄ and NiO, effectively lowered the O binding energy of TiO₂ by electronic interaction across the junction. The OER activity of Ni_0.33Fe_0.67O_y superior to the other Fe-doped Ni oxides suggested that the conductive OER intermediates generated on Ni_0.33Fe_0.67O_y could also facilitate the ClER as an ohmic contact. Stability tests and NH₄⁺ degradation in synthetic and real wastewater confirmed the feasibility of Ni_0.33Fe_0.67O_y/TiO₂ heterojunction anode for mediated water treatments in mild pH.

Keywords: Ni−Fe oxide; TiO2; chlorine evolution reaction; descriptor; water treatment.