Photocatalytic Oxidation of Dissolved Mn2+ by TiO2 and the Formation of Tunnel Structured Manganese Oxides

Jung, Haesung; Snyder, Colin; Xu, Wenqian; Wen, Ke; Zhu, Mengqiang; Li, Yan; Lu, Anhuai; Tang, Yuanzhi

doi:10.1021/acsearthspacechem.1c00154

Photocatalytic Oxidation of Dissolved Mn²⁺ by TiO₂ and the Formation of Tunnel Structured Manganese Oxides

Journal Article · Mon Aug 09 00:00:00 EDT 2021 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.1c00154· OSTI ID:1865089

^[1]; Snyder, Colin ^[2]; Xu, Wenqian ^[3]; ^[4]; ^[4]; Li, Yan ^[5]; Lu, Anhuai ^[5]; ^[2]

Georgia Inst. of Technology, Atlanta, GA (United States); Changwon National University (Korea, Republic of)
Georgia Inst. of Technology, Atlanta, GA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Wyoming, Laramie, WY (United States)
Peking Univ., Beijing (China)

The redox reaction of manganese (Mn) is of great environmental, geological, and public health significance, as Mn oxides control the distribution and electron flow of numerous nutrients and contaminants in natural and engineered environments. Current understanding on the oxidation pathways of Mn(II) to Mn(III/IV) mainly focuses on biotic processes due to their much higher oxidation rates than those of abiotic processes. This study demonstrates rapid photocatalytic oxidation of Mn²⁺(aq) under circumneutral conditions catalyzed by naturally abundant semiconducting TiO₂ minerals. Notably, the photocatalytic oxidation rates are comparable to or even higher than those of reported biotic/abiotic processes. In addition, the rapid photocatalytic oxidation leads to the formation of large tunnel structured Mn oxides (todorokite and romanechite) on the surface of TiO₂. These findings suggest that photocatalytic oxidation of Mn²⁺(aq) by natural semiconducting minerals is likely an important yet previously overlooked pathway for understanding the occurrence of natural Mn oxide coatings on rock surfaces. In addition, considering the increasing input of photoreactive engineered nanoparticles into environmental systems, this work shows the potential impacts of nanoparticles on influencing natural redox cycles.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Research Foundation (NRF) of Korea; National Science Foundation (NSF); National Science Foundation of China; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515; SC0012704

OSTI ID:: 1865089

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 8 Vol. 5; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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