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Facile and scalable synthesis of Ti6Mn2 oxo-cluster nanocrystals with flower-like morphology and excellent photocatalytic properties

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Abstract

Three new phenylphosphonate (PhPO3) and salicylate (Sal) substituted heterometallic titanium-oxo clusters (ST-M), namely [Ti6Mn2O4(OEt)4(PhPO3)2(Sal)6(EtOH)2] (ST-Mn), [Ti6Zn2O4(OEt)4(PhPO3)2(Sal)6(EtOH)2(H2O)2] (ST-Zn) and [Ti6Tb2O4(OiPr)4(PhPO3)2(Sal)6Cl2(iPrOH)2iPrOH (ST-Tb), were synthesized. The most impressive structural feature of these compounds is the calixarene-type carboxylate endpoint in the Ti6-oxo core, which can readily capture metal ions with different radii and coordination geometries, for example, Mn2+, Zn2+ and Tb3+ ions in this case, to generate neutral mixed-metal Ti6M2-oxo clusters. Flower-like ST-Mn (denoted as FST-Mn) nanocrystals formed by nanosheets can be facilely obtained in gram-scale quantities from a simple solution reaction using Triton X-100 as a conditioning agent. The catalytic activity of these materials was evaluated by photocatalytic degradation of rhodamine B (RhB), among which FST-Mn showed the highest catalytic activity. Under visible light, 93.0% of RhB (50 ppm, 100 mL) was decomposed within 30 min catalyzed by FST-Mn without adding hydrogen peroxide, which is quite preeminent among Ti based catalysts. The catalytic decomposition efficiency under the same experimental conditions was 80.0% for ST-Mn, 24.6% for ST-Zn and 17.6% for ST-Tb. Investigation of the degradation mechanism showed that h+ and ·OH were the dominant active species in the decomposition of RhB. Moreover, the reusability and stability of FST-Mn were also verified.

Graphical abstract: Facile and scalable synthesis of Ti6Mn2 oxo-cluster nanocrystals with flower-like morphology and excellent photocatalytic properties

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Supplementary files

Article information


Submitted
25 Dec 2019
Accepted
22 Jan 2020
First published
24 Jan 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Facile and scalable synthesis of Ti6Mn2 oxo-cluster nanocrystals with flower-like morphology and excellent photocatalytic properties

K. Zhang, P. Lin and S. Du, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04886C

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