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Highly efficient visible-light-driven reduction of Cr(vi) from water by porphyrin-based metal–organic frameworks: effect of band gap engineering on the photocatalytic activity

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Abstract

Highly efficient visible-light-assisted photocatalytic reduction of Cr(VI) to Cr(III) from water using multifunctional Zr(IV)-porphyrin MOFs, Zr63-OH)8(OH)8(MTCPP)2, (PCN-222(M)) (M = H2, ZnII, CuII, NiII, CoII, FeIIICl, and MnIIICl) is presented. The remarkable chemical stability of these Zr-MOFs in water and the visible-light harvesting property of the porphyrin-linker promoted efficient photocatalytic activity for the reduction of Cr(VI) to Cr(III) in the aqueous phase. Interestingly, the pristine MOF, PCN-222, showed an unprecedentedly high photocatalytic activity with 100% reduction of Cr(VI) to Cr(III) within 25 min with the highest rate (0.1289 min−1) amongst the MOFs reported so far. The superior photocatalytic activity of PCN-222 (no metal) over PCN-222(M) MOFs has been attributed to its lower band gap and efficient transfer of photo-excited electrons to the catalytic site, supported by combined experimental and theoretical studies. Remarkably, the PCN-222 MOF catalyst could be reused for up to 10 cycles without significant loss of catalytic activity. Further, a detailed mechanistic investigation of the visible light-assisted photoreduction of Cr(VI) by combined experimental and theoretical studies is presented. Overall, this work represents a unique demonstration of the influence of band gap engineering of porphyrin MOFs for efficient aqueous-phase photoreduction of Cr(VI) from water under visible light irradiation.

Graphical abstract: Highly efficient visible-light-driven reduction of Cr(vi) from water by porphyrin-based metal–organic frameworks: effect of band gap engineering on the photocatalytic activity

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Article information


Submitted
11 May 2020
Accepted
09 Sep 2020
First published
09 Sep 2020

Catal. Sci. Technol., 2020, Advance Article
Article type
Paper

Highly efficient visible-light-driven reduction of Cr(VI) from water by porphyrin-based metal–organic frameworks: effect of band gap engineering on the photocatalytic activity

N. Sharma, A. K. Dey, R. Y. Sathe, A. Kumar, V. Krishnan, T. J. D. Kumar and C. M. Nagaraja, Catal. Sci. Technol., 2020, Advance Article , DOI: 10.1039/D0CY00969E

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