4.7 Article

Topotactic Transformation of Solvated MgCr-LDH Nanosheets to Highly Efficient Porous MgO/MgCr2O4 Nanocomposite for Photocatalytic H-2 Evolution

Journal

INORGANIC CHEMISTRY
Volume 57, Issue 14, Pages 8646-8661

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b01517

Keywords

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Funding

  1. Siksha 'O' Anusandhan Deemed to be University

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The hybrid structure of nanoparticles (NPs) with nano sheets has the advantage of both anisotropic properties of NPs and large specific surface areas of nanosheets, which is desirable for many technological applications. In this study, MgCr2O4 spine] NPs decorated on highly porous MgO nanosheets forming MgO/MgCr2O4(x) nano composites were synthesized by a one pot coprecipitation method followed by a heat treatment process of the solvated wet gel of MgCrLDH with polar solvent N,N-dimethylformamide (DMF) at 400 degrees C. This novel synthetic methodology generates materials consisting of porous metal oxides nanosheets adhered with spinel phase NPs due to the slow generation of gases such as H2O, CO2, and NH3 under moderate temperature during the heat treatment process. The synergistic effect of much wider band gap MgO nanosheets and narrow band gap MgCr2O4 NPs added increased stability due to the stronger bonding coordination of MgCr2O4 NPs with MgO nanosheets. The obtained MgO/MgCr2O4(x) nanocomposites possess large specific surface areas, highly porous structure, and excellent interface between MgCr2O4 NPs and MgO nanosheets, which proved from N-2 sorption isotherm, TEM, HR-TEM study. With metallic ratio of MgCr3:1, MgO/MgCr2O4(MgCr3:1) nanocomposites exhibit highest H-2 evolution rate of 840 mu molg(-1)2h(-1), which was 2 times higher than that of pure MgCr2O4(420 mu molg(-1)2h(-1)). The LSV measurement study of MgO/MgCr2O4 (MgCr3:1) nanocomposite shows an enhancement of light current density of 0.22 mu A/cm(2) at potential bias of -1.1 V. The Mott-Schottky analysis suggested the band edge positions of the n-type constituents and formation of n-n type heterojunctions in MgO/MgCr2O4 (MgCr3:1) nanocomposite, which facilitates the flow of charge carriers. The EIS and Bode phase plot of MgO/MgCr2O4 (MgCr3:1) nanocomposite signifies the lower interfacial charge transfer resistance and higher lifetime of electrons (2.7 ms) for enhanced H-2 production. Lastly, the enhanced photocatalytic H-2 production activity and long-term stability of MgO/MgCr2O4(MgCr3:1) could be attributed to maximum specific surface area, porous structure, close intimacy contact angle between two cubic phases of MgCr2O4 NPs and MgO nanosheets, abundant oxygen vacancies sites, reduced charge transfer resistance and suitable band edge potential to drive the thermodynamic energy for H-2 production. This work highlighted an effective strategy for the synthesis of cost-effective 2D porous heterojunctions nanocomposite photocatalyst for promising applications in the field of clean H-2 production utilizing abundant solar energy.

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