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Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution

Nature Energy volume 2, Article number: 16185 (2017) Cite this article

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Abstract

The solar-driven splitting of hydrohalic acids (HX) is an important and fast growing research direction for H2 production. In addition to the hydrogen, the resulting chemicals (X2/X3−) can be used to propagate a continuous process in a closed cycle and are themselves useful products. Here we present a strategy for photocatalytic hydrogen iodide (HI) splitting using methylammonium lead iodide (MAPbI3) in an effort to develop a cost-effective and easily scalable process. Considering that MAPbI3 is a water-soluble ionic compound, we exploit the dynamic equilibrium of the dissolution and precipitation of MAPbI3 in saturated aqueous solutions. The I− and H+ concentrations of the aqueous solution are determined to be the critical parameters for the stabilization of the tetragonal MAPbI3 phase. Stable and efficient H2 production under visible light irradiation was demonstrated. The solar HI splitting efficiency of MAPbI3 was 0.81% when using Pt as a cocatalyst.

Splitting hydrogen iodide (HI) to generate H2 has been extensively investigated, especially in thermochemical water splitting processes1,2,3. When iodine and sulfur participate in this process, in the form of hydrogen iodide and sulfuric acid, hydrogen from the water splitting can be continuously generated with high efficiency in a large-scale closed system, known as the iodine–sulfur cycle. Because of the thermodynamic requirement for high temperatures, centralized production systems coupled with nuclear power have been explored the most4,5,6,7.

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Figure 1: Dynamic equilibrium between MAPbI3 powder and aqueous HI solution.
Figure 2: Phase conversion of MAPbI3 powder in aqueous HI solution with various [I−] and [H+].
Figure 3: Characterization of MAPbI3 powder for band diagram construction.
Figure 4: Photocatalytic reaction results of the MAPbI3 powder in a saturated solution system for HI splitting.
Figure 5: H2 evolution activity of various MAPbI3 catalyst systems and at various light intensities.

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  • 14 July 2017

    In the PDF version of this article previously published, the year of publication provided in the footer of each page and in the 'How to cite' section was erroneously given as 2017, it should have been 2016. This error has now been corrected. The HTML version of the article was not affected.

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Acknowledgements

This research was supported by the Global Frontier R&D Program of the Center for Multiscale Energy System funded by the National Research Foundation under the Ministry of Science, ICT & Future, Korea (2012M3A6A7054855), by KIST Institutional Program (0543-20160004), and by the Ministry of Trade, Industry & Energy (MOTIE) under Industrial Strategic Technology Development Program, Korea (0417-2016-0019).

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Author notes

  1. Sunghak Park and Woo Je Chang: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Seoul National University, Seoul 151-744, Korea

    Sunghak Park, Chan Woo Lee, Sangbaek Park, Hyo-Yong Ahn & Ki Tae Nam

  2. Interdisciplinary Program for Bioengineering, Seoul National University, Seoul 151-742, Korea

    Woo Je Chang & Ki Tae Nam

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  1. Sunghak Park
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Contributions

K.T.N. conceived and supervised the project. S.P. conceived, synthesized and characterized the MAPbI3 inside the aqueous solution system, designed experiments and co-wrote the manuscript. W.J.C. characterized the photocatalytic reaction and co-wrote the manuscript. C.W.L. and S.P. supported analysis of the GC data of HI splitting reaction. H.-Y.A. measured the SEM image of MAPbI3 powder. The manuscript was mainly written and revised by K.T.N., S.P. and W.J.C. All authors discussed the results and commented on the manuscript.

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Correspondence to Ki Tae Nam.

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Supplementary information

Supplementary Information

Supplementary Figures 1–14, Supplementary Table 1 and 2, Supplementary References. (PDF 1539 kb)

Supplementary Video 1

Phase change of MAPbI3 powder (black) into MAPb(I1−xBrx)3 (orange) immediately after dipping into HBr saturated solution (transparent) because of the dynamic equilibrium between powder and saturated solution, with the powder changing colour from black to orange as the Br atoms substituted and the solution changing to yellow due to I atoms dissolving into the solution resulting in the formation of PbI3− ions. (AVI 32912 kb)

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Park, S., Chang, W., Lee, C. et al. Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution. Nat Energy 2, 16185 (2017). https://doi.org/10.1038/nenergy.2016.185

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