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Published February 14, 2018 | Supplemental Material
Journal Article Open

Pb-activated Amine-assisted Photocatalytic Hydrogen Evolution Reaction on Organic-Inorganic Perovskites


We report here the reaction mechanism for explicit aqueous solvent quantum mechanics (QM) studies determining the energetics and reaction barriers for the photocatalytic hydrogen evolution reaction (HER) on CH_3NH_3PbI_3 surface. We find that both the lead (Pb) atoms and the surface organic molecules play essential roles, leading to a two-step Pb-activated amine-assisted (PbAAA) reaction mechanism involving an intermediate lead hydride state. Both H of H_2 product are extracted from surface organic molecules, while two protons from the solution migrate along water chains via the Grotthuss mechanism to replace the H in organic molecule. We obtain a reaction barrier of 1.08 eV for photochemical generation of H_2 on CH_3NH_3PbI_3 compared to 2.61 eV for the dark reaction. We expect this HER mechanism can also apply to the other organic perovskites, but the energy barriers and reaction rates may depend on the basicity of electrolyte and intrinsic structures of perovskites.

Additional Information

© 2018 American Chemical Society. Received: November 13, 2017; Published: January 19, 2018. This work was supported by the National Key Research and Development Program of China (Grants 2017YFA0204800 and 2017YFB0701600), the National Natural Science Foundation of China (Grants 21403146, 51761145013, 21673149). This research was also supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No.DE-SC0004993. This project is also supported by the Fund for Collaborative Innovation Center of Suzhou Nano Science & Technology, the Priority Academic Program Development of Jiangsu Higher Education Institutions. The authors declare no competing financial interest.

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