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Title: Pb-Activated Amine-Assisted Photocatalytic Hydrogen Evolution Reaction on Organic–Inorganic Perovskites

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States); Soochow Univ., Jiangsu (China)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  3. Soochow Univ., Jiangsu (China)
Publication Date:
Research Org.:
California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1467624
Grant/Contract Number:  
SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 6; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Lu, Xiao, Hai, Cheng, Tao, Li, Youyong, and Goddard, III, William A. Pb-Activated Amine-Assisted Photocatalytic Hydrogen Evolution Reaction on Organic–Inorganic Perovskites. United States: N. p., 2018. Web. doi:10.1021/jacs.7b12028.
Wang, Lu, Xiao, Hai, Cheng, Tao, Li, Youyong, & Goddard, III, William A. Pb-Activated Amine-Assisted Photocatalytic Hydrogen Evolution Reaction on Organic–Inorganic Perovskites. United States. doi:10.1021/jacs.7b12028.
Wang, Lu, Xiao, Hai, Cheng, Tao, Li, Youyong, and Goddard, III, William A. Fri . "Pb-Activated Amine-Assisted Photocatalytic Hydrogen Evolution Reaction on Organic–Inorganic Perovskites". United States. doi:10.1021/jacs.7b12028. https://www.osti.gov/servlets/purl/1467624.
@article{osti_1467624,
title = {Pb-Activated Amine-Assisted Photocatalytic Hydrogen Evolution Reaction on Organic–Inorganic Perovskites},
author = {Wang, Lu and Xiao, Hai and Cheng, Tao and Li, Youyong and Goddard, III, William A.},
abstractNote = {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 CH3NH3PbI3 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 H2 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 H2 on CH3NH3PbI3 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.},
doi = {10.1021/jacs.7b12028},
journal = {Journal of the American Chemical Society},
number = 6,
volume = 140,
place = {United States},
year = {2018},
month = {1}
}

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