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In Silico Optimization of Organic-Inorganic Hybrid Perovskites for Photocatalytic Hydrogen Evolution Reaction in Acidic Solution

Wang, Lu and Goddard, William A., III and Cheng, Tao and Xiao, Hai and Li, Youyong (2018) In Silico Optimization of Organic-Inorganic Hybrid Perovskites for Photocatalytic Hydrogen Evolution Reaction in Acidic Solution. Journal of Physical Chemistry C, 122 (36). pp. 20918-20922. ISSN 1932-7447. http://resolver.caltech.edu/CaltechAUTHORS:20180806-125347513

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Abstract

We previously reported the atomistic reaction mechanism for the photocatalytic hydrogen evolution reaction (HER) on the CH_3NH_3PbI_3 organic–inorganic hybrid perovskites based on quantum mechanics calculations of the transition-state barriers, including several layers of explicit acidic solvent. Here, we extend these studies using in silico optimization to discover additional promising photocatalysts. We consider replacing (i) Pb with Sn, (ii) I with Br, and (iii) CH_3NH_3 cation with several organic cations, including NH_2(CH)NH_2 cation as the photocatalyst for HER. We compared the activation barriers and reaction energies for each case. In our previous studies, we found that both H atoms of the H_2 product are extracted from surface organic cations with protons from the solution migrating along Grotthuss water chains to replace the H of the organic cations. This two-step reaction mechanism involves formation of an intermediate lead hydride bond, with the lead atoms and the surface organic cations both playing essential roles. Among the perovskites investigated here, we predict that NH_2(CH)NH_2PbI_3 exhibits the best HER performance with a predicted 10-fold improvement in the reaction rate compared to CH_3NH_3PbI_3. We also suggest that the lead-free tin iodide perovskites might exhibit a rate comparable to that of lead iodide perovskites with the same organic cations. However, replacing iodine by bromine significantly increases the activation barrier. We find for these lead iodide perovskites, the increased proton affinity of the surface organic cations enhances the photocatalytic efficiency, with NH2(CH)NH2 the best case examined.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/acs.jpcc.8b07380DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.8b07380PublisherSupporting Information
ORCID:
AuthorORCID
Wang, Lu0000-0001-5263-3123
Goddard, William A., III0000-0003-0097-5716
Cheng, Tao0000-0003-4830-177X
Xiao, Hai0000-0001-9399-1584
Li, Youyong0000-0002-5248-2756
Additional Information:© 2018 American Chemical Society. Received: July 31, 2018; Published: August 4, 2018. This work was supported by the National Key Research and Development Program of China (Grants 2018YFB0703900, 2017YFA0204800 and 2017YFB0701600), the National Natural Science Foundation of China (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. The work was carried out at National Supercomputer Center in Tianjin, and the calculations were performed on TianHe-1 (A). 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.
Group:JCAP
Funders:
Funding AgencyGrant Number
National Key Research and Development Program of China2018YFB0703900
National Key Research and Development Program of China2017YFA0204800
National Key Research and Development Program of China2017YFB0701600
National Natural Science Foundation of China51761145013
National Natural Science Foundation of China21673149
Joint Center for Artificial Photosynthesis (JCAP)UNSPECIFIED
Department of Energy (DOE)DE-SC0004993
Priority Academic Program Development of Jiangsu Higher Education InstitutionsUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1293
Record Number:CaltechAUTHORS:20180806-125347513
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180806-125347513
Official Citation:In Silico Optimization of Organic–Inorganic Hybrid Perovskites for Photocatalytic Hydrogen Evolution Reaction in Acidic Solution. Lu Wang, William A. Goddard, III, Tao Cheng, Hai Xiao, and Youyong Li. The Journal of Physical Chemistry C 2018 122 (36), 20918-20922. DOI: 10.1021/acs.jpcc.8b07380
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88603
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:06 Aug 2018 22:25
Last Modified:03 Oct 2018 20:38

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