Open AccessTailoring Surface Frustrated Lewis Pairs of In 2 O 3− x (OH) y for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO 2 by Isomorphous Substitution of In 3+ with Bi 3+
Author(s) -
Dong Yuchan,
Ghuman Kulbir Kaur,
Popescu Radian,
Duchesne Paul N.,
Zhou Wenjie,
Loh Joel Y. Y.,
Ali Feysal M.,
Jia Jia,
Wang Di,
Mu Xiaoke,
Kübel Christian,
Wang Lu,
He Le,
Ghoussoub Mireille,
Wang Qiang,
Wood Thomas E.,
Reyes Laura M.,
Zhang Peng,
Kherani Nazir P.,
Singh Chandra Veer,
Ozin Geoffrey A.
Publication year - 2018
Publication title -
advanced science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.388
H-Index - 100
ISSN - 2198-3844
DOI - 10.1002/advs.201700732
Subject(s) - lewis acids and bases , frustrated lewis pair , chemistry , steric effects , heterolysis , photocatalysis , catalysis , density functional theory , borane , reactivity (psychology) , oxide , hydride , crystallography , stereochemistry , computational chemistry , organic chemistry , medicine , hydrogen , alternative medicine , pathology
Frustrated Lewis pairs (FLPs) created by sterically hindered Lewis acids and Lewis bases have shown their capacity for capturing and reacting with a variety of small molecules, including H 2 and CO 2 , and thereby creating a new strategy for CO 2 reduction. Here, the photocatalytic CO 2 reduction behavior of defect‐laden indium oxide (In 2 O 3− x (OH) y ) is greatly enhanced through isomorphous substitution of In 3+ with Bi 3+ , providing fundamental insights into the catalytically active surface FLPs (i.e., InOH···In) and the experimentally observed “volcano” relationship between the CO production rate and Bi 3+ substitution level. According to density functional theory calculations at the optimal Bi 3+ substitution level, the 6s 2 electron pair of Bi 3+ hybridizes with the oxygen in the neighboring InOH Lewis base site, leading to mildly increased Lewis basicity without influencing the Lewis acidity of the nearby In Lewis acid site. Meanwhile, Bi 3+ can act as an extra acid site, serving to maximize the heterolytic splitting of reactant H 2 , and results in a more hydridic hydride for more efficient CO 2 reduction. This study demonstrates that isomorphous substitution can effectively optimize the reactivity of surface catalytic active sites in addition to influencing optoelectronic properties, affording a better understanding of the photocatalytic CO 2 reduction mechanism.