Abstract
Heterogeneous catalysts with atomically defined active centers hold great promise for high-performance applications. Among them, catalysts featuring active moieties with more than one metal atom are important for chemical reactions that require synergistic effects but are rarer than single atom catalysts (SACs). The difficulty in synthesizing such catalysts has been a key challenge. Recent progress in preparing dinuclear heterogeneous catalysts (DHCs) from homogeneous molecular precursors has provided an effective route to address this challenge. Nevertheless, only side-on bound DHCs, where both metal atoms are affixed to the supporting substrate, have been reported. The competing end-on binding mode, where only one metal atom is attached to the substrate and the other metal atom is dangling, has been missing. Here, we report the first observation that end-on binding is indeed possible for Ir DHCs supported on WO3. Unambiguous evidence supporting the binding mode was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy and high-angle annular dark-field scanning transmission electron microscopy. Density functional theory calculations provide additional support for the binding mode, as well as insights into how end-on bound DHCs may be beneficial for solar water oxidation reactions. The results have important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions.
| Original language | English |
|---|---|
| Pages (from-to) | 1166-1172 |
| Number of pages | 7 |
| Journal | ACS Central Science |
| Volume | 4 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - Sep 26 2018 |
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ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
Cite this
End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation. / Zhao, Yanyan; Yan, Xingxu; Yang, Ke R.; Cao, Sufeng; Dong, Qi; Thorne, James E.; Materna, Kelly L.; Zhu, Shasha; Pan, Xiaoqing; Flytzani-Stephanopoulos, Maria; Brudvig, Gary W; Batista, Victor S.; Wang, Dunwei.
In: ACS Central Science, Vol. 4, No. 9, 26.09.2018, p. 1166-1172.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation
AU - Zhao, Yanyan
AU - Yan, Xingxu
AU - Yang, Ke R.
AU - Cao, Sufeng
AU - Dong, Qi
AU - Thorne, James E.
AU - Materna, Kelly L.
AU - Zhu, Shasha
AU - Pan, Xiaoqing
AU - Flytzani-Stephanopoulos, Maria
AU - Brudvig, Gary W
AU - Batista, Victor S.
AU - Wang, Dunwei
PY - 2018/9/26
Y1 - 2018/9/26
N2 - Heterogeneous catalysts with atomically defined active centers hold great promise for high-performance applications. Among them, catalysts featuring active moieties with more than one metal atom are important for chemical reactions that require synergistic effects but are rarer than single atom catalysts (SACs). The difficulty in synthesizing such catalysts has been a key challenge. Recent progress in preparing dinuclear heterogeneous catalysts (DHCs) from homogeneous molecular precursors has provided an effective route to address this challenge. Nevertheless, only side-on bound DHCs, where both metal atoms are affixed to the supporting substrate, have been reported. The competing end-on binding mode, where only one metal atom is attached to the substrate and the other metal atom is dangling, has been missing. Here, we report the first observation that end-on binding is indeed possible for Ir DHCs supported on WO3. Unambiguous evidence supporting the binding mode was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy and high-angle annular dark-field scanning transmission electron microscopy. Density functional theory calculations provide additional support for the binding mode, as well as insights into how end-on bound DHCs may be beneficial for solar water oxidation reactions. The results have important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions.
AB - Heterogeneous catalysts with atomically defined active centers hold great promise for high-performance applications. Among them, catalysts featuring active moieties with more than one metal atom are important for chemical reactions that require synergistic effects but are rarer than single atom catalysts (SACs). The difficulty in synthesizing such catalysts has been a key challenge. Recent progress in preparing dinuclear heterogeneous catalysts (DHCs) from homogeneous molecular precursors has provided an effective route to address this challenge. Nevertheless, only side-on bound DHCs, where both metal atoms are affixed to the supporting substrate, have been reported. The competing end-on binding mode, where only one metal atom is attached to the substrate and the other metal atom is dangling, has been missing. Here, we report the first observation that end-on binding is indeed possible for Ir DHCs supported on WO3. Unambiguous evidence supporting the binding mode was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy and high-angle annular dark-field scanning transmission electron microscopy. Density functional theory calculations provide additional support for the binding mode, as well as insights into how end-on bound DHCs may be beneficial for solar water oxidation reactions. The results have important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions.
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U2 - 10.1021/acscentsci.8b00335
DO - 10.1021/acscentsci.8b00335
M3 - Article
VL - 4
SP - 1166
EP - 1172
JO - ACS Central Science
JF - ACS Central Science
SN - 2374-7943
IS - 9
ER -