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Title: Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation

Abstract

Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-Fe 2 O 3 is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-Fe 2 O 3 anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward H 2 O photooxidation.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [1];  [1];  [1];  [7];  [2];  [5];  [1];  [6];  [8]; ORCiD logo [9];  [10];  [6];  [5];  [2] more »;  [2]; ORCiD logo [1] « less
+ Show Author Affiliations
  1. Boston College, Chestnut Hill, MA (United States). Dept. of Chemistry. Merkert Chemistry Center
  2. Yale Univ., New Haven, CT (United States). Dept. of Chemistry. Yale Energy Sciences Inst.
  3. Forschungszentrum Julich (Germany). Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons; Tsinghua Univ., Beijing (China). National Center for Electron Microscopy in Beijing. School of Materials Science and Engineering
  4. Nanjing Univ. (China). National Lab. of Solid State Microstructures. College of Engineering and Applied Sciences. Collaborative Innovation Center of Advanced Microstructures; Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science
  5. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  7. Forschungszentrum Julich (Germany). Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons
  8. Tsinghua Univ., Beijing (China). National Center for Electron Microscopy in Beijing. School of Materials Science and Engineering
  9. Nanjing Univ. (China). National Lab. of Solid State Microstructures. College of Engineering and Applied Sciences. Collaborative Innovation Center of Advanced Microstructures
  10. Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science. Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); National Key Research and Development Program (China); National Basic Research Program of China; National Natural Science Foundation of China (NNSFC); Natural Science Foundation of Jiangsu Province (China); Fundamental Research Funds for the Central Universities (China)
OSTI Identifier:
1423731
Alternate Identifier(s):
OSTI ID: 1506300
Grant/Contract Number:  
AC02-05CH11231; SC0001059; SC0014430; FG02-05ER15730; DMR 1055762; 2016YFB0700402; 2015CB654901; 11474147; BK20151383; 021314380077; SC0024430
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 115; Journal Issue: 12; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalyst; water splitting; solar energy; STEM; spectroscopy

Citation Formats

Zhao, Yanyan, Yang, Ke R., Wang, Zechao, Yan, Xingxu, Cao, Sufeng, Ye, Yifan, Dong, Qi, Zhang, Xizi, Thorne, James E., Jin, Lei, Materna, Kelly L., Trimpalis, Antonios, Bai, Hongye, Fakra, Sirine C., Zhong, Xiaoyan, Wang, Peng, Pan, Xiaoqing, Guo, Jinghua, Flytzani-Stephanopoulos, Maria, Brudvig, Gary W., Batista, Victor S., and Wang, Dunwei. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation. United States: N. p., 2018. Web. doi:10.1073/pnas.1722137115.
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Zhao, Yanyan, Yang, Ke R., Wang, Zechao, Yan, Xingxu, Cao, Sufeng, Ye, Yifan, Dong, Qi, Zhang, Xizi, Thorne, James E., Jin, Lei, Materna, Kelly L., Trimpalis, Antonios, Bai, Hongye, Fakra, Sirine C., Zhong, Xiaoyan, Wang, Peng, Pan, Xiaoqing, Guo, Jinghua, Flytzani-Stephanopoulos, Maria, Brudvig, Gary W., Batista, Victor S., & Wang, Dunwei. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation. United States. doi:10.1073/pnas.1722137115.
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Zhao, Yanyan, Yang, Ke R., Wang, Zechao, Yan, Xingxu, Cao, Sufeng, Ye, Yifan, Dong, Qi, Zhang, Xizi, Thorne, James E., Jin, Lei, Materna, Kelly L., Trimpalis, Antonios, Bai, Hongye, Fakra, Sirine C., Zhong, Xiaoyan, Wang, Peng, Pan, Xiaoqing, Guo, Jinghua, Flytzani-Stephanopoulos, Maria, Brudvig, Gary W., Batista, Victor S., and Wang, Dunwei. Mon . "Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation". United States. doi:10.1073/pnas.1722137115.
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@article{osti_1423731,
title = {Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation},
author = {Zhao, Yanyan and Yang, Ke R. and Wang, Zechao and Yan, Xingxu and Cao, Sufeng and Ye, Yifan and Dong, Qi and Zhang, Xizi and Thorne, James E. and Jin, Lei and Materna, Kelly L. and Trimpalis, Antonios and Bai, Hongye and Fakra, Sirine C. and Zhong, Xiaoyan and Wang, Peng and Pan, Xiaoqing and Guo, Jinghua and Flytzani-Stephanopoulos, Maria and Brudvig, Gary W. and Batista, Victor S. and Wang, Dunwei},
abstractNote = {Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-Fe 2 O 3 is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-Fe 2 O 3 anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward H 2 O photooxidation.},
doi = {10.1073/pnas.1722137115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 12,
volume = 115,
place = {United States},
year = {2018},
month = {3}
}
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Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1722137115
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Cited by: 14 works
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Figures / Tables:

Fig. 1 Fig. 1: Synthesis procedure of Ir DHC. It starts with the immobilization of molecular Ir catalysts, followed by photochemical removal of organic ligands. The binding details of H2O and OH groups are proposed.
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    Works referencing / citing this record:

    Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis
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