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Title: Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks

Abstract

Conductive metal organic frameworks (MOFs) represent a promising class of porous crystalline materials that have demonstrated potential in photo-electronics and photocatalytic applications. However, the lack of fundamental understanding on charge transport (CT) mechanism as well as the correlation of CT mechanism with their structure hampered their further development. Herein, we report the direct evidence of CT mechanism in 2D Cu-THQ MOFs and the correlation of temporal and spatial behaviors of charge carriers with their photoconductivity by combining three advanced spectroscopic methods including time resolved optical and X-ray absorption spectroscopy and terahertz spectroscopy. In addition to Cu-THQ, the CT in Cu/Zn-THQ after incorporating Zn2+ guest metal was also examined to uncover the contribution of through space pathway as the presence of the redox inactive 3d10 Zn2+ is expected to perturb the long range in-plane CT. We show that the hot carriers in Cu-THQ generated after photoexcitation are highly mobile and undergo fast localization to a lower energy state (cool carriers) with electrons occupying Cu center and holes in ligands. The cool carriers, which have super long lifetime (> 17 ns) are responsible for the long-term photoconductivity in Cu-THQ and transport through O-Cu-O motif with negligible contribution from interlayer ligand π-π stackingmore » as incorporation of Zn2+ in Cu-THQ significantly reduced photoconductivity. These unprecedent results not only demonstrate the capability to experimentally probe CT mechanism but also provide important insight in the rational design of 2D MOFs for photoelectronic and photocatalytic applications.« less

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [1];  [5]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Marquette Univ., Milwaukee, WI (United States)
  2. Yale Univ., New Haven, CT (United States). Yale Energy Science Institute
  3. Yale Univ., New Haven, CT (United States). Yale Microbial Sciences Institute
  4. Univ. of Nebraska, Lincoln, NE (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Yale Univ., New Haven, CT (United States); Marquette Univ., Milwaukee, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1783275
Alternate Identifier(s):
OSTI ID: 1777887; OSTI ID: 2335702
Grant/Contract Number:  
AC02-06CH11357; FG02-07ER15909; SC0020122; ACI-1053575; CHE-1338173
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 50; 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; Excitons; Photonics; Ligands; Metal organic frameworks; Carrier dynamics; 14 SOLAR ENERGY

Citation Formats

Nyakuchena, James, Ostresh, Sarah, Streater, Daniel, Pattengale, Brian, Neu, Jens, Fiankor, Christian, Hu, Wenhui, Kinigstein, Eli Diego, Zhang, Jian, Zhang, Xiaoyi, Schmuttenmaer, Charles A., and Huang, Jier. Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks. United States: N. p., 2020. Web. doi:10.1021/jacs.0c09000.
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Nyakuchena, James, Ostresh, Sarah, Streater, Daniel, Pattengale, Brian, Neu, Jens, Fiankor, Christian, Hu, Wenhui, Kinigstein, Eli Diego, Zhang, Jian, Zhang, Xiaoyi, Schmuttenmaer, Charles A., & Huang, Jier. Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks. United States. https://doi.org/10.1021/jacs.0c09000
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Nyakuchena, James, Ostresh, Sarah, Streater, Daniel, Pattengale, Brian, Neu, Jens, Fiankor, Christian, Hu, Wenhui, Kinigstein, Eli Diego, Zhang, Jian, Zhang, Xiaoyi, Schmuttenmaer, Charles A., and Huang, Jier. Mon . "Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks". United States. https://doi.org/10.1021/jacs.0c09000. https://www.osti.gov/servlets/purl/1783275.
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@article{osti_1783275,
title = {Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks},
author = {Nyakuchena, James and Ostresh, Sarah and Streater, Daniel and Pattengale, Brian and Neu, Jens and Fiankor, Christian and Hu, Wenhui and Kinigstein, Eli Diego and Zhang, Jian and Zhang, Xiaoyi and Schmuttenmaer, Charles A. and Huang, Jier},
abstractNote = {Conductive metal organic frameworks (MOFs) represent a promising class of porous crystalline materials that have demonstrated potential in photo-electronics and photocatalytic applications. However, the lack of fundamental understanding on charge transport (CT) mechanism as well as the correlation of CT mechanism with their structure hampered their further development. Herein, we report the direct evidence of CT mechanism in 2D Cu-THQ MOFs and the correlation of temporal and spatial behaviors of charge carriers with their photoconductivity by combining three advanced spectroscopic methods including time resolved optical and X-ray absorption spectroscopy and terahertz spectroscopy. In addition to Cu-THQ, the CT in Cu/Zn-THQ after incorporating Zn2+ guest metal was also examined to uncover the contribution of through space pathway as the presence of the redox inactive 3d10 Zn2+ is expected to perturb the long range in-plane CT. We show that the hot carriers in Cu-THQ generated after photoexcitation are highly mobile and undergo fast localization to a lower energy state (cool carriers) with electrons occupying Cu center and holes in ligands. The cool carriers, which have super long lifetime (> 17 ns) are responsible for the long-term photoconductivity in Cu-THQ and transport through O-Cu-O motif with negligible contribution from interlayer ligand π-π stacking as incorporation of Zn2+ in Cu-THQ significantly reduced photoconductivity. These unprecedent results not only demonstrate the capability to experimentally probe CT mechanism but also provide important insight in the rational design of 2D MOFs for photoelectronic and photocatalytic applications.},
doi = {10.1021/jacs.0c09000},
journal = {Journal of the American Chemical Society},
number = 50,
volume = 142,
place = {United States},
year = {Mon Nov 23 00:00:00 EST 2020},
month = {Mon Nov 23 00:00:00 EST 2020}
}
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https://doi.org/10.1021/jacs.0c09000
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