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Title: 2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO 2 Reduction

Abstract

Covalent organic framework (COF) represents an emerging class of porous materials that have exhibited great potential in various applications, particularly in catalysis. Here, we report a newly designed 2D COF with incorporated Re complex, which exhibits intrinsic light absorption and charge separation (CS) properties. We show that this hybrid catalyst can efficiently reduce CO2 to form CO under visible light illumination with high electivity (98%) and better activity than its homogeneous Re counterpart. Moreover, using advanced transient optical and X-ray absorption spectroscopy and in situ diffuse reflectance spectroscopy, we unraveled three key intermediates that are responsible for CS, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion but also provide unprecedented insight into the mechanistic origins for light-driven CO2 reduction.

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1];  [3];  [4]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [1]
  1. Marquette Univ., Milwaukee, WI (United States)
  2. Univ.of Nebraska−Lincoln, Lincoln, NE (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Univ. of Wisconsin−Madison, Madison, WI (United States)
  5. Univ.of Nebraska−Lincoln, Lincoln, NE (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1504460
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 44; 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

Citation Formats

Yang, Sizhuo, Hu, Wenhui, Zhang, Xin, He, Peilei, Pattengale, Brian, Liu, Cunming, Cendejas, Melissa, Hermans, Ive, Zhang, Xiaoyi, Zhang, Jian, and Huang, Jier. 2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO 2 Reduction. United States: N. p., 2018. Web. doi:10.1021/jacs.8b09705.
Yang, Sizhuo, Hu, Wenhui, Zhang, Xin, He, Peilei, Pattengale, Brian, Liu, Cunming, Cendejas, Melissa, Hermans, Ive, Zhang, Xiaoyi, Zhang, Jian, & Huang, Jier. 2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO 2 Reduction. United States. doi:https://doi.org/10.1021/jacs.8b09705
Yang, Sizhuo, Hu, Wenhui, Zhang, Xin, He, Peilei, Pattengale, Brian, Liu, Cunming, Cendejas, Melissa, Hermans, Ive, Zhang, Xiaoyi, Zhang, Jian, and Huang, Jier. Wed . "2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO 2 Reduction". United States. doi:https://doi.org/10.1021/jacs.8b09705. https://www.osti.gov/servlets/purl/1504460.
@article{osti_1504460,
title = {2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO 2 Reduction},
author = {Yang, Sizhuo and Hu, Wenhui and Zhang, Xin and He, Peilei and Pattengale, Brian and Liu, Cunming and Cendejas, Melissa and Hermans, Ive and Zhang, Xiaoyi and Zhang, Jian and Huang, Jier},
abstractNote = {Covalent organic framework (COF) represents an emerging class of porous materials that have exhibited great potential in various applications, particularly in catalysis. Here, we report a newly designed 2D COF with incorporated Re complex, which exhibits intrinsic light absorption and charge separation (CS) properties. We show that this hybrid catalyst can efficiently reduce CO2 to form CO under visible light illumination with high electivity (98%) and better activity than its homogeneous Re counterpart. Moreover, using advanced transient optical and X-ray absorption spectroscopy and in situ diffuse reflectance spectroscopy, we unraveled three key intermediates that are responsible for CS, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion but also provide unprecedented insight into the mechanistic origins for light-driven CO2 reduction.},
doi = {10.1021/jacs.8b09705},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 140,
place = {United States},
year = {2018},
month = {10}
}

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Figures / Tables:

Figure 2 Figure 2: Transient optical spectra of COF (a) and Re-COF (c) following 530 nm excitation. (b) The comparison of kinetics for ICT of COF and Re-COF. (d) The XANES spectrum of Re-COF at Re L3-edge. The bottom panel is the difference spectrum after subtracting the laser-off spectrum from laser-on spectrummore » collected at 150 ps delay time.« less

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