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Title: Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production

Abstract

Redox cocatalysts play crucial roles in photosynthetic reactions, yet simultaneous loading of oxidative and reductive cocatalysts often leads to enhanced charge recombination that is detrimental to photosynthesis. This study introduces an approach to simultaneously load two redox cocatalysts, atomically dispersed cobalt for improving oxidation activity and anthraquinone for improving reduction selectivity, onto graphitic carbon nitride (C3N4) nanosheets for photocatalytic H2O2 production. Spatial separation of oxidative and reductive cocatalysts was achieved on a two-dimensional (2D) photocatalyst, by coordinating cobalt single atom above the void center of C3N4 and anchoring anthraquinone at the edges of C3N4nanosheets. Such spatial separation, experimentally confirmed and computationally simulated, was found to be critical for enhancing surface charge separation and achieving efficient H2O2 production. This center/edge strategy for spatial separation of cocatalysts may be applied on other 2D photocatalysts that are increasingly studied in photosynthetic reactions.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [1];  [4];  [1];  [1];  [3]; ORCiD logo [4];  [5];  [1]
+ Show Author Affiliations
  1. Yale Univ., New Haven, CT (United States)
  2. Univ. of Tokyo, Bunkyo-ku (Japan)
  3. Arizona State Univ., Tempe, AZ (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  5. Univ. of Tokyo, Bunkyo-ku (Japan); Shinshu Univ., Nagano (Japan)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1614978
Report Number(s):
BNL-213841-2020-JAAM
Journal ID: ISSN 0027-8424
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 117; Journal Issue: 12; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 2D photocatalyst; spatially separated cocatalysts; single-atom catalyst; hydrogen peroxide

Citation Formats

Chu, Chiheng, Zhu, Qianhong, Pan, Zhenhua, Gupta, Srishti, Huang, Dahong, Du, Yonghua, Weon, Seunghyun, Wu, Yueshen, Muhich, Christopher, Stavitski, Eli, Domen, Kazunari, and Kim, Jae-Hong. Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production. United States: N. p., 2020. Web. doi:10.1073/pnas.1913403117.
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Chu, Chiheng, Zhu, Qianhong, Pan, Zhenhua, Gupta, Srishti, Huang, Dahong, Du, Yonghua, Weon, Seunghyun, Wu, Yueshen, Muhich, Christopher, Stavitski, Eli, Domen, Kazunari, & Kim, Jae-Hong. Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production. United States. https://doi.org/10.1073/pnas.1913403117
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Chu, Chiheng, Zhu, Qianhong, Pan, Zhenhua, Gupta, Srishti, Huang, Dahong, Du, Yonghua, Weon, Seunghyun, Wu, Yueshen, Muhich, Christopher, Stavitski, Eli, Domen, Kazunari, and Kim, Jae-Hong. Wed . "Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production". United States. https://doi.org/10.1073/pnas.1913403117. https://www.osti.gov/servlets/purl/1614978.
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@article{osti_1614978,
title = {Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production},
author = {Chu, Chiheng and Zhu, Qianhong and Pan, Zhenhua and Gupta, Srishti and Huang, Dahong and Du, Yonghua and Weon, Seunghyun and Wu, Yueshen and Muhich, Christopher and Stavitski, Eli and Domen, Kazunari and Kim, Jae-Hong},
abstractNote = {Redox cocatalysts play crucial roles in photosynthetic reactions, yet simultaneous loading of oxidative and reductive cocatalysts often leads to enhanced charge recombination that is detrimental to photosynthesis. This study introduces an approach to simultaneously load two redox cocatalysts, atomically dispersed cobalt for improving oxidation activity and anthraquinone for improving reduction selectivity, onto graphitic carbon nitride (C3N4) nanosheets for photocatalytic H2O2 production. Spatial separation of oxidative and reductive cocatalysts was achieved on a two-dimensional (2D) photocatalyst, by coordinating cobalt single atom above the void center of C3N4 and anchoring anthraquinone at the edges of C3N4nanosheets. Such spatial separation, experimentally confirmed and computationally simulated, was found to be critical for enhancing surface charge separation and achieving efficient H2O2 production. This center/edge strategy for spatial separation of cocatalysts may be applied on other 2D photocatalysts that are increasingly studied in photosynthetic reactions.},
doi = {10.1073/pnas.1913403117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 12,
volume = 117,
place = {United States},
year = {Wed Mar 11 00:00:00 EDT 2020},
month = {Wed Mar 11 00:00:00 EDT 2020}
}
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https://doi.org/10.1073/pnas.1913403117
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