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

Chiheng Chu; Qianhong Zhu; Zhenhua Pan; Srishti Gupta; Dahong Huang; Yonghua Du; Seunghyun Weon; Yueshen Wu; Christopher Muhich; Eli Stavitski; Kazunari Domen; Jae-Hong Kim

doi:10.1073/pnas.1913403117

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

Chiheng Chu, Qianhong Zhu, Zhenhua Pan, Srishti Gupta, Dahong Huang, Yonghua Du, Seunghyun Weon, Yueshen Wu, Christopher Muhich, Eli Stavitski, Kazunari Domen, Jae-Hong Kim

Research output: Contribution to journal › Article › peer-review

279 Scopus citations

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 C3N4 nanosheets. 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.

Original language	English (US)
Pages (from-to)	6376-6382
Number of pages	7
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	117
Issue number	12
DOIs	https://doi.org/10.1073/pnas.1913403117
State	Published - Mar 11 2020
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2022-06-14
Acknowledgements: This work was partially supported by National Science Foundation (NSF) Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (Grant EEC-1449500). C.C. was financially supported by an Early Postdoctoral Mobility Fellowship, Swiss National Science Foundation (Award P2EZP2_168796) and D.H. was supported by the China Scholarship Council. We thank S. Zhuo and P. Wang at King Abdullah University of Science and Technology for STEM image analysis, J. Karosas at Yale University for ICP-MS analysis, and P. Kelleher at Yale University for help with XAFS sample preparation. We also thank D. Lu at Brookhaven National Laboratory (BNL) Center of Functional Materials for helpful discussions. This research used beamlines 8-BM and 8-ID (ISS) of the NSLS-II, US Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by BNL under Contract DESC0012704. Computational work used the Extreme Science and Engineering Discovery Environment, supported by NSF (Grant ACI-1548562), through the Bridges high-performance computer at the Pittsburgh Supercomputing Center (Allocation ECD190001).
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

General

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10.1073/pnas.1913403117

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Chu, C., Zhu, Q., Pan, Z., Gupta, S., Huang, D., Du, Y., Weon, S., Wu, Y., Muhich, C., Stavitski, E., Domen, K., & Kim, J.-H. (2020). Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production. Proceedings of the National Academy of Sciences of the United States of America, 117(12), 6376-6382. https://doi.org/10.1073/pnas.1913403117

@article{a1042535acdf47cda02f1acdf205a56e,

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 C3N4 nanosheets. 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.",

author = "Chiheng Chu and Qianhong Zhu and Zhenhua Pan and Srishti Gupta and Dahong Huang and Yonghua Du and Seunghyun Weon and Yueshen Wu and Christopher Muhich and Eli Stavitski and Kazunari Domen and Jae-Hong Kim",

note = "KAUST Repository Item: Exported on 2022-06-14 Acknowledgements: This work was partially supported by National Science Foundation (NSF) Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (Grant EEC-1449500). C.C. was financially supported by an Early Postdoctoral Mobility Fellowship, Swiss National Science Foundation (Award P2EZP2_168796) and D.H. was supported by the China Scholarship Council. We thank S. Zhuo and P. Wang at King Abdullah University of Science and Technology for STEM image analysis, J. Karosas at Yale University for ICP-MS analysis, and P. Kelleher at Yale University for help with XAFS sample preparation. We also thank D. Lu at Brookhaven National Laboratory (BNL) Center of Functional Materials for helpful discussions. This research used beamlines 8-BM and 8-ID (ISS) of the NSLS-II, US Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by BNL under Contract DESC0012704. Computational work used the Extreme Science and Engineering Discovery Environment, supported by NSF (Grant ACI-1548562), through the Bridges high-performance computer at the Pittsburgh Supercomputing Center (Allocation ECD190001). This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2020",

month = mar,

day = "11",

doi = "10.1073/pnas.1913403117",

language = "English (US)",

volume = "117",

pages = "6376--6382",

journal = "Proceedings of the National Academy of Sciences of the United States of America",

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publisher = "National Academy of Sciences",

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Chu, C, Zhu, Q, Pan, Z, Gupta, S, Huang, D, Du, Y, Weon, S, Wu, Y, Muhich, C, Stavitski, E, Domen, K & Kim, J-H 2020, 'Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production', Proceedings of the National Academy of Sciences of the United States of America, vol. 117, no. 12, pp. 6376-6382. https://doi.org/10.1073/pnas.1913403117

TY - JOUR

T1 - Spatially separating redox centers on 2D carbon nitride with cobalt single atom for photocatalytic H2O2 production

AU - Chu, Chiheng

AU - Zhu, Qianhong

AU - Pan, Zhenhua

AU - Gupta, Srishti

AU - Huang, Dahong

AU - Du, Yonghua

AU - Weon, Seunghyun

AU - Wu, Yueshen

AU - Muhich, Christopher

AU - Stavitski, Eli

AU - Domen, Kazunari

AU - Kim, Jae-Hong

N1 - KAUST Repository Item: Exported on 2022-06-14 Acknowledgements: This work was partially supported by National Science Foundation (NSF) Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (Grant EEC-1449500). C.C. was financially supported by an Early Postdoctoral Mobility Fellowship, Swiss National Science Foundation (Award P2EZP2_168796) and D.H. was supported by the China Scholarship Council. We thank S. Zhuo and P. Wang at King Abdullah University of Science and Technology for STEM image analysis, J. Karosas at Yale University for ICP-MS analysis, and P. Kelleher at Yale University for help with XAFS sample preparation. We also thank D. Lu at Brookhaven National Laboratory (BNL) Center of Functional Materials for helpful discussions. This research used beamlines 8-BM and 8-ID (ISS) of the NSLS-II, US Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by BNL under Contract DESC0012704. Computational work used the Extreme Science and Engineering Discovery Environment, supported by NSF (Grant ACI-1548562), through the Bridges high-performance computer at the Pittsburgh Supercomputing Center (Allocation ECD190001). This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2020/3/11

Y1 - 2020/3/11

N2 - 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 C3N4 nanosheets. 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.

AB - 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 C3N4 nanosheets. 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.

UR - http://hdl.handle.net/10754/678945

UR - http://www.pnas.org/lookup/doi/10.1073/pnas.1913403117

UR - http://www.scopus.com/inward/record.url?scp=85082333555&partnerID=8YFLogxK

U2 - 10.1073/pnas.1913403117

DO - 10.1073/pnas.1913403117

M3 - Article

C2 - 32161133

SN - 1091-6490

VL - 117

SP - 6376

EP - 6382

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

IS - 12

ER -

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

Abstract

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