Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

Somphonh P. Phivilay; Charles A. Roberts; Andrew D. Gamalski; Eric A. Stach; Shiran Zhang; Luan Nguyen; Yu Tang; Anke Xiong; Alexander A. Puretzky; Franklin Feng Tao; Kazunari Domen; Israel E. Wachs

doi:10.1021/acscatal.8b01388

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

Somphonh P. Phivilay, Charles A. Roberts, Andrew D. Gamalski, Eric A. Stach, Shiran Zhang, Luan Nguyen, Yu Tang, Anke Xiong, Alexander A. Puretzky, Franklin Feng Tao, Kazunari Domen, Israel E. Wachs

Functional Hybrid Nanomaterials

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

28 Scopus citations

Abstract

The supported mixed oxide (Rh_2-yCr_yO₃)/(Ga_1-xZn_x)(N_1-xO_x) photocatalyst, highly active for splitting of H₂O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga_1-xZn_x)(N_1-xO_x) support are not perturbed by the deposition of the (Rh_2-yCr_yO₃) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga_1-xZn_x)(N_1-xO_x) support is the source of excited electrons/holes and the (Rh_2-yCr_yO₃) NPs greatly reduce the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh_2-yCr_yO₃) NPs consist of Rh³⁺ and Cr³⁺ mixed oxide species. In situ AP-XPS help to reveal that the Rh³⁺ and surface N atoms are involved in water splitting. Dispersed RhO_x species on the (Ga_1-xZn_x)(N_1-xO_x) support and on CrO_x NPs were found to be the photocatalytic active sites for H₂ generation and N and Zn sites from the (Ga_1-xZn_x)(N_1-xO_x) support are the photocatalytic active site for O₂ generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.

Original language	English
Pages (from-to)	6650-6658
Number of pages	9
Journal	ACS Catalysis
Volume	8
Issue number	7
DOIs	https://doi.org/10.1021/acscatal.8b01388
State	Published - Jul 6 2018

Funding

The authors gratefully acknowledge the financial support by the Department of Energy grant: DOE-FG02-93ER14350. The PL and TR-PL measurements were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. A.G. acknowledges support through Laboratory Directed Research and Development funds at Brookhaven National Laboratory. The assistance of Dr. A. Miller at Lehigh University in obtaining and interpreting the HR-XPS and HS-LEIS data is also gratefully acknowledged. ∇Present address: Toyota Motor Engineering & Manufacturing North America, Inc., 1555 Woodridge Ave., Ann Arbor, MI 48105, USA. Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding This research was financially supported by the Department of Energy grant: DOE-FG02-93ER14350. Notes The authors declare no competing financial interest.

Keywords

AP-XPS
HS-LEIS
photocatalysis
photocatalyst
spectroscopy
water splitting

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10.1021/acscatal.8b01388

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title = "Anatomy of a Visible Light Activated Photocatalyst for Water Splitting",

abstract = "The supported mixed oxide (Rh2-yCryO3)/(Ga1-xZnx)(N1-xOx) photocatalyst, highly active for splitting of H2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga1-xZnx)(N1-xOx) support are not perturbed by the deposition of the (Rh2-yCryO3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga1-xZnx)(N1-xOx) support is the source of excited electrons/holes and the (Rh2-yCryO3) NPs greatly reduce the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh2-yCryO3) NPs consist of Rh3+ and Cr3+ mixed oxide species. In situ AP-XPS help to reveal that the Rh3+ and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga1-xZnx)(N1-xOx) support and on CrOx NPs were found to be the photocatalytic active sites for H2 generation and N and Zn sites from the (Ga1-xZnx)(N1-xOx) support are the photocatalytic active site for O2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.",

keywords = "AP-XPS, HS-LEIS, photocatalysis, photocatalyst, spectroscopy, water splitting",

author = "Phivilay, {Somphonh P.} and Roberts, {Charles A.} and Gamalski, {Andrew D.} and Stach, {Eric A.} and Shiran Zhang and Luan Nguyen and Yu Tang and Anke Xiong and Puretzky, {Alexander A.} and Tao, {Franklin Feng} and Kazunari Domen and Wachs, {Israel E.}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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doi = "10.1021/acscatal.8b01388",

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T1 - Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

AU - Phivilay, Somphonh P.

AU - Roberts, Charles A.

AU - Gamalski, Andrew D.

AU - Stach, Eric A.

AU - Zhang, Shiran

AU - Nguyen, Luan

AU - Tang, Yu

AU - Xiong, Anke

AU - Puretzky, Alexander A.

AU - Tao, Franklin Feng

AU - Domen, Kazunari

AU - Wachs, Israel E.

PY - 2018/7/6

Y1 - 2018/7/6

N2 - The supported mixed oxide (Rh2-yCryO3)/(Ga1-xZnx)(N1-xOx) photocatalyst, highly active for splitting of H2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga1-xZnx)(N1-xOx) support are not perturbed by the deposition of the (Rh2-yCryO3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga1-xZnx)(N1-xOx) support is the source of excited electrons/holes and the (Rh2-yCryO3) NPs greatly reduce the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh2-yCryO3) NPs consist of Rh3+ and Cr3+ mixed oxide species. In situ AP-XPS help to reveal that the Rh3+ and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga1-xZnx)(N1-xOx) support and on CrOx NPs were found to be the photocatalytic active sites for H2 generation and N and Zn sites from the (Ga1-xZnx)(N1-xOx) support are the photocatalytic active site for O2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.

AB - The supported mixed oxide (Rh2-yCryO3)/(Ga1-xZnx)(N1-xOx) photocatalyst, highly active for splitting of H2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga1-xZnx)(N1-xOx) support are not perturbed by the deposition of the (Rh2-yCryO3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga1-xZnx)(N1-xOx) support is the source of excited electrons/holes and the (Rh2-yCryO3) NPs greatly reduce the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh2-yCryO3) NPs consist of Rh3+ and Cr3+ mixed oxide species. In situ AP-XPS help to reveal that the Rh3+ and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga1-xZnx)(N1-xOx) support and on CrOx NPs were found to be the photocatalytic active sites for H2 generation and N and Zn sites from the (Ga1-xZnx)(N1-xOx) support are the photocatalytic active site for O2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.

KW - AP-XPS

KW - HS-LEIS

KW - photocatalysis

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VL - 8

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EP - 6658

JO - ACS Catalysis

JF - ACS Catalysis

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ER -

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

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