Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters

Xingjie Wang; Fanrui Sha; Haomiao Xie; Ziyu Zengcai; Karam B. Idrees; Qingchong Xu; Yao Liu; Lauren S. Cho; Jing Xiao; Kent O. Kirlikovali; Junli Ren; Justin M. Notestein; Omar K. Farha

doi:10.1021/acsami.4c02961

Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters

Xingjie Wang^*, Fanrui Sha, Haomiao Xie, Ziyu Zengcai, Karam B. Idrees, Qingchong Xu, Yao Liu, Lauren S. Cho, Jing Xiao, Kent O. Kirlikovali, Junli Ren, Justin M. Notestein, Omar K. Farha^*

^*Corresponding author for this work

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

2 Scopus citations

Abstract

Titanium-oxo clusters, with their robust structure and suitable optical and electronic properties, have been widely investigated as photocatalysts. Heterometallic Ti/M-oxo clusters provide additional tunability and functionality, which enable systematic structure-activity investigations to elucidate the reaction mechanisms and improve the catalyst design. Incorporating cerium into Ti-oxo clusters can provide additional redox (Ce^IV/Ce^III) and oxygen harvesting ability, but to date, only a limited number of structurally defined titanium-cerium (Ti/Ce) clusters have been reported due to their synthetic challenges. Herein, we report the synthesis and photocatalytic properties of two structurally defined Ti/Ce-oxo clusters, Ti₈Ce₂(BA)₁₆ and Ti₉Ce₄(BA)₂₀, as well as a TiCe-BA cluster with a calculated formula of Ti₂₀Ce₉O₃₆(BA)₄₂. Photocatalytic study of these clusters demonstrates that the amount of Ce³⁺ species greatly impacts its photocatalytic oxidation performance, and their superior photocatalytic reactivity toward aerobic alcohol oxidation can be contributed to the synergistic effects of the multiple radical species generated upon light absorption. This work represents a significant milestone in the construction of stable Ti/Ce-oxo clusters, enriching the current library of known heterometallic Ti/M-oxo clusters, and providing a series of crystalline materials with great promise of photoluminescence and photovoltaic chemistry.

Original language	English (US)
Pages (from-to)	30020-30030
Number of pages	11
Journal	ACS Applied Materials and Interfaces
Volume	16
Issue number	23
DOIs	https://doi.org/10.1021/acsami.4c02961
State	Published - Jun 12 2024

Funding

This work was supported as part of the Catalysis in Energy Processes (ICEP) for work done at Northwestern University, funded by the DOE, Office of Basic Energy Sciences (award number DE-FG02-03ER15457). O.K.F. acknowledges the Catalyst Design for 594 Decarbonization Center, an Energy Frontier Research Center 595 funded by the U.S. Department of Energy, Office of Science, 596 Basic Energy Sciences under Award No. DE-SC0023383. X.W. gratefully acknowledges support from State Key Laboratory of Pulp and Paper Engineering (202303), Guangzhou Municipal Science and Technology Bureau (no. 2024A04J3650). F.S. gratefully acknowledges support from the CBC-NU Cell-free Biomanufacturing Institute funded by the U.S. Army Contracting Command Award W52P1J-21-9-3023, Ryan Fellowship, and the International Institute for Nanotechnology at Northwestern University. This work made use of the J.B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. ICP-OES metal analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center. This work made use of Keck-II and EPIC facilities of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); SHyNE Resource (NSF NNCI-1542205); the State of Illinois; and IIN. This work made use of the IMSERC NMR facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), Int. Institute of Nanotechnology, and Northwestern University.

Keywords

benzyl alcohol
heterometallic cluster
lanthanide-titanium-oxo cluster
photocatalytic oxidation
titanium−cerium oxo cluster

ASJC Scopus subject areas

General Materials Science

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsami.4c02961

Cite this

@article{1b49b0ef1ee345bd861f035032f55060,

title = "Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters",

abstract = "Titanium-oxo clusters, with their robust structure and suitable optical and electronic properties, have been widely investigated as photocatalysts. Heterometallic Ti/M-oxo clusters provide additional tunability and functionality, which enable systematic structure-activity investigations to elucidate the reaction mechanisms and improve the catalyst design. Incorporating cerium into Ti-oxo clusters can provide additional redox (CeIV/CeIII) and oxygen harvesting ability, but to date, only a limited number of structurally defined titanium-cerium (Ti/Ce) clusters have been reported due to their synthetic challenges. Herein, we report the synthesis and photocatalytic properties of two structurally defined Ti/Ce-oxo clusters, Ti8Ce2(BA)16 and Ti9Ce4(BA)20, as well as a TiCe-BA cluster with a calculated formula of Ti20Ce9O36(BA)42. Photocatalytic study of these clusters demonstrates that the amount of Ce3+ species greatly impacts its photocatalytic oxidation performance, and their superior photocatalytic reactivity toward aerobic alcohol oxidation can be contributed to the synergistic effects of the multiple radical species generated upon light absorption. This work represents a significant milestone in the construction of stable Ti/Ce-oxo clusters, enriching the current library of known heterometallic Ti/M-oxo clusters, and providing a series of crystalline materials with great promise of photoluminescence and photovoltaic chemistry.",

keywords = "benzyl alcohol, heterometallic cluster, lanthanide-titanium-oxo cluster, photocatalytic oxidation, titanium−cerium oxo cluster",

author = "Xingjie Wang and Fanrui Sha and Haomiao Xie and Ziyu Zengcai and Idrees, {Karam B.} and Qingchong Xu and Yao Liu and Cho, {Lauren S.} and Jing Xiao and Kirlikovali, {Kent O.} and Junli Ren and Notestein, {Justin M.} and Farha, {Omar K.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = jun,

day = "12",

doi = "10.1021/acsami.4c02961",

language = "English (US)",

volume = "16",

pages = "30020--30030",

journal = "ACS Applied Materials and Interfaces",

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publisher = "American Chemical Society",

number = "23",

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T1 - Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters

AU - Wang, Xingjie

AU - Sha, Fanrui

AU - Xie, Haomiao

AU - Zengcai, Ziyu

AU - Idrees, Karam B.

AU - Xu, Qingchong

AU - Liu, Yao

AU - Cho, Lauren S.

AU - Xiao, Jing

AU - Kirlikovali, Kent O.

AU - Ren, Junli

AU - Notestein, Justin M.

AU - Farha, Omar K.

PY - 2024/6/12

Y1 - 2024/6/12

N2 - Titanium-oxo clusters, with their robust structure and suitable optical and electronic properties, have been widely investigated as photocatalysts. Heterometallic Ti/M-oxo clusters provide additional tunability and functionality, which enable systematic structure-activity investigations to elucidate the reaction mechanisms and improve the catalyst design. Incorporating cerium into Ti-oxo clusters can provide additional redox (CeIV/CeIII) and oxygen harvesting ability, but to date, only a limited number of structurally defined titanium-cerium (Ti/Ce) clusters have been reported due to their synthetic challenges. Herein, we report the synthesis and photocatalytic properties of two structurally defined Ti/Ce-oxo clusters, Ti8Ce2(BA)16 and Ti9Ce4(BA)20, as well as a TiCe-BA cluster with a calculated formula of Ti20Ce9O36(BA)42. Photocatalytic study of these clusters demonstrates that the amount of Ce3+ species greatly impacts its photocatalytic oxidation performance, and their superior photocatalytic reactivity toward aerobic alcohol oxidation can be contributed to the synergistic effects of the multiple radical species generated upon light absorption. This work represents a significant milestone in the construction of stable Ti/Ce-oxo clusters, enriching the current library of known heterometallic Ti/M-oxo clusters, and providing a series of crystalline materials with great promise of photoluminescence and photovoltaic chemistry.

AB - Titanium-oxo clusters, with their robust structure and suitable optical and electronic properties, have been widely investigated as photocatalysts. Heterometallic Ti/M-oxo clusters provide additional tunability and functionality, which enable systematic structure-activity investigations to elucidate the reaction mechanisms and improve the catalyst design. Incorporating cerium into Ti-oxo clusters can provide additional redox (CeIV/CeIII) and oxygen harvesting ability, but to date, only a limited number of structurally defined titanium-cerium (Ti/Ce) clusters have been reported due to their synthetic challenges. Herein, we report the synthesis and photocatalytic properties of two structurally defined Ti/Ce-oxo clusters, Ti8Ce2(BA)16 and Ti9Ce4(BA)20, as well as a TiCe-BA cluster with a calculated formula of Ti20Ce9O36(BA)42. Photocatalytic study of these clusters demonstrates that the amount of Ce3+ species greatly impacts its photocatalytic oxidation performance, and their superior photocatalytic reactivity toward aerobic alcohol oxidation can be contributed to the synergistic effects of the multiple radical species generated upon light absorption. This work represents a significant milestone in the construction of stable Ti/Ce-oxo clusters, enriching the current library of known heterometallic Ti/M-oxo clusters, and providing a series of crystalline materials with great promise of photoluminescence and photovoltaic chemistry.

KW - benzyl alcohol

KW - heterometallic cluster

KW - lanthanide-titanium-oxo cluster

KW - photocatalytic oxidation

KW - titanium−cerium oxo cluster

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SN - 1944-8244

VL - 16

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EP - 30030

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 23

ER -

Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

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CCDC 2231590: Experimental Crystal Structure Determination

CCDC 2231589: Experimental Crystal Structure Determination

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Unveiling Synergetic Photocatalytic Activity from Heterometallic Ti/Ce Clusters

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2231590: Experimental Crystal Structure Determination

CCDC 2231589: Experimental Crystal Structure Determination

Cite this