Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores

Chandan Kumar Tiwari; Shubasis Roy; Tal Tubul-Sterin; Mark Baranov; Nitai Leffler; Mu Li; Panchao Yin; Alevtina Neyman; Ira A. Weinstock

doi:10.1002/anie.202213762

Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores

Chandan Kumar Tiwari, Shubasis Roy, Tal Tubul-Sterin, Mark Baranov, Nitai Leffler, Mu Li, Panchao Yin, Alevtina Neyman, Ira A. Weinstock

Department of Chemistry

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

4 Scopus citations

Abstract

The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb₆O₁₉]⁸⁻, can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs (1), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of very small semiconductor NCs as the cores of versatile, entirely-inorganic complexes.

Original language	English
Article number	e202213762
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	10
DOIs	https://doi.org/10.1002/anie.202213762
State	Published - 1 Mar 2023

Keywords

Copper Oxide
Hexaniobate Anion
Photocatalysis
Water Oxidation

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202213762

Cite this

@article{e1b8069e83224dccacdf63530f584bec,

title = "Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores",

abstract = "The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb6O19]8−, can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs (1), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of very small semiconductor NCs as the cores of versatile, entirely-inorganic complexes.",

keywords = "Copper Oxide, Hexaniobate Anion, Photocatalysis, Water Oxidation",

author = "{Kumar Tiwari}, Chandan and Shubasis Roy and Tal Tubul-Sterin and Mark Baranov and Nitai Leffler and Mu Li and Panchao Yin and Alevtina Neyman and Weinstock, {Ira A.}",

note = "Funding Information: I.A.W. thanks the Israel Science Foundation (280/21), I.A.W. and P.Y. thank the Joint Project of the National Science Foundation of China and the ISF (3102/19) and CBMM (S{\~a}o Paulo, Brazil) for niobium pentoxide; C.K.T. and S.R. thank the Kreitman School of Advanced Graduate Studies of the Ben‐Gurion University of the Negev for post‐doctoral and doctoral fellowships, respectively. Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2023",

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doi = "10.1002/anie.202213762",

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T1 - Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores

AU - Kumar Tiwari, Chandan

AU - Roy, Shubasis

AU - Tubul-Sterin, Tal

AU - Baranov, Mark

AU - Leffler, Nitai

AU - Li, Mu

AU - Yin, Panchao

AU - Neyman, Alevtina

AU - Weinstock, Ira A.

N1 - Funding Information: I.A.W. thanks the Israel Science Foundation (280/21), I.A.W. and P.Y. thank the Joint Project of the National Science Foundation of China and the ISF (3102/19) and CBMM (São Paulo, Brazil) for niobium pentoxide; C.K.T. and S.R. thank the Kreitman School of Advanced Graduate Studies of the Ben‐Gurion University of the Negev for post‐doctoral and doctoral fellowships, respectively. Publisher Copyright: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2023/3/1

Y1 - 2023/3/1

N2 - The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb6O19]8−, can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs (1), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of very small semiconductor NCs as the cores of versatile, entirely-inorganic complexes.

AB - The formation of small 1 to 3 nm organic-ligand free metal-oxide nanocrystals (NCs) is essential to utilization of their attractive size-dependent properties in electronic devices and catalysis. We now report that hexaniobate cluster-anions, [Nb6O19]8−, can arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by formation of hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs (1), whose ca. 350 Cu-atom cores feature quantum-confinement effects that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs. The findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the size-dependent properties of very small semiconductor NCs as the cores of versatile, entirely-inorganic complexes.

KW - Copper Oxide

KW - Hexaniobate Anion

KW - Photocatalysis

KW - Water Oxidation

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DO - 10.1002/anie.202213762

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JO - Angewandte Chemie - International Edition

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ER -

Emergence of Visible-Light Water Oxidation Upon Hexaniobate-Ligand Entrapment of Quantum-Confined Copper-Oxide Cores

Abstract

Keywords

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