Polyoxometalate-templated assembly of homo- and heterometallic silver clusters

Xiaoyi Liu; Zichen Zhao; Mengyun Zhao; Yeqin Feng; Guo Yu Yang; Hongjin Lv

doi:10.1007/s11426-026-3404-y

Polyoxometalate-templated assembly of homo- and heterometallic silver clusters

Xiaoyi Liu
, Zichen Zhao
, Mengyun Zhao
, Yeqin Feng
, Guo Yu Yang^*
, Hongjin Lv^*

^*Corresponding author for this work

Beijing Institute of Technology

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

Abstract

In this work, we have synthesized and characterized three heterometallic [Ni₄(OH)₃(NO₃)₃(SiW₉O₃₄)@Ag₃₉(^tBuC≡C)₂₄(NO₃)₆](NO₃) (Ag₃₉Ni₄), [Co₄(OH)₃(NO₃)₃(SiW₉O₃₄)@Ag₃₉(^tBuC≡C)₂₄(NO₃)₆](NO₃) (Ag₃₉Co₄) and [Cu₃(OH)₂O(SiW₉O₃₄)@Ag₄₂(^tBuC≡C)₂₇(NO₃)₃Cl](NO₃)₃·CH₃CN (Ag₄₂Cu₃) clusters and one homometallic [(SiW₉O₃₄)@Ag₄₄(^tBuC≡C)₂₆Cl₈]·CH₃CN (Ag₄₄) cluster using lacunary polyoxometalates (POMs) as anionic templates under facile solvothermal conditions. Structural analyses reveal their similar core-shell architectures featuring a POM anionic template and a bowl-shaped silver shell stabilized by surface organic alkynyl (^tBuC≡C⁻) ligands. Various physicochemical and catalytic studies have characterized their temperature-dependent photoluminescence, photothermal conversion performance, and catalytic activity. Particularly, the enhanced catalytic performance towards 4-nitrophenol reduction is observed in the heterometallic cluster-catalyzed systems, where Ag₃₉Ni₄, Ag₃₉Co₄, and Ag₄₂Cu₃ exhibit higher catalytic activity than Ag₄₄. Such remarkable catalytic enhancement reveals that incorporating heterometal atoms into Ag clusters will be a feasible strategy to adjust the catalytic performance of POMs-templated Ag clusters.

Original language	English
Journal	Science China Chemistry
DOIs	https://doi.org/10.1007/s11426-026-3404-y
Publication status	Accepted/In press - 2026
Externally published	Yes

Keywords

3d metal doping
heterometallic cluster
polyoxometalates
silver cluster

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10.1007/s11426-026-3404-y

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@article{cd236580a7db47f786e0eb385013ce63,

title = "Polyoxometalate-templated assembly of homo- and heterometallic silver clusters",

abstract = "In this work, we have synthesized and characterized three heterometallic [Ni4(OH)3(NO3)3(SiW9O34)@Ag39(tBuC≡C)24(NO3)6](NO3) (Ag39Ni4), [Co4(OH)3(NO3)3(SiW9O34)@Ag39(tBuC≡C)24(NO3)6](NO3) (Ag39Co4) and [Cu3(OH)2O(SiW9O34)@Ag42(tBuC≡C)27(NO3)3Cl](NO3)3·CH3CN (Ag42Cu3) clusters and one homometallic [(SiW9O34)@Ag44(tBuC≡C)26Cl8]·CH3CN (Ag44) cluster using lacunary polyoxometalates (POMs) as anionic templates under facile solvothermal conditions. Structural analyses reveal their similar core-shell architectures featuring a POM anionic template and a bowl-shaped silver shell stabilized by surface organic alkynyl (tBuC≡C−) ligands. Various physicochemical and catalytic studies have characterized their temperature-dependent photoluminescence, photothermal conversion performance, and catalytic activity. Particularly, the enhanced catalytic performance towards 4-nitrophenol reduction is observed in the heterometallic cluster-catalyzed systems, where Ag39Ni4, Ag39Co4, and Ag42Cu3 exhibit higher catalytic activity than Ag44. Such remarkable catalytic enhancement reveals that incorporating heterometal atoms into Ag clusters will be a feasible strategy to adjust the catalytic performance of POMs-templated Ag clusters.",

keywords = "3d metal doping, heterometallic cluster, polyoxometalates, silver cluster",

author = "Xiaoyi Liu and Zichen Zhao and Mengyun Zhao and Yeqin Feng and Yang, \{Guo Yu\} and Hongjin Lv",

note = "Publisher Copyright: {\textcopyright} Science China Press 2026.",

year = "2026",

doi = "10.1007/s11426-026-3404-y",

language = "English",

journal = "Science China Chemistry",

issn = "1674-7291",

publisher = "Science China Press",

}

TY - JOUR

T1 - Polyoxometalate-templated assembly of homo- and heterometallic silver clusters

AU - Liu, Xiaoyi

AU - Zhao, Zichen

AU - Zhao, Mengyun

AU - Feng, Yeqin

AU - Yang, Guo Yu

AU - Lv, Hongjin

PY - 2026

Y1 - 2026

N2 - In this work, we have synthesized and characterized three heterometallic [Ni4(OH)3(NO3)3(SiW9O34)@Ag39(tBuC≡C)24(NO3)6](NO3) (Ag39Ni4), [Co4(OH)3(NO3)3(SiW9O34)@Ag39(tBuC≡C)24(NO3)6](NO3) (Ag39Co4) and [Cu3(OH)2O(SiW9O34)@Ag42(tBuC≡C)27(NO3)3Cl](NO3)3·CH3CN (Ag42Cu3) clusters and one homometallic [(SiW9O34)@Ag44(tBuC≡C)26Cl8]·CH3CN (Ag44) cluster using lacunary polyoxometalates (POMs) as anionic templates under facile solvothermal conditions. Structural analyses reveal their similar core-shell architectures featuring a POM anionic template and a bowl-shaped silver shell stabilized by surface organic alkynyl (tBuC≡C−) ligands. Various physicochemical and catalytic studies have characterized their temperature-dependent photoluminescence, photothermal conversion performance, and catalytic activity. Particularly, the enhanced catalytic performance towards 4-nitrophenol reduction is observed in the heterometallic cluster-catalyzed systems, where Ag39Ni4, Ag39Co4, and Ag42Cu3 exhibit higher catalytic activity than Ag44. Such remarkable catalytic enhancement reveals that incorporating heterometal atoms into Ag clusters will be a feasible strategy to adjust the catalytic performance of POMs-templated Ag clusters.

AB - In this work, we have synthesized and characterized three heterometallic [Ni4(OH)3(NO3)3(SiW9O34)@Ag39(tBuC≡C)24(NO3)6](NO3) (Ag39Ni4), [Co4(OH)3(NO3)3(SiW9O34)@Ag39(tBuC≡C)24(NO3)6](NO3) (Ag39Co4) and [Cu3(OH)2O(SiW9O34)@Ag42(tBuC≡C)27(NO3)3Cl](NO3)3·CH3CN (Ag42Cu3) clusters and one homometallic [(SiW9O34)@Ag44(tBuC≡C)26Cl8]·CH3CN (Ag44) cluster using lacunary polyoxometalates (POMs) as anionic templates under facile solvothermal conditions. Structural analyses reveal their similar core-shell architectures featuring a POM anionic template and a bowl-shaped silver shell stabilized by surface organic alkynyl (tBuC≡C−) ligands. Various physicochemical and catalytic studies have characterized their temperature-dependent photoluminescence, photothermal conversion performance, and catalytic activity. Particularly, the enhanced catalytic performance towards 4-nitrophenol reduction is observed in the heterometallic cluster-catalyzed systems, where Ag39Ni4, Ag39Co4, and Ag42Cu3 exhibit higher catalytic activity than Ag44. Such remarkable catalytic enhancement reveals that incorporating heterometal atoms into Ag clusters will be a feasible strategy to adjust the catalytic performance of POMs-templated Ag clusters.

KW - 3d metal doping

KW - heterometallic cluster

KW - polyoxometalates

KW - silver cluster

UR - https://www.scopus.com/pages/publications/105044804844

U2 - 10.1007/s11426-026-3404-y

DO - 10.1007/s11426-026-3404-y

M3 - Article

AN - SCOPUS:105044804844

SN - 1674-7291

JO - Science China Chemistry

JF - Science China Chemistry

ER -

Polyoxometalate-templated assembly of homo- and heterometallic silver clusters

Abstract

Keywords

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