image: The four clusters identified were found to contain Keggin-type PM4Mo8 motifs, which exhibit redox properties akin to those of typical PMo12O403− (PMo12), along with superior structural stability. The substitution of the four metal Mo center with M (Co or Ni) in the PMo12 skeleton, in conjunction with the capping by the TC4A ligand and VO unit, significantly modulated the visible-light absorption, thereby enhancing photothermal conversion in both solid-state and organic solutions. The efficiency of photothermal conversion depends on electron transfer pathways in the cluster.
Credit: Polyoxometalates, Tsinghua University Press
“All those clusters contain a PMo8 unit with MoVI centers, combining the incorporation of a VO3+ group (in 3 and 4) on the surface of PMo8 and abundant M-S bonds. These structural characteristics have the potential to enhance the synergistic properties in catalytic reactions,” explained Prof. Yanfeng Bi, corresponding author of the study.
In this study, the team examined the electrochemical performance and electrocatalytic IO3- model reactions of these clusters, which suggest that the distinct components of the clusters, particularly the incorporation of V atoms, lead to larger packing voids and increased exposure of active surfaces, which are responsible for the improved electrochemical performance. Photothermal conversion experiments were conducted on these clusters in both the solid state and in DMF solution assessed the impact of the arrangement of Mo-M and Mo-V, as well as their interaction with thiacalixarene within the clusters, on their photothermal performance under visible light irradiation.
This work highlights the transport pathway of hot electrons in the photothermal conversion process based on cluster band structures, DFT calculations, and XPS characterization. The metal-organic hybrid clusters exhibited bifunctional electrochemical and photothermal conversion properties, which may provide insights into the design and synthesis of POM-based multifunctional materials.
The first author of this work is Qing Zhao from School of Petrochemical Engineering, Liaoning Petrochemical University, China. This research was funded by the National Natural Science Foundation of China (Nos. 91961110, 22171122, and 22201123).
About the Author
The corresponding author Prof. Yanfeng Bi specializes in the design and synthesis, structural evolution, and application of atomically precise metal clusters.
About Polyoxometalates
Polyoxometalates (POM) is a peer-reviewed, open-access and interdisciplinary journal, published quarterly by Tsinghua University Press, released exclusively on SciOpen. POM publishes original high-quality research papers and significant review articles that focus on cutting-edge advancements in polyoxometalates, and clusters of metals, metal oxides and chalcogenides. It is dedicated to exploring all topical areas, ranging from basic aspects of the science of polyoxometalates, and clusters of metals, metal oxides and chalcogenides to practical applications of such materials. The journal is indexed by Scopus (CiteScore 2024 = 14.7), Ei Compendex, CAS, and DOAJ.
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Journal
Polyoxometalates
Article Title
Thiacalix[4]arene-functionalized molecular clusters involving the Keggin-type PM4Mo8 (M = Co, Ni) motif: Electrochemical and photothermal conversion properties
Article Publication Date
16-Jun-2025