Magic‐Sized Nanoclusters‐Induced Cascade Tandem Charge Transfer for Solar Water Oxidation

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 21; no. 13; pp. e2409513 - n/a
• Main Authors: Li, Zhuang‐Yan, Yuan, Meng, Xiao, Fang‐Xing
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.04.2025
• Subjects: Catalysis; Charge transfer; charge transport; Energy bands; Heterostructures; layer‐by‐layer assembly; Light irradiation; magic‐sized nanoclusters; Multilayers; Nanoclusters; non‐conjugated polymer; Oxidation; photoelectrochemical water splitting; Photoredox catalysis; Quantum confinement; Separation; Solar energy conversion; Substrates; Transition metal compounds; layer‐by‐layer assembly; magic‐sized nanoclusters; photoelectrochemical water splitting; non‐conjugated polymer; charge transport
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202409513

Magic‐sized nanoclusters (MSCs) have been attracting enduring interest by virtue of the quantum confinement effect, discrete energy band structure, and enriched catalytic active sites. Nevertheless, up to date, exploration of MSCs artificial photosystems and fine‐tuning of spatial vectorial charge transfer in photoredox catalysis have so far been scarcely reported. Hence, we employed a facile and easily accessible layer‐by‐layer (LbL) assembly strategy to highly ordered, alternately, and periodically deposit oppositely charged tailor‐made transition metal chalcogenides (TMCs) MSCs and non‐conjugated polymer (NCP) building blocks on the MO substrate, resulting in the MO/(NCP‐TMCs MSCs)n multilayer heterostructures. It is affirmed that the ultra‐thin NCP uniformly intercalated at the interface of every TMCs MSCs layer fosters the unidirectional electron flow from TMCs MSCs to MO substrate with the assistance of NCP, and moreover the multilayered interface configuration benefits the establishment of cascade tandem charge transfer route, synergistically giving rise to the significantly enhanced charge separation and boosted solar water oxidation performances of MO/(TMCs MSCs‐NCP)n heterostructure under simulated solar light irradiation. Our work elucidates the specific roles of NCP and MSCs as charge relay mediators and photosensitizers, affording a quintessential paradigm to rationally regulate the photocarrier transport and separation over MSCs for solar energy conversion. Non‐conjugated polymer (PDDA) and tailor‐made magic‐sized nanoclusters (MSCs) are utilized as building blocks for layer‐by‐layer assembly of WO3/(PDDA/CdSe MSCs)n photoanode toward solar water oxidation. The photoanode demonstrates significantly enhanced photoelectrochemical water oxidation performances, attributed to the generation of cascade tandem electron transfer pathway by judiciously harnessing the pivotal role of PDDA as charge transfer mediators and CdSe MSCs as photosensitizers.