Effective Photocatalytic Ethanol Reforming into High‐Value‐Added Multicarbon Compound Coupled with H2 Production Over Pt‐S3 Sites at PtSA–ZnIn2S4 Interface

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-05, Vol.20 (20), p.e2307386-n/a
• Main Authors: Wu, Shiting, Li, Xiaohui, Liu, Jiaqi, Wu, Hanfeng, Xu, Hanshuai, Bai, Wangfeng, Mao, Liang, Shi, Xiaowei
• Format: Article
• Language: English
• Subjects: Acetaldehyde; Biofuels; Catalysts; Catalytic activity; Dehydrogenation; electron transfer; Electrons; Ethanol; Hydrogen bonds; Hydrogen evolution; interface; Mass transfer; Photocatalysis; Protons; Pt‐S3 sites; Quantum efficiency; Reforming; Substrates
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.202307386

Selective photocatalytic production of high‐value acetaldehyde concurrently with H2 from bioethanol is an appealing approach to meet the urgent environment and energy issues. However, the difficult ethanol dehydrogenation and insufficient active sites for proton reduction within the catalysts, and the long spatial distance between these two sites always restrict their catalytic activity. Here, guided by the strong metal‐substrate interaction effect, an atomic‐level catalyst design strategy to construct Pt‐S3 single atom on ZnIn2S4 nanosheets (PtSA‐ZIS) is demonstrated. As active center with optimized H adsorption energy to facilitate H2 evolution reaction, the unique Pt single atom also donates electrons to its neighboring S atoms with electron‐enriched sites formed to activate the O─H bond in *CH3CHOH and promote the desorption of *CH3CHO. Thus, the synergy between Pt single atom and ZIS together will reduce the energy barrier for the ethanol oxidization to acetaldehyde, and also narrow the spatial distance for proton mass transfer. These features enable PtSA‐ZIS photocatalyst to produce acetaldehyde with a selectivity of ≈100%, which will spontaneously transform into 1,1‐diethoxyethane via acetalization to avoid volatilization. Meanwhile, a remarkable H2 evolution rate (184.4 µmol h−1) is achieved with a high apparent quantum efficiency of 10.50% at 400 nm. Pt‐S3 single atom is designed on ZnIn2S4 nanosheets for ethanol photoreforming. The strong metal‐substrate interaction effect can reduce the energy barrier in photocatalytic ethanol dehydrogenation, as well as narrow the spatial distance of proton mass transfer. The unique electronic property of Pt‐S3 species contributes to a remarkable activity for co‐production of high‐value chemical 1,1‐diethoxyethane and H2 with selectivity of ≈100%.