PtCu/PCN-224 Heterojunction for Photothermal-Driven Selective Oxidation of Benzyl Alcohol

doi:10.6023/A26030071

Abstract

The selective oxidation of benzyl alcohol to benzaldehyde represents an important transformation within the fine chemical industry. Conventional synthetic routes, however, typically require harsh conditions involving high temperatures/pressures, and stoichiometric strong oxidants, leading to substantial energy consumption, severe environmental concerns, and low aldehyde selectivity. Therefore, the development of green and efficient catalytic systems capable of operating under mild conditions is of considerable significance. Herein, we propose a PtCu/PCN-224 heterojunction constructed by integrating metal nanocrystals with a porphyrinic metal-organic framework (MOF), PCN-224. This hybrid architecture not only inherits the intrinsic advantages of both components but also integrates the host-guest synergy between PtCu nanocrystals (NCs) and PCN-224, guest-guest synergy between Pt and Cu species, and the enhanced photothermal properties of the composite. Consequently, the PtCu/PCN-224 heterojunction achieves complete conversion of benzyl alcohol to benzaldehyde (> 99% selectivity) under ambient conditions using visible light irradiation. Furthermore, the composite material exhibits excellent catalytic stability during cycle test. Experimental results demonstrated that the synergistic interaction between nanocrystals and MOF significantly enhances the electron transfer efficiency for the singlet oxygen (¹O₂) generation. Besides, the high light-to-thermal efficiency benefiting from the strong light harvesting capacity of both PtCu NCs and PCN-224 greatly promotes the aerobic reaction of alcohol oxidation. This performance was substantially superior to that of its monometallic counterparts, PtCu and Pt/PCN-224. More importantly, density functional theory (DFT) calculations were employed to elucidate the alcohol oxidation mechanism of ¹O₂. We demonstrate the feasibility of ¹O₂-mediated benzyl alcohol oxidation and identify the PtCu active sites as critical for lowering the reaction energy barrier and facilitating substrate activation. Significantly, ¹O₂ is confirmed as the predominant reactive oxygen species governing the oxidation process under photoexcitation. This work not only establishes a green and efficient photothermal catalytic platform but also provides a fundamental direction for the controlled generation of ¹O₂ and its application in selective alcohol oxidation.

Key words: metal-organic framework, metal nanocrystal, singlet oxygen, photothermal catalysis, benzyl alcohol oxidation

Cite this article

Zhang Hui, Chen Yuzhen. PtCu/PCN-224 Heterojunction for Photothermal-Driven Selective Oxidation of Benzyl Alcohol[J]. Acta Chimica Sinica, doi: 10.6023/A26030071.

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PtCu/PCN-224异质结光热催化苯甲醇选择性氧化