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

Hui Zhang, Yuzhen Chen. PtCu/PCN-224 Heterojunction for Photothermal-Driven Selective Oxidation of Benzyl Alcohol[J]. Acta Chimica Sinica, 2026, 84(7): 1096-1104.

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Fig. & Tab. 8

Figure 1. Schematic illustration of photothermal catalytic oxidation of benzyl alcohol over PtCu/PCN-224

Figure 2. PXRD patterns of metal NCs loaded on PCN-224

Figure 3. (a) SEM and (b) TEM images of PCN-224; (c) TEM and (d) HRTEM images of PtCu/PCN-224

Figure 4. (a) UV-vis spectra of different samples; (b) Mott-Schottky plots for PCN-224 at different frequencies (inset: Tauc plot of PCN-224); (c) transient photocurrent responses for different samples at 120 mW•cm－2; (d) ESR spectra of samples under light irradiation or dark conditions

Entry	Catalyst	Time/min	T/℃	Yield^c/%
1^a	Pt NCs	30	34	39
1^a	Pt NCs	60	36	>99
2^a	Pt₁Cu₁ NCs	60	30	>99
3^a	Pt/PCN-224	20	32	68
3^a	Pt/PCN-224	60	36	>99
4^a	Pt₂Cu₁/PCN-224	10	26	56
4^a	Pt₂Cu₁/PCN-224	25	34	>99
5^a	Pt₁Cu₁/PCN-224	10	25	70
5^a	Pt₁Cu₁/PCN-224	15	30	>99
6^a	Pt₁Cu₂/PCN-224	60	36	81
6^a	Pt₁Cu₂/PCN-224	80	36	95
7^a	Cu/PCN-224	60	29	0
8^a	PtCu＋PCN-224	60	27	55
9^a	Pt₁Cu₁/PCN-224 ＋carotene	60	28	44
10^b	Pt₁Cu₁/PCN-224	60	35	10
11^a	Pt₁Cu₁/ZIF-8	60	26	66

Table 1. Photocatalytic oxidation of benzyl alcohol over different catalysts

Figure 5. In-situ XPS spectra of Pt1Cu1/PCN-224 under dark and irradiation 5 min: (a) Pt 4f; (b) Cu 2p; (c) Zr 3d; (d) Electron transfer mechanism between PtCu and PCN-224 under visible light irradiation (VB: valence band, CB: conduction band, Ef represents the Fermi level of PCN-224 or PtCu NCs, Ef' represents the Fermi level of Pt1Cu1/PCN-224)

Figure 6. (a) Gibbs free energy diagram of Pt1Cu1/PCN-224 during photocatalytic oxidation of benzyl alcohol; (b) proposed reaction mechanism of benzyl alcohol over Pt1Cu1/PCN-224

Entry	Time/min	Yield^b/%	Selectivity/%	Entry	Time/min	Yield^b/%	Selectivity/%
1	15	>99	100	7	30	>99	100
2	20	>99	100	8	15	>99	100
3	15	>99	100	9	90	>99	100
4	15	>99	100	10	50	>99	100
5	30	>99	100	11	15	>99	100
6	30	>99	100

Table 2. Photooxidation reactions of various aromatic alcohols over PtCu/PCN-224

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PtCu/PCN-224异质结光热催化苯甲醇选择性氧化