PtCu/PCN-224异质结光热催化苯甲醇选择性氧化

doi:10.6023/A26030071

摘要/Abstract

苯甲醇选择性氧化到高附加值的苯甲醛是精细化工领域的重要反应. 传统合成工艺通常需要高温、高压和强氧化剂等, 能耗高、环境污染严重且醛选择性低. 本研究将金属纳米晶和卟啉金属-有机框架材料(MOF, PCN-224)复合得到PtCu/PCN-224异质结. 该材料不仅继承了纳米晶和卟啉MOF各自的优势, 还集合了纳米晶与MOF间的主客体协同、双金属间的客体协同及二者良好的光热效应. 因此, PtCu/PCN-224在室温、可见光下实现了苯甲醇完全氧化到苯甲醛的高效转化. 其性能显著优于单金属、PtCu合金和Pt/PCN-224催化剂. 此外, 本研究通过理论计算从理论层面深入探讨了单线态氧氧化苯甲醇的可行性, 并明确了PtCu对反应能垒的降低及底物的活化机制. 该工作为单线态氧的调控合成及其醇氧化提供了重要指示和理论依据.

关键词: 金属有机框架材料, 金属纳米晶, 单线态氧, 光热催化, 苯甲醇氧化

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

引用此文

张辉, 陈玉贞. PtCu/PCN-224异质结光热催化苯甲醇选择性氧化[J]. 化学学报, 2026, 84(7): 1096-1104.

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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图/表 8

图1. PtCu/PCN-224光热催化苯甲醇氧化的示意图

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

图2. PCN-224负载金属纳米晶的PXRD谱图

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

图3. PCN-224的(a) SEM; (b) TEM图像; (c) PtCu/PCN-224的TEM图像; (d) PtCu/PCN-224的HRTEM图像

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

图4. (a)样品的紫外可见吸收谱图; (b)不同频率下的PCN-224的莫特-肖特基曲线图(插图: PCN-224的Tauc图); (c)不同样品的光电流响应图(光照强度为120 mW•cm－2); (d)光照前后样品的自由基ESR光谱

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

表1. 不同催化剂光热催化苯甲醇选择性氧化活性对比

Table 1. Photocatalytic oxidation of benzyl alcohol over different catalysts

图5. Pt1Cu1/PCN-224在避光和光照5 min下的原位XPS谱图: (a) Pt 4f; (b) Cu 2p; (c) Zr 3d; (d)在光照下PtCu纳米晶与PCN-224界面处的电子转移机制(VB: 价带, CB: 导带, Ef表示PCN-224或PtCu纳米晶的费米能级, Ef'表示PtCu/PCN-224的费米能级)

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)

图6. (a) Pt1Cu1/PCN-224光催化氧化苯甲醇的吉布斯自由能图; (b)苯甲醇在Pt1Cu1/PCN-224上的反应机理

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

表2. PtCu/PCN-224光热催化不同取代基的芳香醇的选择性氧化a

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

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