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、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, doi: 10.6023/A26030071.

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

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Zhang T.; Cai X.D.;Liu N.; Xu, C.L. Acta Chim. Sinica2016, 74, 441(in Chinese). (张婷, 蔡雪刁, 刘娜, 许春丽, 化学学报, 2016, 74, 441.)
[2] Diez A.; Piqueras C. M.; Araiza D.; Díaz G.; Volpe, M. A. Mater. Chem. Phys.2019, 232, 265.
[3] Gao G. D.; Rong R.; Zhang Z.; Pan B. B.; Sun X.; Zhang Q. L.; Zheng G. X.; Xu K.; Gao, L. F. Catal. Commun.2023, 183, 6.
[4] Zhou Z. Y.; Xie Y. N.; Zhu W. Z.; Zhao H. Y.; Yang N. J.; Zhao, G. H. Appl. Catal. B Environ2021, 286, 12.
[5] Shariatinia Z.; Karimzadeh, Z. Coord. Chem. Rev.2025, 526, 216372.
[6] Qin Y. J.; Han X.; Li Y. P.; Han A. J.; Liu W. X.; Xu H. J.; Liu, J. F. ACS Catal.2020, 10, 5973.
[7] Goldberg M. A.; Eseva E. A.; Donskaya N. O.; Fomin A. S.; Antonova O. S.; Leonov A. V.; Konovalov A. A.; Murzakhanov F. F.; Kudryavtsev E. A.; Akopyan A. V.; Gafurov M. R.; Barinov S. M.; Komlev, V. S. Ceram. Int.2025, 51, 10302.
[8] Shoukat H.; Altaf A. A.; Hamayun M.; Ullah S.; Kausar S.; Hamza M.; Muhammad S.; Badshah A.; Rasool N.; Imran M. ACS Omega2021, 6, 19606.
[9] An G.; Zhang X.; Zhang C.; Gao H.; Liu S.; Qin G.; Qi H.; Kasemchainan J.; Zhang J.; Wang, G. Chin. J. Catal.2023, 50, 126.
[10] Wang H.; Yong D.; Chen S.; Jiang S.; Zhang X.; Shao W.; Zhang Q.; Yan W.; Pan B.; Xie, Y. J. Am. Chem. Soc.2018, 140, 1760
[11] Assal M. E.; Shaik M. R.; Kuniyil M.; Khan M.; Al-Warthan A.; Siddiqui M. R. H.; Khan S. M. A.; Tremel W.; Tahir M. N.; Adil, S. F. RSC Adv.2017, 7, 55336.
[12] Chevallier M. L.; Dessolin S.; Serres F.; Bruyas L.; Chatel G. Molecules2019, 24, 4157.
[13] Montagnon T.; Tofi M.; Vassilikogiannakis, G. Acc. Chem. Res.2008, 41, 1001.
[14] Chen Y. Z.; Wang Z. U.; Wang H.; Lu J.; Yu S. H.; Jiang H. L.J. Am. Chem. Soc. 2017, 139, 2035.
[15] Strassfeld D. A.; Chen C. Y.; Park H. S.; Phan D. Q.; Yu J. Q. Nature2023, 622, 80.
[16] Gupta M.; Charpe V. P.; Hwang, K. C. ACS Sustainable Chem. Eng.2024, 12, 16297.
[17] Wang N.N.; Chen, Y. Z. Acta Chim. Sinica2024, 82, 621(in Chinese). (王南南, 陈玉贞, 化学学报, 2024, 82, 621.)
[18] Zhou H. C.; Kitagawa, S. Chem. Soc. Rev.2014, 43, 5415.
[19] Xie C.; Xu Y. P.; Gao M. L.; Xu Z. N.; Jiang, H. L. Acta Chim. Sinica2022, 80, 867(in Chinese). (谢晨帆, 徐玉平, 高明亮, 徐忠宁, 江海龙, 化学学报, 2022, 80, 867.)
[20] Liao P. Q.; Huang N. Y.; Zhang W. X.; Zhang J. P.; Chen X. M. Science2017, 356, 1193.
[21] Sui J.; Gao M. L.; Qian B.; Liu C.; Pan Y.; Meng Z.; Yuan D.; Jiang, H. L. Sci. Bull.2023, 68, 1886.
[22] Jing C.; Liu J.; Chen Y. Z.; Li Z.Angew. Chem. Int. Ed. 2026, e2783900.
[23] Konnerth H.; Matsagar B. M.; Chen S. S.; Prechtl M. H. G.; Shieh F. K.; Wu, K. C. W. Coord. Chem. Rev.2020, 416, 24.
[24] Navalón S.; Dhakshinamoorthy A.; Álvaro M.; Ferrer B.; García H. Chem. Rev.2023, 123, 445.
[25] Liang B.; Zhang X.; Xie Y.; Lin R. B.; Krishna R.; Cui H.; Li Z. Q.; Shi Y. S.; Wu H.; Zhou W.; Chen, B. L. J. Am. Chem. Soc.2020, 142, 17795.
[26] Ding G. X.; Li C. X.; Chen L. H.; Liao, G. F. Energy Environ. Sci.2024, 17, 5311.
[27] Feng D.; Chung W. C.; Wei Z.; Gu Z. Y.; Jiang H. L.; Chen Y. P.; Darensbourg D. J.; Zhou, H. C. J. Am. Chem. Soc.2013, 135, 17105.
[28] Fang Z. B.; Liu T. T.; Liu J.; Jin S.; Wu X. P.; Gong X. Q.; Wang K.; Yin Q.; Liu T. F.; Cao R.; Zhou, H. C. J. Am. Chem. Soc.2020, 142, 12515.
[29] Xu H. Q.; Hu J.; Wang D.; Li Z.; Zhang Q.; Luo Y.; Yu S. H.; Jiang, H. L. J. Am. Chem. Soc.2015, 137, 13440.
[30] Lu Z. X.; Gao J. S.; Rao S. S.; Jin C.; Jiang H. P.; Shen J.; Yu X. H.; Wang W. K.; Wang L. L.; Yang J.; Liu, Q. Q. Appl. Catal. B Environ2024, 342, 12.
[31] Ran Q.; Tao B. B.; Li M. H.; Zheng K. D.; She Y. Y.; Wu W. J.; Li Z. T.; Luo D.; Xu, X. T. Coord. Chem. Rev.2025, 525, 22.
[32] Huang N.; Yuan S.; Drake H.; Yang X.; Pang J.; Qin J.; Li J.; Zhang Y.; Wang Q.; Jiang D.; Zhou, H. C. J. Am. Chem. Soc.2017, 139, 18590.
[33] Zhai G.; Liu Y.; Lei L.; Wang J.; Wang Z.; Zheng Z.; Wang P.; Cheng H.; Dai Y.; Huang B.ACS Catal. 2021, 11, 1988.
[34] Yang J.; Jing J.; Zhu, Y. H. Adv Mater.2021, 33, e2101026.
[35] Chen Y. H.; Gu L. J.; Ma B. H.; Li X.; Mei Y. B.; Zhou J. L.; Chong Y.; Ma M. H.; Zhang M. Z.; Wang L.; Cheng Y. F.; Wu K. J.; Zeng J.; Cheng M.; Guo P.; Zhang P. H.; He, D. L. Chem. Eng. J.2023, 454, 14.
[36] Zhong Y. H.; Wang Y.; Zhao S. Y.; Xie Z. X.; Chung L. H.; Liao W. M.; Yu L.; Wong W. Y.; He, J. Adv. Funct. Mater.2024, 34, 2316199.
[37] Wang Z.; Zhang R.; Zhang W.; Liao L.; Han J.; Xie G.; Chen S. Anal Chem.2025, 97, 15895.
[38] Zhu Z.; Xiao J.; Zhang M.; Huang Y.; Yuan S. Chem Sci.2025, 16, 22638.
[39] Jing C. X.; Liu, F. S; Chen, Y. Z.; Li, Z. B. Coord. Chem. Rev.2025, 540, 216771.
[40] Zhao Y.; Kornienko N.; Liu Z.; Zhu C.; Asahina S.; Kuo T. R.; Bao W.; Xie C.; Hexemer A.; Terasaki O.; Yang P.; Yaghi O. M.J. Am. Chem. Soc. 2015, 137, 2199.
[41] Aslam U.; Rao V. G.; Chavez S.; Linic S. Nat. Catal.2018, 1, 656.
[42] Li S.; Mei H. M.; Yao S. L.; Chen Z. Y.; Lu Y. L.; Zhang L.; Su, C. Y. Chem. Sci.2019, 10, 10577.
[43] Liu J.; Zhang J.Chem. Rev. 2020, 120, 2123.
[44] Gu D. X.; Liu Y.; Li X. L.; Zhu H. Y.; Cui Y. L.; Yang W. T.; Hao, J. Y. Appl. Surf. Sci.2023, 614, 10.
[45] Zhang Q.; Wu M.; Fang Y.; Deng C.; Shen H. H.; Tang Y.; Wang Y. Nanomaterials-Basel2023, 13, 2633.
[46] Shan M.; Arif S.; Khairi F. M.; Muhamad M. R.; Alzahrani A.; Alghamdi A.; Khan A. U. Materials-Basel2026, 19, 243.
[47] Ma W.; Yu L.; Kang P.; Chu Z.; Li Y. Molecules2024, 29, 5834.
[48] He S.; Chen Y.; Fang J.; Liu Y.; Lin Z.Chem. Soc. Rev. 2025, 54, 2154.
[49] Liu J.; Zhang K.; Chen Z.; Wei Z. W.; Zhang, L. Chem. Asian. J.2020, 15, 1118.
[50] Moualhi Y.; Mabrouki A.; Rahmouni H.; Dhahri E. Mater. Adv.2025, 6, 9051.
[51] Zhao J.; Lyu C.; Zhang R.; Han Y.; Wu Y. D.; Wu, X. L. J. Hazard. Mater.2023, 442, 141274.
[52] Chen H. Y.; Zhu H. L.; Liao P. Q.; Chen, X. M. Acta Phys. Chim. Sin.2024, 40, 7.
[53] Shi R. F.; Lv D. F.; Chen Y. W.; Wu H. X.; Liu B. Y.; Xia Q. B.; Li, Z. Sep. Purif. Technol.2018, 207, 262.
[54] Liu Y. N.; Chen H. Y.; Chai L.; Liu J.; Huang S.; Liu F.; Wei M. J.; Zhu X. H.; Zhang Y. Y.; Liu M. L.; Yao, S. Z. Sens. Actuators, B2024, 418, 11.
[55] Deng S.; Hao Y.; Yang L.; Yu T.; Wang X.; Liu H.; Liu Y.; Xie M. Biosens Bioelectron2025, 278, 117339.
[56] Cui J. L.; Cui Y. J.; Tan J. J.; Zhang H. R.; Gu M. Y.; Huang, L. J. Environ. Chem. Eng.2024, 12, 9.
[57] Wang J.; Zhang X.; Liu Y.; Wang Z.; Wang P.; Zheng Z.; Cheng H.; Dai Y.; Huang, B. J. Colloid Interface Sci.2021, 602, 300.
[58] Niu K. K.; Luan T. X.; Cui J.; Liu H.; Xing L. B.; Li, P. Z. ACS Catal.2024, 14, 2631.
[59] Francés-Soriano L.; Bellezza D.; Ferrera-González J.; González-Béjar M.; Pérez-Prieto J. Nanoscale Adv.2024, 6, 5889.
[60] Zhang T.; Xing G.; Chen W.; Chen, L. Mater. Chem. Front.2020, 4, 332.