光催化二氧化碳（CO2）还原已成为减少温室气体排放并同步生产高附加值化学品与燃料的重要策略。然而,光生载流子的快速复合严重制约太阳能驱动光催化系统的效率,成为该技术发展的关键瓶颈。本研究通过分子空腔限域策略,成功将超小WO3纳米簇限域封装于PCN-250的微孔骨架中。与主要依赖Fe3+活性位点的原始PCN-250不同,封装WO3纳米簇构筑了紧密结合的Z型异质结。该独特结构不仅抑制了WO3纳米颗粒的聚集,克服了传统WO3纳米片层间电荷传输受限的问题,同时实现了高效电荷分离,并保留了各组分的高氧化还原能力,显著提升了光催化CO2还原性能。HAADF-STEM分析证实WO3纳米簇被有效限域封装于PCN-250内部,其自组装形成的超小纳米簇直径范围为0.8-1.4 nm。UV-Vis光谱表明,这种纳米级封装显著拓宽了材料的光学吸收范围,将吸收边延伸至800 nm,实现了对整个可见光区域的响应。以H2O蒸气为质子源时,优化后的WO3@PCN-250-2（W@P-2）复合材料CO2光还原效率达516.07 μmol·g-1,是纯WO3的9.1倍。机理研究表明,WO3/PCN-250界面遵循Z型电荷转移路径;原位红外光谱证实*COOH为CO2还原生成CO的关键中间体。该工作为设计面向高效CO2光还原的Z型异质结提供了重要参考。
杨苗苗
,
任静
,
王野
,
董文文
,
赵君
,
李东升
,
张志明
. PCN-250封装超小WO3纳米团簇用于水蒸气中高效光还原CO2制CO★[J]. 化学学报, 0
: 0
.
DOI: 10.6023/A26020050
Renewable light-driven photocatalytic CO2 reduction (CO2RR) has emerged as a promising strategy to mitigate greenhouse gas emissions while producing value-added chemicals and fuels. However, the efficiency of solar-driven photocatalytic systems remains limited by rapid recombination of photogenerated charge carriers, which represents a critical bottleneck for technological progress. Herein, ultrasmall WO3 nanoclusters were successfully immobilized within the microporous framework of PCN-250 via a molecular cavity confinement strategy. Unlike pristine PCN-250, which primarily relies on monocomponent Fe3+ active sites, the immobilization of WO3 nanoclusters enables the construction of a Z-scheme heterojunction. This unique architecture not only promotes efficient charge separation but also preserves the strong redox potentials of both components, thereby significantly enhancing the photocatalytic CO2 reduction performance. HAADF-STEM analysis confirms the effective confinement and encapsulation of WO3 nanoclusters within the PCN-250, where WO3 species self-assemble into ultrathin nanoclusters with diameters ranging from 0.8 to 1.4 nm. UV-Vis spectroscopy reveals that this nanoscale encapsulation markedly broadens the optical absorption, extending the absorption edge to 800 nm and thus spanning the entire visible light region. Using H2O vapor as a proton source, the optimized WO3@PCN-250-2 (W@P-2) composite exhibits a CO2 photoreduction rate of 516.07 μmol·g-1, which is 9.1 times higher than that of pristine WO3. Mechanistic studies indicate a Z-scheme charge transfer pathway at the WO3/PCN-250 interface. In-situ FTIR spectroscopy identifies *COOH as the key intermediate during CO2 reduction to CO. This work offers a valuable reference for designing Z-scheme heterojunctions toward efficient CO2 photoreduction.
[1] Fang S. Y.; Rahaman M.; Bharti J.; Reisner E.; Robert M.; Ozin G. A.; Hu, Y. H. Nat. Rev. Methods. Primers.2023, 3, 61.
[2] Cheng C.; Xu H. Y.; Ni M. M.; Guo C. F.; Zhao Y. Y.; Hu, Y. Appl. Catal. B: Environ.2024, 345,123705.
[3] Qi G. D.; Ba D.; Zhang Y. J.; Jiang X. Q.; Chen Z. H.; Yang M. M.; Cao J. M.; Dong W. W.; Zhao J.; Li D. S.; Zhang, Q. C. Adv. Sci.2024, 11, 2402645.
[4] Zhao J. S.; Mu Y. F.; Wu L. Y.; Luo Z. M.; Velasco L.; Sauvan M.; Moonshiram D.; Wang J. W.; Zhang Z. M.; Lu, T. B. Angew. Chem. Int. Ed.2024, 63, e202401344.
[5] Dong W. W.; Jia J.; Wang Y.; An J. R.; Yang O. Y.; Gao X. J.; Liu Y. L.; Zhao J.; Li, D. S. Chem. Eng. J.2022, 438, 135622.
[6] Zhu R. M.; Liu L. M.; Zhang G. X.; Zhang Y.; Jiang Y. X.; Pang H. Nano. Energy.2024, 122, 109333.
[7] Luo C.; Li P. H.; Liao W. M.; Li Q. C.; Zhou X. X.; He, J. Chin. J. Struct. Chem2025, 44, 100621.
[8] Li M. J.; Xia T.; Wang M. Y.; Peng Y. J.; Zhang S. H.; Jiang X. L.; Yang, H. Chin. J. Struct. Chem2025, 44, 100627.
[9] Ma X. L.;Shi W. X.; Guo S.; Zhao Q. P.; Lin W. B.; Lu T. B.; Zhang Z. M.Adv. Mater. 2025, 37, 2506133.
[10] Huang W. Y.; Zhang Z. Y.; Xu J. W.; Cui H. P.; Tang K. X.; Crawshaw D.; Wu J. X.; Zhang X. D.; Tang L.; Liu N. JACS Au.2025, 5, 1184-1195.
[11] Zheng F. B.; Wang K.; Lin T.; Wang Y. L.; Li G. D.; Tang, Z. Y. Acta Chim Sinica.2023, 81, 669-980.
[12] Guo S.; Pan C. W.; Hou M.; Hou Y. T.; Yao S.; Lu T. B.; Zhang, Z. M. Angew. Chem. Int. Ed.2025, 64, e202420398.
[13] Gao C.; Zhang S. T.; Pang, H. Acta Chim Sinica.2025, 83, 962-980.
[14] Fu S. S.; Yao S.; Guo S.; Guo G. C.; Yuan W. J.; Lu T. B.; Zhang, Z. M. J. Am. Chem. Soc.2021, 143, 20792-20801.
[15] Yao S.; Jiang S. Y.; Wang B. F.; Yin H. Q.; Xiang X. Y.; Tang Z.; An C. H.; Lu T. B.; Zhang, Z. M. Angew. Chem. Int. Ed.2025, 64, e202418637.
[16] Huang T. Y.; Han J. Y.; Li Z. Q.; Hong Y. X.; Gu X. F.; Wu Y. F.; Zhang Y. J.; Liu S. Q.Angew. Chem. Int. Ed. 2025, e202500269.
[17] Kirchon A.; Li J. L.; Xia F. Q.; Day G. S.; Becker B.; Chen W. M.; Sue H. J.; Fang Y.; Zhou, H. C. Angew. Chem. Int. Ed.2019, 58, 12425-12430.
[18] Dong Y. J.; Jiang Y.; Liao J. F.; Chen H. Y.; Kuang D. B.; Su, C. Y. Sci. China. Mater.2022, 65, 1550-1559.
[19] Zhang X.; Zhang Z. Q.; Sun Y. D.; Ma X. J.; Jin F. X.; Zhang F. Y.; Han W. G.; Shen B. X.; Guo, S. Q. Rare Met.2024, 43, 3441-3459.
[20] Zhao C. B.; Jiang Z.; Liu Y.; Zhou Y.; Yin P. C.; Ke Y. B.; Deng, H. X. J. Am. Chem. Soc.2022, 144, 23560-23571.
[21] Yang M. M.; Cao J. M.; Qi G. D.; Shen X. Y.; Yan G. Y.; Wang Y.; Dong W. W.; Zhao J.; Li D. S.; Zhang, Q. C. Inorg. Chem.,2023, 62, 15963-15970.
[22] Dong C.; Yang J. J.; Xie H. L.; Cui J. L.; Fang W. H.; Li, J. R. Nat. Commun.2022, 13, 4991.
[23] Ling P. Q.; Zhu J. C.; Wang Z. Q.; Hu J.; Zhu J. F.; Yan W. S.; Sun Y. F.; Xie Y. Nanoscale.2022, 14, 14023.
[24] Jiang C.; Qiu Y.; Xin X. Nano Res.2024, 17, 6281-6293.
[25] Jiang H. P.; Wang L. L.; Yu X. H.; Sun L. J.; Li J. H.; Yang J.; Liu, Q. Q. Chem. Eng. J.2023, 466, 143129.
[26] Dong H.; Fang L.; Chen K. X.; Wei J. X.; Li J. X.; Qiao X.; Wang Y.; Zhang F. M.; Lan Y. Q.Angew. Chem. Int. Ed. 2024, e202414287.
