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★

doi:10.6023/A26020050

化学学报 ›› 2026, Vol. 84 ›› Issue (5): 643-650.DOI: 10.6023/A26020050 上一篇下一篇

研究论文

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^★

杨苗苗^a^,^c, 任静^c, 王野^a^,^b^,^*(), 董文文^a^,^b, 赵君^a^,^b^,^*(), 李东升^a^,^b, 张志明^c^,^*()

^a 三峡大学材料与化学工程学院无机非金属晶体与能源转换材料国家重点实验室宜昌 443002
^b 湖北三峡实验室宜昌 443007
^c 天津理工大学材料科学与工程学院新能源材料与低碳技术研究院天津 300384

投稿日期:2026-02-07 发布日期:2026-03-27
通讯作者: 王野, 赵君, 张志明
作者简介:
★“框架材料化学”专辑
基金资助:
国家自然科学基金(22301159); 国家自然科学基金(22471141); 湖北省自然科学基金(2023AFB129); 111工程(DT20015); 湖北三峡实验室开放/创新基金(SC232013)

Encapsulation of Ultrasmall WO₃ Nanoclusters in PCN-250 for Efficient CO₂ Photoreduction to CO with Water Vapor^★

Miaomiao Yang^a^,^c, Jing Ren^c, Ye Wang^a^,^b^,^*(), Wenwen Dong^a^,^b, Jun Zhao^a^,^b^,^*(), Dongsheng Li^a^,^b, Zhiming Zhang^c^,^*()

^a Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, College of Materials and Chemical Engineering,China Three Gorges University, Yichang 443002, China
^b Hubei Three Gorges Laboratory, Yichang 443007, China
^c Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, Tianjin University of Technology, Tianjin 300384, China

Received:2026-02-07 Published:2026-03-27
Contact: Ye Wang, Jun Zhao, Zhiming Zhang
About author:
★ For the VSI “Chemistry of Framework Materials”.
Supported by:
National Natural Science Foundation of China(22301159); National Natural Science Foundation of China(22471141); Natural Science Foundation of Hubei Province(2023AFB129); 111 Project(DT20015); Hubei Three Gorges Laboratory Open/Innovation Fund project(SC232013)

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1. Supporting Information-A26020050.pdf(1596KB)

摘要/Abstract

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Fe^3＋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. 高角环形暗场扫描透射电子显微镜(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.

关键词: 超小WO₃纳米簇, PCN-250, Z型异质结, CO₂光还原, 水蒸气

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 Fe^3＋ 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. High-angle annular dark field scanning transmission electron microscopy (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.

Key words: ultrathin WO₃ nanocluster, PCN-250, Z-scheme heterojunction, CO₂ photoreduction, water vapor

引用此文

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, 2026, 84(5): 643-650.

Miaomiao Yang, Jing Ren, Ye Wang, Wenwen Dong, Jun Zhao, Dongsheng Li, Zhiming Zhang. Encapsulation of Ultrasmall WO₃ Nanoclusters in PCN-250 for Efficient CO₂ Photoreduction to CO with Water Vapor^★[J]. Acta Chimica Sinica, 2026, 84(5): 643-650.

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图/表 5

Figure 1. (a) Synthetic scheme of W@P-x, (b) HRTEM images of W@P-2, (c, d) enlarged HAADF-STEM images of W@P-2 (Inset: particle size distribution of WO3), and (e~i) corresponding elemental mapping images of W@P-2

Figure 2. (a) PXRD patterns of WO3, PCN-250 and W@P-x, (b) UV-vis spectra of WO3, PCN-250 and W@P-2, (c) FT-IR spectra of WO3, PCN-250 and W@P-2, and (d) TGA spectra of PCN-250 and W@P-2

Figure 3. (a) Fe 2p XPS spectra of PCN-250 and W@P-2 and (b) W 4f XPS spectra of WO3 and W@P-2

Figure 4. (a) Time-dependent CO evolution curves over W@P-2, (b) control experiments for CO2 photoreduction, (c) recycle experiments for CO2 photoreduction over W@P-2, and (d) PXRD of W@P-2 before and after the recycle experiments

Figure 5. (a) EPR spectra of W@P-2 under light irradiation and dark, (b) in-situ DRIFTS spectra of the photocatalytic CO2 reduction on W@P-2, and (c) schematic illustration of the formation and working mechanism of the Z-scheme heterojunction in W@P-x

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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^★

Encapsulation of Ultrasmall WO₃ Nanoclusters in PCN-250 for Efficient CO₂ Photoreduction to CO with Water Vapor^★

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