异质结
光催化
化学
X射线光电子能谱
光电效应
选择性
带隙
纳米技术
化学工程
光电子学
催化作用
材料科学
有机化学
工程类
作者
Pan Zhang,Tianyu Wang,Hongxia Ma,Ren Ma,Zhengqiang Xia,Qi Yang,Xin Yang,Gang Xie,Sanping Chen
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2023-11-21
卷期号:62 (49): 20401-20411
被引量:1
标识
DOI:10.1021/acs.inorgchem.3c03391
摘要
Merging metal–organic frameworks (MOFs) and polyoxometalates (POMs) into heterogeneous heterojunction photocatalysts through in situ encapsulation is an effective approach to suppress the leachability of POMs and enhance their electron supply. The heterointerfacial connection in POMs@MOFs directly determines the performance of stability and charge separation, and the suited interaction between MOFs and POMs for POMs@MOFs heterojunctions photocatalyst is of vital importance. Here, a distinctive Keggin-type POM [(n-C4H9)N]10[SiW9Co3 (H2O)3O37]·17H2O (SiW9Co3) with near-total visible region absorption, narrow band gap of 2.23 eV, and powerful electron supply activity was prepared and tightly immobilized in the cavities of UiO-67-NH2 and UiO-68-NH2 to construct two Z-scheme heterojunctions SiW9Co3@UiO-67-NH2 and SiW9Co3@UiO-68-NH2, which were used for photocatalytic reduction of CO2 to CO. Their compositions, structures, and energy band features were fully characterized by a series of tests including XRD, FT-IR, SEM, XPS, UV–vis-DRS, UPS, and so forth. SiW9Co3@UiO-67-NH2 showed optimal photocatalytic performance with an excellent CO yield of 153.3 μmol–1·g–1·h–1 and a selectivity of 100%, which is 3.3-fold higher than that of SiW9Co3@UiO-68-NH2 and far superior to most reported POM-based heterojunctions. Comprehensive investigations with extensive photoelectric characterizations and microcalorimetric experiments demonstrated that the exceptional photocatalytic performances of SiW9Co3@UiO-67-NH2 could be attributed to the fact that (i) strong host–guest interactions were formed due to the well-matched dimensions between SiW9Co3 cluster and MOF cavity, which generated an intimate heterointerface to effectively accelerate interface electron transfer; (ii) the intimate heterointerface promoted SiW9Co3 to yield multielectron supply for efficient interfacial carrier neutralization owing to its donor–acceptor structure and narrow band gap. Additionally, the excellent durability of SiW9Co3@UiO-67-NH2 was also supported by the solidly locked SiW9Co3 and a stable MOF framework.
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