Heterointerface Connection with Multiple Hydrogen-Bonding in Z-Scheme Heterojunction SiW9Co3@UiO-67-NH2 Deciding High Stability and Photocatalytic CO2 Reduction Performance.
Heterointerface Connection with Multiple Hydrogen-Bonding in Z-Scheme Heterojunction SiW9Co3@UiO-67-NH2 Deciding High Stability and Photocatalytic CO2 Reduction Performance.
复制标题
DOI：
10.1021/acs.inorgchem.3c03391
复制
发表时间：
2023-11
影响因子：
4.6
通讯作者：
Pan Zhang;Tianyu Wang;Huiyang Ma;Ren Ma;Zhengqiang Xia;Qi Yang;Xin Yang;G. Xie;Sanping Chen
中科院分区：
文献类型：
--
作者：
Pan Zhang;Tianyu Wang;Huiyang Ma;Ren Ma;Zhengqiang Xia;Qi Yang;Xin Yang;G. Xie;Sanping Chen
将金属有机骨架（MOFs）和聚氧乙烯酸盐（POMs）通过原位包埋的方法组装成异质异质结光催化剂，是抑制POMs可组装性、提高其电子供应能力的有效途径。POMs@MOFs异质界面的连接直接决定了POMs@ MOFs异质结光催化剂的稳定性和电荷分离性能，合适的MOFs与POMs之间的相互作用对POMs@MOFs异质结光催化剂的制备至关重要。在这里，独特的Keggin型POM [（n-C4 H9）N]10[SiW 9 Co 3（H2O）3 O37]·17 H2O（SiW 9 Co 3）具有近全可见光区吸收，窄带隙为2.23 eV，并将其紧密固定在UiO-67-NH_2和UiO-68-NH_2的空穴中，构建了两个Z型异质结SiW_9Co_3@UiO-67-NH_2和SiW_9Co_3@UiO-68-NH_2。采用XRD、FT-IR、SEM、XPS、UV-vis-DRS、UPS等测试手段对催化剂的组成、结构和能带特征进行了表征。SiW9Co3@UiO-67-NH 2表现出最佳的光催化性能，CO产率为153.3 μmol-1·g-1·h-1，选择性为100%，是SiW9Co3@UiO-68-NH 2的3.3倍，远上级大多数报道的POM基异质结。通过大量的光电特性和微量热实验研究表明，SiW_9Co_3@UiO-67-NH_2具有优异的光催化性能，其原因在于：（i）SiW_9Co_3团簇与MOF腔体之间的尺寸匹配形成了强的主客体相互作用，形成了紧密的异质界面，有效地促进了界面电子转移;（ii）由于SiW_9Co_3的施主-受主结构和窄禁带宽度，紧密的异质界面促进了SiW_9Co_3的多电子供应，从而有效地中和了界面载流子。此外，SiW9Co3@UiO-67-NH 2的优异耐久性也得到了牢固锁定的SiW 9 Co 3和稳定的MOF框架的支持。
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.