Elucidating charge-transfer mechanisms and their effect on the light-induced reactivity of metastable MIL-125(Ti)

被引：8

作者：

Pietro, Rassu ^{[1
]}

Luca, Cappai ^{[3
]}

Luigi, Stagi ^{[2
]}

Ruirui, Liu

Stefano, Enzo ^{[3
]}

Gabriele, Mulas ^{[3
]}

Sebastiano, Garroni ^{[3
]}

Luca, Malfatti ^{[2
]}

Plinio, Innocenzi ^{[2
]}

Xiaojie, Ma ^{[1
]}

Bo, Wang ^{[1
]}

机构：

[1] Beijing Inst Technol, Sch Chem & Chem Engn, 5 South Zhongguancun St, Beijing 100081, Peoples R China

[2] Univ Sassari, Dipartimento Sci Biomed, Viale S Pietro 43C, I-07100 Sassari, Italy

[3] Univ Sassari, Dipartimento Sci Chim Fis Matemat & Nat, Via Vienna 2, I-07100 Sassari, Italy

来源：

APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2024年 / 345卷

关键词：

Metal-organic frameworks; Charge-transfer mechanisms; Photocatalysis; Hydroxylation; METAL-ORGANIC FRAMEWORK; HYDROXYL RADICALS; TEREPHTHALIC ACID; OXYGEN EVOLUTION; PHOTOCATALYTIC DEGRADATION; OPTICAL-PROPERTIES; ELECTRON-TRANSFER; WATER OXIDATION; TITANIUM; TIO2;

D O I：

10.1016/j.apcatb.2024.123692

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Alcohol and water photooxidation reactions are employed in concert with optical spectroscopy analyses to demonstrate the occurrence of multiple and distinctive charge-transfer (CT) mechanisms in the environmental photocatalyst MIL-125(Ti). The contribution of ligand-to-metal CT (LMCT) mechanisms increases at wavelengths lower than 320 nm while that of node oxygen-to-metal CT (OMCT) mechanisms increases at longer wavelengths. The localization of photogenerated holes on different atoms leads to a selective reactivity of the framework depending on the mechanism and, during hydroxylation processes, to its spontaneous transition to the isostructural MIL-125-OH(Ti) and the development of an additional LMCT mechanism with a long-lived emission. Furthermore, a previously unidentified and extrinsic CT mechanism is spectroscopically related to the formation of terephthalate-based oligomers. The coexistence of distinctive CT mechanisms in MIL-125(Ti) implies their critical role in catalyst efficiency, and mastering them proves to be a powerful and simple strategy to produce the valuable MIL-125-OH(Ti).

引用

页数：10

共 97 条

[11] Crystallographic facet heterojunction of MIL-125-NH2(Ti) for carbon dioxide photoreduction [J].