An Amine‐Functionalized Titanium Metal–Organic Framework Photocatalyst with Visible‐Light‐Induced Activity for CO₂ Reduction

Abstract

Let your light shine: the photocatalytic reduction of carbon dioxide to the formate anion under visible light irradiation is for the first time realized over a photoactive Ti-containing metal-organic framework, NH(2)-MIL-125(Ti), which is fabricated by a facile substitution of ligands in the UV-responsive MIL-125(Ti) material.

Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study

“…10 However, because of the large optical band gap (3.6 eV), 10 MIL-125 is only active under UV irradiation. Therefore, it is necessary to modify the organic ligands or 5,16 After introducing the amine group, the band gap of MIL-125 is obviously reduced to about 2.6 eV, 12,18,19 and similar decreasing of the band gap by amine-functionalization is also observed for zirconium-based MOF (NH 2 -Uio-66). 11 A recent investigation indicates that the number of amine group also has obviously influence on the photocatalytic performances of NH 2 -MIL-125.…”

“…MOFs have many excellent properties that are different from those of traditional porous and crystal materials, such as nanoscale controlled pore structure, high surface area, and metal-organic ligand combination diversity, etc. Correspondingly, MOF has a variety of potential applications in many fields, including gas separation and storage, [1][2][3][4] catalysis, [5][6][7] biochemistry 8 and so on. Especially, many investigations have demonstrated that MOF materials are promising catalysts in photocatalysis.…”

“…Especially, many investigations have demonstrated that MOF materials are promising catalysts in photocatalysis. 5,6,[9][10][11][12][13][14][15][16] As one of the most popular MOF, 1,[5][6][7] the titanium-based MIL-125 can catalyze the oxidation of alcohols to aldehydes under the UV irradiation, indicating that MIL-125 is an active photocatalyst. 10 However, because of the large optical band gap (3.6 eV), 10 MIL-125 is only active under UV irradiation.…”

In situ synthesis of ordered mesoporous Co-doped TiO2 and its enhanced photocatalytic activity and selectivity for the reduction of CO2

“…11,12 In artificial photosynthesis, the semiconductor should have appropriate conduction band minimum for the reduction half-reaction and valence band maximum for the oxidation half-reaction. Therefore, the main components of the common photocatalysts for CO 2 36,37 are quite difficult to promote the oxidation half-reaction, which leads to the generation of oxygen through the oxidation of water.…”

Metal-Organic Frameworks for Catalysis

“…结果表明, 功能化配体修 饰的 UiO-67 催化剂对不同反应有着很好的光催化活性, 并且在光催化后 MOF 还保持高结晶性, 可循环使用. (2) proposed mechanism for photocatalytic CO 2 reduction of NH 2 -MIL-125(Ti) [103] Xiong 等 [104] 合成了 HKUST-1@TiO 2 的核壳结构, Figure 19 Schematic illustration for the preparation of porous carbon from BMZIFs for highly efficient oxygen reduction reaction [106] Yu 等 [107] …”