Exploring electronic structure and photophysical properties of metalloporphyrin-based metal-organic frameworks for photocatalysis: A quantum chemistry study

被引：2

作者：

Hidalgo-Rosa, Yoan ^{[1
,8
]}

Saavedra-Torres, Mario ^{[2
]}

Koivisto, Bryan D. ^{[3
]}

Treto-Suarez, Manuel A. ^{[4
]}

Paez-Hernandez, Dayan ^{[5
]}

Zarate, Ximena ^{[6
]}

Schott, Eduardo ^{[2
,7
]}

机构：

[1] Univ Mayor, Fac Ciencias Ingn & Tecnol, Ctr Nanotecnol Aplicada, Camino Piramide 5750, Huechuraba 8580745, Santiago, Chile

[2] Millennium Nuclei Catalyt Proc Sustainable Chem CS, ANID, Millennium Sci Initiat Program, Santiago, Chile

[3] Toronto Metropolitan Univ, Dept Chem & Biol, 350 Victoria St, Toronto, ON, Canada

[4] Univ Autonoma Chile, Fac Ingn, Dept Fis & Quim, IDETECO, Ave Alemania 01090, Temuco 4810101, Chile

[5] Univ Andres Bello, Ctr Appl Nanosci CANS, Ave Republ 275, Santiago 8370146, Chile

[6] Univ Autonoma Chile, Fac Ingn, Inst Ciencias Aplicadas, Ave Pedro De Valdivia 425, Santiago, Chile

[7] Pontificia Univ Catolica Chile, Fac Quim & Farm, Ctr Energia UC, Dept Quim Inorgan,CIEN UC, Santiago 8320000, Chile

[8] Univ Mayor, Escuela Ingn Medio Ambiente & Sustentabil, Fac Ciencias Ingn & Tecnol, Camino Piramide 5750, Huechuraba 8580745, Santiago, Chile

来源：

INORGANIC CHEMISTRY COMMUNICATIONS | 2025年 / 172卷

关键词：

Metalloporphyrins-based MOFs; Periodic-DFT calculations; Water splitting; TD-DFT; Photocatalysis; ABSORPTION-SPECTRA; DFT CALCULATIONS; FUNCTIONALS; CATALYSTS; NBO;

D O I：

10.1016/j.inoche.2024.113635

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Hydrogen production is gaining interest as a clean energy source, with photocatalytic water-splitting being a key method due to its eco-friendly nature. Metalloporphyrins-based MOFs (TCPP(M)-MOFs), due to their tunable optical properties, are excellent materials for hydrogen evolution via water-splitting using sunlight. In this research, TCPP(M)-MOFs containing nodes based on metal ion d 10 Zn2+ and TCPP(M) as linkers (M = Fe2+, Ni2+, Co2+and Cu2+) has been studied using theoretical approach. The electronic structure and optical properties of all Zn-TCPP(M)-MOFs were investigated using the density functional theory (DFT) and periodic-DFT calculations. The study revealed a bandgap reduction related to the open-shell metals in the TCPP linker, with an optimal value for the photocatalytic process under sunlight. TD-DFT calculations show that the inclusion of open shell ions enhances the linker-centered ligand-to-metal charge transfer process. Finally, it was suggested some directions for the design of new melloporphyrine-based MOFs, potentially leading to new materials for photo- catalytic water-splitting.

引用

页数：9

共 85 条

[1] Synthesis, spectroscopic characterization, first order nonlinear optical properties and DFT calculations of novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with 1,3-diphenyl-4-phenylazo-5-pyrazolone ligand [J].