Zn (II) Porphyrin Built-in D–A Covalent Organic Framework for Efficient Photocatalytic H2 Evolution

Abstract

Covalent organic frameworks (COFs) with donor–acceptor (D–A) units are credible photocatalysts for their per-designed structure, inherent porosity, large surface area, splendid stability and so forth. Developing COFs with an excellent photocatalytic efficiency for hydrogen evolution is of a great significance in alleviating the energy crisis. Herein, a D–A type imine-linked crystalline Zn-Por-TT COF was fabricated successfully via the co-polymerization of electron-deficient Zinc (II) 5,10,15,20-tetrakis(para-aminophenyl) porphyrin (Zn-TAPP), and electron-rich thieno[3,2-b]thiophene-2,5-dicarbaldehyde (TT). Profiting from the D–A complex structure, the obtained Zn-Por-TT COF showcases an excellent photocatalytic activity with a hydrogen evolution rate of 8200 μmol/g/h, while the Zn-TAPP monomer presents practically no capacity for the generation of hydrogen under identical conditions. In addition, the counterparts Por-TT COF and COF-366-Zn were employed to illustrate the enhancement of the photocatalytic performance by metal catalytic sites and D–A structures. In addition, the counterparts Por-TT COF and COF-366-Zn were employed to illustrate the enhancement of metal catalytic sites and D–A structures for the photocatalytic performance.

Recent advances on covalent organic frameworks (COFs) as photocatalysts: different strategies for enhancing hydrogen generation

“…Therefore, several attempts have been made to enhance the photocatalytic capability by introducing metal active centers into COF skeletons through coordination interactions (Table 3). [103][104][105][106][107][108][109][110][111][112][113][114][115][116][117] Based on an aldol-amine condensation reaction between 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa), a series of b-ketoenamine-linked COFs were constructed via introducing metal species. Recently, a chiral b-ketoenamine-linked COF was designed and prepared by Guo et al, followed by atomically dispersed Cu(II) being incorporated to form TpPa-Cu(II)-COF.…”

“…Therefore, several attempts have been made to enhance the photocatalytic capability by introducing metal active centers into COF skeletons through coordination interactions (Table 3). 103–117…”

Biohybrid Molecule‐Based Photocatalysts for Water Splitting Hydrogen Evolution

“…M. Lv et al. fabricated a donor‐acceptor imine‐linked crystalline Zn‐Por‐TT COF via the co‐polymerization of the electron‐deficient Zinc(II) 5, 10, 15, 20‐tetrakis (para‐aminophenyl) porphyrin (Zn‐TAPP), and electro‐rich thieno [2b,3] thiophene‐2, 5‐dicarbaldehyde (TT) [101] . As the result, under the irradiation of λ>400 nm, the Zn‐Por‐TT COF showed outstanding H 2 evolution rate of 4100 μmol g −1 h −1 and enhanced to 8200 μmol g −1 h −1 after illumination for 10 h and can maintain at least 40 h. Z. Zhao et al.…”

Novel Microwave-Assisted Synthesis of COFs: 2020–2022

“…Several applications for COFs have been explored, including molecular separations [ 2 ], removal of toxic compounds [ 3 ], gas capture [ 4 ], enzyme immobilization [ 5 ], optoelectronic applications [ 6 ], analytical chemistry [ 7 ], photocatalysis [ 8 , 9 ], electrocatalysis [ 10 ], electrochemical sensors [ 11 ], batteries [ 12 ], and solar fuel production [ 13 ].…”