Cobalt Imidazolate Metal–Organic Frameworks Photosplit CO₂ under Mild Reaction Conditions

Abstract

Metal-organic frameworks (MOFs) have shown great promise for CO2 capture and storage. However, the operation of chemical redox functions of framework substances and organic CO2 -trapping entities which are spatially linked together to catalyze CO2 conversion has had much less attention. Reported herein is a cobalt-containing zeolitic imidazolate framework (Co-ZIF-9) which serves as a robust MOF cocatalyst to reduce CO2 by cooperating with a ruthenium-based photosensitizer. The catalytic turnover number of Co-ZIF-9 was about 450 within 2.5 hours under mild reaction conditions, while still keeping its original reactivity during prolonged operation.

Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

“…Although still in the early stage of exploration, ZIFs have been used as photocatalysts for dye and phenol degradation as well as CO2 reduction. 15,[17][18][19] In these systems, photoactive nanostructures/molecules are incorporated into the highly porous structure of ZIFs, where ZIFs are used as a simple host or passive medium for dispersing the catalytic active species. This strategy has been widely used in developing zeolite-based photocatalysts 20 and recently in preparing MOF/nanocomposite or MOF/molecular catalyst hybrids, 19,21,22 yet suffers from challenges, notably the difficulty in preventing the guest material aggregation and the lack of the control over spatial distribution and homogeneity.…”

Artificial Photosynthetic Systems for CO2 Reduction: Progress on Higher Efficiency with Cobalt Complexes as Catalysts

“…Co-ZIF-9 was first used as ac atalyst for photocatalytic CO 2 reduction by Wang et al in 2014. [37] They reported that the MOFs exhibited not only gas absorption properties, but also CO 2 reduction activity under photochemical conditions. Ah eterogeneouss ystem composedo fC o-ZIF-9 as catalyst, P1 as PS, and TEOA as SED in aC O 2 -saturated CH 3 CN/H 2 O solventmixture produced CO and H 2 under visible light irradiation.…”

Construction of Four Zn(II) Coordination Polymers Used as Catalysts for the Photodegradation of Organic Dyes in Water

“…Interestingly, such 2D layer parallels to the equivalent one with a interleaving, resulting in a rare bilayer structure extending along the ac plane (Figure 3c,d). From the topological view [43], if the Zn centres are considered as nodes and the 5-HO-1,3-BDC and bpmb ligands are considered as linkers, the bilayer structure of 2 can be specified by a Schläfli symbol of 4 4 …”

“…Topologically, the overall structure of 4 can be described as a pcu net with the six-connected 4 12 6 3 topology (Figure 5d). 4 ] unit serves as a four-fold node, which links four equivalent ones via sharing of four ADB ligands to form a 2D wrinkled network extending along the bc plane (Figure 5b). Furthermore, the bpmb ligands are employed as linkers (pink) to bridge the 2D networks producing a 3D framework (Figure 5c).…”

“…In recent years, increasing attention on functional coordination polymers (CPs) has led to the fast development of this type of solid material, which are due to their intriguing aesthetic structures and topological features, as well as their potential applications in catalysis, adsorption, separation and so on [1][2][3][4][5][6][7][8][9][10][11][12]. Significant effort has been devoted to producing CPs with desired structures and properties using various approaches [13].…”