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Review
. 2022 Oct 5;144(39):17723-17736.
doi: 10.1021/jacs.2c04144. Epub 2022 Sep 20.

A Potential Roadmap to Integrated Metal Organic Framework Artificial Photosynthetic Arrays

Bradley Gibbons  1 , Meng Cai  1 , Amanda J Morris  1
Affiliations
Review

A Potential Roadmap to Integrated Metal Organic Framework Artificial Photosynthetic Arrays

Bradley Gibbons et al. J Am Chem Soc. .

Abstract

Metal organic frameworks (MOFs), a class of coordination polymers, gained popularity in the late 1990s with the efforts of Omar Yaghi, Richard Robson, Susumu Kitagawa, and others. The intrinsic porosity of MOFs made them a clear platform for gas storage and separation. Indeed, these applications have dominated the vast literature in MOF synthesis, characterization, and applications. However, even in those early years, there were hints to more advanced applications in light-MOF interactions and catalysis. This perspective focuses on the combination of both light-MOF interactions and catalysis: MOF artificial photosynthetic assemblies. Light absorption, charge transport, H2O oxidation, and CO2 reduction have all been previously observed in MOFs; however, work toward a fully MOF-based approach to artificial photosynthesis remains out of reach. Discussed here are the current limitations with MOF-based approaches: diffusion through the framework, selectivity toward high value products, lack of integrated studies, and stability. These topics provide a roadmap for the future development of fully integrated MOF-based assemblies for artificial photosynthesis.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Schematics for artificial photosynthetic assemblies showing DSPECs featuring a photosensitizer (PS), water oxidation catalyst (WOC), and CO2 reduction catalyst (CRC) (a), multijunction semiconductors with catalytic nanoparticles (NP) (b), and a proposed all-MOF artificial photosynthetic assembly (c). Figure created using VESTA visualization software.
Figure 2
Figure 2
Illustration of photocatalytic water splitting by MOF-based catalysts immobilized in a liposome vesicle with a hydrogen evolution catalyst imbedded into the hydrophobic bilayer and the water oxidation catalyst located in the hydrophilic interior. Reprinted with permission from ref (36). Copyright 2021 Springer Nature.
Figure 3
Figure 3
Time resolved confocal microscopy of dye diffusion into MOFs of different morphologies. While some frameworks may have larger channels to promote diffusion in one direction (bottom), overall loading can be limited since diffusion is limited to one direction. Reprinted with permission from ref (45). Copyright 2021 American Chemical Society.
Figure 4
Figure 4
Examples of proton conductivity through a charged node in Fe-CAT-5 (a) and linker modification of an insulating framework like UiO-66 with −SO3H (pink spheres) groups (b). Reprinted with permission from refs (51) and (53). Copyright 2015 American Chemical Society.
Figure 5
Figure 5
Comparison of market price and energy content of various CO2 reduction products. Lines represent cost of energy from solar energy installations as an average ($50/MWh) and record low ($20/MWh). Reprinted with permission from ref (75). Copyright 2019 American Chemical Society.
Figure 6
Figure 6
New MOF-based catalyst with extremely active Co sites which dimerize in solution to form inactive species. Reprinted with permission from (98). Copyright 2016 American Chemical Society.
Figure 7
Figure 7
AFM and SEM of an HKUST-1 modified electrode after an applied potential. Arrows and degradation due to formation of Cu nanoparticles. Adapted with permission from ref (130). Copyright 2007 American Chemical Society.
Figure 8
Figure 8
TEM images of Cu-X-bpy MOFs showing formation of nanoparticles. Adapted with permission from ref (22). Copyright 2017, John Wiley and Sons.
See this image and copyright information in PMC

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