Abstract
In the effort to generate sustainable clean energy from abundant resources such as water and carbon dioxide, solar fuel production—the combination of solar-light harvesting and the generation of efficient chemical energy carriers—by artificial molecular photosystems is very attractive. Molecular constituents that display attractive features for chemical energy conversion (such as high product selectivity and atom economy) have been developed, and their interfacing with host materials has enabled recyclability, controlled site positioning, as well as access to fundamental insights into the catalytic mechanism and environment-governed selectivity. Among the wide variety of supports, metal–organic frameworks (MOFs) possess valuable characteristics (such as their porosity and versatility) that can influence the reaction environment and material architecture in a unique fashion. Here we highlight the various existing synthetic strategies to graft molecular complexes such as catalysts and photosensitizers onto MOFs for solar fuel production. The opportunities and limitations of one-pot and stepwise approaches are critically assessed, and the resulting materials are discussed based on their photocatalytic performances and the practical applicability of selected examples.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
Source data are provided with this paper.
References
Nocera, D. G. Solar fuels and solar chemicals industry. Acc. Chem. Res. 50, 616–619 (2017).
Bard, A. J. & Fox, M. A. Artificial photosynthesis: solar splitting of water to hydrogen and oxygen. Acc. Chem. Res. 28, 141–145 (1995).
Armaroli, N. & Balzani, V. Solar electricity and solar fuels: status and perspectives in the context of the energy transition. Chem. Eur. J. 22, 32–57 (2016).
Montoya, J. H. et al. Materials for solar fuels and chemicals. Nat. Mater. 16, 70–81 (2016).
White, J. L. et al. Light-driven heterogeneous reduction of carbon dioxide: photocatalysts and photoelectrodes. Chem. Rev. 115, 12888–12935 (2015).
Schild, J. et al. Approaching industrially relevant current densities for hydrogen oxidation with a bioinspired molecular catalytic material. J. Am. Chem. Soc. 143, 18150–18158 (2021).
Ren, S. et al. Molecular electrocatalysts can mediate fast, selective CO2 reduction in a flow cell. Science 365, 367–369 (2019).
DuBois, D. L. Development of molecular electrocatalysts for energy storage. Inorg. Chem. 53, 3935–3960 (2014).
Rao, H., Schmidt, L. C., Bonin, J. & Robert, M. Visible-light-driven methane formation from CO2 with a molecular iron catalyst. Nature 548, 74–77 (2017).
Bachmeier, A. & Armstrong, F. Solar-driven proton and carbon dioxide reduction to fuels - lessons from metalloenzymes. Curr. Opin. Chem. Biol. 25, 141–151 (2015).
Dalle, K. E. et al. Electro- and solar-driven fuel synthesis with first row transition metal complexes. Chem. Rev. 119, 2752–2875 (2019).
Zhang, B. & Sun, L. Artificial photosynthesis: opportunities and challenges of molecular catalysts. Chem. Soc. Rev. 48, 2216–2264 (2019).
Fabian, D. M. et al. Particle suspension reactors and materials for solar-driven water splitting. Energy Environ. Sci. 8, 2825–2850 (2015).
Wang, Q. & Domen, K. Particulate photocatalysts for light-driven water splitting. Mechanisms, challenges and design strategies. Chem. Rev. 120, 919–985 (2020).
Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013).
Wei, Y.-S., Zou, L., Wang, H.-F., Wang, Y. & Xu, Q. Micro/nano-scaled metal-organic frameworks and their derivatives for energy applications. Adv. Energy Mater 12, 2003970 (2022).
Luo, Y.-H., Dong, L.-Z., Liu, J., Li, S.-L. & Lan, Y.-Q. From molecular metal complex to metal-organic framework: the CO2 reduction photocatalysts with clear and tunable structure. Coordin. Chem. Rev. 390, 86–126 (2019).
Mialane, P. et al. Heterogenisation of polyoxometalates and other metal-based complexes in metal-organic frameworks: from synthesis to characterisation and applications in catalysis. Chem. Soc. Rev. 50, 6152–6220 (2021).
Majewski, M. B., Peters, A. W., Wasielewski, M. R., Hupp, J. T. & Farha, O. K. Metal-organic frameworks as platform materials for solar fuels catalysis. ACS Energy Lett. 3, 598–611 (2018).
Yoon, J.-W., Kim, J.-H., Kim, C., Jang, H. W. & Lee, J.-H. MOF-based hybrids for solar fuel production. Adv. Energy Mater. 4, 2003052 (2021).
Dhakshinamoorthy, A., Li, Z. & Garcia, H. Catalysis and photocatalysis by metal organic frameworks. Chem. Soc. Rev. 47, 8134–8172 (2018).
Semrau, A. L. et al. Surface-mounted metal-organic frameworks: past, present and future perspectives. Langmuir 37, 6847–6863 (2021).
Castner, A. T., Johnson, B. A., Cohen, S. M. & Ott, S. Mimicking the electron transport chain and active site of FeFe hydrogenases in one metal-organic framework. factors that influence charge transport. J. Am. Chem. Soc. 143, 7991–7999 (2021).
Zhong, H. et al. Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal–organic frameworks. Nat. Commun. 11, 1409 (2020).
Downes, C. A. & Marinescu, S. C. Electrocatalytic metal-organic frameworks for energy applications. ChemSusChem 10, 4374–4392 (2017).
Wagner, A., Sahm, C. D. & Reisner, E. Towards molecular understanding of local chemical environment effects in electro- and photocatalytic CO2 reduction. Nat. Catal. 3, 775–786 (2020).
Leung, J. J. et al. Solar-driven reduction of aqueous CO2 with a cobalt bis(terpyridine)-based photocathode. Nat. Catal. 2, 354–365 (2019).
Reuillard, B., Warnan, J., Leung, J. J., Wakerley, D. W. & Reisner, E. A poly(cobaloxime)/carbon nanotube electrode: freestanding buckypaper with polymer-enhanced H2-evolution performance. Angew. Chem. Int. Ed. 55, 3952–3957 (2016).
Hemmer, K., Cokoja, M. & Fischer, R. A. Exploitation of intrinsic confinement effects of MOFs in catalysis. ChemCatChem 13, 1683–1691 (2021).
Ryu, U. J. et al. Synergistic interaction of Re complex and amine functionalized multiple ligands in metal-organic frameworks for conversion of carbon dioxide. Sci. Rep. 7, 612 (2017).
Stanley, P. M. et al. Entrapped molecular photocatalyst and photosensitizer in metal-organic framework nanoreactors for enhanced solar CO2 reduction. ACS Catal. 11, 871–882 (2021).
Feng, X. et al. Metal-organic frameworks significantly enhance photocatalytic hydrogen evolution and CO2 reduction with earth-abundant copper photosensitizers. J. Am. Chem. Soc. 142, 690–695 (2020).
So, M. C., Wiederrecht, G. P., Mondloch, J. E., Hupp, J. T. & Farha, O. K. Metal-organic framework materials for light-harvesting and energy transfer. Chem. Commun. 51, 3501–3510 (2015).
Johnson, B. A., Beiler, A. M., McCarthy, B. D. & Ott, S. Transport phenomena: challenges and opportunities for molecular catalysis in metal-organic frameworks. J. Am. Chem. Soc. 142, 11941–11956 (2020).
Sharp, C. H. et al. Nanoconfinement and mass transport in metal-organic frameworks. Chem. Soc. Rev. 50, 11530–11558 (2021).
Johnson, E. M., Ilic, S. & Morris, A. J. Design strategies for enhanced conductivity in metal-organic frameworks. ACS Cent. Sci. 7, 445–453 (2021).
Sun, L., Campbell, M. G. & Dincă, M. Electrically conductive porous metal-organic frameworks. Angew. Chem. Int. Ed. 55, 3566–3579 (2016).
Son, H.-J. et al. Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks. J. Am. Chem. Soc. 135, 862–869 (2013).
Fei, H., Sampson, M. D., Lee, Y., Kubiak, C. P. & Cohen, S. M. Photocatalytic CO2 reduction to formate using a Mn(I) molecular catalyst in a robust metal-organic framework. Inorg. Chem. 54, 6821–6828 (2015).
Choi, K. M. et al. Plasmon-enhanced photocatalytic CO2 conversion within metal-organic frameworks under visible light. J. Am. Chem. Soc. 139, 356–362 (2017).
Wang, C., Xie, Z., deKrafft, K. E. & Lin, W. Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. J. Am. Chem. Soc. 133, 13445–13454 (2011).
Gao, X. et al. Zirconium-based metal-organic framework for efficient photocatalytic reduction of CO2 to CO: the influence of doped metal ions. ACS Appl. Mater. Interfaces 12, 24059–24065 (2020).
An, Y. et al. Improving the photocatalytic hydrogen evolution of UiO-67 by incorporating Ce4+-coordinated bipyridinedicarboxylate ligands. Sci. Bull. 64, 1502–1509 (2019).
Blake, A. J. et al. Photoreactivity examined through incorporation in metal–organic frameworks. Nat. Chem. 2, 688–694 (2010).
Yang, S. et al. Elucidating charge separation dynamics in a hybrid metal-organic framework photocatalyst for light-driven H2 evolution. J. Phys. Chem. C 122, 3305–3311 (2018).
Qi, X. et al. Single metal-organic cage decorated with an Ir(III) complex for CO2 photoreduction. ACS Catal. 11, 7241–7248 (2021).
Lee, H. S. et al. A highly active, robust photocatalyst heterogenized in discrete cages of metal-organic polyhedra for CO2 reduction. Energy Environ. Sci. 13, 519–526 (2020).
Ghosh, A. C. et al. Rhodium-based metal-organic polyhedra assemblies for selective CO2 photoreduction. J. Am. Chem. Soc. 144, 3626–3636 (2022).
Chang, Q. et al. Metal-organic cages with {SiW9Ni4} polyoxotungstate nodes. Angew. Chem. Int. Ed. 61, e202117637 (2022).
Mollick, S., Fajal, S., Mukherjee, S. & Ghosh, S. K. Stabilizing metal-organic polyhedra (MOP): issues and strategies. Chem. Asian J. 14, 3096–3108 (2019).
Juan-Alcañiz, J., Gascon, J. & Kapteijn, F. Metal-organic frameworks as scaffolds for the encapsulation of active species: state of the art and future perspectives. J. Mater. Chem. 22, 10102 (2012).
Li, N. et al. Adenine components in biomimetic metal-organic frameworks for efficient CO2 photoconversion. Angew. Chem. Int. Ed. 58, 5226–5231 (2019).
Bennett, T. H. et al. Jolly green MOF. Confinement and photoactivation of photosystem I in a metal-organic framework. Nanoscale Adv. 1, 94–104 (2019).
Kollmannsberger, K. L. et al. From phosphine-stabilised towards naked Au8 clusters through ZIF-8 encapsulation. Mol. Syst. Des. Eng. 6, 876–882 (2021).
Liédana, N., Galve, A., Rubio, C., Téllez, C. & Coronas, J. CAF@ZIF-8. One-step encapsulation of caffeine in MOF. ACS Appl. Mater. Interfaces 4, 5016–5021 (2012).
Shieh, F.-K. et al. Imparting functionality to biocatalysts via embedding enzymes into nanoporous materials by a de novo approach. Size-selective sheltering of catalase in metal-organic framework microcrystals. J. Am. Chem. Soc. 137, 4276–4279 (2015).
Luo, Y. et al. Fabrication of Au25(SG)18-ZIF-8 nanocomposites: a facile strategy to position Au25(SG)18 nanoclusters inside and outside ZIF-8. Adv. Mater. 30, 1704576 (2018).
Luo, Y.-C. et al. Heterogenization of photochemical molecular devices: embedding a metal-organic cage into a ZIF-8-derived matrix to promote proton and electron transfer. J. Am. Chem. Soc. 141, 13057–13065 (2019).
Zhang, Z.-M. et al. Photosensitizing metal-organic framework enabling visible-light-driven proton reduction by a Wells-Dawson-type polyoxometalate. J. Am. Chem. Soc. 137, 3197–3200 (2015).
Chen, W.-H., Vázquez-González, M., Zoabi, A., Abu-Reziq, R. & Willner, I. Biocatalytic cascades driven by enzymes encapsulated in metal–organic framework nanoparticles. Nat. Catal. 1, 689–695 (2018).
Schrimpf, W. et al. Chemical diversity in a metal–organic framework revealed by fluorescence lifetime imaging. Nat. Commun. 9, 1647 (2018).
Kim, M., Cahill, J. F., Su, Y., Prather, K. A. & Cohen, S. M. Postsynthetic ligand exchange as a route to functionalization of ‘inert’ metal-organic frameworks. Chem. Sci. 3, 126–130 (2012).
Stanley, P. M. & Warnan, J. Molecular dye-sensitized photocatalysis with metal-organic framework and metal oxide colloids for fuel production. Energies 14, 4260 (2021).
Willkomm, J. et al. Dye-sensitised semiconductors modified with molecular catalysts for light-driven H2 production. Chem. Soc. Rev. 45, 9–23 (2016).
Choi, S. et al. Rapid exciton migration and amplified funneling effects of multi-porphyrin arrays in a Re(I)/porphyrinic MOF hybrid for photocatalytic CO2 reduction. ACS Appl. Mater. Interfaces 13, 2710–2722 (2021).
Chambers, M. B. et al. Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks. ChemSusChem 8, 603–608 (2015).
Benseghir, Y. et al. Co-immobilization of a Rh catalyst and a Keggin polyoxometalate in the UiO-67 Zr-based metal-organic framework. In depth structural characterization and photocatalytic properties for CO2 reduction. J. Am. Chem. Soc. 142, 9428–9438 (2020).
Kajiwara, T. et al. Photochemical reduction of low concentrations of CO2 in a porous coordination polymer with a ruthenium(II)-CO complex. Angew. Chem. Int. Ed. 55, 2697–2700 (2016).
Kim, D., Whang, D. R. & Park, S. Y. Self-healing of molecular catalyst and photosensitizer on metal-organic framework. Robust molecular system for photocatalytic H2 evolution from water. J. Am. Chem. Soc. 138, 8698–8701 (2016).
Karmakar, S., Barman, S., Rahimi, F. A. & Maji, T. K. Covalent grafting of molecular photosensitizer and catalyst on MOF-808. Effect of pore confinement toward visible light-driven CO2 reduction in water. Energy Environ. Sci. 14, 2429–2440 (2021).
Stanley, P. M. et al. Host-guest interactions in metal-organic framework isoreticular series for molecular photocatalytic CO2 reduction. Angew. Chem. Int. Ed. 60, 17854–17860 (2021).
Paille, G. et al. A fully noble metal-free photosystem based on cobalt-polyoxometalates immobilized in a porphyrinic metal-organic framework for water oxidation. J. Am. Chem. Soc. 140, 3613–3618 (2018).
Han, J. et al. Polyoxometalate immobilized in MIL-101(Cr) as an efficient catalyst for water oxidation. Appl. Catal. A Gen. 521, 83–89 (2016).
Deng, X., Albero, J., Xu, L., García, H. & Li, Z. Construction of a stable Ru-Re hybrid system based on multifunctional MOF-253 for efficient photocatalytic CO2 reduction. Inorg. Chem. 57, 8276–8286 (2018).
Zhuo, T.-C. et al. H-bond-mediated selectivity control of formate versus CO during CO2 photoreduction with two cooperative Cu/X sites. J. Am. Chem. Soc. 143, 6114–6122 (2021).
Wang, X., Wisser, F. M., Canivet, J., Fontecave, M. & Mellot-Draznieks, C. Immobilization of a full photosystem in the large-pore MIL-101 metal-organic framework for CO2 reduction. ChemSusChem 11, 3315–3322 (2018).
Hu, H. et al. Metal-organic frameworks embedded in a liposome facilitate overall photocatalytic water splitting. Nat. Chem. 13, 358–366 (2021).
Roy, S., Bhunia, A., Schuth, N., Haumann, M. & Ott, S. Light-driven hydrogen evolution catalyzed by a cobaloxime catalyst incorporated in a MIL-101(Cr) metal-organic framework. Sustain. Energy Fuels 2, 1148–1152 (2018).
Yuan, S. et al. Stable metal-organic frameworks: design, synthesis and applications. Adv. Mater. 30, 1704303 (2018).
McCormick, T. M. et al. Impact of ligand exchange in hydrogen production from cobaloxime-containing photocatalytic systems. Inorg. Chem. 50, 10660–10666 (2011).
Stanley, P. M., Parkulab, M., Rieger, B., Warnan, J. & Fischer, R. A. Understanding entrapped molecular photosystem and metal-organic framework synergy for improved solar fuel production. Faraday Discuss. 231, 281–297 (2021).
Chen, Y. et al. Integration of enzymes and photosensitizers in a hierarchical mesoporous metal-organic framework for light-driven CO2 reduction. J. Am. Chem. Soc. 142, 1768–1773 (2020).
Nepal, B. & Das, S. Sustained water oxidation by a catalyst cage-isolated in a metal-organic framework. Angew. Chem. Int. Ed. 52, 7224–7227 (2013).
Li, Z., Xiao, J.-D. & Jiang, H.-L. Encapsulating a Co(II) molecular photocatalyst in metal-organic framework for visible-light-driven H2 production. Boosting catalytic efficiency via spatial charge separation. ACS Catal. 6, 5359–5365 (2016).
Nasalevich, M. A. et al. Co@NH2-MIL-125(Ti): cobaloxime-derived metal-organic framework-based composite for light-driven H2 production. Energy Environ. Sci. 8, 364–375 (2015).
Meyer, K. et al. Photocatalyzed hydrogen evolution from water by a composite catalyst of NH2-MIL-125(Ti) and surface nickel(II) species. Chem. Eur. J. 22, 13894–13899 (2016).
Yan, Z.-H. et al. Encapsulating a Ni(II) molecular catalyst in photoactive metal-organic framework for highly efficient photoreduction of CO2. Sci. Bull. 64, 976–985 (2019).
Artero, V. & Fontecave, M. Solar fuels generation and molecular systems. Is it homogeneous or heterogeneous catalysis? Chem. Soc. Rev. 42, 2338–2356 (2013).
Warnan, J. & Reisner, E. Synthetic organic design for solar fuel systems. Angew. Chem. Int. Ed. 59, 17344–17354 (2020).
Ong, W.-J., Tan, L.-L., Ng, Y. H., Yong, S.-T. & Chai, S.-P. Graphitic carbon nitride (g-C3N4)-based photocatalysts for artificial photosynthesis and environmental remediation: are we a step closer to achieving sustainability? Chem. Rev. 116, 7159–7329 (2016).
Wang, D.-G. et al. Covalent organic framework-based materials for energy applications. Energy Environ. Sci. 14, 688–728 (2021).
Rahman, M., Tian, H. & Edvinsson, T. Revisiting the limiting factors for overall water-splitting on organic photocatalysts. Angew. Chem. Int. Ed 59, 16278–16293 (2020).
Banerjee, T. et al. Single-site photocatalytic H2 evolution from covalent organic frameworks with molecular cobaloxime Co-catalysts. J. Am. Chem. Soc. 139, 16228–16234 (2017).
Fu, Z. et al. A stable covalent organic framework for photocatalytic carbon dioxide reduction. Chem. Sci. 11, 543–550 (2020).
Wang, H.-Y. et al. Photocatalytic hydrogen evolution from rhenium(I) complexes to FeFe hydrogenase mimics in aqueous SDS micellar systems. A biomimetic pathway. Langmuir 26, 9766–9771 (2010).
Pannwitz, A. et al. Roadmap towards solar fuel synthesis at the water interface of liposome membranes. Chem. Soc. Rev. 50, 4833–4855 (2021).
Qureshi, M. & Takanabe, K. Insights on measuring and reporting heterogeneous photocatalysis: efficiency definitions and setup examples. Chem. Mater. 29, 158–167 (2017).
Uekert, T., Pichler, C. M., Schubert, T. & Reisner, E. Solar-driven reforming of solid waste for a sustainable future. Nat. Sustain. 4, 383–391 (2021).
Liu, B., Vikrant, K., Kim, K.-H., Kumar, V. & Kailasa, S. K. Critical role of water stability in metal-organic frameworks and advanced modification strategies for the extension of their applicability. Environ. Sci. Nano 7, 1319–1347 (2020).
Roy, S. et al. Electrocatalytic hydrogen evolution from a cobaloxime-based metal-organic framework thin film. J. Am. Chem. Soc. 141, 15942–15950 (2019).
Kornienko, N. Operando spectroscopy of nanoscopic metal/covalent organic framework electrocatalysts. Nanoscale 13, 1507–1514 (2021).
Shaikh, S. M. et al. Role of a 3D structure in energy transfer in mixed-ligand metal-organic frameworks. J. Phys. Chem. C 125, 22998–23010 (2021).
Singh, A. K., Montoya, J. H., Gregoire, J. M. & Persson, K. A. Robust and synthesizable photocatalysts for CO2 reduction. A data-driven materials discovery. Nat. Commun. 10, 443 (2019).
Burger, B. et al. A mobile robotic chemist. Nature 583, 237–241 (2020).
Acknowledgements
P.M.S. thanks the Chemical Industry Fonds (FCI) for a PhD fellowship. J.H. and N.B.S. thank the TUM Institute for Advanced Study (IAS) for funding. This work was supported by the German Research Foundation (DFG) Priority Program 1928 ‘Coordination Networks: Building Blocks for Functional Systems’, the research project MOFMOX (grant no. FI 502/43-1) and the Excellence Cluster 2089 ‘e-conversion’ (Fundamentals of Energy Conversion Processes).
Author information
Authors and Affiliations
Contributions
P.M.S., J.H. and J.W. conceived the idea and outline for this Review and wrote the manuscript with contributions from N.B.S. and R.A.F. All authors have approved the final version of this manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Chemistry thanks the anonymous reviewer(s) for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Source data
Source Data Table 2
Source data used to compile Table 2 including brief category and synthesis descriptions, as well as the references backing the presented data
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Stanley, P.M., Haimerl, J., Shustova, N.B. et al. Merging molecular catalysts and metal–organic frameworks for photocatalytic fuel production. Nat. Chem. 14, 1342–1356 (2022). https://doi.org/10.1038/s41557-022-01093-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41557-022-01093-x
This article is cited by
-
Analysis of metal–organic framework-based photosynthetic CO2 reduction
Nature Synthesis (2024)
-
Carbon quantum dots-modified tetra (4-carboxyphenyl) porphyrin/BiOBr S-scheme heterojunction for efficient photocatalytic antibiotic degradation
Science China Materials (2024)
-
Recent advances in bimetallic metal-organic frameworks and their derivatives for thermal catalysis
Nano Research (2023)