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Review
. 2021 Oct 26;6(44):29291-29324.
doi: 10.1021/acsomega.1c04018. eCollection 2021 Nov 9.

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO2 Reduction

Bilal Masood Pirzada  1 , Arif Hassan Dar  2 , M Nasiruzzaman Shaikh  3 , Ahsanulhaq Qurashi  1
Affiliations
Review

Reticular-Chemistry-Inspired Supramolecule Design as a Tool to Achieve Efficient Photocatalysts for CO2 Reduction

Bilal Masood Pirzada et al. ACS Omega. .

Abstract

Photocatalytic CO2 reduction into C1 products is one of the most trending research subjects of current times as sustainable energy generation is the utmost need of the hour. In this review, we have tried to comprehensively summarize the potential of supramolecule-based photocatalysts for CO2 reduction into C1 compounds. At the outset, we have thrown light on the inert nature of gaseous CO2 and the various challenges researchers are facing in its reduction. The evolution of photocatalysts used for CO2 reduction, from heterogeneous catalysis to supramolecule-based molecular catalysis, and subsequent semiconductor-supramolecule hybrid catalysis has been thoroughly discussed. Since CO2 is thermodynamically a very stable molecule, a huge reduction potential is required to undergo its one- or multielectron reduction. For this reason, various supramolecule photocatalysts were designed involving a photosensitizer unit and a catalyst unit connected by a linker. Later on, solid semiconductor support was also introduced in this supramolecule system to achieve enhanced durability, structural compactness, enhanced charge mobility, and extra overpotential for CO2 reduction. Reticular chemistry is seen to play a pivotal role as it allows bringing all of the positive features together from various components of this hybrid semiconductor-supramolecule photocatalyst system. Thus, here in this review, we have discussed the selection and role of various components, viz. the photosensitizer component, the catalyst component, the linker, the semiconductor support, the anchoring ligands, and the peripheral ligands for the design of highly performing CO2 reduction photocatalysts. The selection and role of various sacrificial electron donors have also been highlighted. This review is aimed to help researchers reach an understanding that may translate into the development of excellent CO2 reduction photocatalysts that are operational under visible light and possess superior activity, efficiency, and selectivity.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Interplay of activity, efficiency, and selectivity of photocatalysts for reduction of CO2 into C1 compounds.
Figure 2
Figure 2
Ring-shaped rhenium(I) trinuclear complex where the constituent complexes are connected by bidentate phosphine ligands; reprinted with permission from ref (1). Copyright [2015] [American Chemical Society].
Figure 3
Figure 3
Structures and abbreviations of the iridium(III) complexes; reprinted with permission from ref (79). Copyright [2016] [American Chemical Society].
Figure 4
Figure 4
(a) Interlayer structures of a-ZrP (Zr(HPO4)2·H2O) complexes, (b) rhodamine B molecule, and (c) [Re(bpy)(CO)3Cl] complex. Reprinted with permission from ref (93). Copyright [2015] [Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim].
Chart 1
Chart 1. Ru(II)–Ni(II) and Ru(II)–Co(III)-Based Supramolecule Complexes: Various Chemical Structures and Designations
Chart 2
Chart 2. Dinuclear Complexes of Ru and Co
Chart 3
Chart 3. Various Chemical Structures and Designations of Ru(II)–Re(I)-Based Supramolecule Complexes
Scheme 1
Scheme 1. Solvent-Based Deactivation of the [Ru(4dmb)3]2+ Photosensitizer on Accepting the Electron from the Sacrificial Reductant
Chart 4
Chart 4. Various Chemical Structures and Designations of Ru(II)–Re(I)-Based Supramolecule Complexes Having a Central Phenylene Ring Bridging Ligand Containing Three Ethylene Chains at its 1, 3, and 5 Positions, which Are Connected to the 2,2′-Bipyridine Moieties of the Ru Photosensitizer or Re Catalyst Units
Chart 5
Chart 5. Structure and Abbreviations of Various Bridging Ligands and a Representative Ru(II)–Re(I)-Based Supramolecule Photocatalyst Based on These Ligands
Chart 6
Chart 6. Ru(II)–Re(I)-Based Supramolecule Complexes with Various Substituents on the Ligands
Chart 7
Chart 7. Representative Structure of the Ir(III)–Re(I)-Based Complex
Chart 8
Chart 8. Os(II)–Re(I)-Based Supramolecule Complexes with Various Substituents on Their Ligands
Chart 9
Chart 9. Trinuclear Os(II)–Re(I)–Ru(II) Supramolecular Complexes and Constituent Fragments
Chart 10
Chart 10. Ru(II)–Ru(II)-Based Photocatalyst Systems
Scheme 2
Scheme 2. Polymerization of the Catalyst Components during the Photocatalytic Reaction
Chart 11
Chart 11. Various Structures and Designations of Porphyrin–Re(I)-Based Supramolecule Complexes
Chart 12
Chart 12. Structures of M-Por and M-Por-Re Compounds where M = H2, Cu, Pd, Co, Zn, and Fe
Chart 13
Chart 13. Various Structures and Designations of CuI Photosensitizers (a) and FeII-Based Catalyst Component (b)
Chart 14
Chart 14. Cobalt-Based Porphyrin-Type Catalyst and Its Fe-Based Analogue
Figure 5
Figure 5
Possible regulation mechanism for photocatalytic CO2 reduction by 1 or 2/Ru(bpy). Reprinted with permission from ref (185). Copyright [2020] [Elsevier B.V.].
Figure 6
Figure 6
UV–visible spectra of various metal complexes dissolved in acetonitrile: (A) S88 (dashed line), S89 (dot-dashed line), and S78 (solid line); (B) S90 (dot-dashed line) and S81 (solid line). Reprinted with permission from ref (52). Copyright [2005] [American Chemical Society].
Chart 15
Chart 15. Multinuclear Ru(II)–Re(I)-Based Supramolecule Photocatalysts with Different Bridging Ligandsa
Scheme 3
Scheme 3. Oxidative and Reductive Quenching Pathways for the Photochemical Generation of OERS from the Ru(II)–Re(I)-Based System
Chart 16
Chart 16. Binuclear Complexes Based on Ru(II)–Re(I) with Varying Substituents on the Ligands and Structures of BNAH and BIH Reductants
Chart 17
Chart 17. Ru(II)–Re(I) Supramolecule Complex with Different Alkyl Chain Lengths
Chart 18
Chart 18. Ru(II)–Re(I)-Based Supramolecule Photocatalysts with Different Peripheral Ligands
Chart 19
Chart 19. Representative Structure of Ru(II)–Re(I)-Based Supramolecular Photocatalyst
Figure 7
Figure 7
Schematic representation showing the electron transport in a semiconductor–supramolecule hybrid for CO2 reduction.
Figure 8
Figure 8
NiO-Ru(II)–Re(I) hybrid supramolecule photocatalyst anchored by methylphosphonate groups; reprinted with permission from ref (210). Copyright [2019] [American Chemical Society].
Figure 9
Figure 9
PMO having acridone groups in its framework and the Ru(II)–Re(I) supramolecule photocatalyst immobilized on it. Reprinted with permission from ref (54). Copyright [2015] [Elsevier Ltd].
Chart 20
Chart 20. Ru(II)–Ru(II) Supramolecule Photocatalyst with Methylphosphonate Groups as Anchoring Groups to Attach a Solid Substrate
Scheme 4
Scheme 4. Mechanism of Sacrificial Reduction by BNAH and BIH Reductants
See this image and copyright information in PMC

References

    1. Sahara G.; Ishitani O. Efficient Photocatalysts for CO2 Reduction. Inorg. Chem. 2015, 54, 5096–5104. 10.1021/ic502675a. - DOI - PubMed
    1. Nocera D. G. Living healthy on a dying planet. Chem. Soc. Rev. 2009, 38, 13–15. 10.1039/B820660K. - DOI - PubMed
    1. Li L.; Zhao N.; Wei W.; Sun Y. A review of research progress on CO2 capture, storage, and utilization in Chinese Academy of Sciences. Fuel 2013, 108, 112–130. 10.1016/j.fuel.2011.08.022. - DOI
    1. Su T.-m.; Qin Z.-z.; Ji H.-b.; Jiang Y.-x.; Huang G. Recent advances in the photocatalytic reduction of carbon dioxide. Environ. Chem. Lett. 2016, 14, 99–112. 10.1007/s10311-015-0528-0. - DOI
    1. Guadalupe-Medina V.; Wisselink H. W.; Luttik M. A.; de Hulster E.; Daran J.-M.; Pronk J. T.; van Maris A. J. Carbon dioxide fixation by Calvin-Cycle enzymes improves ethanol yield in yeast. Biotechnol. Biofuels 2013, 6, 12510.1186/1754-6834-6-125. - DOI - PMC - PubMed