Single-site photocatalysts with a porous structure

Xiao, Wei; Wang, Kai‐Xue; Guo, Xingxing; Chen, Jie‐Sheng

doi:10.1098/rspa.2012.0071

Cited by 17 publications

(9 citation statements)

References 70 publications

(81 reference statements)

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“…Currently, enormous attention has been paid to photocatalytic hydrogen production from water, which is a promising way to produce hydrogen as a potential clean energy source [ 1 , 2 ]. In this line, the hybridization of organic and inorganic materials opens up a new field in the design and preparation of applicable photocatalysts for water splitting reaction by the integration of useful organic and inorganic characteristics within a single composite [ 3 , 4 ].…”

Section: Introductionmentioning

confidence: 99%

Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

et al. 2016

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A series of 3D oxalate-bridged ruthenium-based coordination polymers with the formula of {[Z II (bpy) (2) has been synthesized at room temperature through a self-assembly reaction in aqueous media and characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared and diffuse reflectance UV-Vis spectroscopy and thermogravimetric analysis. The crystal structures of all compounds comprise chiral 3D honeycomb-like polymeric nets of the srs-type, which possess triangular anionic cages where [Z II (bpy) 3 ] 2+ cationic templates are selectively embedded. Structural analysis reveals that the electronic configuration of the cationic guests is affected by electrostatic interaction with the anionic framework. Moreover, the MLCT bands gaps values for 1-8 can be tuned in a rational way by judicious choice of [Z II (bpy) 3 ] 2+ guests. The 3D host-guest polymeric architectures can be used as self-supported heterogeneous photocatalysts for the reductive splitting of water, exhibiting photocatalytic activity for the evolution of H 2 under UV light irradiation.

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Section: Introductionmentioning

confidence: 99%

Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

et al. 2016

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“…Using both zinc-modified zeolites (see Li et al (2011) and Wei et al (2012)) as well as novel uranyl naphthalene-dicarboxylate coordination polymeric compounds (see Xia et al 2010), Chen and co-workers, as outlined in their contribution in this issue, have made detailed quantitative studies of single-site photocatalysis involving porous structures. It is clear from their paper that much may be expected in future from the deployment of such nanoporous solids for the important reactions that Chen et al-e.g.…”

Section: (B) Single-site Photocatalytic Systemsmentioning

confidence: 99%

The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts

Thomas

2012

Proc. R. Soc. A.

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The concept of single-site heterogeneous catalysis, herein defined and extensively illustrated, offers a strategy for the design of new solid catalysts. By capitalizing on the opportunities presented by nanoporous materials to assemble a wide range of new, well-defined, catalytically active centres, it is possible to bring about numerous environmentally benign processes that can replace traditional methods of chemical production. The latter often employs aggressive, corrosive or hazardous reagents. By using both microporous (less than 20 Å diameter) and mesoporous solids (20-500 Å diameter), abundant scope exists for the construction and application of shape-selective, regio-selective and enantioselective catalysts.Keywords: nanoporous solids; selectivity; benign reagents; renewable resources; clean technology; sustainability BackgroundIt would be difficult to overestimate or exaggerate the practical importance of heterogeneous catalysis. Think of the products of petroleum and natural gas upon which civilized life now relies. All the following are manufactured through the agency of solid catalysts: fuels (for transport and heating), fabrics, flavours, fragrances, fertilizers, certain foodstuffs and most pharmaceuticals. Moreover, many of the molecular building blocks for the production of a wide range of the commodities used in everyday life are also generated catalytically: propylene, benzene, toluene, xylene, benzaldehyde, terephthalic acid, adipic acid, caprolactam (precursor of nylon 6) and a variety of monomers for polymeric composites.In fundamental, academic terms, the phenomenon of catalysis is endlessly fascinating and perennially new. Its study presents a multiplicity of intellectual and technological challenges. If we are to understand how and why certain molecules transform readily and others do not when they impinge upon an active site, it is necessary, continually, to devise, develop and deploy new techniques of investigation. This is equally true if our aim-and it is one of prime importanceis to know more about the nature of the active site itself. Without a detailed understanding of the atomic architecture of the catalytically active centre, we are unlikely to be in a position to improve existing catalysts or design superior new ones (Thomas 1997).Because they readily facilitate the separation of products from unreacted reagents, and also because they are amenable to the various processes of thermal reactivation, heterogeneous catalysts (which almost invariably involve solid, active phases) are much more convenient to use than homogeneous ones. Consequently, they now figure eminently in the drive towards green chemistry, clean technology and sustainability. Those scientists concerned with such topics are currently exploring new ways of generating both energy and novel materials and in this regard, solid catalysts are of pivotal importance.There is now an exigent need to design and develop catalysts that can cope with and transform readily available reactants in an environmentally benign manner. N...

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“…Dye molecules, particularly metallo-organic dye Ru(bpy) 3 2+ , have been extensively studied as photocatalysts in homogeneous systems for their beneficial photophysical properties, which include strong visible-light absorption and long-lived excited states. − ,, Building on the seminal results obtained using photoinduced electron transfer (PET), researchers have demonstrated various dye molecules to be very efficient in photoredox reactions through excitation. − Incorporation of these photoredox-capable dye molecules into MOFs broadens and deepens the MOF photocatalysis to achieve more sophisticated and meaningful photoconversions. Meanwhile, MOFs enable the high-density and orderly distribution of isolated dye-photocatalysts along the heterogeneous support; by contrast, in homogeneous systems, the same concentration of dyes often induces detrimental aggregation that suppresses activity or causes self-quenching. − Most importantly, the crystalline nature of the MOF structure provides other possibilities for the transport of excited states or photoinduced electrons and holes. − For example, Lin and co-workers recently reported that the “through space” energy jumping of singlet excited states beyond the nearest neighbor can account for up to 67% of the energy transfer rate in truxene-based materials (Figure ). This phenomenon can be observed only in highly ordered networks and may provide an additional pathway for energy transfer and exciton migration, which are in favor of photocatalysis.…”

Section: Type II Mofs With Dye Molecules As Organic Linkersmentioning

confidence: 99%

Metal–Organic Frameworks: Versatile Materials for Heterogeneous Photocatalysis

et al. 2016

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Photocatalysis is one of the most important chemical methods to mitigate the energy and environmental crisis via converting inexhaustible solar energy into clean chemical potential. The general history of the development of photocatalysis based on porous metal−organic frameworks (MOFs) is simply divided into three branches with a focus placed on the distinct structural role of the photocatalytic center: the inorganic cluster nodes, the organic linkers, and the guests in the pores of MOFs. In each branch, these photocatalytic centers are considered to be monodispersed within the crystal lattices with the other two structure roles regularly distributed to isolate the active centers and sometimes to provide more functions other than photoactivity. This distinctive nature has rendered MOFs as promising candidates for photocatalysis not only because they combine the benefits of heterogeneous catalysis and homogeneous catalysis but also because they facilitate the possibility of merging multifunctional catalytic sites for concerted or cascade photocatalysis. The design strategy and improvement approaches for MOF-based photocatalysts are also introduced with an emphasis on structure. Our intention is for this comprehensive view of MOFs-involved photocatalysts to inspire new ideas for designing heterogeneous photocatalysts toward the better utilization of solar energy.

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Single-site photocatalysts with a porous structure

Cited by 17 publications

References 70 publications

Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts

Metal–Organic Frameworks: Versatile Materials for Heterogeneous Photocatalysis

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