Photocatalytic CO<sub>2</sub> Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites

Kuramochi, Yusuke; Sekine, Masato; Kitamura, Kyohei; Maegawa, Yoshifumi; Goto, Yasutomo; Shirai, Soichi; Inagaki, Shinji; Ishida, Hideyuki

doi:10.1002/chem.201701466

Cited by 41 publications

(45 citation statements)

References 52 publications

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“…The durability of the catalyst was assessed by irradiation of the Ru 0.04 ‐Re 0.04 ‐BPy‐PMO with high intensity visible light (>385 nm, 800 mW) for 280 h (Figure ). The TON app CO reached a value of 402, which is higher than the values previously reported for Ru(PS)‐Ru(Cat)‐BPy‐PMO catalysts …”

Section: Resultscontrasting

confidence: 71%

“…The BPy‐PMO photocatalysts including Re and Ru complexes are denoted herein as Ru(X)‐Re(Y)‐BPy‐PMO, in which X and Y are the molar ratios of Ru and Re to the total BPy in the BPy‐PMO, respectively. Recently, we reported CO 2 reduction photocatalysts based on BPy‐PMO containing both a [Ru(bpy) 3 ] 2+ photosensitizer (Ru(PS)) and a Ru(bpy)(CO) 2 Cl 2 catalyst (Ru(Cat)) . In this material, active Ru(Cat)‐Ru(PS) pairs formed at adjacent BPy ligands on the surface and acted as efficient photocatalytic sites for CO 2 reduction.…”

Section: Resultsmentioning

confidence: 99%

“…The BPy-PMOp hotocatalystsi ncluding Re and Ru complexes are denoted herein as Ru(X)-Re(Y)-BPy-PMO, in which Xa nd Y are the molar ratios of Ru and Re to the total BPy in the BPy-PMO, respectively.R ecently,w er eported CO 2 reduction photocatalysts based on BPy-PMO containing both a[ Ru(bpy) 3 ] 2 + photosensitizer (Ru(PS)) and aR u(bpy)(CO) 2 Cl 2 catalyst (Ru(Cat)). [27] In this material, activeR u(Cat)-Ru(PS) pairs formed at adjacent BPy ligandso nt he surfacea nd acted as efficient photocatalytic sites for CO 2 reduction.T he numberso ft he ad-jacentR u(PS)-Ru(Cat) pairs were calculated for various BPy-PMOs with different loading amountso fR u(PS) and Ru(Cat)b y MonteC arlo simulation. The simulated number of the Ru(PS)-Ru(Cat)p airs was well-correlated to the activity of photochemical CO 2 reduction for Re(PS)-Re(Cat)-BPy-PMOs.…”

Section: Photocatalysiso Fr U-re-bpy-pmomentioning

confidence: 99%

“…The TON app CO reached av alue of 402, which is higher than the values previously reported for Ru(PS)-Ru(Cat)-BPy-PMOc atalysts. [27] The recycling test of Ru 0.04 -Re 0.04 -BPy-PMO catalyst was carried out ( Figure S11i the electronic andc oordination structures of Re in Ru 0.04 -Re 0.04 -BPy-PMOb efore anda fter reaction for 24 h( Figure S13 in the Supporting Information). The deactivation was caused through filtration and washing because the catalytic activity was almost completely preserved before the filtration.T he reaction between Re active species and oxygen in air seems to be the most plausible explanation for the observedd eactivation.…”

Section: Photocatalysiso Fr U-re-bpy-pmomentioning

confidence: 99%

“…In particular, the combination of BPy‐PMO with [Ru(bpy) 3 ] 2+ and Pt nanoparticles exhibits efficient photocatalysis during the generation of hydrogen from water . Very recently, we reported BPy‐PMOs in which both [Ru(bpy) 3 ] 2+ and Ru(bpy)(CO) 2 Cl 2 were immobilized on the pore surfaces, as well as the application of these materials to photocatalytic CO 2 reduction . We have also synthesized Re(bpy)(CO) 3 Cl‐immobilized BPy‐PMO, but the physicochemical and photocatalytic properties of this material have not yet been determined, although it may have practical applications.…”

Section: Introductionmentioning

confidence: 99%

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Re(bpy)(CO)₃Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO₂ Reduction

Waki

Yamanaka

Shirai

et al. 2018

Chemistry A European J

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This paper describes the physicochemical properties of a rhenium (Re) complex [Re(bpy)(CO) Cl] immobilized on a bipyridine-periodic mesoporous organosilica (BPy-PMO) acting as a solid support. The immobilized Re complex generated a metal-to-ligand charge transfer absorption band at 400 nm. This wavelength is longer than that exhibited by Re(bpy)(CO) Cl in the polar solvent acetonitrile (371 nm) and is almost equal to that in nonpolar toluene (403 nm). The photocatalytic activity of this heterogeneous Re complex was lower than that of a homogeneous Re complex due to the reduced phosphorescence lifetime resulting from immobilization. However, the catalytic activity was enhanced by the co-immobilization of the ruthenium (Ru) photosensitizer [Ru(bpy) ] on the PMO pore surfaces. Quantum chemical calculations suggest that electron transfer between the Ru and Re complexes occurs through interactions between the molecular orbitals in the pore walls. These results should have applications to the design of efficient heterogeneous CO reduction photocatalysis systems.

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Section: Resultscontrasting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: Photocatalysiso Fr U-re-bpy-pmomentioning

confidence: 99%

Section: Photocatalysiso Fr U-re-bpy-pmomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Re(bpy)(CO)₃Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO₂ Reduction

Waki

Yamanaka

Shirai

et al. 2018

Chemistry A European J

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Formation of CX Bonds in CO₂ Chemical Fixation Catalyzed by Metal−Organic Frameworks

2019

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Transformation of CO2 based on metal−organic framework (MOF) catalysts is becoming a hot research topic, not only because it will help to reduce greenhouse gas emission, but also because it will allow for the production of valuable chemicals. In addition, a large number of impressive products have been synthesized by utilizing CO2. In fact, it is the formation of new covalent bonds between CO2 and substrate molecules that successfully result in CO2 solidly inserting into the products, and only four types of new CX bonds, including CH, CC, CN, and CO bonds, are observed in this exploration. An overview of recent progress in constructing CX bonds for CO2 conversion catalyzed by various MOF catalysts is provided. The catalytic mechanism of generating different CX bonds is further discussed according to both structural features of MOFs and the interactions among CO2, substrates, as well as MOFs. The future opportunities and challenges in this field are also tentatively covered.

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Recyclable, Immobilized Transition‐Metal Photocatalysts

et al. 2021

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The use of transition-metal complexes as photocatalysts have allowed the performance of diverse organic transformations in an outstanding manner, characterized not only by high yields, TOF, and selectivity values, but also by modulating and providing access to novel molecular structures that, without them, would be difficult if not impossible. However, one of the biggest concerns regarding the use of these photocatalysts relies on the difficulties associated with their isolation from reaction media and reutilization once the chemical process ends. The above, besides contaminating reaction products and requiring out tedious purification processes, prompts the inevitable loss of the catalyst, directly affecting its recyclability. In addition, this situation results in negative outcomes from an economic and environmental perspective, since transition-metal complexes are usually expensive materials, and their unsuccessful recovery could result in leakage into the environment. These drawbacks served as inspiration for the elaboration of the present review focused on the development of novel strategies developed during the last decade for the successful recovery of these species. The strategies summarized herein, whether for homogeneous or heterogeneous systems, are based on the use of thermotropic solvents, changes in the hydrophilic balance of the catalyst, the employment of polymers, copolymers, porous macromolecular structures, and inorganic nanostructures as support of these entities. Moreover, the use of organized and confining media, such as micelles and gels in this context, is also discussed. We hope that this review will motivate the search for new strategies to develop novel catalytic systems, understanding that high performance is based not only on yields but also on recyclability, sustainability, and responsibility to the environment.

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Photocatalytic CO₂ Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites

Cited by 41 publications

References 52 publications

Re(bpy)(CO)₃Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO₂ Reduction

Re(bpy)(CO)₃Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO₂ Reduction

Formation of CX Bonds in CO₂ Chemical Fixation Catalyzed by Metal−Organic Frameworks

Recyclable, Immobilized Transition‐Metal Photocatalysts

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Photocatalytic CO2 Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites

Cited by 41 publications

References 52 publications

Re(bpy)(CO)3Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO2 Reduction

Re(bpy)(CO)3Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO2 Reduction

Formation of CX Bonds in CO2 Chemical Fixation Catalyzed by Metal−Organic Frameworks

Recyclable, Immobilized Transition‐Metal Photocatalysts

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Product

Resources

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Photocatalytic CO₂ Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites

Re(bpy)(CO)₃Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO₂ Reduction

Re(bpy)(CO)₃Cl Immobilized on Bipyridine‐Periodic Mesoporous Organosilica for Photocatalytic CO₂ Reduction

Formation of CX Bonds in CO₂ Chemical Fixation Catalyzed by Metal−Organic Frameworks