Highly efficient, selective, and durable photocatalytic system for CO<sub>2</sub> reduction to formic acid

Tamaki, Yusuke; Koike, Kazuhide; Ishitani, Osamu

doi:10.1039/c5sc02018b

Cited by 134 publications

(99 citation statements)

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“…This was ascribed to fast back electron transfers as a consequence of the rather slow decomposition kinetics of (BNA)2 [23,24,115]. In contrast to the findings of the Ishitani group, where BNAH and (BNA)2 act as competing excited state quenchers during the photocatalysis, several other reports indicate that the dimeric species can also serve as an effective electron donor.…”

Section: Nad(p)h Formation Using the [(Bpy)rh(cp*)x] N+ Motivecontrasting

confidence: 41%

“…Therefore, they hypothesized that the dimeric species (BNA) 2 , despite its higher reduction potential in comparison to the monomeric BNAH, represents the endpoint of the photooxidation pathway. This was ascribed to fast back electron transfers as a consequence of the rather slow decomposition kinetics of (BNA) 2 [23,24,115].…”

Section: Nad(p)h Formation Using the [(Bpy)rh(cp*)x] N+ Motivementioning

confidence: 99%

“…Impressive selectivities and TONs (turnover numbers) have also recently been obtained with a cobalt cryptate as the catalyst [22]. In contrast to the mentioned Re complexes, the Ru-based catalyst of the general composition [(NN)Ru(CO)2Cl2] or [(NN)2RuX2] (X = CO, Cl, DMF; NN = N,N-chelating diimine ligand) shows a selectivity towards formate production in the majority of cases, although sometimes CO can also be obtained as the major product [8,[23][24][25].…”

Section: Application Of [(Bpy)rh(cp*)x] N+ -Like Coordination Compounmentioning

confidence: 99%

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Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts

Mengele¹,

Rau²

2017

Inorganics

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Due to the limited amount of fossil energy carriers, the storage of solar energy in chemical bonds using artificial photosynthesis has been under intensive investigation within the last decades. As the understanding of the underlying working principle of these complex systems continuously grows, more focus will be placed on a catalyst design for highly selective product formation. Recent reports have shown that multifunctional photocatalysts can operate with high chemoselectivity, forming different catalysis products under appropriate reaction conditions. Within this context [(bpy)Rh(Cp*)X] n+ -based catalysts are highly relevant examples for a detailed understanding of product selectivity in artificial photosynthesis since the identification of a number of possible reaction intermediates has already been achieved.

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Section: Nad(p)h Formation Using the [(Bpy)rh(cp*)x] N+ Motivecontrasting

confidence: 41%

Section: Nad(p)h Formation Using the [(Bpy)rh(cp*)x] N+ Motivementioning

confidence: 99%

Section: Application Of [(Bpy)rh(cp*)x] N+ -Like Coordination Compounmentioning

confidence: 99%

See 1 more Smart Citation

Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts

Mengele¹,

Rau²

2017

Inorganics

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“…As part of the Food and Drug Administration safety assessment process, more than 80 % of all drugs have used radioactive materials in their testing program. [48] Ongoing efforts in our group aim to further optimize the two-chamber system. The escalating price of 14 C labeling building blocks, and the high costs for disposal of radioactive wastes represent major drawbacks in the field.…”

Section: Isotope Labelingmentioning

confidence: 99%

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

et al. 2018

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A convenient and safe approach in valorizing carbon monoxide (CO) produced from the photocatalytic reduction of carbon dioxide (CO 2 ) has been investigated. Visible light was used to drive an optimized photocatalytic reduction using a ruthenium trisbipyridine complex as a sensitizer and a rhenium bipyridyl carbonyl complex as a catalyst to perform an efficient reduction of CO 2 to CO, which was then simultaneously utilized in a palladium-catalyzed aminocarbonylation reaction at room temperature. This approach provides safe handling of the produced CO which also opens the way for a more efficient application of 13 C-isotope and 14 C-radioisotope-labeled CO 2 in pharmaceutically relevant drug labeling.The constraints we are exerting on our environment due to the extensive use of fossil fuels have reached alarming levels. There is a consensus that we have to develop a circular economy scheme in order to drop to a zero-carbon emission scenario. One challenge in front of chemists is to convert the everincreasing CO 2 level into a fuel or to use it as a source of carbon in chemical transformations. However, due to its high chemical stability, its activation or reduction is scientifically challenging, requiring appropriate catalyst and energy input. [1][2][3][4][5][6] The energy can be ideally provided by solar energy, a strategic scheme of artificial photosynthesis.One of the most robust and selective photocatalyst for CO 2 reduction was first reported by Lehn et al. using fac-Re(bpy)(-CO) 3 Cl. [7,8] Since then, researchers have tried to improve its efficiency by (i) modifying the nature of the ligands in the coordination sphere to improve catalysis and to shift the absorption properties in the visible range, [9][10][11][12][13][14][15] and/or (ii) incorporating photosensitizers to photo-activate the catalyst in the visible spectral window. [16][17][18][19][20][21][22][23][24][25][26] From turnover numbers (TON) of 5-20 when it was first published, current improvements show TONs of ca. 3000. [27] Efforts are also guided towards designing photocatalysts employing earth-abundant metals (Cu, Ni, Co, Mn, Fe) for cost efficiency and such systems show equally promising results. [28] Though most studies in photocatalytic reduction of CO 2 to CO have focused on improving the efficiency, selectivity, cost, and stability of the catalyst, only little has been reported in addressing the need for capturing and storing the produced CO. The reduced product can be segregated from the headspace mixture by techniques such as swing adsorption, [29] cryogenic distillation, [30] and membrane gas separation, [31] but these usually employ specialized equipment, and high pressure and temperature, which require extra energy input. Furthermore, the inherent toxicity and flammability of CO gas impose strict handling precautions and safety procedures.In nature, CO dehydrogenase enzymes transport the CO produced from the catalytic reduction of CO 2 in its C cluster site to the acetyl CoA synthase via direct gas channels to insert CO in a carbony...

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“…For the development of artificial photosynthetic schemes, variousm etal complexes [1][2][3][4][5][6][7][8][9][10][11][12][13] and semiconductors, [14][15][16][17][18][19] as well as their hybrids, [20][21][22][23][24][25][26][27][28] have been examined as photocatalystsf or CO 2 reduction. For the development of artificial photosynthetic schemes, variousm etal complexes [1][2][3][4][5][6][7][8][9][10][11][12][13] and semiconductors, [14][15][16][17][18][19] as well as their hybrids, [20][21][22]…”

Section: Introductionmentioning

confidence: 99%

Activation of the Carbon Nitride Surface by Silica in a CO‐Evolving Hybrid Photocatalyst

et al. 2016

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Photocatalytic reduction of CO2 to CO proceeded by visible light (λ>400 nm) using mesoporous graphitic carbon nitride (C3N4) coupled with a RuII–ReI binuclear complex (RuRe) containing a photosensitizer and catalytic units. The selectivity to CO exceeded 90 % during the initial stage. Photocatalytic reactions (including isotope tracer experiments) and electrochemical measurements revealed that the reaction proceeded according to a two‐step photoexcitation of C3N4 and the RuII photosensitizer unit, that is, it followed the Z‐Scheme mechanism. Modification of C3N4 with highly dispersed silica was found to improve the ability of C3N4 to accommodate RuRe, which enhanced the photocatalytic activity for CO production.

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Highly efficient, selective, and durable photocatalytic system for CO₂ reduction to formic acid

Abstract: Photocatalytic reduction of CO2 to formic acid with high efficiency, durability, and rate.

Cited by 134 publications

References 20 publications

Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts

Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

Activation of the Carbon Nitride Surface by Silica in a CO‐Evolving Hybrid Photocatalyst

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Highly efficient, selective, and durable photocatalytic system for CO2 reduction to formic acid

Abstract: Photocatalytic reduction of CO2 to formic acid with high efficiency, durability, and rate.

Cited by 134 publications

References 20 publications

Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts

Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts

Visible‐Light‐Driven Reduction of CO2 to CO and Its Subsequent Valorization in Carbonylation Chemistry and 13C Isotope Labeling

Activation of the Carbon Nitride Surface by Silica in a CO‐Evolving Hybrid Photocatalyst

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Product

Resources

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Highly efficient, selective, and durable photocatalytic system for CO₂ reduction to formic acid

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling