Making Plastics from Carbon Dioxide:  Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO<sub>2</sub>

Darensbourg, Donald J.

doi:10.1021/cr068363q

Cited by 1,473 publications

(915 citation statements)

References 109 publications

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“…Its use for the production of chemicals is doubly beneficial, since in addition to its availability, it would represent a decrease in the carbon footprint for the manufacturing of the particular chemical. Catalytic processes are crucial for improving efficiency and conversion in the use of CO 2 for the manufacture of a wide range of substances, including methanol [1][2][3][4], carboxylic acids [1,4], polycarbonates [1,4,5], polylactones [1,6] or hydrocarbons [1,4,7,8]. As a particularly important matter, the catalytic production of hydrocarbon fuels from CO 2 constitutes a highly desirable strategy for the potential of closing the carbon cycle in future energy schemes.…”

Section: Introductionmentioning

confidence: 99%

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

Gonell

Puga

Julián‐López

et al. 2016

Applied Catalysis B: Environmental

105

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Copper-doped titanium dioxide materials with anatase phase (Cu-TiO 2 , atomic Cu contents ranging from 0 to 3% relative to the sum of Cu and Ti), and particle sizes of 12-15 nm, were synthesised by a solvo-thermal method using ethanol as the solvent and small amounts of water to promote the hydrolysis-condensation processes. Diffuse reflectance UV-vis spectroscopy show that the edges of absorption of the titania materials are somewhat shifted to higher wavelengths due to the presence of Cu. X-Ray Photoelectron Spectroscopy (XPS) indicate that Cu(II) is predominant. Photocatalytic CO 2 reduction experiments were performed in aqueous Cu-TiO 2 suspensions under UV-rich light and in the presence of different solutes. Sulfide was found to promote the efficient production of H 2 from water and formic acid from CO 2 . The effect of the Cu content on the photoactivity of Cu-TiO 2 was also studied, showing that copper plays a role on the photocatalytic reduction of CO 2 . IntroductionCarbon dioxide is an inexpensive and widely available feedstock. Its use for the production of chemicals is doubly beneficial, since in addition to its availability, it would represent a decrease in the carbon footprint for the manufacturing of the particular chemical. Other researchers have reported lower but noticeable methanol yields using similarly prepared photocatalysts and Hg lamp irradiation (10-23 µmol g cat −1 h −1 ) [19,20]. In gas-phase reactions, the formation of methanol was also reported, but in considerably lower yields (2 nmol g cat −1 h −1 ), being methane the major product formed by Cu/TiO 2 photocatalysis [21]. In contrast, similar materials were found to promote the formation of several hydrocarbons including methane, ethane and ethylene in conjunction with larger amounts of H 2 [22], whereas CO and methane were major products found in a more recent study [23]. A significant degree of discrepancy regarding the identity of the reaction products (in addition to their selectivities and yields) is apparent by considering the aforementioned literature data, although this could be in part due to the different synthetic procedures used for the preparation of the photocatalysts and to the varied irradiation conditions used.Despite the notable progress in this field of research, there is no clear trend which may allow to conclude on the actual mechanistic route and to gain knowledge on the role of copper on the reaction. Thorough kinetic and in situ spectroscopic studies would provide valuable information on the reaction at the surface of the photocatalyst and may guide future design of more active copper-titania materials. An important issue to focus on is the possible back-reactions of the reduction products on the photocatalyst. For example, it was observed that methanol and formaldehyde, initially formed by a photocatalytic process using Cu(0) powder and TiO 2 , were 3 rapidly consumed by in situ formed Cu/TiO 2 [24]. The simultaneous occurrence of CO 2 reduction and decomposition of the products should result in stat...

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Section: Introductionmentioning

confidence: 99%

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

Gonell

Puga

Julián‐López

et al. 2016

Applied Catalysis B: Environmental

105

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“…Various metal complexes are successful copolymerisation catalysts, usually having Zn(II), Co(II/III), Cr(III) or Al(III) active sites. 6,7 There is much scope for new metal catalysts, including those that operate at low CO 2 pressure, thereby 30 improving the energy balance and net CO 2 consumption. Recently, we reported various bimetallic Zn(II) and Co(II/III) copolymerisation catalysts which displayed impressive activity, at only 1 atm CO 2 pressure.…”

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confidence: 99%

“…[5][6][7] Furthermore, the formation of cis-CHC is unusual: the trans-isomer is more commonly formed, usually by back-biting reactions under thermodynamic control (Scheme 3). 7,25 However, the low pressure and moderate temperature used here are insufficient to yield significant competing copolymerisation. Increasing the pressure of CO 2 to 10 atm, keeping all other conditions the same, led to an increase in production of PCHC (with 99% carbonate linkages), with low amounts of the trans-CHC also being observed (entry 9).…”

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confidence: 99%

A bimetallic iron(iii) catalyst for CO₂/epoxide coupling

et al. 2011

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“…Salen and Salen* present similar metal coordination behavior but the nature of the substituents on the Salen ligand is known to affect the properties of the metal complex, as observed in ring opening polymerization [79]. Recently Shaver et al reported that electron donating ortho-substituents in Salen*-like cobalt complexes enhanced their efficiency in CMRP of VAc but bimodal mass distributions were observed under the hard experimental conditions employed (120°C) [80].…”

Section: Resultsmentioning

confidence: 99%

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

Kermagoret

Jérôme

Detrembleur

et al. 2015

European Polymer Journal

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a b s t r a c tOrganometallic-mediated radical polymerization (OMRP) has seen a significant growth in the last years notably due to the development of new metal complexes, especially cobalt derivatives. Despite of this, none of the reported complexes offers optimal control for monomers with very different reactivity, which somewhat limits the synthesis of copolymers. In order to expand the scope of cobalt-mediated radical polymerization (CMRP), we investigated an in situ ligand exchange reaction for modulating the properties of the cobalt complex at the polymer chain-end and adjusting the CACo bond strength involved in the control process. With the aim of improving the synthesis of poly(vinyl acetate)-b-poly (n-butyl acrylate) copolymers, bidentate acetylacetonate ligands, which impart high level of control to the polymerization of vinyl acetate (VAc), were replaced in situ at the PVAcAcobalt chain-end by tetradentate Salen type ligands that are more suited to acrylates.

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Making Plastics from Carbon Dioxide: Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO₂

Cited by 1,473 publications

References 109 publications

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

A bimetallic iron(iii) catalyst for CO₂/epoxide coupling

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

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Making Plastics from Carbon Dioxide: Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO2

Cited by 1,473 publications

References 109 publications

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H2 from aqueous sulfide

A bimetallic iron(iii) catalyst for CO2/epoxide coupling

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

Contact Info

Product

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Making Plastics from Carbon Dioxide: Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO₂

A bimetallic iron(iii) catalyst for CO₂/epoxide coupling