Carbon dioxide reduction with homogenous early transition metal complexes: Opportunities and challenges for developing CO 2 catalysis

Grice, Kyle A.

doi:10.1016/j.ccr.2017.01.007

Cited by 179 publications

(130 citation statements)

References 263 publications

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“…Therefore, new approaches are needed to develop electrolyzers operating at industrially relevant scales while fulfilling customer needs and requirements. Regarding the catalysts employed, molecular complexes have been widely investigated for the carbon dioxide reduction reaction (CO 2 RR) due to the possibility of fine tuning the ligand structure (steric and electronic effects, as well as second coordination sphere effects) . Earth abundant metal‐based catalysts have been shown to efficiently catalyze the production of CO and formate in organic solvents and in water, even if examples in pure aqueous solutions are less numerous.…”

Section: Methodsmentioning

confidence: 99%

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO₂ to CO in a Flow Cell

Torbensen

Han

Boudy

et al. 2020

Chemistry A European J

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Molecular catalysts have been shown to have high selectivity for CO2 electrochemical reduction to CO, but with current densities significantly below those obtained with solid‐state materials. By depositing a simple Fe porphyrin mixed with carbon black onto a carbon paper support, it was possible to obtain a catalytic material that could be used in a flow cell for fast and selective conversion of CO2 to CO. At neutral pH (7.3) a current density as high as 83.7 mA cm−2 was obtained with a CO selectivity close to 98 %. In basic solution (pH 14), a current density of 27 mA cm−2 was maintained for 24 h with 99.7 % selectivity for CO at only 50 mV overpotential, leading to a record energy efficiency of 71 %. In addition, a current density for CO production as high as 152 mA cm−2 (>98 % selectivity) was obtained at a low overpotential of 470 mV, outperforming state‐of‐the‐art noble metal based catalysts.

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Section: Methodsmentioning

confidence: 99%

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO₂ to CO in a Flow Cell

Torbensen

Han

Boudy

et al. 2020

Chemistry A European J

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“…These systems can broadly be classified as either electrocatalytic, photocatalytic or photoelectrocatalytic . In all three cases transition metal α‐diimine complexes have emerged as the leading class of catalytic systems, boasting both high levels of selectivity and activity . fac ‐[Re(CO) 3 (bipy)Cl] (bipy=2,2′‐bipyridine), is a prime example, having first been identified as an electrocatalyst by Lehn and co‐workers, and two decades later as a photocatalyst by Ishitani and co‐workers .…”

Section: Introductionmentioning

confidence: 99%

Photo‐Assisted Electrocatalytic Reduction of CO₂: A New Strategy for Reducing Catalytic Overpotentials

2019

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Electrochemical and photochemical reduction of CO2 are both well‐established, independent catalytic routes toward producing added‐value chemicals. The potential for any cross‐reactivity has, however, hardly been explored so far. In this report, we assess a system primarily using spectroelectrochemical monitoring, where photochemistry assists the cathodic activation of precursor complexes fac‐[Mn(CO)3(2,2′‐bipyridine)Br] and [Mo(CO)4(6,6′‐dimethyl‐2,2′‐bipyridine)] to lower the catalytic overpotential needed to trigger the electrocatalytic reduction of CO2 to CO. Following the complete initial 1e− reduction of the parent complexes, the key photochemical cleavage of the Mn−Mn and Mo−CO bonds in the reduction products, [Mn(CO)3(2,2′‐bipyridine)]2 and [Mo(CO)4(6,6′‐dimethyl‐2,2′‐bipyridine)].−, respectively, generates the 2e−‐reduced, 5‐coordinate catalysts, [Mn(CO)3(2,2′‐bipyridine)]− and [Mo(CO)3(6,6′‐dimethyl‐2,2′‐bipyridine)]2− appreciably closer to the initial cathodic wave R1. Experiments under CO2 confirm the activity of both electrocatalysts under the photoirradiation with 405 nm and 365 nm light, respectively. This remarkable achievement corresponds to a ca. 500 mV positive shift of the catalytic onset compared to the exclusive standard electrocatalytic activation.

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“…[1] Despite the increasing number of homogeneous catalysts based on earth-abundant transition metals that are able to reduce CO 2 , [2] furtherc atalyst development is needed not only to achieve high catalytic rates,b etter selectivity for as pecific product, and long durability,b ut also to better understand the operative mechanisms for CO 2 reduction. [1] Despite the increasing number of homogeneous catalysts based on earth-abundant transition metals that are able to reduce CO 2 , [2] furtherc atalyst development is needed not only to achieve high catalytic rates,b etter selectivity for as pecific product, and long durability,b ut also to better understand the operative mechanisms for CO 2 reduction.…”

mentioning

confidence: 99%

“…[1][2][3] In particular, Mn fac-tricarbonyl derivatives with polypyridyl moieties are able to catalyse the production of CO from CO 2 with high faradaic efficiencies (h CO )inthe presence of Brønsted or Lewis acids ( Figure 1). [1][2][3] In particular, Mn fac-tricarbonyl derivatives with polypyridyl moieties are able to catalyse the production of CO from CO 2 with high faradaic efficiencies (h CO )inthe presence of Brønsted or Lewis acids ( Figure 1).…”

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confidence: 99%

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

et al. 2018

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We report here the first purely organometallic fac-[Mn I (CO) 3 (bis-Me NHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO 2 to CO,e xceeding 100 turnovers with excellent faradaic yields (h CO % 95 %) in anhydrous CH 3 CN.U nder the same conditions,amaximum turnover frequency (TOF max )of2100 s À1 was measured by cyclic voltammetry,w hichc learly exceeds the values reported for other manganese-based catalysts.M oreover,t he addition of water leads to the highest TOF max value (ca. 320 000 s À1 )ever reported for amanganese-based catalyst. AMn I tetracarbonyl intermediate was detected under catalytic conditions for the first time.

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Carbon dioxide reduction with homogenous early transition metal complexes: Opportunities and challenges for developing CO 2 catalysis

Cited by 179 publications

References 263 publications

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO₂ to CO in a Flow Cell

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO₂ to CO in a Flow Cell

Photo‐Assisted Electrocatalytic Reduction of CO₂: A New Strategy for Reducing Catalytic Overpotentials

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

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Carbon dioxide reduction with homogenous early transition metal complexes: Opportunities and challenges for developing CO 2 catalysis

Cited by 179 publications

References 263 publications

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO2 to CO in a Flow Cell

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO2 to CO in a Flow Cell

Photo‐Assisted Electrocatalytic Reduction of CO2: A New Strategy for Reducing Catalytic Overpotentials

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO2 Reduction to CO

Contact Info

Product

Resources

About

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO₂ to CO in a Flow Cell

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO₂ to CO in a Flow Cell

Photo‐Assisted Electrocatalytic Reduction of CO₂: A New Strategy for Reducing Catalytic Overpotentials

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO