Reduction of CO<sub>2</sub> to CO at Low Overpotential in Neutral Aqueous Solution by a Ni(cyclam) Complex Attached to Poly(allylamine)

Saravanakumar, Duraisamy; Song, Jieun; Jung, Nayoung; Jirimali, Harishchandra D.; Shin, Woonsup

doi:10.1002/cssc.201100481

Cited by 34 publications

(24 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An approach is based on the electrochemical reduction of CO 2 on metallic cathodes. Although this method requires a very negative potential, the use of a metal complex catalyst such as [Ni(cyclam)] 2 + [8] and its derivatives [9] was shown to allow the conversion of CO 2 into CO at a reasonable voltage [approximately -1.25 vs. saturated calomel electrode (SCE)]. However, some limitations remain, since at negative potentials the use of mercury electrodes is essential to optimize the selectivity of the process, by suppressing or, at least, minimizing, the competitive reduction of proton to hydrogen occurring at the electrode (recently, the use of a glassy carbon electrode has been proposed [10]).…”

Section: Introductionmentioning

confidence: 99%

Experiments with the titanium dioxide-ruthenium tris-bipyridine-nickel cyclam system for the photocatalytic reduction of CO2

Montanaro

Herrero²,

Merli

et al. 2013

Green Processing and Synthesis

View full text Add to dashboard Cite

Ruthenium tris-bipyridine derived complexes functionalized by either carboxyl or phosphonyl groups were tested as sensitizers for the photocatalytic reduction of carbon dioxide in the presence of nickel cyclam acting as a catalyst, and a sacrificial donor. These systems were shown to be as efficient as the unsubstituted compounds in solution. Covalent binding to titania nanoparticles gave slightly different results from those with the untreated semiconductor.

show abstract

Section: Introductionmentioning

confidence: 99%

Experiments with the titanium dioxide-ruthenium tris-bipyridine-nickel cyclam system for the photocatalytic reduction of CO2

Montanaro

Herrero²,

Merli

et al. 2013

Green Processing and Synthesis

View full text Add to dashboard Cite

show abstract

“…16−18 Although recent work has shown that immobilization of a cobalt porphyrin onto conducting diamond 19 or nickel cyclam onto a conducting poly(allylamine) support 20 can promote the electrocatalytic production of CO, these heterogeneous architectures do not currently display technologically relevant current densities (fast kinetics) for CO 2 conversion applications.…”

Section: Introductionmentioning

confidence: 99%

Efficient Reduction of CO₂ to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials

2014

View full text Add to dashboard Cite

The development of inexpensive electrocatalysts that can promote the reduction of CO2 to CO with high selectivity, efficiency, and large current densities is an important step on the path to renewable production of liquid carbon-based fuels. While precious metals such as gold and silver have historically been the most active cathode materials for CO2 reduction, the price of these materials precludes their use on the scale required for fuel production. Bismuth, by comparison, is an affordable and environmentally benign metal that shows promise for CO2 conversion applications. In this work, we show that a bismuth–carbon monoxide evolving catalyst (Bi-CMEC) can be formed under either aqueous or nonaqueous conditions using versatile electrodeposition methods. In situ formation of this thin-film catalyst on an inexpensive carbon electrode using an organic soluble Bi3+ precursor streamlines preparation of this material and generates a robust catalyst for CO2 reduction. In the presence of appropriate imidazolium based ionic liquid promoters, the Bi-CMEC platform can selectively catalyze conversion of CO2 to CO without the need for a costly supporting electrolyte. This inexpensive system can catalyze evolution of CO with current densities as high as jCO = 25–30 mA/cm2 and attendant energy efficiencies of ΦCO ≈ 80% for the cathodic half reaction. These metrics highlight the efficiency of Bi-CMEC, since only noble metals have been previously shown to promote this fuel forming half reaction with such high energy efficiency. Moreover, the rate of CO production by Bi-CMEC ranges from approximately 0.1–0.5 mmol·cm−2·h−1 at an applied overpotential of η ≈ 250 mV for a cathode with surface area equal to 1.0 cm2. This CO evolution activity is much higher than that afforded by other non-noble metal cathode materials and distinguishes Bi-CMEC as a superior and inexpensive platform for electrochemical conversion of CO2 to fuel.

show abstract

“…It has been previously established that histidine residues can be used to attach synthetic metal compounds to macromolecules, and [1] is known to bind pyridine, 22 which has similar electronic and geometric properties to imidazole. Wild-type (WT) azurin has a single, partially-exposed His residue at position 83 that is available for coordinating [1]; putative secondary sphere interactions around His83 are detailed in Figure S1.…”

mentioning

confidence: 99%

An internal electron reservoir enhances catalytic CO₂ reduction by a semisynthetic enzyme

Schneider

Shafaat

2016

Chem. Commun.

View full text Add to dashboard Cite

The development of an artificial metalloenzyme for CO2 reduction is described. The small-molecule catalyst [NiII (cyclam)]2+ has been incorporated within azurin. Selectivity for CO generation over H+ reduction is enhanced within the protein environment, while the azurin active site metal impacts the electrochemical overpotential and photocatalytic activity. The enhanced catalysis observed for copper azurin suggests an important role for intramolecular electron transfer, analogous to native CO2 reducing enzymes.

show abstract

Reduction of CO₂ to CO at Low Overpotential in Neutral Aqueous Solution by a Ni(cyclam) Complex Attached to Poly(allylamine)

Cited by 34 publications

References 23 publications

Experiments with the titanium dioxide-ruthenium tris-bipyridine-nickel cyclam system for the photocatalytic reduction of CO2

Experiments with the titanium dioxide-ruthenium tris-bipyridine-nickel cyclam system for the photocatalytic reduction of CO2

Efficient Reduction of CO₂ to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials

An internal electron reservoir enhances catalytic CO₂ reduction by a semisynthetic enzyme

Contact Info

Product

Resources

About

Reduction of CO2 to CO at Low Overpotential in Neutral Aqueous Solution by a Ni(cyclam) Complex Attached to Poly(allylamine)

Cited by 34 publications

References 23 publications

Experiments with the titanium dioxide-ruthenium tris-bipyridine-nickel cyclam system for the photocatalytic reduction of CO2

Experiments with the titanium dioxide-ruthenium tris-bipyridine-nickel cyclam system for the photocatalytic reduction of CO2

Efficient Reduction of CO2 to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials

An internal electron reservoir enhances catalytic CO2 reduction by a semisynthetic enzyme

Contact Info

Product

Resources

About

Reduction of CO₂ to CO at Low Overpotential in Neutral Aqueous Solution by a Ni(cyclam) Complex Attached to Poly(allylamine)

Efficient Reduction of CO₂ to CO with High Current Density Using in Situ or ex Situ Prepared Bi-Based Materials

An internal electron reservoir enhances catalytic CO₂ reduction by a semisynthetic enzyme