Effects of ligand structure on the adsorption of nickel tetraazamacrocyclic complexes and electrocatalytic CO2 reduction

Bujno, Krzysztof; Bilewicz, Renata; Siegfried, Liselotte; Kaden, Thomas A.

doi:10.1016/s0022-0728(97)00603-7

Cited by 44 publications

(37 citation statements)

References 27 publications

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“…[333] Ap roton-coupled electron transfer facilitated by the cyclam ligand was reported to be the key to the reduction of CO 2 . [339,340] In addition, the application of Hg electrodes was shownt o have as ignificant influence on the efficiency of the reduction process duet os tabilization of the [Ni I (cyclam)] intermediate upon adsorption on Hg. Catalytic testingi nt he presence of glassy carbon electrodes revealed slower kinetics at more negative potentials (À1.6 Vv s. NHE) and lower Faradaic efficiency for CO formation (90 %).…”

Section: Homogeneouscatalyst Mimics Of the Co Dehydrogenasementioning

confidence: 99%

From Enzymes to Functional Materials—Towards Activation of Small Molecules

Möller

Piontek

Miller

et al. 2017

Chemistry A European J

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The design of non-noble metal-containing heterogeneous catalysts for the activation of small molecules is of utmost importance for our society. While nature possesses very sophisticated machineries to perform such conversions, rationally designed catalytic materials are rare. Herein, we aim to raise the awareness of the overall common design and working principles of catalysts incorporating aspects of biology, chemistry, and material sciences.

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Section: Homogeneouscatalyst Mimics Of the Co Dehydrogenasementioning

confidence: 99%

From Enzymes to Functional Materials—Towards Activation of Small Molecules

Möller

Piontek

Miller

et al. 2017

Chemistry A European J

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show abstract

“… 25 − 27 Additionally, nickel and cobalt cyclam systems bearing four secondary amines were shown to electrochemically convert CO 2 into CO. 1 , 3 , 5 , 9 , 28 − 33 DFT studies proposed that CO 2 is activated through cooperative hydrogen-bonding interactions between the Ni-bound substrate and the secondary amines in the ligand framework. 9 , 30 , 34 , 35 Electrochemical studies of nickel complexes supported by mono-, di-, tri-, and tetramethylated cyclam ligands revealed that both the catalytic activity and faradaic efficiency for CO 2 -to-CO conversion decrease upon methylation of the ligand framework. 30 , 35 Methylation of the cyclam ligands impacts both the first and second coordination spheres of the nickel complexes.…”

Section: Introductionmentioning

confidence: 99%

“… 9 , 30 , 34 , 35 Electrochemical studies of nickel complexes supported by mono-, di-, tri-, and tetramethylated cyclam ligands revealed that both the catalytic activity and faradaic efficiency for CO 2 -to-CO conversion decrease upon methylation of the ligand framework. 30 , 35 Methylation of the cyclam ligands impacts both the first and second coordination spheres of the nickel complexes. Hence, the effects of the two cannot be decoupled and a direct correlation between the number of pendant proton donors and the activity of the catalyst could not be established.…”

Section: Introductionmentioning

confidence: 99%

Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

et al. 2018

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The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO2 to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO2, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO2, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO2 substrate.

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“…CO, the liberated reaction product, can bind to Ni(II)cyclam, which then can be reduced to Ni(0)cyclam-CO. This product is poorly soluble, can precipitate at the electrode and thus block the electroactive surface [21,25,28], which leads to a decrease of the reduction wave after several successive potential cycles. The small oxidation wave at À 500 mV (wave 5 in the Figure 1) is thought to be due to the anodic dissolution of the blocking precipitate and occurs only if CO 2 has been reduced.…”

Section: àmentioning

confidence: 99%

Ni(II)cyclam Catalyzed Reduction of CO₂ – Towards a Voltammetric Sensor for the Gas Phase

Jacquinot

Hauser

2003

Electroanalysis

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The detection of CO 2 in the gas phase is possible in presence of oxygen with an amalgamated Au-poly(tetrafluoroethylene) gas diffusion electrode and an internal electrolyte solution containing Ni(II)cyclam. For concentrations between 0.1 to 1% the electrochemical cell has a sensitivity of 3.58 mA % À1 and the detection limit is 500 ppm. In preliminary experiments at rotating disk electrodes the optimum pH-range was found to be between 3.5 to 6 and a selectivity ratio of the catalyst for CO 2 /H of 5 : 1 could be determined. The relationship between reduction current and the square root of the angular speed is linear, indicating that the electrochemical process is limited by diffusion of CO 2 . Tl and Pb are presented as alternative electrode materials at which the Ni(II)cyclam catalyzed reduction of CO 2 can be observed. Problems arise from fouling effects at the sensing electrode and a non-linearity of the calibration plot at higher concentrations.

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Effects of ligand structure on the adsorption of nickel tetraazamacrocyclic complexes and electrocatalytic CO2 reduction

Cited by 44 publications

References 27 publications

From Enzymes to Functional Materials—Towards Activation of Small Molecules

From Enzymes to Functional Materials—Towards Activation of Small Molecules

Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

Ni(II)cyclam Catalyzed Reduction of CO₂ – Towards a Voltammetric Sensor for the Gas Phase

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Effects of ligand structure on the adsorption of nickel tetraazamacrocyclic complexes and electrocatalytic CO2 reduction

Cited by 44 publications

References 27 publications

From Enzymes to Functional Materials—Towards Activation of Small Molecules

From Enzymes to Functional Materials—Towards Activation of Small Molecules

Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction

Ni(II)cyclam Catalyzed Reduction of CO2 – Towards a Voltammetric Sensor for the Gas Phase

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Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

Ni(II)cyclam Catalyzed Reduction of CO₂ – Towards a Voltammetric Sensor for the Gas Phase