RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

Pokharel, Uttam R.; Fronczek, Frank R.; Maverick, Andrew W.

doi:10.1038/ncomms6883

Cited by 108 publications

(79 citation statements)

References 35 publications

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“…Inserted: highlight of the CV at pH = 3. [102] More recently, Weng et al have developed a Cu(II) phthalocyanine complex with an excellent activity and selectivity. Adapted with permission.…”

Section: Other Metal-based Catalystsmentioning

confidence: 99%

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Elouarzaki

Kannan

Jose

et al. 2019

Advanced Energy Materials

160

102

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provides a promising alternative to hydrocarbon sources for petrochemical feedstock. Thanks to the electrochemical nature of the CO 2 conversion to fuels and chemicals, the electrical energy invested to convert CO 2 in the form of a chemical fuel can be stored and redistributed using established supply chains for future use. Additionally, the integration of renewable energy systems (green electricity) into the grid can potentially create a carbon neutral energy cycle, and when driven by solar energy, offers a completely renewable energy cycle or negative carbon technology. Converting CO 2 electrochemically into compounds with high energy densities, such as alcohols (methanol, ethanol), formates, and CO, represents a form of energy storage and is also adaptable to demand response or energy arbitrage technologies. [3][4][5][6][7] The recoverable energy density of the chemicals that can be converted from CO 2 is substantially higher than most battery technologies.Given CO 2 electroreduction's immense economic and environmental potential, it has been the subject of much research activity over the past decades. [8][9][10][11] One of the greatest challenges of reducing CO 2 in an electrochemical cell is overcoming the immense energy barrier required to do so; the single electron reduction of CO 2 to CO 2 −˙, a common step in many CO 2 reduction mechanisms, requires an applied potential of −1.97 V measured versus standard hydrogen electrode (SHE). To alleviate this problem, many catalytic cathodes have been developed to avoid this intermediate and to reroute the reduction mechanism through alternate pathways requiring much lower applied potentials (a necessity if CO 2 electroreduction is to be implemented at industrial scale). [12][13][14] However, despite the low potentials offered by catalytic electrodes, the cost of electrodes is not always viable when upscaled to industrial levels. [15,16] Therefore, recent research trends in electrocatalytic reduction of CO 2 have been shifting toward the development of molecular catalysts that can exist as either solutes in electrolytes or can be surface-confined on electrodes. [13,16] The tunable nature and electronic characteristics of molecular catalysts give access to a large variety of catalysts with high activity, selectivity, and durability, as well as their ability to be integrated into sophisticated nanoassemblies. [17][18][19] Thanks to the aforementioned proprieties, performing CO 2 reduction using molecularly defined compounds offer several advantages compared to classical solid-state counterparts. Molecular catalysts usually exhibit well-defined homogeneous and/or CO 2 reduction using molecular catalysts is a key area of study for achieving electrical-to-chemical energy storage and feedstock chemical synthesis. Compared to classical metallic solid-state catalysts, these molecular catalysts often result in high performance and selectivity, even under unfavorable aqueous environments. This review considers the recent state-of-the-art molecular catalysts for CO 2 electro...

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Section: Other Metal-based Catalystsmentioning

confidence: 99%

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Elouarzaki

Kannan

Jose

et al. 2019

Advanced Energy Materials

160

102

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“…Nitschke and co‐workers found that Zn II and Cd II M 5 ( L ) 6 where L = a napthalene‐linked bis‐pyridylimine trigonal bipyramidal architectures can fix CO 2 from the air and encapsulate the gas as carbonate anions (CO 3 2− ) . In a similar study, Maverick and co‐workers showed that a Cu I metallomacrocycle [Cu 2 ( L ) 2 ] n + where L = 1,4‐bis((4‐pyridin‐2‐yl)‐1,2,3‐triazol‐1‐yl)methyl)benzene would react with CO 2 in solution and convert it into oxalate …”

Section: Introductionmentioning

confidence: 97%

Solid‐State Gas Adsorption Studies with Discrete Palladium(II) [Pd₂(L)₄]⁴⁺ Cages

Preston

White

Lewis

et al. 2017

Chemistry A European J

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The need for effective CO capture systems remains high, and due to their tunability, metallosupramolecular architectures are an attractive option for gas sorption. While the use of extended metal organic frameworks for gas adsorption has been extensively explored, the exploitation of discrete metallocage architectures to bind gases remains in its infancy. Herein the solid state gas adsorption properties of a series of [Pd (L) ] lantern shaped coordination cages (L = variants of 2,6-bis(pyridin-3-ylethynyl)pyridine), which had solvent accessible internal cavities suitable for gas binding, have been investigated. The cages showed little interaction with dinitrogen gas but were able to take up CO . The best performing cage reversibly sorbed 1.4 mol CO per mol cage at 298 K, and 2.3 mol CO per mol cage at 258 K (1 bar). The enthalpy of binding was calculated to be 25-35 kJ mol , across the number of equivalents bound, while DFT calculations on the CO binding in the cage gave ΔE for the cage-CO interaction of 23-28 kJ mol , across the same range. DFT modelling suggested that the binding mode is a hydrogen bond between the carbonyl oxygen of CO and the internally directed hydrogen atoms of the cage.

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“…This then raises the question of whether L6 can access other coordination geometries with less flexible metal ions. One metal ion of particular interest due to its redox properties, and its contribution to acridine‐assisted photocleavage of biological targets is copper(II). In contrast to triazole–pyridine complexes self‐assembled with metal ions of tetrahedral or octahedral coordination geometries, in the presence of square‐planar metals such as copper(II), the strong preference of the triazole–pyridine chelate for a head‐to‐tail geometry (reinforced by hydrogen bonding between the pyridine H6 proton and the triazole N2 atom) provides access to a much more planar chelate orientation, thereby influencing the self‐assembly outcome as well as the topology of the selected assembly –…”

Section: Resultsmentioning

confidence: 99%

To Loop or Not to Loop: Influence of Hinge Flexibility on Self‐Assembly Outcomes for Acridine‐Based Triazolylpyridine Chelates with Zinc(II), Iron(II), and Copper(II)

Miron

Fleischel

Petitjean

2018

Chemistry A European J

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Coordination‐driven self‐assembly has been established as an effective strategy for the efficient construction of intricate architectures in both natural and artificial systems, for applications ranging from gene regulation to metal–organic frameworks. Central to these systems is the need for carefully designed organic ligands, generally with rigid components, that can undergo self‐assembly with metal ions in a predictable manner. Herein, we report the synthesis and study of three novel organic ligands that feature 3,6‐disubstituted acridine as a rigid spacer connected to two 2‐(1,2,3‐triazol‐4‐yl)pyridine “click” chelates through hinges of the same length but differing flexibility. The flexibility of these “three‐atom” hinges was modulated by i) moving from secondary to tertiary amide functional groups and ii) replacing an sp2 amide carbon with an sp3 methylene carbon. In an effort to understand the role of hinge flexibility in directing self‐assembly into mononuclear loops or dinuclear cylinders, the impact of these changes on self‐assembly outcomes with zinc(II), iron(II), and copper(II) ions is described.

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RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

Cited by 108 publications

References 35 publications

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Solid‐State Gas Adsorption Studies with Discrete Palladium(II) [Pd₂(L)₄]⁴⁺ Cages

To Loop or Not to Loop: Influence of Hinge Flexibility on Self‐Assembly Outcomes for Acridine‐Based Triazolylpyridine Chelates with Zinc(II), Iron(II), and Copper(II)

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RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

Cited by 108 publications

References 35 publications

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO2 by Molecular Catalysts

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO2 by Molecular Catalysts

Solid‐State Gas Adsorption Studies with Discrete Palladium(II) [Pd2(L)4]4+ Cages

To Loop or Not to Loop: Influence of Hinge Flexibility on Self‐Assembly Outcomes for Acridine‐Based Triazolylpyridine Chelates with Zinc(II), Iron(II), and Copper(II)

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Product

Resources

About

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Solid‐State Gas Adsorption Studies with Discrete Palladium(II) [Pd₂(L)₄]⁴⁺ Cages