Cobalt-porphine catalyzed CO<sub>2</sub> electro-reduction: a novel protonation mechanism

Yao, Cang Lang; Li, Jian Chen; Wang, Gao; Jiang, Qing

doi:10.1039/c7cp01881a

Cited by 39 publications

(38 citation statements)

References 36 publications

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“…[64][65][66][67] This is because existing cobalt molecular catalysts perform very well in organic solvents when reducing CO 2 ; however, in aqueous environments, cobalt selectively promotes proton reduction and generates HER. [64][65][66][67] This is because existing cobalt molecular catalysts perform very well in organic solvents when reducing CO 2 ; however, in aqueous environments, cobalt selectively promotes proton reduction and generates HER.…”

Section: Cobalt-based Catalystsmentioning

confidence: 99%

“…Developments with regards to cobalt molecular catalysts have revolved around immobilizing and optimizing the loading of various cobalt catalysts in the electrochemical cell. [64][65][66][67] This is because existing cobalt molecular catalysts perform very well in organic solvents when reducing CO 2 ; however, in aqueous environments, cobalt selectively promotes proton reduction and generates HER. [68][69][70] Thus, many heterogeneous loading methods have been developed over the past couple of years, to enable the catalyst's use in aqueous electrolytes, which are cost effective than organic solvents.…”

Section: Cobalt-based Catalystsmentioning

confidence: 99%

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

Elouarzaki

Kannan

Jose

et al. 2019

Advanced Energy Materials

168

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: Cobalt-based Catalystsmentioning

confidence: 99%

Section: Cobalt-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

168

102

View full text Add to dashboard Cite

show abstract

“…[19] This would be favorable for the furtherreduction of CO. For *CO, it has two protonation ways, one to *COH (by forming an OÀHb ond) and one to *CHO (by forming aC ÀHb ond). [19] This would be favorable for the furtherreduction of CO. For *CO, it has two protonation ways, one to *COH (by forming an OÀHb ond) and one to *CHO (by forming aC ÀHb ond).…”

Section: Resultsmentioning

confidence: 99%

An Integrated Design with new Metal‐Functionalized Covalent Organic Frameworks for the Effective Electroreduction of CO₂

Yao

Wang

et al. 2018

Chemistry A European J

Self Cite

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One of the long-standing issues that prohibits large-scale CO reutilization is the low aqueous solubility of CO and the incurring inefficient mass transport of CO . Herein, we suggest a feasible way to promote the CO reutilization by integrating the storage and reduction, with a new covalent organic framework (COF) series constituted by cobalt-phthalocyanine and boronic acid linkers. We find that the porous structure of the cobalt COF is competitive in the CO storage and can sustain a high CO concentration around the reduction center, whereas the mass transport of CO as well as the efficiency of the CO reduction is significantly improved. The predicted cobalt COF exhibits an overpotential of 0.27 V and a CO production rate, which is 97.7 times higher than in aqueous solution, for the CO reduction. Our work provides a promising candidate for the CO reutilization, with valuable insights and an important prototype for future practical design.

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“…[160] Beyond the single metal atom catalytic reaction, Sun's group studied the metal dimers supported by graphene derivatives as the active sites for CO2RR. [169] Moreover, the protonated species acted as a local proton source to facilitate following reduction. [161] A graphene-like 2D phthalocyanine sheet could also bind to Mn 2 dimer via coordination bond, which electrocatalyzed CO2RR to methane.…”

Section: Carbon-based Materialsmentioning

confidence: 99%

“…Yao et al demonstrated that the self-protonation of the porphyrin was a key step, resulting in a decouple proton-electron transfer rather than PCET. [169] Moreover, the protonated species acted as a local proton source to facilitate following reduction. Herein, pH and applied potential that affected protonation also played a critical role in CO 2 reduction rate.…”

Section: Carbon-based Materialsmentioning

confidence: 99%

Recent Progress in the Theoretical Investigation of Electrocatalytic Reduction of CO₂

Tian

Priest

Chen

2018

Advcd Theory and Sims

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The worldwide combustion of fossils produces anthropogenic CO 2 , which has deleterious effects on global climate patterns. An ideal solution is to develop high-performance CO 2 capture and utilization technologies that can convert CO 2 into commercial products by means of electrocatalytic reduction with renewable energy. The design of electrocatalysts can be facilitated by accurate computational simulations based on density functional theory (DFT). Herein, commonly used models, from the computational hydrogen electrode model with constant charge assumption, to the explicit and implicit solvation model under constant potential condition, are reviewed. Thereafter, the applications of recent data-driven methods, such as neutral network and machine learning, are introduced. Also, based on DFT calculations, four composition based classes of electrodes are further discussed, including (1) bulk metals and alloys, (2) nanoparticles, (3) metal-nonmetal compounds and (4) carbon-based materials. In this Review, several theoretical investigations which have been realized in practice are highlighted in particular, such as metal-hydride nanocluster and carbon nitride supported copper complex for high-efficiency CO 2 reduction. It shows that the theoretical study can not only explain experimental phenomena but also predict improved candidates.

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Cobalt-porphine catalyzed CO₂ electro-reduction: a novel protonation mechanism

Cited by 39 publications

References 36 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

An Integrated Design with new Metal‐Functionalized Covalent Organic Frameworks for the Effective Electroreduction of CO₂

Recent Progress in the Theoretical Investigation of Electrocatalytic Reduction of CO₂

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Cobalt-porphine catalyzed CO2 electro-reduction: a novel protonation mechanism

Cited by 39 publications

References 36 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

An Integrated Design with new Metal‐Functionalized Covalent Organic Frameworks for the Effective Electroreduction of CO2

Recent Progress in the Theoretical Investigation of Electrocatalytic Reduction of CO2

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Product

Resources

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Cobalt-porphine catalyzed CO₂ electro-reduction: a novel protonation mechanism

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

An Integrated Design with new Metal‐Functionalized Covalent Organic Frameworks for the Effective Electroreduction of CO₂

Recent Progress in the Theoretical Investigation of Electrocatalytic Reduction of CO₂