Efficient electrocatalytic CO<sub>2</sub> reduction with a molecular cofacial iron porphyrin dimer

Mohamed, Eman A.; Zahran, Zaki N.; Naruta, Yoshinori

doi:10.1039/c5cc04273a

Cited by 129 publications

(178 citation statements)

References 37 publications

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“…In o-Fe 2 DTPP, the Fe-Fe separation was estimated to be 3.4-4.0 Å which can accommodate a CO 2 molecule of linear length 2.3 Å. Mechanistically, Fe 2 DTPP's effectiveness is due to the local electron push/pull effect undergone by the electro-activated o-Fe 2 DTPP; with the Fe + center acting as a Lewis base and the Fe° center as a Lewis acid. [48] Copyright 2015, Royal Society of Chemistry. Reduction potentials (E 1/2 ) of each sample determined by CV (V vs NHE, Scan rate: 50 mV s −1 ).…”

Section: Wwwadvancedsciencenewscommentioning

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

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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: Wwwadvancedsciencenewscommentioning

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

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“…[84][85][86] A recent example addressing some of these issues is the synthesis of Fe porphyrin dimers with finely tuned spacing of the Fe centres. [82] Presence of two metal centres exhibited concerted stabilisation and binding of CO 2 molecules which improved activity and stability without the need of co-catalysts.…”

Section: Porphyrin Materialsmentioning

confidence: 99%

“…[82] Usually, a co-catalyst must be employed in solution with homogenous porphyrin-based catalysts, such as a weak Lewis and Brønsted acids, in order to synergistically enhance their stability and efficiency. [84][85][86] A recent example addressing some of these issues is the synthesis of Fe porphyrin dimers with finely tuned spacing of the Fe centres.…”

Section: Porphyrin Materialsmentioning

confidence: 99%

“…Consequently, a range of porphyrins are able to be functionalised with a range of transition metal centres (Co, Fe, Zn, Cu etc. ), [10,[79][80][81][82][83] and the resultant electrocatalysts have well-defined active centres which can be finely tuned for high activity and selectivity towards the CO 2 RR. In regards to heterogeneous electrocatalysts, the active centres are often hard to define and performance optimisation is often challenging.…”

Section: Porphyrin Materialsmentioning

confidence: 99%

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Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO₂

Vasileff

Zheng

Qiao

2017

Advanced Energy Materials

351

222

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The electrochemical reduction of CO2 to useful molecules offers an elegant technological solution to current energy security and sustainability issues because it sequesters carbon from the atmosphere, provides an energy storage solution for intermittent renewable sources, and can be used to produce fuels and industrial chemicals. Nanostructured carbon materials have been extensively used to catalyse some key electrochemical processes because of their excellent electrical conductivity, chemical stability, and abundant active sites. This progress report focuses on nanostructured carbon materials, namely graphene materials, carbon nanotubes, porphyrin materials, nanodiamond, and glassy carbon, which have recently shown promise as high performing CO2 reduction electrocatalysts and supports. Along with discussion regarding materials synthesis, structural characterisation, and electrochemical performance characterisation techniques used, this report will discuss the findings of recent computational CO2RR studies which have been key to elucidating active sites and reaction mechanisms, and developing strategies to break conventional scaling relationships. Lastly, challenges and future perspective of these carbon‐based materials for CO2 reduction applications will be given. Much work is still required to realise the commercial viability of the technology, but advanced experimental techniques coupled with theoretical calculations are expected to facilitate future development of the technology.

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“…Due to the phenolic hydroxyl substituents, the enhanced activity appeared to be due to the high local concentration of protons. Meanwhile, inspired by the Ni-Fe containing metalloenzyme, a cofacial iron(0) tetraphenyl porphyrin dimer, o-Fe2DTPP (Scheme 2), was also reported to be highly effective in the electroreduction of CO2 [20]. The electrogenerated Fe 0 (por) species exhibited excellent CO selectivity from the aspects of a high FE of 95% and a TOF of 4300 s −1 at a moderate overpotential of 0.66 V. Another pentadendate N5 ligand (2,13-dimethyl-3,6,9,12,18-penta-azabicyclo[12.3.1]octadeca-1 (18),2,12,14,16-pentaene) was used to synthesize two effective electrocatalysts [21].…”

Section: Metal Complexes With Macrocyclic Ligandsmentioning

confidence: 99%

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

et al. 2017

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Abstract:Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO 2 ) to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO 2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO 2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.

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Efficient electrocatalytic CO₂ reduction with a molecular cofacial iron porphyrin dimer

Cited by 129 publications

References 37 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

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO₂

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

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Efficient electrocatalytic CO2 reduction with a molecular cofacial iron porphyrin dimer

Cited by 129 publications

References 37 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

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO2

Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

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Efficient electrocatalytic CO₂ reduction with a molecular cofacial iron porphyrin dimer

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

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO₂