Construction of secondary coordination sphere boosts electrochemical CO2 reduction of iron porphyrins

Iron porphyrins with simple aminophenyl substitution are synthesized and their electrochemical CO[Formula: see text] reduction properties are studied. Fe-1, bearing an amino group in the ortho position of the phenyl ring exhibits an improved catalytic turn over frequency (TOF), lower overpotential and higher selectivity, compared with para-amino-substituted iron porphyrin (Fe-2) and the control iron tetraphenylporphyrin (Fe-3). DFT calculations also support the importance of hydrogen bonds on the reactivity of Fe-1, which facilitates the formation [Fe–CO[Formula: see text]][Formula: see text] adduct by lowering 1.45 kcal mol[Formula: see text].

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Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins

Chemical Science ◽

10.1039/c7sc04682k ◽

2018 ◽

Vol 9 (11) ◽

pp. 2952-2960 ◽

Cited By ~ 70

Author(s):

Eva M. Nichols ◽

Jeffrey S. Derrick ◽

Sepand K. Nistanaki ◽

Peter T. Smith ◽

Christopher J. Chang

Keyword(s):

Carbon Dioxide ◽

Greenhouse Gas ◽

Electrochemical Reduction ◽

Energy Input ◽

Sustainable Energy ◽

Co2 Reduction ◽

Value Added ◽

Iron Porphyrins ◽

Electrochemical Co2 Reduction ◽

Positional Effects

The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input.

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Iron Porphyrins Embedded into a Supramolecular Porous Organic Cage for Electrochemical CO2 Reduction in Water

Angewandte Chemie International Edition ◽

10.1002/anie.201803873 ◽

2018 ◽

Vol 57 (31) ◽

pp. 9684-9688 ◽

Cited By ~ 58

Author(s):

Peter T. Smith ◽

Bahiru Punja Benke ◽

Zhi Cao ◽

Younghoon Kim ◽

Eva M. Nichols ◽

...

Keyword(s):

Co2 Reduction ◽

Iron Porphyrins ◽

Electrochemical Co2 Reduction

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Correction: Anion exchange-induced single-molecule dispersion of cobalt porphyrins in a cationic porous organic polymer for enhanced electrochemical CO2 reduction via secondary-coordination sphere interactions

Journal of Materials Chemistry A ◽

10.1039/d0ta90220a ◽

2020 ◽

Vol 8 (38) ◽

pp. 20192-20193

Author(s):

Jia-Kang Tang ◽

Chen-Yuan Zhu ◽

Tian-Wen Jiang ◽

Lei Wei ◽

Hui Wang ◽

...

Keyword(s):

Anion Exchange ◽

Coordination Sphere ◽

Single Molecule ◽

Co2 Reduction ◽

Organic Polymer ◽

Porous Organic Polymer ◽

Electrochemical Co2 Reduction ◽

Secondary Coordination Sphere ◽

Cobalt Porphyrins

Correction for ‘Anion exchange-induced single-molecule dispersion of cobalt porphyrins in a cationic porous organic polymer for enhanced electrochemical CO2 reduction via secondary-coordination sphere interactions’ by Jia-Kang Tang et al., J. Mater. Chem. A, 2020, DOI: 10.1039/d0ta07068h.

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Iron Porphyrins Embedded into a Supramolecular Porous Organic Cage for Electrochemical CO2 Reduction in Water

Angewandte Chemie ◽

10.1002/ange.201803873 ◽

2018 ◽

Vol 130 (31) ◽

pp. 9832-9836 ◽

Cited By ~ 24

Author(s):

Peter T. Smith ◽

Bahiru Punja Benke ◽

Zhi Cao ◽

Younghoon Kim ◽

Eva M. Nichols ◽

...

Keyword(s):

Co2 Reduction ◽

Iron Porphyrins ◽

Electrochemical Co2 Reduction

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Anion exchange-induced single-molecule dispersion of cobalt porphyrins in a cationic porous organic polymer for enhanced electrochemical CO2 reduction via secondary-coordination sphere interactions

Journal of Materials Chemistry A ◽

10.1039/d0ta07068h ◽

2020 ◽

Vol 8 (36) ◽

pp. 18677-18686

Author(s):

Jia-Kang Tang ◽

Chen-Yuan Zhu ◽

Tian-Wen Jiang ◽

Lei Wei ◽

Hui Wang ◽

...

Keyword(s):

Anion Exchange ◽

Coordination Sphere ◽

Single Molecule ◽

Co2 Reduction ◽

Organic Polymer ◽

Synergistic Catalysis ◽

Promising Strategy ◽

Electrochemical Co2 Reduction ◽

Secondary Coordination Sphere ◽

Cobalt Porphyrins

Anion exchange is a promising strategy to achieve synergistic catalysis via secondary coordination sphere interactions between the catalyst and the support.

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An NADH-Inspired Redox Mediator Strategy to Promote Second-Sphere Electron and Proton Transfer for Cooperative Electrochemical CO2 Reduction Catalyzed by Iron Porphyrin

10.26434/chemrxiv.12159207.v1 ◽

2020 ◽

Cited By ~ 1

Author(s):

Peter T. Smith ◽

Sophia Weng ◽

Christopher Chang

Keyword(s):

Proton Transfer ◽

Co2 Reduction ◽

Iron Porphyrin ◽

Redox Mediators ◽

Reservoir Properties ◽

Proton Reduction ◽

Electrochemical Co2 Reduction ◽

Starting Point ◽

Rate Improvement ◽

Molecular Catalysts

We present a bioinspired strategy for enhancing electrochemical carbon dioxide reduction catalysis by cooperative use of base-metal molecular catalysts with intermolecular second-sphere redox mediators that facilitate both electron and proton transfer. Functional synthetic mimics of the biological redox cofactor NADH, which are electrochemically stable and are capable of mediating both electron and proton transfer, can enhance the activity of an iron porphyrin catalyst for electrochemical reduction of CO2 to CO, achieving a 13-fold rate improvement without altering the intrinsic high selectivity of this catalyst platform for CO2 versus proton reduction. Evaluation of a systematic series of NADH analogs and redox-inactive control additives with varying proton and electron reservoir properties reveals that both electron and proton transfer contribute to the observed catalytic enhancements. This work establishes that second-sphere dual control of electron and proton inventories is a viable design strategy for developing more effective electrocatalysts for CO2 reduction, providing a starting point for broader applications of this approach to other multi-electron, multi-proton transformations.

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