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Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO2.

ABSTRACT: A broad review of homogeneous and heterogeneous catalytic approaches toward CO2 reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes. In both cases, their immobilization on electrodes is discussed and compared to homogeneous catalysts in solution.

SUBMITTER: Apaydin DH

PROVIDER: S-EPMC5708279 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO<sub>2</sub>.

Apaydin Dogukan Hazar DH Schlager Stefanie S Portenkirchner Engelbert E Sariciftci Niyazi Serdar NS

Chemphyschem : a European journal of chemical physics and physical chemistry 20170531 22

A broad review of homogeneous and heterogeneous catalytic approaches toward CO<sub>2</sub> reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes. In both cases, their immobil ...[more]

PMID: 28383174

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Project description:Metal-organic frameworks (MOFs) have been an excellent platform for carbon dioxide reduction reactions (CO2RR). In this work, the feasibility of electrochemical reduction of CO2 to obtain C2-deep value-added products was investigated by the preparation of Mg-containing MOF-74 samples combined with transition metal cations (Ni2+, Co2+ and Zn2+). The prepared MOFs were used as electrocatalysts in CO2RR. Chronoamperometric analysis coupled to ATR-FTIR spectroscopy was employed to characterize the CO2 reduction products and subsequently via 1H NMR. Although an isostructural crystalline structure was observed in all synthesized MOFs, the pore diameter distribution was significantly affected due to the Mg coordination along with each transition metal nuclei with the organic ligand to form the MOF-74. Our results showed that Mg-containing MOF-74 electrocatalysts combined with Ni, Co and Zn ions successfully reduced CO2 to C2-deep products, while the monometallic Mg-MOF-74 showed only CO2 mineralization. An ester acetate, isopropyl alcohol, and formic acid were produced by Mg/Ni-MOF-74; isopropyl alcohol was provided by Mg/Co-MOF-74, and ethanol was generated by Mg/Zn-MOF-74. We observed that the change of the transition cation was a key factor in the selectivity of the obtained products, while the degree of Mg ions effectively incorporated into the MOF structure tuned the porosity and the electrocatalytic activity. Among them, Mg/Zn-MFOF-74 showed the highest Mg content loaded after synthesis and thus the most favorable electrocatalytic behavior towards CO2 reduction. Highlights • CO2-derived C2-deep reduction products were obtained by Mg-containing MOF-74 bimetallic electrocatalysts.• Mg-containing MOF-74 bimetallic electrocatalysts reduced CO2 to ester acetate, isopropanol, formic acid, and ethanol.• Mg/Zn-MOF-74 displayed the highest current density at a lower onset potential in CO2-saturated electrolyte.• The pore network could be tuned by the effective Mg content on a MOF-74 bimetallic sample.• Mg/Zn-MOF-74 showed the highest Mg content among all bimetallic electrocatalysts after the synthesis.

Dataset Information

Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO2.

Publications

Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO<sub>2</sub>.

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