124901-08-2Relevant academic research and scientific papers
Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution
Weng, Zhe,Jiang, Jianbing,Wu, Yueshen,Wu, Zishan,Guo, Xiaoting,Materna, Kelly L.,Liu, Wen,Batista, Victor S.,Brudvig, Gary W.,Wang, Hailiang
, p. 8076 - 8079 (2016/07/16)
Exploration of heterogeneous molecular catalysts combining the atomic-level tunability of molecular structures and the practical handling advantages of heterogeneous catalysts represents an attractive approach to developing high-performance catalysts for important and challenging chemical reactions such as electrochemical carbon dioxide reduction which holds the promise for converting emissions back to fuels utilizing renewable energy. Thus, far, efficient and selective electroreduction of CO2 to deeply reduced products such as hydrocarbons remains a big challenge. Here, we report a molecular copper-porphyrin complex (copper(II)-5,10,15,20-tetrakis(2,6-dihydroxyphenyl)porphyrin) that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media. At -0.976 V vs the reversible hydrogen electrode, the catalyst is able to drive partial current densities of 13.2 and 8.4 mA cm-2 for methane and ethylene production from CO2 reduction, corresponding to turnover frequencies of 4.3 and 1.8 molecules·site-1·s-1 for methane and ethylene, respectively. This represents the highest catalytic activity to date for hydrocarbon production over a molecular CO2 reduction electrocatalyst. The unprecedented catalytic performance is attributed to the built-in hydroxyl groups in the porphyrin structure and the reactivity of the copper(I) metal center.
Porphyrin synthesis in surfactant solution: Multicomponent assembly in micelles
Bonar-Law, Richard P.
, p. 3623 - 3634 (2007/10/03)
A synthesis of meso-substituted porphyrins in anionic sodium dodecyl sulfate micelles has been developed. Polar, functionalized aromatic aldehydes condense reversibly with pyrrole in the micellar phase. Oxidation of the porphyrinogen then provides functionalized porphyrins in yields of 10-48%. Hydrophobic aldehydes condense irreversibly to give low yields at practical substrate concentrations. Synthesis in D2O solution results in per-β-deuterated porphyrins. A two-phase model is used to rationalize the dependence of porphyrin yield on reactant and surfactant concentration. Micelles are viewed as potential wells which promote porphyrinogen assembly by binding products more tightly than reactants.
