Metallo-porphyrin complexes such as cobalt and iron porphyrins (CoP and FeP) have shown potential as electrocatalysts for CO 2 reduction. Here we report that introducing amino substituents enhances the electrocatalytic activity of these systems toward CO 2 reduction through a dual active site approach. We developed a flexible synthesis of Coand Fe-porphyrins having variable amino groups and found that monoamino FeP reduces CO 2 to carbon monoxide (CO) at ambient pressure and temperature with competitive turnover numbers (TONs). This efficiency enhancement approach opens a new path to designing and optimizing next generation homogeneous catalysts.
B(npy)Ar 2 (npy = 2-(naphthalen-1-yl)pyridine) compounds bearing various nonbulky aryl groups undergo ac lean and sequential two-step photoisomerization in which two aryl substituents on boron migrate to acarbon atom of the naphthyl moiety.T he second isomerization step is the first example of areversible photoisoermization between aborepin and ab orirane.B oth steric and electronic factors have been found to have ag reat impact on this photoreactivity.F urthermore,t he borirane isomer reacts with oxygen, forming ar are oxaborepin dimer.
Electrochemical
reduction of carbon dioxide (CO2) is
a sustainable solution to conversion of CO2 into value-added
products such as hydrocarbons and carbon monoxide (CO). However, designing
high-efficiency molecule-based electrocatalysts is challenging. In
this work, we designed and synthesized iron-porphyrin-pyridine (Fe-TPPy)
catalysts in a strategy that combined molecular design and a nanoscale
approach. The catalytic activity of these compounds toward CO2 reduction was evaluated under both homogeneous and heterogeneous
conditions. Tuning of Fe-TPPy with anisole electron-donating substituents
improved the catalytic efficiency up to 76% with a current density
of −1.3 mA/cm2 and a turnover frequency (TOF) of
1 s–1. The faradaic efficiency was further enhanced
to 92% with a current density of −30 mA/cm2 and
a TOF of 5 s–1 after immobilization of the porphyrins
onto carbon nanotubes. Density functional theory calculations confirmed
that the push–pull pyridine–anisole interaction facilitates
CO2 binding, resulting in an enhancement of the overall
catalytic efficiency. This work provides an effective strategy for
improvement of electrocatalytic performance that could inspire the
design of future molecular catalysts.
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