FeOOH with Low Spin State Iron as Electron Acceptors for High Yield Rate Electrosynthesis of Urea from Nitrate and Carbon Dioxide.
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; 20(11): e2307349, 2024 Mar.
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| MEDLINE
| ID: mdl-38105349
ABSTRACT
Co electroreduction of carbon dioxide and nitrate to synthesize urea provides an alternative strategy to high energy-consumption traditional methods. However, the complexity of the reaction mechanism and the high energy barrier of nitrate reduction result in a diminished production of urea. Herein, a convenient electrodeposition technique to prepare the FeOOH with low spin state iron that increases the yield rate of urea efficiently is employed. According to soft X-ray Absorption Spectroscopy and theoretical calculations, the unique configuration of low spin state iron as electron acceptors can effectively induce electron pair transfer from the occupied σ orbitals of intermediate * NO to empty d orbitals of iron. This σâd donation mechanism leads to a reduction in the energy barrier associated with the rate-determining step (* NOOHâ* NO + * OH), hence augmenting the urea generation. The low spin state iron presents a high urea yield rate of 512 µg h-1 cm-2 , representing approximately two times compared to the medium spin state iron. The key intermediates (* NH2 and * CO) in the formation of CâN bond are detected with in situ Fourier transform infrared spectroscopy. The coupling of * NH2 and * CO contributes to the formation of * CONH2 , which subsequently endures multi-step proton-coupled electron transfer to generate urea.
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2024
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Article