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Pd Nanoparticles/Tubular In2O3 Heterostructures as a Catalyst for the Electrosynthesis of Cyclohexanone Oxime
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DOI：10.1021/acsanm.6c00592.png)
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Abstract
En 中文
Cyclohexanone oxime (C6H11NO) is a key intermediate in the production of nylon-6. Conventional industrial synthesis methods for C6H11NO often suffer from low conversion efficiency, high energy consumption, and a significant environmental impact. Electrocatalytic synthesis of cyclohexanone oxime from nitrate and cyclohexanone (C6H10O) presents a sustainable and potentially more efficient alternative to those energy-intensive processes. However, the efficiency of current electrocatalytic systems remains insufficient, primarily due to the mismatched adsorption/activation of reactants and the instability of the key hydroxylamine (*NH2OH) intermediate. Herein, we constructed a Pd-doped tubular In2O3 interface to address these challenges through electronic structure modulation. The p–d orbital hybridization at the Pd/In2O3 interface effectively regulates the formation and stability of hydroxylamine intermediates, thereby promoting the electrochemical synthesis of C6H11NO from C6H10O and nitrate under ambient conditions. By systematically optimizing the Pd nanoparticle loading, the 3% Pd/In2O3 catalyst achieves a Faradaic efficiency (FE) of 55.59% and a production rate of 13.79 mmol·h–1·g–1 at a low potential of −0.2 V versus the reversible hydrogen electrode (RHE). In situ Fourier transform infrared (FTIR) spectroscopy and density functional theory (DFT) calculations demonstrate that orbital hybridization between the d-block metal Pd and the p-block metal In ions significantly lowers the energy barrier of the potential-determining step (*NO to NHO), which facilitates the formation of hydroxylamine intermediates at lower potentials and promotes subsequent coupling, thereby substantially enhancing the FE and overall yield of cyclohexanone oxime. This study provides fundamental insights into interface engineering through p–d hybridization for steering complex electrocatalytic C–N coupling reactions.
Keywords:
Anions
Catalysts
Electrosynthesis
Palladium
nitrate electroreduction
cyclohexanone oxime
C–N bond formation
electrosynthesis
p–d orbital hybridization
Pd nanoparticles
indium oxide
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