Defect-Enriched Titania-Supported Ni Nanoparticle Catalyst for the Reductive Amination of Furfural to Furfurylamine
Krishan Kumar1, Atul Kumar1, Rajendra Srivastava1
1Catalysis Research Laboratory, Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, India.
Abstract:
The sustainable synthesis of nitrogen-containing compounds from biomass-derived platform molecules offers a viable route toward green chemical production. Herein, we report a selective and efficient strategy for the reductive amination of furfural (FUR) to furfurylamine (FAM) using a Ni(5%)/TiO2 catalyst under mild conditions. The catalyst was prepared via the wet impregnation method and comprehensively characterized using powder X-ray diffraction (PXRD), Raman spectroscopy, electron paramagnetic resonance (EPR), H2-TPR, NH3-TPD, field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS) techniques. These analyses confirmed the successful dispersion of Ni nanoparticles on TiO2 and revealed strong metal-support interaction (SMSI), modulated surface acidity, and oxygen vacancies that facilitate the reductive amination of FUR. Catalytic evaluation demonstrated an exceptional FAM yield of 98.6% at 90°C in a NH3(aq.):CH3OH solvent system, with NH3(aq.) serving as the nitrogen source. The superior performance is attributed to the synergistic interplay between metallic Ni sites, surface oxygen defects, and tailored acidity, which enhance imine formation and subsequent hydrogenation. The catalyst also exhibited excellent reusability over multiple cycles with negligible activity loss. Furthermore, a qualitative and quantitative assessment using the CHEM21 toolkit indicated that the process has a low environmental impact. Overall, this work identifies Ni(5%)/TiO2 as an efficient, cost-effective, and environmentally benign non-noble metal catalyst for the selective synthesis of FAM from renewable FUR, offering a promising pathway for valorizing biomass into value-added nitrogenated chemicals.
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