Sarki Naina, Kumar Raju, Singh Baint, Ray Anjan, Naik Ganesh, Natte Kishore, Narani Anand
Chemical and Material Sciences Division, Biofuels Division, and Analytical Sciences Division, CSIR-Indian Institute of Petroleum, Haridwar Road, Mohkampur, Dehradun 248005, India.
Academy of Scientific and Innovative Research (AcSIR), CSIR-HRDC Campus, Joggers Road, Kamla Nehru Nagar, Ghaziabad 201002, Uttar Pradesh, India.
ACS Omega. 2022 Jun 3;7(23):19804-19815. doi: 10.1021/acsomega.2c01566. eCollection 2022 Jun 14.
Heterogeneous iron-based catalysts governing selectivity for the reduction of nitroarenes and aldehydes have received tremendous attention in the arena of catalysis, but relatively less success has been achieved. Herein, we report a green strategy for the facile synthesis of a lignin residue-derived carbon-supported magnetic iron (γ-FeO/LRC-700) nanocatalyst. This active nanocatalyst exhibits excellent activity and selectivity for the hydrogenation of nitroarenes to anilines, including pharmaceuticals (e.g., flutamide and nimesulide). Challenging and reducible functionalities such as halogens (e.g., chloro, iodo, and fluoro) and ketone, ester, and amide groups were tolerated. Moreover, biomass-derived aldehyde (e.g., furfural) and other aromatic aldehydes were also effective for the hydrogenation process, often useful in biomedical sciences and other important areas. Before and after the reaction, the γ-FeO/LRC-700 nanocatalyst was thoroughly characterized by X-ray diffraction (XRD), N adsorption-desorption, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), Raman spectroscopy, and thermogravimetric analysis (TGA). Additionally, the γ-FeO/LRC-700 nanocatalyst is stable and easily separated using an external magnet and recycled up to five cycles with no substantial drop in the activity. Eventually, sustainable and green credentials for the hydrogenation reactions of 4-nitrobenzamide to 4-aminobenzamide and benzaldehyde to benzyl alcohol were assessed with the help of the CHEM21 green metrics toolkit.
用于控制硝基芳烃和醛类还原选择性的多相铁基催化剂在催化领域受到了极大关注,但取得的成功相对较少。在此,我们报告了一种绿色策略,用于简便合成木质素残渣衍生的碳负载磁性铁(γ-FeO/LRC-700)纳米催化剂。这种活性纳米催化剂对硝基芳烃加氢生成苯胺表现出优异的活性和选择性,包括药物(如氟他胺和尼美舒利)。具有挑战性且可还原的官能团,如卤素(如氯、碘和氟)以及酮、酯和酰胺基团都能被耐受。此外,生物质衍生的醛(如糠醛)和其他芳香醛对加氢过程也有效,这在生物医学科学和其他重要领域常常很有用。反应前后,通过X射线衍射(XRD)、N吸附-脱附、X射线光电子能谱(XPS)、高分辨率透射电子显微镜(HR-TEM)、拉曼光谱和热重分析(TGA)对γ-FeO/LRC-700纳米催化剂进行了全面表征。此外,γ-FeO/LRC-700纳米催化剂稳定,使用外部磁铁易于分离,可循环使用多达五个周期,活性无显著下降。最终,借助CHEM21绿色指标工具包评估了4-硝基苯甲酰胺加氢生成4-氨基苯甲酰胺以及苯甲醛加氢生成苯甲醇反应的可持续性和绿色资质。