Ni–Co Catalyst with an Engineered Electronic Structure via Membrane Dispersion Microreactor Synthesis for the Highly Efficient and Selective Hydrogenation of Aromatic Nitro Compounds

4,4′-Oxydianiline (ODA) is a crucial intermediate in fine chemical synthesis. This study proposes a continuous preparation strategy based on a membrane-dispersed microreactor, successfully synthesizing a Ni–Co bimetallic catalyst supported on SiO2 for the efficient catalytic selective hydrogenation of 4,4′-dinitrodiphenyl ether (DNDPE) to produce ODA, achieving a high yield of 99.11%. System characterization combined with density functional theory (DFT) calculations confirms that the formation of the Ni–Co alloy facilitates electron transfer from Co to Ni, thereby optimizing the electronic structure of the active center. Further calculations of d-band centers and adsorption energy indicate that this electronic restructuring enhances the catalyst’s adsorption of reactants and electron-withdrawing intermediates while reducing the adsorption of electron-donating products (ODA), significantly improving reaction efficiency. Additionally, the membrane-dispersed microreactor effectively regulates the catalyst’s microstructure, yielding uniformly dispersed metal nanoparticles (average size 5.81 nm) with a high specific surface area (232.65 m2/g), providing abundant active sites for the reaction. The catalyst demonstrates excellent versatility and cycling stability in the hydrogenation of various functionalized nitroaromatics. This study provides a green and efficient synthetic pathway for developing high-performance hydrogenation catalysts that can replace precious metals, with promising industrial application prospects.