MOF-Derived Ni/CM Catalytic Membranes for Efficient Forced-Flow Hydrogenation of p -Nitrophenol

Catalytic membranes offer significant potential for process intensification in continuous-flow reactions, yet simultaneously achieving high active site stability and efficient mass transfer remains challenging. In this study, multi-channel Ni/CM catalytic membranes were fabricated via a MOF-derivative strategy using Ni-MOF-NH2 as the precursor, followed by controlled thermal pyrolysis. The effects of pyrolysis atmosphere and temperature on the physicochemical properties, surface chemistry, and pore structure of the membranes were systematically examined. The optimized Ni/CM-H2–Ar-700 membrane featured a hierarchically porous carbon framework with uniformly dispersed Ni nanoparticles (average size 7.3 nm) and exhibited excellent permeability, retaining approximately 80% of the pure water flux of the pristine substrate (584.2 L·m–2·h–1·bar–1). In the selective hydrogenation of p-nitrophenol to p-aminophenol under forced-flow conditions with short residence time, the membrane achieved a high specific reaction rate of 40 h–1, outperforming most reported non-noble metal catalysts. This superior performance is attributed to the synergistic combination of preferential p-nitrophenol adsorption on Lewis basic pyridinic nitrogen sites and rapid hydrogen activation on highly dispersed metallic Ni0 centers, which enable efficient reactant utilization even under short residence time. Furthermore, the membrane demonstrated excellent cycling stability with negligible Ni leaching or particle agglomeration. This study offers a rational and cost-effective approach for designing high-performance non-noble metal catalytic membranes for continuous selective hydrogenation.