Low-cost and highly stable Ni@NC materials synthesized from metal-organic framework precursors for selectively catalytic hydrogenation of p-nitrophenol under mild conditions.

Using inexpensive terephthalic acid as a substitute for isophthalic acid, nitrogen-doped carbon coated nickel nanoparticles (Ni@NC) materials were synthesized by pyrolysis of Ni-MOF precursor, which were applied to the selective hydrogenation of p-nitrophenol under mild conditions (60 °C, 2 h) and showed better catalytic performance (>99.9 % conversion of p-nitrophenol and >99.9 % selectivity for p-aminophenol). The excellent catalytic performance may be mainly attributed to their core–shell structure, i.e., zero-valent nickel nanoparticles encapsulated within a nitrogen-doped carbon layer with an appropriate microporous structure, whereas zero-valent nickel nanoparticles have the ability to activate dihydrogen and block dioxygen. [Display omitted] The catalytic hydrogenation of aromatic nitro compounds under mild conditions to generate amino compounds is a great challenge in terms of conversion, selectivity and stability. In this paper, two classes of nitrogen-doped carbon coated nickel nanoparticles, coined Ni@NC-P and displaced Ni@NC-T were prepared by high-temperature pyrolysis of MOFs using inexpensive terephthalic acid and high-priced trimesic acid as carbon source, respectively. One from the former class, namely the Ni@NC-P-500 catalyst, exhibits the best catalytic performance, which is superior to Ni@NC-T-500 Samples. For the selective hydrogenation of p -nitrophenol under mild conditions (60 °C, 2 h), the Ni@NC-P-500 catalyst shows >99.9 % conversion of p -nitrophenol and >99.9 % selectivity for p -aminophenol and can be recycled five times without obvious decrease of conversion and selectivity, thanks to its larger specific surface area (382.02 m2·g−1), smaller nickel particle size (8.2 nm), higher nitrogen content (especially pyridine nitrogen), higher electron-rich nickel content and less hydrophilic properties than that of the Ni@NC-T-500. The excellent stability and recyclability of the catalysts are mainly attributed to their core–shell structure, i.e., zero-valent nickel nanoparticles encapsulated within a nitrogen-doped carbon layer with an appropriate microporous structure, whereas zero-valent nickel nanoparticles have the ability to activate dihydrogen and block dioxygen. [ABSTRACT FROM AUTHOR]