Surface‐Group‐Oriented, Condensation Cyclization‐Driven, Nitrogen‐Doping Strategy for the Preparation of a Nitrogen‐Species‐Tunable, Carbon‐Material‐Supported Pd Catalyst

Abstract

A nitrogen‐carbon framework with the thickness of several molecules was fabricated through a straightforward nitrogen‐doping strategy, in which specially designed surface‐oxygen‐containing groups (SOGs) first introduced onto the porous carbon support were used to guide the generation of a surface‐nitrogen‐containing structure through condensation reactions between SOGs and the amidogen group of organic amines under hydrothermal conditions. The results indicate that different kinds of SOGs generate different types and abundances of N species. The CO‐releasing groups are apt to form a high proportion of amino groups, whereas the CO2‐releasing groups, especially carboxyl and lactones, are mainly transformed into pyrrolic‐type nitrogen. In the framework with dominant pyrrolic‐type nitrogen, an electron‐rich Pd activated site composed of Pd, pyrrolic‐type N and C is built, in which electron transfer occurs from N to C and Pd atoms. This activated site contributes to the formation of electron‐rich activated hydrogen and desorption of p‐chloroaniline, which work together to achieve the superior selectivity about 99.90 % of p‐chloroaniline and the excellent reusable performance. This strategy not only provides low‐cost, nitrogen‐doped carbon materials, but also develops a new method for the fabrication of different kinds of nitrogen species structures.

Predominant Catalytic Performance of Nickel Nanoparticles Embedded into Nitrogen-Doped Carbon Quantum Dot-Based Nanosheets for the Nitroreduction of Halogenated Nitrobenzene

“…Halogenated aromatic amines, as important organic intermediates, are widely used in the synthesis of fine chemicals such as medicines, pesticides, synthetic fibers, liquid crystal materials, and so forth. − The chemical selective hydrogenation of nitroarenes over metal catalysts − has been a significant and green approach to produce aromatic amines. In the past, supported noble metal catalysts have been widely used in the selective hydrogenation of nitroarenes due to their excellent catalytic activity and reusability; − however, the scarcity, huge expenses, and especially poor chemical selectivity to haloanilines greatly limit their industrial application . Consequently, tremendous efforts have been devoted to developing selective hydrogenation catalysts that have the advantages of low cost, rich sources, and high chemical selectivity and stability.…”

Palladium Nanoparticles Inset into the Carbon Sphere with Robust Acid Resistance for Selective Hydrogenation of Chloronitrobenzene

“…The Pd catalyst, supported on the activated carbon (Pd/AC) as a contrast sample, was prepared by the impregnation method using H 2 PdCl 4 as a precursor at room temperature . A 1 g portion of activated carbon made by France Arkema CECA (particle size 250–300 mesh, BET surface area 980 m 2 ·g –1 , ash content ≤3%) and 15 mL of deionized water were added to a 100-mL beaker under vigorous stirring for 30 min.…”

“…Today over 90% of industrial chemicals are produced with the aid of catalysts, which require suitable parameters for various harsh reaction conditions, i.e., high corrosion, high temperature, and high pressure. , Thus, it is significant for catalysts to be both stable and active, especially for carbon materials with poor mechanical strength and weak adsorption. Metal supported on carbon-based materials is widely applied in areas such as heterogeneous catalysis, − electrochemistry, , photochemistry, , and so on. Unfortunately, due to the weak interaction between the metal particles and the carbon base, the metal nanoparticles usually detach from the carbon base or conglomerate during catalytic reactions.…”

“…However, numerous acid residues are introduced into the crude nitroaromatics of the complicated group substitutions on the benzene molecule for obtaining special characteristics, including halogenation and nitrogenization . Besides, a side reaction of dehalogenation existing in the hydrogenation reaction of halogenated nitrobenzene is inevitable in the industrial processes. , Our previous works ,,,, committed to suppressing the dehalogenation of halogenated nitrobenzene catalytic hydrogenation by heteroatom doping, while the dehalogenation (halogen acid) was still not inhibited completely (∼0.1%). Metal leaching by acid corrosion not only shortens the lifetime of catalysts but also pollutes productions, especially for the fields of pharmacy and the liquid crystal display (LCD) panel industry.…”

Ru/g-C3N4 as an efficient catalyst for selective hydrogenation of aromatic diamines to alicyclic diamines

“…[28][29][30][31] In principle, the surface property of catalyst played a crucial role in regulating the catalytic performance. [32][33][34] The reactants with benzene moieties to be hydrogenated and intermediate formed during the hydrogenation process should adsorb to the catalyst surface with appropriate strength. Actually, g-C 3 N 4 could be used as versatile metalfree basic support.…”