Highly efficient N‐doped carbon supported FeS_x‐Fe₂O₃ catalyst for hydrogenation of nitroarenes via pyrolysis of sulfurized N,Fe‐containing MOFs

Abstract

Integrating MOFs as precursor, especially for employing N-containing organic linkers, with sulfides is an effective method to prepare the highly efficient N-doped carbon supported metal-based catalysts for hydrogenation of nitroarenes. In this work, a N,Fe-containing metal organic frameworks (MOFs; termed as MIL88-HMTA) with spindle-like structure was prepared via self-assembly method, in which hexamethylenetetramine (HMTA) linker was introduced as N source. Subsequently, N-doped carbon supported FeS x -Fe 2 O 3 catalyst (named FeS x -Fe 2 O 3 @CN) was fabricated upon the pyrolysis of sulfurized MIL88-HMTA. Catalytic experiments reveal that the FeS x -Fe 2 O 3 @CN delivered excellent performance for hydrogenation of nitroarenes in comparison with those of catalyst without sulfidation process (Fe 2 O 3 @CN) and conventional MIL88 derived catalyst (Fe 2 O 3 @C). The XRD, TEM, SEM/EDX, Raman, UV, and XPS analyses have revealed that the developed FeS x -Fe 2 O 3 @CN catalyst exhibited outstanding catalytic efficiency was ascribed to synergistic effect between FeS x and Fe 2 O 3 species, abundant structural defects, more Fe-N x species, and strengthened decomposition ability of hydrazine hydrate (N 2 H 4 ÁH 2 O). Furthermore, the effect of sulfidation ratio (the mass ratio between thioacetamide and MIL88-HMTA) towards preparation of the developed FeS x -Fe 2 O 3 @CN on the catalytic activity of hydrogenation reaction was also systematically performed. Notably, the optimized catalyst (denoted as FeS x -Fe 2 O 3 @CN-8) exhibited unexpected performance and recyclability for hydrogenation of nitroarenes under mild condition. The pyrolysis of sulfurized N-containing MOFs may present a facile approach for fabricating MOFsderived N-doped carbon supported catalysts, which provides a potential application in heterogeneous catalytic reactions.

Preparation of N‐doped Co/NC‐CeO2‐hmta by pyrolysis of Co‐Ce‐Salen/hmta toward hydrogenation of nitroarenes under N2H4

“…Catalytic chemoselective hydrogenation of the corresponding nitroarenes is an adept route for producing functionalized anilines. [1][2][3][4] Therefore, developing highly effective catalysts for the reduction of nitroaromatic compounds is of great significance. Notably, the most widely applied catalysts regarding this point are generally made of noble metals and alloys, for example, Pt, Au, Ru, Pd, and Ir.…”

“…Aromatic amines are highly significant fine chemical intermediates that have been extensively applied for the synthesis of pesticides, medicines, and dyes. Catalytic chemoselective hydrogenation of the corresponding nitroarenes is an adept route for producing functionalized anilines 1–4 . Therefore, developing highly effective catalysts for the reduction of nitroaromatic compounds is of great significance.…”

Mechanistic Insights into a Co(II)-Coordinated “Free” Metal Site of 2D Zinc-Based MOFs for β-Alkylation of Secondary Alcohols with Primary Alcohols

“…Metal–organic framework (MOF)-based materials, especially for functional MOFs with unsaturated coordination metal sites and functional organic ligand, have long been a research hotspot in the field of catalysis due to unique properties. − Because the presence of unsaturated coordination metal sites in MOF structures enables the effective fixation of introduced metals onto the ligands, thereby enhancing the stability of the metal introduced in the catalyst preparation process and minimizing the loss of active components during the reaction. Moreover, of utmost importance is that MOF structures containing these unsaturated coordination sites can selectively coordinate with different active metals to prepare catalysts with varying activities for catalyzing different organic reactions. − This feature allows the prepared MOF materials with unsaturated coordination sites to serve as universal templates, simplifying the catalyst preparation process and ultimately improving the overall efficiency of the catalytic process. − Furthermore, this aligns with the current goal of achieving carbon neutrality.…”

Cascade Performance of Nitroarenes with Alcohols Boosted by a Hollow Flying Saucer-Shaped Ni–Al2O3 Catalyst via a MOF-Templated Strategy Induced by the Kirkendall Effect

“…Hollow structure catalysts exhibit extremely strong catalytic advantages in catalytic reactions due to their unique properties (e.g., confinement effect and fast mass transfer). − The utilization of hollow-structured catalysts in heterogeneous catalytic reactions necessitates their heightened demand for cascade reactions. − Because, the cascade catalytic synthesis allows for the execution of multiple steps in a single reaction using a one-pot synthetic procedure. As for hydrogenation–alkylation cascade reaction, the N -methylation reaction takes advantage of the in situ generation of arylamines through the hydrogenation of corresponding nitroarenes. − Numerous heterogeneous catalysts have been specifically designed and optimized with a focus on their stability, ease of separation, and recyclability. − Recently, metal–organic framework (MOF) materials have attracted widespread interest among researchers in the field of catalysis, particularly in the area of organic catalysis reactions. − These crystalline porous materials possess the advantages of both homogeneous and heterogeneous catalysis, making them highly versatile and efficient catalysts. Importantly, the use of MOF materials as catalyst supports shows great potential, especially in the synthesis of highly dispersed nanostructured metal catalysts …”