Amorphous Flowerlike Goethite FeOOH Hierarchical Supraparticles: Superior Capability for Catalytic Hydrogenation of Nitroaromatics in Water

Abstract

Fabrication of anilines from the corresponding nitroaromatics is a hot topic both for academia and for industry; however, conducting this protocol in water over a noble-metal-free catalytic system is still a great challenge. Continuous efforts are being made on exploiting novel catalysts for this transformation. In this work, we developed a scalable method for synthesizing the uniform flowerlike amorphous α-FeOOH hierarchical supraparticles. The well-defined amorphous α-FeOOH was prepared through an environmentally benign method, which is hydrolysis of the self-assembled iron glycolate at room temperature. Compared with other iron-only catalysts, this flowerlike amorphous α-FeOOH hierarchical supraparticle catalyst exhibits the best performance in the catalytic reduction of nitroaromatics to corresponding anilines by using water as the reaction solvent (turn over frequency is 106 h for 4-nitrophenol in water). The further results indicated that the amorphous structure, special nanostructures, and adsorption-desorption synergy offered excellent activity. The kinetics study shows that the reduction of 4-nitrophenol is first order for α-FeOOH, and the apparent active energy E is 75.9 kJ mol. Furthermore, this catalyst can be used for eight times without obvious catalytic activity loss. We believe that this novel flowerlike amorphous α-FeOOH hierarchical supraparticle catalyst is a milestone in the reduction of nitro compounds.

Magnetically Hollow Pt Nanocages with Ultrathin Walls as a Highly Integrated Nanoreactor for Catalytic Transfer Hydrogenation Reaction

“…[50,51] In recent years, we have focused on this highly important reaction and have fabricated a series of catalysts for this transformation. [52][53][54][55][56][57][58] For the Fe 3 O 4 @snPt@PCN, we first conducted the catalytic activity test experiment through the catalytic transfer hydrogenation of 4-nitrophenol (4-NP), which is a representative nitro compound for this protocol. The conversion and chemoselectivity of reaction were applied to evaluate the optimization, and the experiment results concluded in Table 1 were detected by UV-vis spectroscopy, thin layer chromatography (TLC), and gas chromatography-mass spectrometer (GC-MS).…”

In Situ Synthesized Silica‐Supported Co@N‐Doped Carbon as Highly Efficient and Reusable Catalysts for Selective Reduction of Halogenated Nitroaromatics

“…Supported catalysts based on non-noble metals (Fe, Co, Ni) have been studied to substitute for noble metal catalysts. [13][14][15][16][17] The Co-based catalysts attract more attention because they frequently show not only high catalytic activity but also excellent chemoselectivity of aromatic amines for the reduction of various functionalized aromatic nitro compounds. [18][19][20] Nitrogen-doped porous carbon materials have been demonstrated to be excellent catalyst supports for the dispersion of Co species for the reactions.…”

“…Supported catalysts based on non‐noble metals (Fe, Co, Ni) have been studied to substitute for noble metal catalysts . The Co‐based catalysts attract more attention because they frequently show not only high catalytic activity but also excellent chemoselectivity of aromatic amines for the reduction of various functionalized aromatic nitro compounds .…”

In‐situ Construction of Graphite‐Supported Magnetic Carbocatalysts from a Metallo‐Supramolecular Polymer: High Performance for Catalytic Transfer Hydrogenation

“…And the development of novel heterogeneous catalysts for this reaction is highly desirable . Recently, catalysts such as graphene oxides supported bismuth iron oxides nanocomposites, goethite FeOOH hierarchical supraparticles, ultrafine FeCu alloy nanoparticles, Rh/Fe 3 O 4 /g−C 3 N 4 −N, and honeycomblike carbon spheres nanocomposites have been fabricated by our group and were applied for catalyzed this significant and meaningful transformation . Precious metals (Au, Ag, Pt, Pd, Ru, Rh), non‐noble metals (Fe, Co, Ni, Mo, Mn, Cu) and their association contained heterogeneous catalysts were developed for this reaction .…”

“…[43] Recently, catalysts such as graphene oxides supported bismuth iron oxides nanocomposites, goethite FeOOH hierarchical supraparticles, ultrafine FeCu alloy nanoparticles, Rh/Fe 3 O 4 /gÀ C 3 N 4 À N, and honeycomblike carbon spheres nanocomposites have been fabricated by our group and were applied for catalyzed this significant and meaningful transformation. [44][45][46][47][48] Precious metals (Au, Ag, Pt, Pd, Ru, Rh), non-noble metals (Fe, Co, Ni, Mo, Mn, Cu) and their association contained heterogeneous catalysts were developed for this reaction. [31,49] However, for the above catalysts, when the H 2 is taken as the hydrogen source, the selectivity is still a challenge, especially in the presence of other reducible groups.…”