MOF‐Mediated Synthesis of Supported Fe‐Doped Pd Nanoparticles under Mild Conditions for Magnetically Recoverable Catalysis**

Abstract

Metal–organic framework (MOF)‐driven synthesis is considered as a promising alternative for the development of new catalytic materials with well‐designed active sites. This synthetic approach is used here to gradually transform a new bimetallic MOF, with Pd and Fe as the metal components, by the in situ generation of aniline under mild conditions. This methodology results in a compositionally homogeneous nanocomposite formed by Fe‐doped Pd nanoparticles that, in turn, are supported on iron oxide‐doped carbon. The nanocomposite has been fully characterized by several techniques such as IR and Raman spectroscopy, TEM, XPS, and XAS. The performance of this nanocomposite as an heterogeneous catalyst for hydrogenation of nitroarenes and nitrobenzene coupling with benzaldehyde has been evaluated, proving it to be an efficient and reusable catalyst.

Bimetallic Intersection in PdFe@FeOx‐C Nanomaterial for Enhanced Water Splitting Electrocatalysis

“…At higher B.E., signals are to correspond to other Nafion structural units (i.e., CSO 3 , CF 2 , CFO, and CF 3 ). [30,[43][44][45] In the case of N1s (Figure 2b), the signal at 400.1 eV for the MOF should be due to the pyridinic ligand coordinated to Pd, thereby shifted at higher B.E. than expected.…”

“…In that context, we have recently shown a soft and tailored transformation of a PdFe-MOF into Fe-doped Pd-NPs supported on nanoclusters of FeO x @C (PdFe@FeO x -C), improving the nature of the generated material against other synthetic strategies. [30] Furthermore, the synthesis set-up toward carbonsupported PdFe nanoparticles (NPs) involves improving the tailoring of Chaudret's procedure based on the use of an amine (aniline) in the presence of hydrogen (H 2 ), in order to reduce metallic species and to lead to NP formation. [31][32][33] Our modified approach consists of the in situ generation of the amine (i.e., aniline), instead of using it as a solvent, to provide the reaction mixture with a slow supply of amine.…”

“…[31][32][33] Our modified approach consists of the in situ generation of the amine (i.e., aniline), instead of using it as a solvent, to provide the reaction mixture with a slow supply of amine. [30] It results in a slowly generated heterometallic nanomaterial, thereby providing a well-controlled and reproducible material comprising both metallic NPs and FeO x -doped graphitic support. In the previous manuscript, the catalytic activity of this material on a nitroarene hydrogenation reaction was tested, noticing an enhancement of activity due to the bimetallic nature of our material, which presents an intimate interaction between its metallic components.…”

“…[35][36][37] Although PdFe electrocatalysts have been widely studied in ORR [38] and HER [39] (both reduction reactions), their application as bifunctional pH-universal electrocatalysts for overall water splitting has not been successfully attempted to the best of our knowledge. In this sense, the herein synthesized ultrasmall PdFe-NP (2.3 nm with 35% of metal loading), having a vast number of Fe-Pd interactions, [30] is a good candidate to be HER active, while nanometric iron oxide is expected to be OER active. Accordingly, we have employed this bimetallic nanomaterial to build electrodes and evaluate its performance for the half-reactions involved in water splitting (HER/OER).…”

Palladium Nanoparticles Immobilized on a Resorcin[4]arene-Based Metal–Organic Framework for Hydrogenation of Nitroarenes

“…Palladium (Pd)-based catalysts have been previously demonstrated to be active materials for dehydrogenation of NH 3 BH 3 and selective hydrogenation of nitroarenes to anilines. − Although Pd nanoparticles (NPs) feature outstanding catalytic activity for the useful reactions, they are apt to aggregate, thus limiting their wide usages. To overcome this issue, the restriction of Pd NPs inside porous materials is known to be an effective method. − …”