Boosting Chemoselective Hydrogenation of Nitroaromatic via Synergy of Hydrogen Spillover and Preferential Adsorption on Magnetically Recoverable Pt@Fe₂O₃

Abstract

It is highly desired but challenging to design high performance catalyst for selective hydrogenation of nitro compounds into amino compounds. Herein, a boosting chemoselective hydrogenation strategy on Pt@Fe2O3 is proposed with gradient oxygen vacancy by synergy of hydrogen spillover and preferential adsorption. Experimental and theoretical investigations reveal that the nitro is preferentially adsorbed onto oxygen vacancy of Pt@Fe2O3, meanwhile, the H2 dissociated on Pt nanoparticles and then spillover to approach the nitro for selective hydrogenation (>99% conversion of 4‐nitrostyrene, > 99% selectivity of 4‐aminostyrene, TOF of 2351 h−1). Moreover, the iron oxide support endows the catalyst magnetic retrievability. This high activity, selectivity, and easy recovery strategy provide a promising avenue for selective hydrogenation catalysis of various nitroaromatic.

Metal‐2D Semiconductor Hybrid Nano‐Structure Catalyst: A New Frontier of Heterogeneous Catalysis

“…Thus the hydrogenation process is completed. Zhao [6] reported the Pt@Fe 2 O 3 with appropriate oxygen vacancy which was beneficial for the adsorption and activation of the nitro of 4nitrostyrene. For the selective hydrogenation of 4-nitrostyrene to 4-aminostyrene, it showed > 99 % conversion, > 99 % selective and the TOF of 2351 h À 1 .…”

“…Because H 2 is cheaper and readily available, catalytic hydrogenation technology with liquid-phase pressurized H 2 is widely used in industry, and it is also a current research hotspot. [6] The hydrogen sources cause different hydrogenation processes, in situ hydrogenation and heterogeneous hydrogenation. The former was minor procedure risk, cost-effective, and sustainable, and the most used hydrogen sources were hydrazine hydrate, NaBH 4 , alcohol/base, and formic acid or formate salts, but some drawbacks including toxic, lack of selectivity for nitrosubstrate and suffering hydrolysis or trans-esterification or other side reaction.…”

Hydrogen Spillover in Tungsten Oxide Bronzes as Observed by Broadband Neutron Spectroscopy

“…In this work, following our successful protocol [24,25,[31][32][33][34][35][36][37][38][39][40][41][42][43], we employ ab initio density functional theory (DFT)-based on harmonic lattice dynamics (HLD) simulations to predict the values of NMD widths, NKE, and FCs for the first two hydrogen pools. Fixing the NCS response of the first two hydrogen pools in the non-linear constrained fitting of the total NMD of the entire system enables us to obtain the values of the NCS observables for the most elusive and challenging to model theoretically, namely the quasi-free proton pool resulting from the hydrogen spillover process [44][45][46][47][48][49][50][51][52][53][54]. Crucial to this process of elucidation of nuclear dynamical properties are three factors: (i) the mass selective nature of the NCS technique, (ii) the undisputed success of the DFT-based HLD approach in modeling this NCS-specific information [24,25,[31][32][33][34][35][36][37][38][39][40][41][42][43], and (ii) the very high energy and momentum resolution of VESUVIO in the case of hydrogen NCS spectra …”

Symmetrical Localized Built-in Electric Field by Induced Polarization Effect in Ionic Covalent Organic Frameworks for Selective Imaging and Killing Bacteria

“…5,6 Therefore, designing reasonable nanocatalysts with high catalytic ability is promising to achieve an efficient antibacterial performance. Among photocatalysis materials (g-C 3 N 4 , MoS 2 , Fe 3 O 4 , and so on), 7,8 covalent organic frameworks (COFs) can adjust organic building blocks by covalent or coordinated bonds to achieve the different structures. COFs can precisely assemble different molecular species into two-or three-dimensional (2D or 3D) structures.…”

“…Among photocatalysis materials (g-C 3 N 4 , MoS 2 , Fe 3 O 4 , and so on), , covalent organic frameworks (COFs) can adjust organic building blocks by covalent or coordinated bonds to achieve the different structures. COFs can precisely assemble different molecular species into two- or three-dimensional (2D or 3D) structures. , The adjustable topology structures endow COFs with special characteristics, including porous structures, abundant active sites, and excellent electronic properties, which have attracted enormous attention on photocatalysis, sensors, and energy storage. − However, COFs always exhibit limited efficiency for charge separation and photocatalytic performance due to the strong exciton binding energy. ,− The microscopic structures and electronic structure of materials play a crucial role in electron transfer, such as morphology, the size of particles, heterostructure, and so on. − The design of the COF structure provides more possibility to improve the utilization of photogenerated carriers.…”