Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal‐Organic Frameworks in the Aqueous Phase

Chen, Hao; He, Yulian; Pfefferle, Lisa D.; Pu, Weihua; Wu, Youqing; Qi, Suitao

doi:10.1002/cctc.201800211

Cited by 41 publications

(29 citation statements)

References 53 publications

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“…160 Nanocatalysis in particular offers privileged means towards hydrogenation processes, given the extended surface area ratios. 161,162 Pd NPs, for instance, show high reactivity towards H 2 activation [163][164][165][166] as palladium is known to adsorb up to 900 times its own volume. 167,168 Thus, the (chemo)-selectivity of these nanomaterials towards hydrogenation is highly controlled by surface interactions with the modifiers/stabilizers, the substrates or even the supports.…”

Section: Hydroxyl Compounds From Natural Sourcesmentioning

confidence: 99%

Palladium Nanoparticles in Polyols: Synthesis, Catalytic Couplings, and Hydrogenations

2019

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Alcohols, in particular polyols, are well-known for the synthesis of metal nanoparticles often acting as reducing agents, solvents, and stabilizers. Given not only their structural flexibility depending on the number of OH functions and their inherent H bonding interactions, but also the wide range of polyol molecular weights readily available, different physico-chemical properties (boiling point, polarity, viscosity) could be exploited towards the synthesis of well-defined nanomaterials. In particular, the relevance of the supramolecular structure of polyols has a fundamental impact on the formation of metal nanoparticles thereby favoring the dispersion of the nanoclusters. In the field of the metal-based nanocatalysis, palladium occupies a privileged position mainly due to its remarkable versatility in terms of reactivity representing a foremost tool in synthesis. In this review, we describe the controlled synthesis of Pd-based nanoparticles in polyol medium focusing on the progress in terms of tailoring size, morphology, structure, and surface state. Moreover, we discuss the use of 4.2. C(sp)-C(sp 2) Sonogashira cross-coupling 4.3. C(sp 2)-C(sp 2) Hiyama-Denmark cross-coupling 4.4. C(sp 2)-C(sp 2) Heck-Mizoroki cross-coupling 4.5. C(sp 2)-C(sp 2 /sp 3) Suzuki-Miyaura cross-coupling 4.5.1. In PEG and glycerol media 4.5.2. Solid-supported nanocatalysts 4.6. C(sp 2)-C(sp 2)-C(sp 2) Carbonylative Suzuki cross-coupling 4.7. C(sp 2)-C(sp 2) Ullmann-type homo-coupling 4.8. Miscellaneous: SiN and C-N amination reactions 5. Conclusions and outlook

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Section: Hydroxyl Compounds From Natural Sourcesmentioning

confidence: 99%

Palladium Nanoparticles in Polyols: Synthesis, Catalytic Couplings, and Hydrogenations

2019

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“…In recent years, the metal–organic frameworks (MOFs) material, with high specific surface area, tunable and large pore size, and diversity open metal sites, are showing great application potential of gas separation, sensing, energy storage and catalysis . Especially in the field of hydrogen storage, these properties facilitate the adsorption of H 2 on the surface of it.…”

Section: Introductionmentioning

confidence: 99%

Elimination of 4‐chlorophenol in aqueous solution by the Novel Pd/MIL‐101(Cr)‐Hydrogen‐Accelerated catalytic fenton system

Liu

Fan

Liu

et al. 2019

Applied Organom Chemis

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Excessive consumption of Fe (II) and massive generation of sludge containing Fe (III) from classic Fenton process remains a major obstacle for its poor recycling of Fe (III) to Fe (II). Therefore, the MHACF‐MIL‐101(Cr) system, by introducing H2, Pd0 and MIL‐101(Cr) into Fenton reaction system, was developed at normal temperature and pressure. In this system, the reduction of FeIII back to FeII by solid catalyst Pd/MIL‐101(Cr) for the storage and activation of H2, was accelerated significantly by above 10‐fold and 5‐fold controlled with the H2‐MIL‐101(Cr) system and H2‐Pd0 system, respectively. However, the concentration of Fe (II) generated by the reduction of Fe (III) could not be detected with the only input of H2 and without the addition of MOFs material. In addition, the apparent consumption of Fe (II) in MHACF‐MIL‐101(Cr) system was half of that in classical Fenton system, while more Fe (II) might be reused infinitely in fact. Accordingly, only trace amount of Fe (II) vs H2O2 concentration was needed and hydroxyl radicals through the detection of para‐hydroxybenzoic acid (p‐HBA) as the oxidative product of benzoic acid (BA) by·OH could be continuously generated for the effective degradation of 4‐chlorophenol(4‐CP). The effects of initial pH, concentration of 4‐CP, dosage of Fe2+, H2O2 and Pd/MIL‐101(Cr) catalyst, Pd content and H2 flow were investigated, combined with systematic controlled experiments. Moreover, the robustness and morphology change of Pd/MIL‐101(Cr) were thoroughly analyzed. This study enables better understanding of the H2‐mediated Fenton reaction enhanced by Pd/MIL‐101(Cr) and thus, will shed new light on how to accelerate Fe (III)/Fe (II) redox cycle and develop more efficient Fenton system.

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“…Supported Pd catalysts were widely used in the selective hydrogenation of phenol due to their high activity [11–16] . In the process of industrial production, Pd/C catalyst was most widely used.…”

Section: Introductionmentioning

confidence: 99%

Hybrid Nano‐Structured Pd Catalyst for Selective Hydrogenation of Phenol and the Insights of Deactivation Mechanism

Zhang

Zhou

2022

ChemistrySelect

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A catalyst composed of La2O3/AC and Pd nanoparticles is constructed for precise synthesis of cyclohexanone from phenol hydrogenation with high conversion (>99 %) and selectivity (>95 %). The special structure and the synergistic effect remarkably facilitate the high conversion of phenol. The stability test results of the used Pd/@‐La2O3/AC catalyst showed that the phenol conversion decreased from 100 % to 24.5 %. The deactivation reason for the used catalyst was the agglomeration of Pd nanoparticles and the adsorption of organics. Three treatment methods, heat treatment, ethanol wash, and water wash, were regenerated the catalytic activity of the used Pd/@‐La2O3/AC catalyst. The regenerated method of water wash solved the problem of organic matter blockage and residue to a certain extent, but still can not fully recover its high activity. This deactivation mechanism provides important guidance to develop high stable Pd‐based catalyst for the selective hydrogenation of phenol.

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Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal‐Organic Frameworks in the Aqueous Phase

Cited by 41 publications

References 53 publications

Palladium Nanoparticles in Polyols: Synthesis, Catalytic Couplings, and Hydrogenations

Palladium Nanoparticles in Polyols: Synthesis, Catalytic Couplings, and Hydrogenations

Elimination of 4‐chlorophenol in aqueous solution by the Novel Pd/MIL‐101(Cr)‐Hydrogen‐Accelerated catalytic fenton system

Hybrid Nano‐Structured Pd Catalyst for Selective Hydrogenation of Phenol and the Insights of Deactivation Mechanism

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