Highly Chemoselective Hydrogenation of 2-Ethylanthraquinone to 2-Ethylanthrahydroquinone Catalyzed by Palladium Metal Dispersed inside Highly Lipophilic Functional Resins

Biffis, Andrea; Ricoveri, Rossana; Campestrini, Sandro; Králik, Milan; Jeřábek, Karel; Corain, Benedetto

doi:10.1002/1521-3765(20020703)8:13<2962::aid-chem2962>3.0.co;2-5

Cited by 30 publications

(18 citation statements)

References 18 publications

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“…This work was undertaken as a part of our research on the use of polymer‐supported Pd catalysts in the synthesis of H 2 O 2 by both AO and DS . We have focused on the in situ characterization under DS conditions of the catalyst Pd/K2621f, which can be prepared by a simple two‐step procedure (Scheme ): (i) the loading of the Pd precursor by ion exchange, upon the treatment of a water‐swollen sample of the Lewatit K2621 resin with an aqueous solution of [Pd(NH 3 ) 4 ](NO 3 ) 2 and (ii) the reduction of the precursor with 37 % aqueous formaldehyde under reflux conditions.…”

Section: Resultsmentioning

confidence: 99%

In Situ X‐ray Absorption Fine Structure Spectroscopy of a Palladium Catalyst for the Direct Synthesis of Hydrogen Peroxide: Leaching and Reduction of the Metal Phase in the Presence of Bromide Ions

et al. 2015

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For the first time a Pd catalyst for the direct synthesis (DS) of H2O2 from H2 and O2 was investigated using in situ Pd K‐edge X‐ray absorption fine structure spectroscopy. The catalyst was loaded into a continuous reaction cell and fed at room temperature and pressure with a mixture of CO2, O2, H2 (86:10:4, v/v), and methanol. Pd and PdO phases are observed in similar and steady proportions (62 and 28 %, respectively). The same is found if the catalyst is either dry or treated with pure methanol only. With 10 ppm of NaBr in the reaction mixture both the Pd edge jump and the fraction of PdO decrease steadily during the DS. This shows that Br− ions promote both the leaching and the reduction of Pd in a monometallic DS catalyst. It also suggests that they are connected to each other and to the ability of Br− ions to promote Pd in the DS. An unprecedented mechanism of protection and remediation supported by Br− ions against the overoxidation of Pd is proposed and discussed in this context.

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Section: Resultsmentioning

confidence: 99%

In Situ X‐ray Absorption Fine Structure Spectroscopy of a Palladium Catalyst for the Direct Synthesis of Hydrogen Peroxide: Leaching and Reduction of the Metal Phase in the Presence of Bromide Ions

et al. 2015

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“…A new generation of hydrogenation catalysts for both slurry and fixed-bed operation are based on palladium catalysts supported on functionalized resins. [42,43] In the patent literature, [44] a Pd 2+polyethyleneimine system is described that has recently been applied with success. Substrates such as poly(4-vinylpyridine) (PVP) and polyaniline (PANI) (Scheme 2) containing 1-10 % Pd were shown to be efficient for AQ hydrogenation.…”

Section: Hydrogenationmentioning

confidence: 99%

Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process

2006

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Hydrogen peroxide (H2O2) is widely used in almost all industrial areas, particularly in the chemical industry and environmental protection. The only degradation product of its use is water, and thus it has played a large role in environmentally friendly methods in the chemical industry. Hydrogen peroxide is produced on an industrial scale by the anthraquinone oxidation (AO) process. However, this process can hardly be considered a green method. It involves the sequential hydrogenation and oxidation of an alkylanthraquinone precursor dissolved in a mixture of organic solvents followed by liquid-liquid extraction to recover H2O2. The AO process is a multistep method that requires significant energy input and generates waste, which has a negative effect on its sustainability and production costs. The transport, storage, and handling of bulk H2O2 involve hazards and escalating expenses. Thus, novel, cleaner methods for the production of H2O2 are being explored. The direct synthesis of H2O2 from O2 and H2 using a variety of catalysts, and the factors influencing the formation and decomposition of H2O2 are examined in detail in this Review.

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“…The object of our investigation is a Pd 0 /resin material that we described as a chemoselective catalyst for the hydrogenation of 2‐ethylanthraquinone to 2‐ethylanthrahydroquinone,13 slightly superior to the long‐established commercial catalyst (Pd 0 on inorganic supports) industrially employed in a key step of the Ausimont process in the production of hydrogen peroxide. The support is a gel‐type very lipophilic resin, that is polydodecylmethacrylate (92 % mol)–4‐vinylpyridine (4 % mol)–ethylene glycol dimethacrylate (4 % mol), hereafter coded as DOMA‐VP.…”

Section: Isec Characterization Of Resin Doma‐vp In Thf[a]mentioning

confidence: 99%

Generation of Size‐Controlled Pd⁰ Nanoclusters inside Nanoporous Domains of Gel‐Type Resins: Diverse and Convergent Evidence That Supports a Strategy of Template‐Controlled Synthesis

et al. 2004

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In the realm of supported metal catalysis, the metal component is usually present as nanoparticles dispersed on the surface of suitable metal oxides [1] or on active carbon. [2] Synthetic procedures are normally directed to the generation of size-controlled metal nanoclusters, whose circumstances become mandatory when reactions to be catalyzed are "structure sensitive". [3] A paramount example of the necessity of size control is given in the area of Au 0 catalytic chemistry, specifically, the low-temperature oxidation of carbon monoxide in the presence of excess dihydrogen and the case of water gas shift reaction. [4] In general, size control has been achieved by: directly manufacturing metal-oxide-supported catalysts; [5] by the generation of kinetically stabilized metal nanoclusters in the liquid phase [6] and subsequent transfer of the protected nanoclusters on to suitable supports; [7] by generating metal nanoclusters inside isoporous inorganic materials such as mesoporous silicas. [8] In addition to the still-common practice of employing inorganic supports (and active carbon), a few examples of metal catalysts supported on functional resins are cited in the realm of chemical processing (such as industrial synthesis of methylisobutylketone, chemoselective hydrogenation of diolefins, acetylenes, carbonyl compounds in the presence of isobutene) and very efficient removal of dioxygen (down to the ppb levels) from industrial waters upon hydrogenation. [9] A considerable advantage of these catalysts is that they are multifunctional, [9] and may allow size control in the generation of metal nanoclusters inside polymer frameworks after the metallation-reduction steps (Figure 1).[10]Herein, we report on three independent, convergent pieces of structural evidence of this template-controlled synthesis strategy to obtain size-controlled metal nanoclusters suitable for synthesizing resin-supported metal catalysts. In fact, in the course of our long-standing interest in the generation and catalytic exploitation of resin-supported Pd 0 nanoclusters [9] we discovered in 1998 [11] and subsequently confirmed in 2001 [12] that gel-type, lightly cross-linked resins (2-8 % mol, in the absence of any porogenic agent [9] ) are suitable templates for the generation of 2-4 nm Pd 0 nanoclusters. The strategy for this achievement is the dispersion of individual "Pd 2+ " centers in the interior of the organic functional frameworks followed by their chemical reduction to Pd 0 atoms that rapidly evolve into metal nanoclusters, the size of which was tentatively expected to be controlled by the matrix nanoporosity (Figure 1). Details of the concepts outlined in Figure 1 are given in reference [12]. In this context, our previous results were encouraging, [11,12] but a quantitative confirmation of both findings and relevant rationale was lacking. We report herein on a detailed unambiguous quantitative support of the tentative conclusions of our previous papers. II is homogeneously dispersed inside the polymer framework; b) Pd II is reduced t...

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Highly Chemoselective Hydrogenation of 2-Ethylanthraquinone to 2-Ethylanthrahydroquinone Catalyzed by Palladium Metal Dispersed inside Highly Lipophilic Functional Resins

Cited by 30 publications

References 18 publications

In Situ X‐ray Absorption Fine Structure Spectroscopy of a Palladium Catalyst for the Direct Synthesis of Hydrogen Peroxide: Leaching and Reduction of the Metal Phase in the Presence of Bromide Ions

In Situ X‐ray Absorption Fine Structure Spectroscopy of a Palladium Catalyst for the Direct Synthesis of Hydrogen Peroxide: Leaching and Reduction of the Metal Phase in the Presence of Bromide Ions

Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process

Generation of Size‐Controlled Pd⁰ Nanoclusters inside Nanoporous Domains of Gel‐Type Resins: Diverse and Convergent Evidence That Supports a Strategy of Template‐Controlled Synthesis

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Highly Chemoselective Hydrogenation of 2-Ethylanthraquinone to 2-Ethylanthrahydroquinone Catalyzed by Palladium Metal Dispersed inside Highly Lipophilic Functional Resins

Cited by 30 publications

References 18 publications

In Situ X‐ray Absorption Fine Structure Spectroscopy of a Palladium Catalyst for the Direct Synthesis of Hydrogen Peroxide: Leaching and Reduction of the Metal Phase in the Presence of Bromide Ions

In Situ X‐ray Absorption Fine Structure Spectroscopy of a Palladium Catalyst for the Direct Synthesis of Hydrogen Peroxide: Leaching and Reduction of the Metal Phase in the Presence of Bromide Ions

Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process

Generation of Size‐Controlled Pd0 Nanoclusters inside Nanoporous Domains of Gel‐Type Resins: Diverse and Convergent Evidence That Supports a Strategy of Template‐Controlled Synthesis

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Generation of Size‐Controlled Pd⁰ Nanoclusters inside Nanoporous Domains of Gel‐Type Resins: Diverse and Convergent Evidence That Supports a Strategy of Template‐Controlled Synthesis