Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

Ribeiro, Susana; Duarte, Beatriz Paschoal; Castro, Balt­azar de; Granadeiro, Carlos M.; Balula, Salete S.

doi:10.3390/ma11071196

Cited by 37 publications

(30 citation statements)

References 71 publications

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“…[BMIM] 3 [PMo 12 O 40 ] and [BPy] 3 [PMo 12 O 40 ] were available from previous studies and their synthesis and characterization are described elsewhere . [HDPy] 3 [PMo 12 O 40 ] was prepared following the method described in the literature . The synthesis and characterization of [P 6,6,6,14 ] 3 [PMo 12 O 40 ] and [HDPy] 3 [PMo 12 O 40 ] are described here.…”

Section: Resultsmentioning

confidence: 99%

Polyoxometalates‐Based Ionic Liquids (POMs‐ILs) for Electrochemical Applications

et al. 2020

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Four Polyoxometalates based Ionic Liquids (POMs-ILs) have been developed and applied in electrochemical studies. In a conventional 3-electrode configuration cell the POM-ILs possess three quasi reversible electron transfers (ET) when compared to the commercially available POM under the same experimental conditions. It is also important to note that they presented bleaching and coloration processes faster than the commercially ones. In this configuration cell, the bleaching times are much higher than the coloration times. In this approach, POMs and POM-ILs as electrochromic materials and Deep Eutectic Solvents (DES) as electrolytes were tested in order to prepare efficient electrochromic devices (ECDs). The coloration of the ECD can be tuned by changing the counter cation of the POM-ILs as well as the amount of selected POM corresponding to the metals.

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Section: Resultsmentioning

confidence: 99%

Polyoxometalates‐Based Ionic Liquids (POMs‐ILs) for Electrochemical Applications

et al. 2020

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“…The tetra- n -butylammonium [TBA, (C 4 H 9 ) 4 N] salt of monolacunary phosphotungstate [PW 11 O 39 ] 7− (PW 11 ) was prepared according to the literature (Ribeiro et al, 2018b). The mesoporous silica SBA-15 functionalized with N,N,N -trimethylammonium groups (TMA-SBA-15) was initially prepared followed by the impregnation of PW 11 according to previously reported methods (Mirante et al, 2017; Ribeiro et al, 2018a).…”

Section: Methodsmentioning

confidence: 99%

Mesoporous Silica vs. Organosilica Composites to Desulfurize Diesel

et al. 2019

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The monolacunary Keggin-type [PW11O39]7− (PW11) heteropolyanion was immobilized on porous framework of mesoporous silicas, namely SBA-15 and an ethylene-bridged periodic mesoporous organosilica (PMOE). The supports were functionalized with a cationic group (N-trimethoxysilypropyl-N, N, N-trimethylammonium, TMA) for the successful anchoring of the anionic polyoxometalate. The PW11@TMA-SBA-15 and PW11@TMA-PMOE composites were evaluated as heterogeneous catalysts in the oxidative desulfurization of a model diesel. The PW11@TMA-SBA-15 catalyst showed a remarkable desulfurization performance by reaching ultra-low sulfur levels (<10 ppm) after only 60 min using either a biphasic extractive and catalytic oxidative desulfurization (ECODS) system (1:1 MeCN/diesel) or a solvent-free catalytic oxidative desulfurization (CODS) system. Furthermore, the mesoporous silica composite was able to be recycled for six consecutive cycles without any apparent loss of activity. The promising results have led to the application of the catalyst in the desulfurization of an untreated real diesel supplied by CEPSA (1,335 ppm S) using the biphasic system. The system has proved to be a highly efficient process by reaching desulfurization values higher than 90% for real diesel during three consecutive cycles.

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“…Accordingly to what above reported for the immobilization of phosphomolybdic based POMs, several authors published examples describing the preparation of phosphotungstic acid immobilized over ionic liquid-modified SBA-15 support too, having in mind to enhance the stability and the performances of the catalyst system. An interesting paper described the preparation of a series of hybrid polyoxometalates formed by the same anion α-Keggin phosphotungstate PW 12 and three different ionic liquid cations, namely 1-butyl-3-methylimidazolium (BMIM), 1-butylpyridinium (BPy) and hexadecylpyridinium (HDPy), having the general formula [IL] 3 PW 12 [207]. The activity and stability of these catalysts toward the ODS of model diesel under extractive conditions (ECODS), that is using [ [209].…”

Section: Phosphotungstic Containing Pomsmentioning

confidence: 99%

SBA-15 Anchored Metal Containing Catalysts in the Oxidative Desulfurization Process

2019

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Recalcitrant sulfur compounds are common impurities in crude oil. During combustion they produce SOx derivatives that are able to affect the atmospheric ozone layer, increasing the formation of acid rains, and reducing the life of the engine due to corrosion. In the last twenty years, many efforts have been devoted to develop conventional hydrodesulfurization (HDS) procedures, as well as alternative methods, such as selective adsorption, bio-desulfurization, oxidative desulfurization (ODS) under extractive conditions (ECODS), and others. Among them, the oxidative procedures have been usually accomplished by the use of toxic stoichiometric oxidants, namely potassium permanganate, sodium bromate and carboxylic and sulfonic peracids. As an alternative, increasing interest is devoted to selective and economical procedures based upon catalytic methods. Heterogeneous catalysis is of relevance in industrial ODS processes, since it reduces the leaching of active species and favors the recovery and reuse of the catalyst for successive transformations. The heterogenization of different types of high-valent metal transition-based organometallic complexes, able to promote the activation of stoichiometric benign oxidants like peroxides, can be achieved using various solid supports. Many successful cases have been frequently associated with the use of mesoporous silicas that have the advantage of easy surface modification by reaction with organosilanes, facilitating the immobilization of homogeneous catalysts. In this manuscript the application of SBA-15 as efficient support for different active metal species, able to promote the catalytic ODS of either model or real fuels is reviewed, highlighting its beneficial properties such as high surface area, narrow pore size distribution and tunable pore diameter dimensions. Related to this topic, the most relevant advances recently published, will be discussed and critically described.

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Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

Cited by 37 publications

References 71 publications

Polyoxometalates‐Based Ionic Liquids (POMs‐ILs) for Electrochemical Applications

Polyoxometalates‐Based Ionic Liquids (POMs‐ILs) for Electrochemical Applications

Mesoporous Silica vs. Organosilica Composites to Desulfurize Diesel

SBA-15 Anchored Metal Containing Catalysts in the Oxidative Desulfurization Process

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