Etherification of glycerol into short-chain polyglycerols over MgAl LDH/CaCO3 nanocomposites as heterogeneous catalysts to promote circular bioeconomy

Khumho, Rujeeluk; Tocuweang, Kitvara; Sangkhum, Prissana; Kuchonthara, Prapan; Ashokkumar, Veeramuthu; Ngamcharussrivichai, Chawalit

doi:10.1016/j.chemosphere.2021.133091

Cited by 9 publications

(5 citation statements)

References 45 publications

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“…Figure A shows the XRD patterns of various exfoliated LDO-supported Ru catalysts all of which show reflections at 42.5 and 62.5°, representing a periclase MgO structure . The reflection corresponding to the crystalline RuO 2 phase was detected for some samples, clearly indicating that the size, and so dispersion, of RuO 2 crystallites were determined by the preparation method (Table ).…”

Section: Resultsmentioning

confidence: 97%

“…It was postulated that, under a homogeneous base-free system, the basic sites are of importance for alcohol group deprotonation, while the acidity facilitates activation of the aldehyde group. , The distribution of basic and acidic sites of various strengths is presented in Figure S6 and Table . In general, the structure of LDO basic centers was assigned to metal hydroxide (M-OH), metal–oxygen ion pairs (Mg 2+ –O 2– –Al 3+ and Mg 2+ –O 2– –Mg 2+ ), and coordinatively unsaturated oxygen anion (O 2– ) at the edge and corners of crystals as weak, medium, and strong basicity, respectively . The conventional Ru(3)/FSV-LDO catalyst displayed considerably less total basicity compared to the bare FSV-LDO support (Table S4) due to low Ru dispersion.…”

Section: Resultsmentioning

confidence: 99%

“…Figure 2A shows the XRD patterns of various exfoliated LDO-supported Ru catalysts all of which show reflections at 42.5 and 62.5°, representing a periclase MgO structure. 31 The reflection corresponding to the crystalline RuO 2 phase was detected for some samples, clearly indicating that the size, and so dispersion, of RuO 2 crystallites were determined by the preparation method (Table 1). From the N 2 physisorption, except for Ru(3)/FSV-LDO, the exfoliated Rubased catalysts exhibited type IV isotherms with large hysteresis loops (Figure 2B), thus confirming the presence of mesopores originating from loosely packed particles.…”

Section: ■ Introductionmentioning

confidence: 89%

“…In general, the structure of LDO basic centers was assigned to metal hydroxide (M-OH), metal−oxygen ion pairs (Mg 2+ − O 2− −Al 3+ and Mg 2+ −O 2− −Mg 2+ ), and coordinatively unsaturated oxygen anion (O 2− ) at the edge and corners of crystals as weak, medium, and strong basicity, respectively. 31 The conventional Ru(3)/FSV-LDO catalyst displayed considerably less total basicity compared to the bare FSV-LDO support (Table S4) due to low Ru dispersion. The exfoliated Ru-based catalysts had higher total basicity than Ru(3)/FSV-LDO, except for Ru(3)/ESV-LDO.…”

Section: ■ Introductionmentioning

confidence: 98%

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Exfoliated Layered Metal Oxide-Supported Ruthenium Catalysts for Base-Free Oxidation of 5-Hydroxymethylfurfural into a Renewable Bioplastic Precursor

Thiensuwan,

Sankaranarayanan,

Yokoi

et al. 2023

ACS Sustainable Chem. Eng.

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2,5-Furandicarboxylic acid (FDCA) is a potential biopolymer precursor for polyethylene furanoate production. This study focused on synthesizing FDCA via catalytic oxidation of 5-hydroxymethylfurfural (HMF) over Ru-based catalysts supported on exfoliated MgAl-double oxides (LDO) for the first time in a homogeneous base-free system. Effects of the exfoliation solvent, preparation method, and Ru loading level on the physicochemical and catalytic properties of the resulting catalysts were investigated. The exfoliated LDO-supported Ru catalysts exhibited enhanced textural properties, RuO x dispersion, and basicity, resulting in better catalytic activity (at least 6 times higher FDCA yield) than conventional LDO-supported Ru catalysts in the conversion into FDCA. The Ru-based catalyst supported on an exfoliated LDO/carbon nanocomposite, Ru(3)/ESV-LDC, revealed the nearly complete HMF conversion (99.2%) at an FDCA selectivity of >98%. This was attributed to the synergistic effect derived from good RuO x dispersion, providing a high proportion of lattice oxygen for boosting surface oxygen mobility, and high basicity, in terms of both strength and number of basic sites. Moreover, Ru(3)/ESV-LDC exhibited good reusability without a significant loss of HMF conversion and FDCA yield, suggesting strong chemical robustness of RuO x species and a stable interaction between the active metal and support.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 89%

Section: ■ Introductionmentioning

confidence: 98%

See 2 more Smart Citations

Exfoliated Layered Metal Oxide-Supported Ruthenium Catalysts for Base-Free Oxidation of 5-Hydroxymethylfurfural into a Renewable Bioplastic Precursor

Thiensuwan,

Sankaranarayanan,

Yokoi

et al. 2023

ACS Sustainable Chem. Eng.

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“…Monoesters can also be obtained from glycerol via polymerization. Esters and ethers can also be obtained from esterification and etherification of glycerol, respectively [40,41]. Carbonation of glycerol will yield glycerol carbonate.…”

Section: Glycerolmentioning

confidence: 99%

Production of Propanediols through In Situ Glycerol Hydrogenolysis via Aqueous Phase Reforming: A Review

et al. 2022

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Production of 1,2-propanediol and 1,3-propanediol are identified as methods to reduce glycerol oversupply. Hence, glycerol hydrogenolysis is identified as a thermochemical conversion substitute; however, it requires an expensive, high-pressure pure hydrogen supply. Studies have been performed on other potential thermochemical conversion processes whereby aqueous phase reforming has been identified as an excellent substitute for the conversion process due to its low temperature requirement and high H2 yields, factors which permit the process of in-situ glycerol hydrogenolysis which requires no external H2 supply. Hence, this manuscript emphasizes delving into the possibilities of this concept to produce 1,2-propanediol and 1,3-propanediol without “breaking the bank” with expenses. Various heterogenous catalysts of aqueous phase reforming (APR) and glycerol hydrogenolysis were identified, whereby the combination of a noble metal, support, and dopant with a good amount of Brønsted acid sites are identified as the key factors to ensure a high yield of 1,3-propanediol. However, for 1,2-propanediol, a Cu-based catalyst with decent basic support is observed to be the key for good yield and selectivity of product. The findings have shown that it is possible to produce high yields of both 1,2-propanediol and 1,3-propanediol via aqueous phase reforming, specifically 1,2-propanediol, for which some of the findings achieve better selectivity compared to direct glycerol hydrogenolysis to 1,2-propanediol. This is not the case for 1,3-propanediol, for which further studies need to be conducted to evaluate its feasibility.

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Unveiling the catalytic potential of K₂ZnF₆ fluoroperovskite for glycerol oligomerization

Barros,

Moreno‐Tost,

Cecilia

et al. 2024

Biofuels Bioprod Bioref

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This study systematically evaluates fluorine‐containing materials with varying compositions of K, Al, Co, Cu, Mg, and Zn as catalysts for glycerol oligomerization. Comprehensive analyses were conducted for all of the catalysts, considering their structural, compositional, morphological characteristics, and basicity, to understand them in greater depth. Among these analyses, gas chromatography was employed to examine the composition of the reaction products. The investigation extended to a recycling study under optimized conditions. Thermogravimetric analysis and X‐ray photoelectron spectroscopy were used to characterize the spent catalysts. Catalytic activity was found to be influenced strongly by the fluorine content, demonstrating remarkable performance for the materials containing fluoroperovskites such as KMgF3 in the catalyst KMgAFC, and K2ZnF6 in KZAFC. Remarkably, KZAFC with 20% fluorine exhibited superior glycerol conversion (68%) and selectivity for diglycerol (27%). Comparative analysis with ZnAl‐layered double hydroxide highlighted the positive impact of fluorine on catalytic activity. Introducing a calcination step in the catalyst recovery process also demonstrated improved activity during recycling. Interestingly, KZAFC exhibited stability over four reaction cycles, presenting an economic advantage over homogeneous catalysts. The study also shed light on the potential fluorine loss at the surface and potassium leaching into reaction products, correlating these phenomena with the observed decline in activity. These comprehensive findings contribute significantly to advancing sustainable glycerol valorization through heterogeneous catalysis.

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Etherification of glycerol into short-chain polyglycerols over MgAl LDH/CaCO3 nanocomposites as heterogeneous catalysts to promote circular bioeconomy

Cited by 9 publications

References 45 publications

Exfoliated Layered Metal Oxide-Supported Ruthenium Catalysts for Base-Free Oxidation of 5-Hydroxymethylfurfural into a Renewable Bioplastic Precursor

Exfoliated Layered Metal Oxide-Supported Ruthenium Catalysts for Base-Free Oxidation of 5-Hydroxymethylfurfural into a Renewable Bioplastic Precursor

Production of Propanediols through In Situ Glycerol Hydrogenolysis via Aqueous Phase Reforming: A Review

Unveiling the catalytic potential of K₂ZnF₆ fluoroperovskite for glycerol oligomerization

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Etherification of glycerol into short-chain polyglycerols over MgAl LDH/CaCO3 nanocomposites as heterogeneous catalysts to promote circular bioeconomy

Cited by 9 publications

References 45 publications

Exfoliated Layered Metal Oxide-Supported Ruthenium Catalysts for Base-Free Oxidation of 5-Hydroxymethylfurfural into a Renewable Bioplastic Precursor

Exfoliated Layered Metal Oxide-Supported Ruthenium Catalysts for Base-Free Oxidation of 5-Hydroxymethylfurfural into a Renewable Bioplastic Precursor

Production of Propanediols through In Situ Glycerol Hydrogenolysis via Aqueous Phase Reforming: A Review

Unveiling the catalytic potential of K2ZnF6 fluoroperovskite for glycerol oligomerization

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Unveiling the catalytic potential of K₂ZnF₆ fluoroperovskite for glycerol oligomerization