Efficient C–C coupling of bio-based furanics and carbonyl compounds to liquid hydrocarbon precursors over lignosulfonate derived acidic carbocatalysts

Konwar, Lakhya Jyoti; Samikannu, Ajaikumar; Mäki‐Arvela, Päivi; Mikkola, Jyri‐Pekka

doi:10.1039/c7cy02601c

Cited by 34 publications

(39 citation statements)

References 29 publications

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“…The basic structural unit of these materials can be approximated by a flexible amorphous carbon (or oxidized carbon) framework which has been covalently linked with several sulfonic (SO 3 H) acid groups (Figure ). The sulfonic groups are usually introduced onto the carbon framework structure via chemical modification or functionalization techniques in a step commonly referred to as “sulfonation”, whereupon the sulfonic group density varies in the range of 0.05–7.3 mmol/g, depending on the sulfonation method used and framework structure of the parent carbon support. − ,,,− ,− These Brønsted acidic sulfated carbons may be subdivided into several categories on the basis of their textural and surface properties as outlined in Table . In fact, the nature of the carbon support and the method of SO 3 H functionalization have a direct impact on the resulting material properties and cost.…”

Section: So3h-containing Functional Carbon Materialsmentioning

confidence: 99%

SO₃H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

2019

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The "sulfonated carbons" are a new class of metal-free solid protonic acids characterized by their unique carbon structure and Brønsted acidity (−H 0 = 8−11) on par to concentrated H 2 SO 4 . These carbon materials covalently functionalized with SO 3 H groups via C−PhSO 3 H or C−SO 3 H linkages can act as versatile water-tolerant solid acids. Due to their low production costs, unique surface chemistry, high chemical and thermal stability, as well as tailorable pore structures they are regarded as potential substitutes to liquid H 2 SO 4 . Catalysis, in particular, biomass and large molecule catalysis, is one of the important areas in which acidic carbons have demonstrated exceptional activity and selectivity, outperforming traditional solid acid catalysts (cation-exchange resins, sulfated oxides, and acidic zeolites). In this review we address developments in the different types SO 3 H-and PhSO 3 H-functionalized acidic carbon materials, their structure, active sites, and surface properties, applications in catalysis, as well as activation and deactivation characteristics covering important literature since 2004. In particular, we aim to provide a systematic discussion on the specific merits and demerits of such materials obtained from different carbon precursors and functionalization methods which directly influence the structure−stability−acidic properties and catalytic performance. CONTENTSReview pubs.acs.org/CR

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Section: So3h-containing Functional Carbon Materialsmentioning

confidence: 99%

SO₃H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

2019

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“…Staged thermal pyrolysis is one of the most promising approaches to decompose biomass into separate streams, more amenable for subsequent catalytic upgrading to fuels and chemicals. − Furanic compounds obtained from thermal decomposition in the medium range are particularly suited for C–C coupling upgrading. ,− Furfurala representative molecule of this stageis unstable and may easily polymerize and form humins. Then, it would be a good strategy to convert furfural to more stable cyclopentanone via a two-step metal-catalyzed aqueous hydrogenation/isomerization known as the Piancatelli ring rearrangement .…”

Section: Introductionmentioning

confidence: 99%

Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

et al. 2019

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Aldol condensation is a key CC coupling reaction for upgrading of biomass-derived oxygenates to fuels and chemicals. Here, we investigate the effects of added water on the condensation of cyclopentanone (CPO) on hydrophobized MgO catalysts. We have found that the role of water strongly depends on the degree of hydrophobic functionalization of the MgO surface. That is, on a nonfunctionalized (hydrophilic) high-surface-area MgO catalyst, the rate decreases with the addition of water, mostly due to active site blockage. By contrast, on MgO hydrophobized via silylation with octadecyltrichlorosilane (OTS), the rate actually increases with added water. A concomitant change in kinetics is observed from the pristine (hydrophilic) MgO to the hydrophobized sample. Specifically, on the hydrophilic sample, the reaction is first-order, as expected if the rate-limiting step is the formation of an enolate intermediate via α-H abstraction at a basic site, as widely reported in previous literature. By contrast, on the hydrophobized sample, the reaction becomes second-order, indicating a shift in ratelimiting step to the bimolecular CC coupling. On pristine MgO, acid−base pairs are fully available on the surface, with the acid site polarizing the CO group in the second cyclopentanone (electrophile) and making the attack by the enolate very favorable. It is proposed here that grafted OTS molecules interfere between active sites, making the adsorbate−adsorbate interaction on the surface less likely and reducing the rate of CC coupling. Both isotope effect experiments and ab initio molecular dynamics simulations of cyclopentanone adsorption at the MgO/OTS interface further support this argument. Therefore, the promotional role of water seems to be the assistance of the CC bond-forming step. It is proposed that, at low concentrations, water can help the second molecule (electrophile) be polarized from a remote Mg 2+ site through a chain of Hbonded molecules.

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“…To reveal the promotion mechanism of ZnC 2 O 4 on lignin cleavage, in-situ FT-IR measurements of LS and LS/ZnC 2 O 4 from 30 to 450 °C were carried out. As can be seen from Figure a and b, both LS and LS/ZnC 2 O 4 show stretching vibrations of Ar–OH (1516 and 1464 cm –1 ), −SO 3 – (1134 cm –1 ), C–O (1038 cm –1 ), and C–S (617 cm –1 ) at 30 °C, , but the intensity of Ar–OH in the spectra of LS/ZnC 2 O 4 is much weaker owing to the coordination of zinc ions. Also, three strong stretching vibrations of the OC–O groups at 1377, 1315, and 816 cm –1 from ZnC 2 O 4 can be observed in the spectra of LS/ZnC 2 O 4 . , As the temperature rises, the stretching vibration of the Ar–OH groups gradually disappears, and a new peak is visible at 1703 cm –1 in the spectra of LS/ZnC 2 O 4 , which corresponds to the CO stretching vibrations, indicating that ZnC 2 O 4 favors the dehydrogenation of Ar–OH.…”

Section: Resultsmentioning

confidence: 88%

Insights into Gas-Exfoliation and the In-Situ Template Mechanism of Zinc Compound for Lignin-Derived Supercapacitive Porous Carbon

Yang

et al. 2021

ACS Appl. Energy Mater.

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The large-scale production of porous activated carbon is plagued by the overuse of corrosive activators, so developing a green and mild activation strategy is technologically urgent and meaningful. Herein, two gentle activators (ZnCO 3 and ZnC 2 O 4 ) and a traditional corrosive agent (ZnCl 2 ) are utilized to activate lignin for porous carbons, and the microstructures and electrochemical properties of the carbons are systematically investigated. By tracking the evolution of the carbonized products through TG-MS, in-situ FT-IR, and other characterization methods, the gas-exfoliation and in-situ template functions of ZnCO 3 and ZnC 2 O 4 are proposed. It was found that the pyrolysis synergistic effect between ZnC 2 O 4 and lignin boosts the decomposition of oxygen-containing groups, playing a pivotal role in the fabrication of hierarchical porous carbon with crumpled nanosheets. The electrochemical properties of the carbons are closely correlated to their porous structures. Benefiting from the well-developed crumpled lamellar units, the hierarchical porous carbon activated by ZnC 2 O 4 has a high specific surface area and good conductivity. Consequently, it exhibits a higher capacitance than the microporous carbon activated by ZnCl 2 and the mesoporous carbon activated by ZnCO 3 .

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Efficient C–C coupling of bio-based furanics and carbonyl compounds to liquid hydrocarbon precursors over lignosulfonate derived acidic carbocatalysts

Abstract: Synthesis of jet fuel (branched hydrocarbon) precursors from bio based furanics and carbonyls over highly stable, active acidic carbocatalysts derived from Na-lignosulfonate.

Cited by 34 publications

References 29 publications

SO₃H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

SO₃H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

Insights into Gas-Exfoliation and the In-Situ Template Mechanism of Zinc Compound for Lignin-Derived Supercapacitive Porous Carbon

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Efficient C–C coupling of bio-based furanics and carbonyl compounds to liquid hydrocarbon precursors over lignosulfonate derived acidic carbocatalysts

Abstract: Synthesis of jet fuel (branched hydrocarbon) precursors from bio based furanics and carbonyls over highly stable, active acidic carbocatalysts derived from Na-lignosulfonate.

Cited by 34 publications

References 29 publications

SO3H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

SO3H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

Insights into Gas-Exfoliation and the In-Situ Template Mechanism of Zinc Compound for Lignin-Derived Supercapacitive Porous Carbon

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SO₃H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis

SO₃H-Containing Functional Carbon Materials: Synthesis, Structure, and Acid Catalysis