Recyclable Cu Salt-Derived Brønsted Acids for Hydrolytic Hydrogenation of Cellulose on Ru Catalyst

Liu, Yue; Chen, Linxiao; Zhang, Wei; Liu, Haichao

doi:10.31635/ccschem.021.202101506

Cited by 14 publications

(10 citation statements)

References 52 publications

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“…These results clearly show that the different crystalline types of cellulose only influence their hydrolysis rates, which however does not affect the subsequent reaction pathways of glucose intermediate once it is formed, i.e., its hydrogenation, isomerization and decomposition reactions that determine the ultimate product selectivities. Such findings are consistent with the general mechanism for the cellulose reaction to sugar alcohols, involving the acid-catalyzed cellulose hydrolysis to glucose as the rate-determining step. , Therefore, our next discussion focuses only on the effect on the cellulose conversion rates.…”

Section: Resultssupporting

confidence: 79%

“…The overall conversion rate is determined by the hydrolysis step, and the reaction of the glucose intermediate only influences the product selectivity. 59,60 As shown in Figure 2A, all four types of cellulose converted following first-order kinetics, featured by the logarithmic decrease of cellulose concentration with the reaction time. Cellulose II had the highest conversion rate, followed by cellulose III, I, and IV.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

“…The reaction proceeds via Brønsted acid-catalyzed hydrolysis, i.e., protolytic cleavage of the 1,4-β-glycosidic bond, followed by instantaneous hydrogenation of the glucose intermediate to sugar alcohols. The overall conversion rate is determined by the hydrolysis step, and the reaction of the glucose intermediate only influences the product selectivity. , As shown in Figure A, all four types of cellulose converted following first-order kinetics, featured by the logarithmic decrease of cellulose concentration with the reaction time. Cellulose II had the highest conversion rate, followed by cellulose III, I, and IV.…”

Section: Resultsmentioning

confidence: 99%

“…Such findings are consistent with the general mechanism for the cellulose reaction to sugar alcohols, involving the acid-catalyzed cellulose hydrolysis to glucose as the rate-determining step. 59,60 Therefore, our next discussion focuses only on the effect on the cellulose conversion rates.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Effect of Crystalline Structure on the Catalytic Hydrolysis of Cellulose in Subcritical Water

Liu

Zhang

et al. 2022

ACS Sustainable Chem. Eng.

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Depolymerization of cellulose, the most abundant biomass in nature, is a critical step for its catalytic conversion to fuels and chemicals. While cleavage of its glycosidic bond by acid hydrolysis is the rate-determining step to depolymerize cellulose, disrupting its robust crystalline structure is equally important. In this work, we examined the hydrolysis of cellulose of four different crystalline allomorphs, i.e., I, II, III, and IV, with respect to the conversion rate, change in the crystalline structure, and the degree of crystallinity and polymerization during the reaction. Independent of their crystalline structure, the four cellulose samples converted following the first-order reaction kinetics with no essential influence on the product selectivity. However, the rate constants were largely different and decreased in the following sequence: cellulose II > III > I > IV. The high rate of cellulose II is caused by its higher reaction probability, as reflected by its preexponential factor, which is several orders of magnitude higher than that for the other cellulose samples, which overcompensated its high apparent activation energy. It is found that cellulose I and IV undergo surface reactions at 478–508 K, whereas cellulose II and III swell at the reaction temperatures, which allows the hydrolysis reaction to occur in the whole swollen regions, leading to higher accessibility of the glycosidic bond to the H+ catalyst and consequently higher conversion rates. These findings provide the mechanistic basis for an alternative strategy to enhance the efficacy in depolymerization of cellulose via tuning of crystalline phases.

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Section: Resultssupporting

confidence: 79%

Section: ■ Results and Discussionmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

See 2 more Smart Citations

Effect of Crystalline Structure on the Catalytic Hydrolysis of Cellulose in Subcritical Water

Liu

Zhang

et al. 2022

ACS Sustainable Chem. Eng.

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“…With the increasing demand for fossil fuels and their depleting reserve, development of renewable, eco-friendly and cheap energies has attracted much attention these years 1 . Naturallyoccurring biomass provides a renewable alternative to fossil fuels for the production of chemicals, fuels and materials [2][3][4] . One typical example is glycerol.…”

mentioning

confidence: 99%

Selective Hydrogenolysis of Glycerol to 1,3-Propanediol over Supported Platinum-Tungsten Oxide Catalysts

Li¹,

Liu²

2022

Acta Physico Chimica Sinica

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Glycerol is a versatile platform compound that is formed in considerable amounts as a by-product of biodiesel production. The catalytic selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) provides a sustainable route for the synthesis of this important diol. In this study, a series of platinum-tungsten oxide (Pt-WOx) catalysts with different WOx surface densities dispersed on titanium(IV) oxide, zirconium(IV) oxide, and aluminum oxide supports were prepared and evaluated for the glycerol hydrogenolysis to 1,3-PDO. The highest reaction activity and 1,3-PDO selectivity were achieved at a WOx density of approximately 1.5-2.0 W•nm −2 , with all three support materials. Such a strong dependence on the surface density of WOx revealed the critical role of the dispersed WOx domains in the hydrogenolysis of glycerol to 1,3-PDO. The infrared spectra for carbon monoxide adsorption confirmed the electron transfer and strong interaction between the Pt particles and WOx domains. These phenomena were hypothesized to contribute to the superior selectivity to 1,3-PDO over 1,2-PDO of the supported Pt-WOx catalysts when compared with the corresponding supported Pt catalysts. The realized superior 1,3-PDO selectivity was consistent with its higher stability on the Pt-WOx catalysts, as reflected by the lower reaction rate constant of 1,3-PDO than those of 1,2-PDO and glycerol obtained in their hydrogenolysis reactions. There existed a volcano-type dependence of the glycerol reaction activity on the hydrogen partial pressure. Such a dependence, together with the measured ratio (1 : 2) of the secondary to the primary C-H bonds in 1,3-PDO in the presence of deuterium and deuterium oxide (replacing hydrogen and water, respectively), indicated that the glycerol hydrogenolysis proceeds by the kinetically relevant dehydrogenation of glycerol to the glyceraldehyde intermediate, followed by the dehydration and hydrogenation of glyceraldehyde to 1,3-PDO over the Pt-WOx catalysts.

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Insights into the Active Acid Sites for Isosorbide Synthesis from Renewable Sorbitol and Cellulose on Solid Acid Catalysts

Deng

Liu

2022

Chem. Res. Chin. Univ.

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Recyclable Cu Salt-Derived Brønsted Acids for Hydrolytic Hydrogenation of Cellulose on Ru Catalyst

Cited by 14 publications

References 52 publications

Effect of Crystalline Structure on the Catalytic Hydrolysis of Cellulose in Subcritical Water

Effect of Crystalline Structure on the Catalytic Hydrolysis of Cellulose in Subcritical Water

Selective Hydrogenolysis of Glycerol to 1,3-Propanediol over Supported Platinum-Tungsten Oxide Catalysts

Insights into the Active Acid Sites for Isosorbide Synthesis from Renewable Sorbitol and Cellulose on Solid Acid Catalysts

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