Browse
Submit Data
Databases
API
Help

Dataset Information

29 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Ru@hyperbranched Polymer for Hydrogenation of Levulinic Acid to Gamma-Valerolactone: The Role of the Catalyst Support.

ABSTRACT: Hydrogenation of levulinic acid (LA) obtained from cellulose biomass is a promising path for production of γ-valerolactone (GVL)-a component of biofuel. In this work, we developed Ru nanoparticle containing nanocomposites based on hyperbranched pyridylphenylene polymer, serving as multiligand and stabilizing matrix. The functionalization of the nanocomposite with sulfuric acid significantly enhances the activity of the catalyst in the selective hydrogenation of LA to GVL and allows the reaction to proceed under mild reaction conditions (100 °C, 2 MPa of H₂) in water and low catalyst loading (0.016 mol.%) with a quantitative yield of GVL and selectivity up to 100%. The catalysts were successfully reused four times without a significant loss of activity. A comprehensive physicochemical characterization of the catalysts allowed us to assess structure-property relationships and to uncover an important role of the polymeric support in the efficient GVL synthesis.

SUBMITTER: Sorokina SA

PROVIDER: S-EPMC8776037 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Room-Temperature Asymmetric Transfer Hydrogenation of Biomass-Derived Levulinic Acid to Optically Pure γ-Valerolactone Using a Ruthenium Catalyst.

Project description:This study presents a first report on ruthenium-catalyzed asymmetric transfer hydrogenation (ATH) of levulinic acid (LA) to chiral γ-valerolactone (GVL). ATH of LA has been explored with Noyori's chiral catalyst (Ru-TsDPEN) in methanol solvent. Efficacy of ATH reaction of LA was investigated under different reactions conditions such as temperature, catalyst, and hydrogen donor concentration. The effect of various organic tertiary bases along with formic acid (FA) as a hydrogen donor was studied, and N-methylpiperidine with FA (1:1 molar ratio) was revealed as an efficient hydrogen donor for ATH of LA to GVL furnishing chiral GVL with complete conversion and 93% enantiomeric excess (ee). This operationally simple and mild ATH protocol was tested for practical applicability of ATH of LA obtained from biomass waste (rice husk and wheat straw) and furnished chiral GVL with 82% ee.

| S-EPMC6868911 | biostudies-literature

Robust Ruthenium Catalysts Supported on Mesoporous Cyclodextrin-Templated TiO2-SiO2 Mixed Oxides for the Hydrogenation of Levulinic Acid to γ-Valerolactone.

Project description:In this paper, we present a versatile template-directed colloidal self-assembly method for the fabrication in aqueous phase of composition-tuned mesoporous RuO2@TiO2-SiO2 catalysts. Randomly methylated β-cyclodextrin/Pluronic F127 supramolecular assemblies were used as soft templates, TiO2 colloids as building blocks, and tetraethyl orthosilicate as a silica source. Catalysts were characterized at different stages of their synthesis using dynamic light scattering, N2-adsorption analysis, powder X-ray diffraction, temperature programmed reduction, high-resolution transmission electron microscopy, high-angle annular bright-field and dark-field scanning transmission electron microscopy, together with EDS elemental mapping. Results revealed that both the supramolecular template and the silica loading had a strong impact on the pore characteristics and crystalline structure of the mixed oxides, as well as on the morphology of the RuO2 nanocrystals. Their catalytic performance was then evaluated in the aqueous phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild conditions (50 °C, 50 bar H2). Results showed that the cyclodextrin-derived catalyst displayed almost quantitative LA conversion and 99% GVL yield in less than one hour. Moreover, this catalyst could be reused at least five times without loss of activity. This work offers an effective approach to the utilization of cyclodextrins for engineering the surface morphology of Ru nanocrystals and pore characteristics of TiO2-based materials for catalytic applications in hydrogenation reactions.

| S-EPMC7915766 | biostudies-literature

Silylated Zeolites With Enhanced Hydrothermal Stability for the Aqueous-Phase Hydrogenation of Levulinic Acid to ?-Valerolactone.

Project description:A systematic silylation approach using mono-, di-, and trichlorosilanes with different alkyl chain lengths was employed to enhance the hydrothermal stability of zeolite Y. DRIFT spectra of the silylated zeolites indicate that the attachment of the silanes takes place at surface silanol groups. Regarding hydrothermal stability under aqueous-phase processing (APP) conditions, i.e., pH ? 2, 473 K and autogenous pressure, the selective silylation of the zeolite surface using monochlorosilanes has no considerable influence. By using trichlorosilanes, the hydrothermal stability of zeolite Y can be improved significantly as proven by a stability test in an aqueous solution of 0.2 M levulinic acid (LA) and 0.6 M formic acid (FA) at 473 K. However, the silylation with trichlorosilanes results in a significant loss of total specific pore volume and total specific surface area, e.g., 0.35 cm3 g-1 and 507 m2 g-1 for the silylated zeolite Y functionalized with n-octadecyltrichlorosilane compared to 0.51 cm3 g-1 and 788 m2 g-1 for the parent zeolite Y. The hydrogenation of LA to ?-valerolactone (GVL) was conducted over 3 wt.-% Pt on zeolite Y (3PtY) silylated with either n-octadecyltrichlorosilane or methyltrichlorosilane using different reducing agents, e.g., FA or H2. While in the stability test an enhanced hydrothermal stability was found for zeolite Y silylated with n-octadecyltrichlorosilane, its stability in the hydrogenation of LA was far less pronounced. Only by applying an excess amount of methyltrichlorosilane, i.e., 10 mmol per 1 g of zeolite Y, presumably resulting in a high degree of polymerization among the silanes, a recognizable improvement of the stability of the 3 PtY catalyst could be achieved. Nonetheless, the pore blockage found for zeolite Y silylated with an excess amount of methyltrichlorosilane was reflected in a drastically lower GVL yield at 493 K using FA as reducing agent, i.e., 12 vs. 34% for 3PtY after 24 h.

| S-EPMC5964160 | biostudies-literature

High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to ?-valerolactone.

Project description:The catalytic hydrogenation of levulinic acid, a key platform molecule in many biorefinery schemes, into ?-valerolactone is considered as one of the pivotal reactions to convert lignocellulose-based biomass into renewable fuels and chemicals. Here we report on the development of highly active, selective and stable supported metal catalysts for this reaction and on the beneficial effects of metal nano-alloying. Bimetallic random alloys of gold-palladium and ruthenium-palladium supported on titanium dioxide are prepared with a modified metal impregnation method. Gold-palladium/titanium dioxide shows a marked,~27-fold increase in activity (that is, turnover frequency of 0.1?s(-1)) compared with its monometallic counterparts. Although ruthenium-palladium/titanium dioxide is not only exceptionally active (that is, turnover frequency of 0.6?s(-1)), it shows excellent, sustained selectivity to ?-valerolactone (99%). The dilution and isolation of ruthenium by palladium is thought to be responsible for this superior catalytic performance. Alloying, furthermore, greatly improves the stability of both supported nano-alloy catalysts.

| S-EPMC4382690 | biostudies-literature

Nanostructured Nickel/Silica Catalysts for Continuous Flow Conversion of Levulinic Acid to γ-Valerolactone.

Project description:Selective transformation of levulinic acid (LA) to γ-valerolactone (GVL) using novel heterogeneous catalysts is one of the promising strategies for viable biomass processing. In this framework, we developed a continuous flow process for the selective hydrogenation of LA to GVL using several nanostructured Ni/SiO2 catalysts. The structural, textural, acidic, and redox properties of Ni/SiO2 catalysts, tuned by selectively varying the Ni amount from 5 to 40 wt %, were critically investigated using numerous materials characterization techniques. Electron microscopy images showed the formation of uniformly dispersed Ni nanoparticles on the SiO2 support, up to 30% Ni loading (average particle size is 9.2 nm), followed by a drastic increase in the particles size (21.3 nm) for 40% Ni-loaded catalyst. The fine dispersion of Ni particles has elicited a synergistic metal-support interaction, especially in 30% Ni/SiO2 catalyst, resulting in enhanced acidic and redox properties. Among the various catalysts tested, the 30% Ni/SiO2 catalyst showed the best performance with a remarkable 98% selectivity of GVL at complete conversion of LA for 2 h reaction time. Interestingly, this catalyst showed a steady selectivity to GVL (>97%), with a 54.5% conversion of LA during 20 h time-on-stream. The best performance of 30% Ni/SiO2 catalyst was attributed to well-balanced catalytic properties, such as ample amounts of strong acidic sites and abundant active metal sites. The obtained results show a great potential of applying earth-abundant nickel/silica catalysts for upgrading biomass platform molecules into value-added chemicals and high-energy-density fuels.

| S-EPMC6644063 | biostudies-literature

Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over Mesoporous Silica-Supported Cu-Ni Composite Catalysts.

Project description:Monometallic (Cu, Ni) and bimetallic (Cu-Ni) catalysts supported on KIT-6 based mesoporous silica/zeolite composites were prepared using the wet impregnation method. The catalysts were characterized using X-ray powder diffraction, N2 physisorption, SEM, solid state NMR and H2-TPR methods. Finely dispersed NiO and CuO were detected after the decomposition of impregnating salt on the silica carrier. The formation of small fractions of ionic Ni2+ and/or Cu2+ species, interacting strongly with the silica supports, was found. The catalysts were studied in the gas-phase upgrading of lignocellulosic biomass-derived levulinic acid (LA) to γ-valerolactone (GVL). The bimetallic, CuNi-KIT-6 catalyst showed 100% LA conversion at 250 °C and atmospheric pressure. The high LA conversion and GVL yield can be attributed to the high specific surface area and finely dispersed Cu-Ni species in the catalyst. Furthermore, the catalyst also exhibited high stability after 24 h of reaction time with a GVL yield above 80% without any significant change in metal dispersion.

| S-EPMC9458178 | biostudies-literature

Influence of Sulfuric Acid on the Performance of Ruthenium-based Catalysts in the Liquid-Phase Hydrogenation of Levulinic Acid to ?-Valerolactone.

Project description:The presence of biogenic or process-derived impurities poses a major problem on the efficient catalytic hydrogenation of biomass-derived levulinic acid to ?-valerolactone; hence, studies on their influence on catalyst stability are now required. Herein, the influence of sulfuric acid as feed impurity on the performance of Ru-based heterogeneous catalysts, including Ru/ZrO2 and mono- and bimetallic Ru-on-carbon catalysts in dioxane as solvent, was investigated. The carbon-supported Ru catalysts proved to be very sensitive to minor amounts of sulfuric acid. In stark contrast, Ru/ZrO2 showed a remarkable stability in the presence of the same impurity, which is attributed to the sulfate-ion adsorption capacity of the support. Preferential sulfate adsorption onto the surface of ZrO2 effectively protects the Ru active phase from deactivation by sulfur poisoning. A simple catalyst regeneration strategy was effective in removing adsorbed impurities, allowing efficient catalyst recycling.

| S-EPMC5575478 | biostudies-literature

Efficient Vapor-Phase Selective Hydrogenolysis of Bio-Levulinic Acid to γ-Valerolactone Using Cu Supported on Hydrotalcite Catalysts.

Project description:In this work, Cu nanoparticles (Cu NPs, 2-20 nm) supported on Hydrotalcite catalysts exhibit enhanced selectivity for γ-valerolactone (GVL) during hydrogenolysis of levulinic acid (LA). At 260 °C, over 3 wt% Cu achieved 87.5% of LA conversion with a maximum GVL selectivity (95%). In contrast, LA hydrogenolysis over 3Cu/Hydrotalcite catalyst is highly active and stable toward the production of GVL due to balanced acido-basicity and higher Cu dispersion with ultrasmall particle sizes, which are investigated through the temperature programmed desorption (TPD) of ammonia, N2O titration, and transmission electron microscopy (TEM) analysis. Hydrotalcite in combination with inexpensive Cu catalyst is found to be an efficient and environmentally benign for LA hydrogenolysis.

| S-EPMC6360448 | biostudies-literature

Catalyst System for Hydrogenation Catalysis Based on Multiarm Hyperbranched Polymer Templated Metal (Au, Pt, Pd, Cu) Nanoparticles.

Project description:With a hyperbranched poly(amidoamine) core and many water-soluble poly(ethylene glycol) monomethyl ether arms connected by pH-sensitive acylhydrazone bonds, multiarm hyperbranched polymer was used as nanoreactor and reductant to prepare metal nanoparticles endowed with intelligence and biocompatibility. The multiarm hyperbranched polymer encapsulated nanoparticles (NPs) showed excellent catalytic activity for hydrogenation, thus an excellent catalyst system for hydrogenation was established. The rate constants could reach as high as 3.48 L·s-1·m-2, which can be attributed to the lack of surface passivation afforded by the multiarm hyperbranched polymer.

| S-EPMC6418630 | biostudies-literature

Catalytic valorisation of biomass levulinic acid into gamma valerolactone using formic acid as a H<sub>2</sub> donor: a critical review.

Project description:This review sheds light on the catalytic valorisation of agroforestry biomass through levulinic acid and formic acid towards γ-valerolactone and other higher-value chemicals. γ-Valerolactone is produced by the hydrogenation of levulinic acid, which can be achieved through an internal hydrogen transfer reaction with formic acid in the presence of catalyst. By reviewing corresponding catalysts, the paper underlines the most efficient steps constituting an integrated sustainable process that eliminates the need for external H2 sources while producing biofuels as an alternative energy source. Furthermore, the review emphasizes the role of catalysts in the hydrogenation of levulinic acid, with special focus on heterogeneous catalysts. The authors highlighted the dual role of different catalysts by comparing their activity, morphology, electronic structure, synergetic relation between support and doped species, as well as their deactivation and recyclability. Acknowledging the need for green and sustainable H2 production, the review extends to cover the role of photo catalysis in dissociating H2-donor solvents for reducing levulinic acid into γ-valerolactone under mild temperatures. To wrap up, the critical discussion presented enables readers to hone their knowledge about different schools and emphasizes research gaps emerging from experimental work. The review concludes with a comprehensive table summarizing the recent catalysts reported between the years 2017-2021.

| S-EPMC9073962 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data