Hydrogenation Of Levulinic Acid Research Articles

Alkaline modified Zr-loading on nanosheet zeolite towards production of γ-valerolactone from levulinic acid through catalytic transfer hydrogenation

A self-pillared nanosheet ZSM-5 zeolite (SP) loading Zr catalyst is prepared for conversion of levulinic acid (LA) to produce γ-valerolactone (GVL). The hierarchical pore by nanosheet aggregates promotes Zr dispersion with establishment of strong interaction between Zr and zeolite. Moreover, Na ions are introduced to modify the chemical environment of Zr on nanosheet zeolite (Zr/NaSP). In catalytic transfer hydrogenation of LA using isopropanol as H-donor, uniformly dispersed Zr species on SP zeolite is conducive for both conversion of LA as well as production of GVL, in comparison with samples using conventional microporous ZSM-5 as supports (Zr/CZ). More importantly, different from protonated zeolite sample (Zr/HSP), the introduction of alkali sites could attract protons in hydroxyl groups of isopropanol, which accelerates the generation rates of GVL. The as-designed Zr/NaSP catalyst delivers GVL generation rates of 31.9 mmol·g-1·h-1, which provides a potential catalyst for GVL production.

Yolk-shell electron-rich Ru@hollow pyridinic-N-doped carbon nanospheres with tunable shell thickness and ultrahigh surface area for biomass-derived levulinic acid hydrogenation under mild conditions

Aiming to efficiently upgrade renewable biomass-derived levulinic acid (LA) into γ-valerolactone (GVL), we have devised yolk-shell electron-rich Ru@hollow pyridinic-N-doped carbon nanospheres, featuring a tunable shell thickness (20−70 nm) and an ultrahigh surface area (4016 m2 g−1). Experimental and theoretical investigations reveal that the strategic formation of the yolk-shell structure and appropriate thinning of the carbon shell facilitate the generation of electron-rich Ru0 and a positive shift of the d-band center towards the Fermi level by increasing surface pyridinic-N species. These modifications suitably intensify Ru0−H interaction, promote reactant adsorption, stimulate electron transfer between active H and the CO group of LA, and ultimately reduce apparent activation energy. Consequently, a high LA turnover frequency (18733.4 h−1 at 30 °C) and GVL selectivity (99.9%), alongside excellent stability up to eight cycles, are achieved, markedly outperforming externally-supported analogues. These findings afford valuable insights into designing yolk-shell nanostructures for biomass upgrading through microenvironment engineering.

Interplay Between Metallicity and Acidity in the Hydrogenation of Levulinic Acid

Interplay Between Metallicity and Acidity in the Hydrogenation of Levulinic Acid

Impact of aleatory and epistemic uncertainties on thermal risk and production assessment: Application to the hydrogenation of levulinic acid and butyl levulinate

The hydrogenation of levulinates, derivatives from cellulose hydrolysis, leads to the platform molecule γ-valerolactone (GVL). While prior investigations indicate the propensity for thermal runaways in this reaction, a comprehensive sensitivity analysis has been conspicuously absent in the existing literature. This study endeavors to scrutinize the influence of input parameters on both thermal risks and the production rate during GVL synthesis. Distinguished by its dual focus on sensitivity analyses, this manuscript also contrasts the implications of aleatory and epistemic uncertainties on thermal risk and production metrics. Aleatory uncertainties arise from the inherent variability of initial conditions, while epistemic uncertainties emanate from incomplete knowledge of the kinetic model. Employing Sobol global sensitivity analysis on the kinetic model, we delineate the hierarchical importance of various parameters. This analysis incorporates a quantification of uncertainty, and algorithmic approaches are proffered. The findings reveal that the initial temperature, the initial mass of the Ru/C catalyst, and hydrogen pressure are pivotal factors that are directly proportional to thermal risk and production efficiency. The implications of uncertainty on these variables are also discussed.

Ru embedded into N-Doped Porous Carbon Nanosheets as a Robust Catalyst for Efficient Hydrogenation of Levulinic Acid to γ-Valerolactone

Ru embedded into N-Doped Porous Carbon Nanosheets as a Robust Catalyst for Efficient Hydrogenation of Levulinic Acid to γ-Valerolactone

Spontaneously polarized ceramic‒carbon-supported Ni–Co for reinforcing water-assisted proton hopping to facilitate catalytic hydrogenation of levulinic acid

Spontaneously polarized ceramic‒carbon-supported Ni–Co for reinforcing water-assisted proton hopping to facilitate catalytic hydrogenation of levulinic acid

SSZ-39 zeolite-based Ru catalysts for selective hydrogenation of levulinic acid to γ-valerolactone: Influence of synthesis method and zeolite acidity

Novel SSZ-39 zeolite-based Ru catalysts were synthesized by impregnation on as-synthesized metallic and protonated SSZ-39 and a one-pot synthesis strategy. The study focused on the influence of the SSZ-39 zeolite characteristics and catalyst preparation method type toward levulinic acid (LA) selective conversion to γ-valerolactone (GVL) under relatively mild reaction conditions (150 °C, 4 h and 2 MPa of H2 with H2O and THF as solvents). Catalysts exhibited excellent catalytic efficiency (100 % LA conversion and 98.3 % GVL selectivity) and remarkable hydrothermal stability. The results revealed a correlation between excellent catalytic activity and the structural features of the synthesized catalysts, predominantly dependent on their appropriate surface acidity (strong Lewis acid sites) and enhanced electronic interaction between Ru species and SSZ-39. The one-pot method promoted the formation of mesopores besides the zeolitic micropores present in SSZ-39; therefore, the catalyst prepared by the one-pot method (Ru/SSZ-39) showed purer SSZ-39 crystallites and a slightly larger catalytic surface area of 439 m2/g than the original zeolite surface area of 424 m2/g. In addition, the original zeolite crystals retained their morphology as spherical aggregates and remained unaffected by Ru impregnation on the metallic or protonated support during the synthesis of Ru/Na-SSZ-39 and Ru/H-SSZ-39 catalysts, respectively. Notably, it has been demonstrated that SSZ-39 zeolite effectively acts as a support for the preparation of Ru catalyst in biomass conversion reactions. Moreover, the reused catalyst exhibited consistent activity over six cycles, maintaining its structural framework without significant loss in activity.

CeOx‐induced oxygen vacancy‐enhanced Pt‐based titanium silicalite‐1 catalysts for selective conversion of levulinic acid

The selective conversion of levulinic acid (LA) obtained from lignocellulosic biomass represents a crucial pathway for producing the key value‐added chemical compound γ‐valerolactone (GVL). Herein, we constructed a series of Pt‐based titanium‐silicalite‐1 (TS‐1) bifunctional catalysts modified with rare earth metal Ce through a simple spin‐coating impregnation method, and the catalytic performance was significantly improved compared to the unmodified Pt1.2/TS‐1. Pt0.7‐Ce0.5/TS‐1 exhibited the best aqueous‐phase catalytic activity (with a GVL yield of 99.4%). The introduction of CeOx can reduce the particle size of Pt nanoparticles and promote the formation of electron‐rich Pt species while delivering abundant oxygen vacancies (OV) for the catalysts. The characterization and testing results highlight the synergistic effect of OV and electron‐rich Pt sites on the oriented adsorption and selective hydrogenation of LA, providing new insights into constructing more efficient noble metal‐based zeolite catalysts for biomass conversion.

High‐Performance Supported Ru Catalysts for the Aqueous‐Phase Hydrogenation of Levulinic Acid to γ‐Valerolactone

Abstractγ‐Valerolactone (GVL) can be obtained by efficient hydrogenation of levulinic acid using ruthenium‐based catalysts in an aqueous medium. This paper reports an in‐depth study on the activity and selectivity of Ru catalysts supported on zirconia‐alumina, focusing on the effect of Ru concentration (0.5, 1.5 and 3 wt. % of Ru) and the selection of operational reaction variables. The results showed that the activity strongly depends on the number and oxidation state of the supported ruthenium particles. The most active catalyst, Ru3/ZA, presented the highest number of nanometric particles of zerovalent Ru and the highest number of acid sites. This catalyst gave ca. 100 % selectivity towards GVL, at high conversion of levulinic acid (over 99 %) under the best operating conditions evaluated (120 °C, 3 MPa H2 pressure, 1 h of reaction, and 0.1 g of catalyst). In addition, this catalyst kept high levels of conversion and selectivity after successive reuse cycles.

Highly Stable Carbon‐Shell Encapsulated Ni−Cu Bimetallic Catalysts for Efficient Conversion of Levulinic Acid to γ‐Valerolactone

AbstractNon‐noble Ni−Cu alloys serve as an alternative catalytic material for noble metal‐based catalysts that could be applied in the efficient conversion of levulinic acid (LA) into the high value γ‐valerolactone (GVL). However, maintaining the catalytic stability for Ni−Cu nanoparticles in the LA hydrogenation process remains a substantial challenge, Herein, this problem is solved by constructing carbon‐protected catalytic sites within carbon layer‐coated Ni−Cu nanoalloy composite via pyrolysis of NiCux(OH)/glucose precursor. The optimized NiCu0.68@C catalyst exhibits excellent stability and selectivity to GVL (>99 %) in the hydrogenation of LA reaction. Various characterization indicates that the enhancement in stability originates from the protective effect of the carbon layer, which prevents the metal leaching, oxidation and aggregation of Ni−Cu nanoparticles during the reaction process. This work greatly advances non‐noble metal‐catalyzed conversion of LA to GVL and helps the rational design of bimetallic catalysts.

Polymer supported Ru nanoparticles for highly selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone: Does the polymer affect the catalytic performance?

Polymer supported Ru nanoparticles for highly selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone: Does the polymer affect the catalytic performance?

Ferrocene-functionalized zirconium-oxo clusters for achieving high-performance thermocatalytic redox reactions

The Zr(IV) ions are easily hydrolyzed to form oxides, which severely limits the discovery of new structures and applications of Zr-based compounds. In this work, three ferrocene (Fc)-functionalized Zr-oxo clusters (ZrOCs), Zr9Fc6, Zr10Fc6 and Zr12Fc8 were synthesized through inhibiting the hydrolysis of Zr(IV) ions, which show increased nuclearity and regular structural variation. More importantly, these Fc-functionalized ZrOCs were used as heterogeneous catalysts for the transfer hydrogenation of levulinic acid (LA) and phenol oxidation reactions for the first time, and displayed outstanding catalytic activity. In particular, Zr12Fc8 with the largest number of Zr active sites and Fc groups can achieve > 95% yield for LA-to-γ-valerolactone within 4 h (130 °C) and > 98% yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-p-benzoquinone within 30 min (80 °C), showing the best catalytic performance. Catalytic characterization combined with theory calculations reveal that in the Fc-functionalized ZrOCs, the Zr active sites could serve as substrate adsorption sites, while the Fc groups could act as hydrogen transfer reagent or Fenton reagent, and thus achieve effectively intramolecular metal–ligand synergistic catalysis. This work develops functionalized ZrOCs as catalysts for thermal-triggered redox reactions.

Ion-Exchange Synthesis of Surrounded CoNi@Al2O3 Catalyst for Levulinic Acid Hydrogenation to γ-Valerolactone under Mild Conditions

The use of eco-friendly biomass as a resource is an efficient way to address the problems of fossil fuel depletion and climate change. In biomass conversion, versatile γ-valerolactone (GVL) is generally obtained from levulinic acid (LA) hydrogenation via a multimetallic catalyst system. Despite conversion efficiency being enhanced in mild conditions due to metal interactions, maintaining high catalyst stability is still a challenge. In this study, we synthesized a surrounded Co0.52Ni0.48@Al2O3-IE catalyst that exhibited excellent alloying and synergistic interaction between the metal constituents. Under relatively mild reaction conditions, the GVL yield over the catalyst exceeded 99% in LA hydrogenation. The catalyst showed no deactivation in a test of five cycles, displaying superiority in stability, possibly due to reasons of the physical isolation of the shell and the alumina retention on the Co-Ni alloys surface caused by the reversibility of exchange equilibrium. The present work demonstrated that a surrounded structured catalyst fabricated by ion exchange (IE) with active metals physically enclosed can lead to high catalytic activity and superior stability.

Tailoring the Brønsted acidity of Ti-OH species by regulating Pt-TiO2 interaction.

Bifunctional catalysts comprising metal and acid sites are commonly used for many reactions. Interfacial acid sites impact intermediate reactions more than other sites. However, controlling the type and amounts of interfacial acid sites by regulating metal-support interaction (MSI) via traditional methods is difficult. Thus, the influence of MSI on interfacial acid sites remains unclear. We prepared Pt-mTiO2/α-Al2O3 (m represents the cycle number of TiO2) catalysts via atomic layer deposition (ALD). New Brønsted acid sites were generated via Pt-TiO2 interaction, and the acidity was precisely regulated by regulating Pt-TiO2 interaction by changing the TiO2 nanolayer thickness. We chose levulinic acid (LA) hydrogenation as a model reaction. The catalytic activity varied with the TiO2 nanolayer thickness and was linearly correlated with the Ti-OH species (Brønsted acid) content. Pt-40TiO2/α-Al2O3, with the highest acid site content of 0.486 mmol/g, exhibited the best catalytic activity. Hydrogen spillover and water dissociation at the Pt-TiO2 interface promoted Ti-OH species generation.

Tailoring Cu/Hydroxyapatite Catalysts for Selective Hydrogenolysis of Biomass Derived Levulinic Acid to γ-Valerolactone Biofuel Additive

Background: Sustainable synthesis of γ-valerolactone (GVL) from levulinic acid (LA) offers a sustainable approach to converting biomass-derived feedstocks into valuable chemicals and fuel additves. Cu-Hydroxyapatite (Cu-HAp) catalysts are potential candidates for vapor-phase hydrogenation of LA to GVL due to their enhanced catalytic activity and selectivity through Cu nanoparticle support. Objective: This study aimed to investigate the catalytic performance of Cu-HAp catalysts in the hydrogenation of levulinic acid to γ-valerolactone. The primary goal was to optimize reaction conditions and assess the enhanced catalytic activity and selectivity Methods: The influence of copper loading, reaction temperature, and catalyst stability was evaluated. Moreover, the effect of time on stream (TOS) on LA conversion and GVL selectivity was examined by the best optimised Cu/HAp catalyst. Results: Cu-HAp catalysts exhibited favorable catalytic performance, with optimal conditions at approximately 5wt% copper loading. At this loading, maximum LA conversion (60%) and GVL selectivity (90%) were achieved after 8 hours on the stream at 265°C and 0.1 MPa conditions. Conclusion: The study demonstrates the efficacy of Cu-HAp catalysts for the hydrogenation of levulinic acid to γ-valerolactone. The findings indicate that as the copper loading increases from 2 to 20 wt%, the conversion of LA and the selectivity to GVL both decline. The analysis further implies that the dispersion of Cu species corresponds directly to the activity observed during the LA hydrogenation. The conversion of LA rises with a higher reaction temperature ranging from 250-320°C, although the selectivity of GVL decreases above 265°C. The catalyst's stability is crucial for maintaining efficient catalytic activity over time, with observed deactivation attributed to Cu metal particle aggregation and coke formation on active sites. The findings contribute to the development of robust catalyst systems for biomass-derived chemical transformations.

MFI zeolite with confined adjustable synergistic Cu sites for the hydrogenation of levulinic acid

MFI confined Cu zeolites ZKD-5 were synthesized and employed in the selective hydrogenation of levulinic acid. The synergistic catalysis of Cu on different active sites was realized on this catalyst, and the synergistic mechanism was studied.

Mechanism of CO2 in promoting the hydrogenation of levulinic acid to γ-valerolactone catalyzed by RuCl3 in aqueous solution.

A Ru-containing complex shows good catalytic performance toward the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) with the assistance of organic base ligands (OBLs) and CO2. Herein, we report the competitive mechanisms for the hydrogenation of LA to GVL, 4-oxopentanal (OT), and 2-methyltetrahydro-2,5-furandiol (MFD) with HCOOH or H2 as the H source catalyzed by RuCl3 in aqueous solution at the M06/def2-TZVP, 6-311++G(d,p) theoretical level. Kinetically, the hydrodehydration of LA to GVL is predominant, with OT and MFD as side products. With HCOOH as the H source, initially, the OBL (triethylamine, pyridine, or triphenylphosphine) is responsible for capturing H+ from HCOOH, leading to HCOO- and [HL]+. Next, the Ru3+ site is in charge of sieving H- from HCOO-, yielding [RuH]2+ hydride and CO2. Alternatively, with H2 as the H source, the OBL stimulates the heterolysis of H-H bond with the aid of Ru3+ active species, producing [RuH]2+ and [HL]+. Toward the [RuH]2+ formation, H2 as the H source exhibits higher activity than HCOOH as the H source in the presence of an OBL. Thereafter, H- in [RuH]2+ gets transferred to the unsaturated C site of ketone carbonyl in LA. Afterwards, the Ru3+ active species is capable of cleaving the C-OH bond in 4-hydroxyvaleric acid, yielding [RuOH]2+ hydroxide and GVL. Subsequently, CO2 promotes Ru-OH bond cleavage in [RuOH]2+, forming HCO3- and regenerating the Ru3+-active species owing to its Lewis acidity. Lastly, between the resultant HCO3- and [HL]+, a neutralization reaction occurs, generating H2O, CO2, and OBLs. Thus, the present study provides insights into the promotive roles of additives such as CO2 and OBLs in Ru-catalyzed hydrogenation.

Structure sensitivity of Cu supported on manganese oxide catalysts in levulinic acid hydrogenation

Different synthesis methods were used to prepare a series of size-controlled copper nanoparticles supported on manganese oxide octahedral molecular sieves (OMS-2) catalysts.

Catalytic hydrogenation of levulinic acid for the preparation of γ-valerolactone using CuAgZrO2–graphene nanocomposites

The CuAgZrGO catalyst was synthesized by regulating the pH of the precipitation system to achieve a one-pot layered assembly of Zr4+, Cu2+, and Ag+ components on the graphene oxide (GO) surface.

An Overview of Heterogeneous Catalysts Based on Hypercrosslinked Polystyrene for the Synthesis and Transformation of Platform Chemicals Derived from Biomass.

Platform chemicals, also known as chemical building blocks, are substances that serve as starting materials for the synthesis of various value-added products, which find a wide range of applications. These chemicals are the key ingredients for many fine and specialty chemicals. Most of the transformations of platform chemicals are catalytic processes, which should meet the requirements of sustainable chemistry: to be not toxic for humans, to be safe for the environment, and to allow multiple reuses of catalytic materials. This paper presents an overview of a new class of heterogeneous catalysts based on nanoparticles of catalytically active metals stabilized by a polymer matrix of hypercrosslinked polystyrene (HPS). This polymeric support is characterized by hierarchical porosity (including meso- and macropores along with micropores), which is important both for the formation of metal nanoparticles and for efficient mass transfer of reactants. The influence of key parameters such as the morphology of nanoparticles (bimetallic versus monometallic) and the presence of functional groups in the polymer matrix on the catalytic properties is considered. Emphasis is placed on the use of this class of heterogeneous catalysts for the conversion of plant polysaccharides into polyols (sorbitol, mannitol, and glycols), hydrogenation of levulinic acid, furfural, oxidation of disaccharides, and some other reactions that might be useful for large-scale industrial processes that aim to be sustainable. Some challenges related to the use of HPS-based catalysts are addressed and multiple perspectives are discussed.