Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Albani, Davide; Li, Qiang; Vilé, Gianvito; Mitchell, Sharon; Almora‐Barrios, Neyvis; Witte, Peter T.; López, Núria; Pérez‐Ramírez, Javier

doi:10.1039/c6gc02586b

Cited by 59 publications

(47 citation statements)

References 68 publications

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“…Meijboom and colleagues obtained mesoporous supported dendrimers to immobilize Ru and Pt nanopartciels (<2 nm) and achieved 100 % selectivity towards GVL . Albani and coworkers used hexadecyl (2‐hydroxyethyl) dimethylammonium dihydrogen phosphate (HHDMA) to modify surface properties of titanium silicate support (entry#10 in Table ) . While experimental studies confirmed that HHDMA modified Ru catalyst (∼400 h −1 at 130 °C and 1.0 MPa) shows improved activity and stability compared with Ru/C catalyst (∼200 h −1 ), theoretical simulation suggested that H 2 dissociation shows lower activation barrier and is exothermic at the Ru‐HHDMA interface.…”

Section: Figurementioning

confidence: 99%

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Jin

Fang

Wang

et al. 2018

The Chemical Record

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Conversion of biomass to chemicals provides essential products to human society from renewable resources. In this context, achieving atom‐economical and energy‐efficient conversion with high selectivity towards target products remains a key challenge. Recent developments in nanostructured catalysts address this challenge reporting remarkable performances in shape and morphology dependent catalysis by metals on nano scale in energy and environmental applications. In this review, most recent advances in synthesis of heterogeneous nanomaterials, surface characterization and catalytic performances for hydrogenation and oxidation for biorenewables with plausible mechanism have been discussed. The perspectives obtained from this review paper will provide insights into rational design of active, selective and stable catalytic materials for sustainable production of value‐added chemicals from biomass resources.

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Section: Figurementioning

confidence: 99%

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Jin

Fang

Wang

et al. 2018

The Chemical Record

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“…Theover-hydrogenation and decomposition pathways are favored over Pd(111) compared to the formation of H 2 O 2 ( Figure S1). Other hydrogenation pathways,involving the protonation of adsorbed species due to interfacial acidity, [14] are likely not taking place if the low energy barriers for H 2 dissociation and OOH formation are considered. Notably,t he presence of the ligand increases the activation energy of the two side reactions.F urthermore,w ater formation attributed to O 2 dissociation is only feasible on the naked Pd surface,w hile it is thermodynamically impeded on the Pd(111)-HHDMA surface (Table S3).…”

Section: Angewandte Chemiementioning

confidence: 99%

Hybrid Palladium Nanoparticles for Direct Hydrogen Peroxide Synthesis: The Key Role of the Ligand

et al. 2016

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Ligand-modified palladium nanoparticles deposited on ac arbon carrier efficiently catalyze the direct synthesis of H 2 O 2 and the unique performance is due to their hybrid nanostructure.Catalytic testing demonstrated that the selectivity increases with the HHDMA ligand content from 10 %f or naked nanoparticles up to 80 %, rivalling that obtained with state-of-the-art bimetallic catalysts (HHDMA = C 20 H 46 NO 5 P). Furthermore,i tr emains stable over five consecutive reaction runs owingt ot he high resistance towards leaching of the organic moiety,arising from its bond with the metal surface.As rationalized by density functional theory,t his behavior is attributed to the adsorption mode of the reaction intermediates on the metal surface.Whereas they lie flat in the absence of the organic shell, their electrostatic interaction with the ligand result in aunique vertical configuration which prevents further dissociation and over-hydrogenation. These findings demonstrate the importance of understanding substrate-ligand interactions in capped nanoparticles to develop smart catalysts for the sustainable manufacture of hydrogen peroxide.Hydrogen peroxide,H 2 O 2 ,a ttracts growing attention as ag reen alternative to traditional stoichiometric oxidants in awide range of applications within the textile,pulp bleaching, waste water treatment, metallurgy,c osmetic,a nd pharmaceutical industries.Owing to the advantages of its use,that is, the high atom economy and the generation of water as the only byproduct, [1] an increase of its global market value from 3.7 to 6.0 billion USD between 2014 and 2023 is forecasted. [2] Nowadays,t he production of H 2 O 2 relies exclusively on the anthraquinone process,which, despite being safe and suitable for continuous operation, involves the use of quinones and solvents resulting in energy-intensive purification steps and the generation of high amounts of waste,t hus being competitive only at large scale. [1,3] Thedirect synthesis of H 2 O 2 is an appealing alternative that has the potential to be exploited in decentralized plants at any scale due to the 1) absence of organic substrates,2 )use of green solvents such as water or methanol, and 3) simplified purification. [1,4] Its applicability has been widely investigated as such or in tandem with selective oxidation reactions using heterogeneous or, seldom, homogeneous catalysts. [5] Albeit the number of advantages over the traditional route,i ts industrial implementation has been hindered by the limited selectivity of the most active catalyst identified, that is,s upported Pd nanoparticles (NPs). [6] Indeed, besides facilitating the reaction between molecularly adsorbed O 2 and Ha toms,P dN Ps favor O 2 dissociation leading to undesired water formation (Scheme 1). [7] To overcome this limitation, the addition of asecond metal, chiefly Au or Sn, which was shown to generate active sites that prevent O À Ob ond cleavage,r esulted in the most selective catalysts reported to date. [8] Still, the added loading of costly and/or toxic metals h...

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“…In particular, lignocellulosic biomass, consisting of cellulose, hemicellulose, and lignin fractions, represents one of the most abundant and economical starting materials . The use of lignocellulosic biomass as a substrate for the efficient production of building blocks such as levulinic acid, γ‐valerolactone (GVL), 5‐hydroxymethylfuran (HMF), and dimethyl furan (DMF) has already been demonstrated on a laboratory scale . Among these, GVL, which is produced through the hydrodeoxygenation of lignocellulosic biomass, exhibits excellent solvent properties and is one of the main precursors in the synthesis of high‐value fine chemicals and polymers such as pentenoic acid, valeric acid, and α‐methylene‐γ‐valerolactone (MeGVL) .…”

Section: Introductionmentioning

confidence: 99%

“…[1] The use of lignocellulosic biomass as as ubstrate for the efficient production of building blocks such as levulinic acid, g-valerolactone (GVL),5 -hydroxymethylfuran (HMF), and dimethyl furan (DMF)h as already been demonstrated on al aboratorys cale. [4,[8][9][10][11][12][13] Among these, GVL, which is produced through the hydrodeoxygenation of lignocellulosic biomass,e xhibitse xcellent solventp roperties and is one of the main precursors in the synthesis of high-value fine chemicals and polymers such as pentenoic acid, valeric acid, and a-methylene-g-valerolactone (MeGVL). [1,4,14,15] In this regard, MeGVL is at ype of methacrylic monomerw itht he potential tos ubstitute the fossil-based methyl methacrylate (MMA),am onomer produced on al arge scale for the productiono fp oly(methyl methacrylate), the latter having numerous applicationsi nt he automotive, electronics, and medical sectors.…”

Section: Introductionmentioning

confidence: 99%

Sustainable Continuous Flow Valorization of γ‐Valerolactone with Trioxane to α‐Methylene‐γ‐Valerolactone over Basic Beta Zeolites

et al. 2019

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The need for more sustainable products and processes has led to the use of new methodologies with low carbon footprints. In this work, an efficient tandem process is demonstrated for the liquid‐phase catalytic upgrading of lignocellulosic biomass‐derived γ‐valerolactone (GVL) with trioxane (Tx) to α‐methylene‐γ‐valerolactone (MeGVL) in flow system using Cs‐loaded hierarchical beta zeolites. The introduction of mesopores along with the presence of basic sites of mild strength leads to MeGVL productivity 20 times higher than with the bulk beta zeolite, reaching 0.325 mmol min−1 gcat−1 for the best‐performing catalyst, the highest value reported so far. This catalyst proves stable upon reuse in consecutive cycles, which is ascribed to the partial depletion of the basic sites. The obtained MeGVL is subjected to visible‐light‐induced polymerization, resulting in a final material with similar properties to the widely used poly(methyl) methacrylate.

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Interfacial acidity in ligand-modified ruthenium nanoparticles boosts the hydrogenation of levulinic acid to gamma-valerolactone

Cited by 59 publications

References 68 publications

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Hybrid Palladium Nanoparticles for Direct Hydrogen Peroxide Synthesis: The Key Role of the Ligand

Sustainable Continuous Flow Valorization of γ‐Valerolactone with Trioxane to α‐Methylene‐γ‐Valerolactone over Basic Beta Zeolites

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