Sabine Valange

Heterogeneous catalytic oxidation for lignin valorization into valuable chemicals: what results? What limitations? What trends?

Lignin, a renewable polymer derived from the lignocellulosic biomass represents more than 20% of the total mass of the Earths biosphere. However, 98% of lignin is burned as a source of energy in the pulp and paper industry, essentially due to its complex structure. Today, the valorization of lignin into the production of value-added chemicals represents a real challenge in terms of both sustainability and environmental protection. The present contribution aims to provide a critical discussion on the crucial choice of the starting material to study lignin valorization. Next, a comparison between the different oxidation routes investigated by chemists over the past several years is presented, with emphasis on the major difficulties encountered. The main current challenges regarding the heterogeneous catalytic oxidation of lignin and its derivatives are also highlighted. Particular focus is given to innovative strategies favoring mild reaction conditions. Finally, we provide some recommendations and routes worthy of interest in this studied area of research in order to generate value-added chemicals from lignin oxidation through the use of heterogeneous catalysts.

Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: Response surface approach, degradation pathway, and toxicity evaluation

A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5g/L and hydrogen peroxide concentration of 13.5mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150min reaction, indicating that the effluent was suitable for sequential biological treatment.

Properties of iron-based mesoporous silica for the CWPO of phenol: a comparison between impregnation and co-condensation routes.

Iron-based mesoporous silica materials were prepared according to different impregnation and co-condensation procedures. Several complementary techniques, including XRD, TEM/EDX and nitrogen sorption isotherms were used to evaluate the final structural and textural properties of the calcined Fe/SBA-15 materials. While Fe(2)O(3) isolated particles of which the size is close to the silica pore diameter ( approximately 7-8 nm) were obtained using classical wet impregnation procedure, smaller iron oxide particles ( approximately 2-4 nm) homogeneously dispersed within the hexagonal pore structure of the SBA15 host support were generated by self-combustion of an impregnated iron-glycinic complex. By contrast, the various co-condensation routes used in this work were less efficient to generate iron oxide nanoparticles inside the silica mesopores. Catalytic performances of the materials were evaluated in the case of total phenol oxidation by H(2)O(2) in aqueous solution at ambient conditions. Large differences in terms of catalytic activity and iron species stability were observed. While the impregnated solids proved to be the most active catalysts (highest Fe(2)O(3) nanoparticles dispersion), iron leaching was observed in aqueous solution, accounting for a homogeneous catalytic contribution. In contrast, the co-condensed samples exhibiting larger iron oxide clusters stabilized over the silica surface proved more efficient as active sites in Fenton catalysis.

Tuning the hydrophobicity of mesoporous silica materials for the adsorption of organic pollutant in aqueous solution

The ability of various as-prepared and organically modified MCM-41 and HMS mesoporous silica materials to behave as efficient adsorbents for organic pollutants in aqueous solution was investigated by using different surface functionalization procedures, so as to adjust their hydrophilic/hydrophobic balance. The hydrophilic and organophilic properties of the parent silica materials and their corresponding surface functionalized counterparts were studied by using water and toluene adsorption isotherms. Their quantification was determined by the hydrophobic static index value (HI(static)), as well as by the silanol and organic group densities after the functionalization step. A clear correlation could be found between the HI(static) values and either the superficial silanol density, or the amount of organic moieties grafted or incorporated to the silica materials. For the highly organically functionalized samples, the residual superficial silanol groups (<50%) are sufficiently isolated from each other so as to prevent the water capillary condensation within the pores, thereby leading to an increased hydrophobic character of the resulting mesoporous silica. Those hydrophobic samples, for which the water liquid meniscus formation within the mesopores was minimized or avoided, exhibited a storage capacity for an organic pollutant (N,N-diethyl-m-toluamide, DEET) in aqueous solution more than 20 times higher than that of the corresponding unmodified sample, independently of the silica nature (MCM-41 or HMS). For all calcined and silylated samples, the DEET maximum adsorption capacities determined by the Langmuir model could be correlated with the silica surface coverage by trimethylsilyl groups and thus with the remaining silanol amount.

Binary Cu–Al mesophases precursors to uniformly sized copper particles highly dispersed on mesoporous alumina

Abstract A series of binary Cu–Al mesoporous precursors have been prepared by direct synthesis using “catanionic” (mixed cationic and anionic) surfactants. The as-synthesized materials, involving a mesotructured framework composed of minor Cu hydroxynitrate domains overdispersed within the major alumina based mesophase, yielded through controlled calcination and reduction, Cu 0 particles of variable size, well dispersed and quite strongly attached on the alumina support. In each calcined sample, combined transmission electron microscopy and energy dispersive X-ray analyses revealed the presence of both very small, nanometer sized, CuO particles and of larger CuO domains, the size of which depends on the initial copper amount. The fact that each Cu hydroxynitrate domain in the as-synthesized sample yields, upon calcination and subsequent reduction, respectively the corresponding CuO domains and Cu 0 particles of about the same size and similar dispersion, reflects the regular pre-dispersion of the Cu islands during the very first synthesis stages. The (Cu,Al) mesoporous samples have been tested as catalysts for selective hydrogenation of cinnamaldehyde (CNA) and compared to classical Cu-impregnated alumina catalysts. The remarkable selectivity of the (Cu,Al) mesoporous samples towards the formation of unsaturated alcohol (hydrogenation of the carbonyl group of CNA) was attributed to the particular strong interaction of the nanometer sized Cu 0 “islets” with the Al mesoporous walls, while the conjugated CC bond is more readily hydrogenated on larger Cu 0 clusters in weaker interaction with the support.

Stability against color fading of azo dyes encapsulated in Ca-aluminosilicate mesoporous substrates

Abstract Light-fastness properties of composites involving mesoporous calcium-modified aluminosilicate substrates (MCM-41 structure) and dye (Lithol Rubine B) were examined. High surface area Al-MCM-41 materials synthesized in the presence of Ca 2+ ions proved efficient hosts for Lithol Rubine B, yielding mesophase–dye composites with the highest light-fastness qualities, when compared to Ca-exchanged Al-MCM-41 aluminosilicates, to non composite pigment or to smectite–dye composites. The marked resistance of the new composites to fading was attributed to an optimized Ca–dye interaction favored by a controlled heating the Ca(OH) 2 -loaded mesoporous precursors, yielding tiny CaO particles, highly dispersed and retained onto the large internal surface of the substrate.

Evaluation of heterogeneous photo-Fenton oxidation of Orange II using response surface methodology.

A mesoporous SBA-15 doped iron oxide (Fe2O3/SBA-15) was synthesized by co-condensation, characterized and used as heterogeneous catalysts for the photo-Fenton decolorization of azo dye Orange II under UV irradiation. Response surface methodology (RSM) was used to investigate operating condition effects, such as hydrogen peroxide concentration, initial pH and catalyst loadings, on the decolorization rate. UV irradiation is found to enhance the activity of the catalyst in the process. RSM analysis evidenced the influence of the initial pH value and H2O2 concentration on the dye degradation rate. The coupled UV/Fe2O3/SBA-15/H2O2 process at room temperature is revealed as a promising friendly process for wastewater treatment. Indeed, the use of a heterogeneous catalyst allows an easy active phase recycling without multi-step recovering while the heterogeneous catalyst used here exhibits high catalytic activity for the reaction considered.

Al-MCM-41 systems exchanged with alkali–metal cations: FT-IR characterization and catalytic activity towards 1-butene isomerization

Abstract Starting from an as-synthesized Na-bearing MCM-41 sample with Si/Al=20, several Cs or K exchanged samples have been obtained. All samples, both washed after exchange to remove the excess alkali–metal salt and unwashed, were characterized by studying in the IR the adsorption of CO at a nominal temperature of 77 K, and of CO 2 at room temperature. On unwashed samples, after thermal treatment at 500 °C, a basic alkali-oxide phase and a surface silicate were detected. In contrast, washed samples did not exhibit basic character and only Lewis acidic cationic centers were detected, the strength of which is close to that of alkali-cation exchanged ZSM-5 systems. Unwashed samples were inactive in the isomerization of 1-butene. Washed samples converted 1-butene to cis/trans -2-butene, with a ratio close to one (the presence of isobutene was negligible), as typical of mildly acidic Bronsted centers, which are probably present even after exchange: indeed, a sample of Al-MCM-41 in the protonic form, tested as reference, gave the same reaction with highest activity.

Sonochemical oxidation of vanillyl alcohol to vanillin in the presence of a cobalt oxide catalyst under mild conditions

The heterogeneous oxidation of vanillyl alcohol to vanillin was investigated on new grounds under eco-friendly conditions in the presence of hydrogen peroxide as an oxidant and water as solvent, coupled with low frequency ultrasonic irradiation. The sono-Fenton-like-assisted vanillyl alcohol oxidation was performed with a high-surface area nanostructured spinel cobalt oxide catalyst exhibiting small crystallites size. The catalytic reaction was also carried out under conventional heating conditions for comparison purposes. The influence of the reaction parameters, namely catalyst loading and hydrogen peroxide concentration was studied with the aim of determining the optimum yield and selectivity to the desired vanillin product. The chemical effects of ultrasound (ability to generate hydroxyl radicals) along with increased mass transfer appeared to be key prerequisites for enhancing the efficiency of the process, while decreasing the overall energy consumption.

A Combined Approach using Sonochemistry and Photocatalysis: How to Apply Sonophotocatalysis for Biomass Conversion?

The innovative combination of sonochemistry (power ultrasound) and photocatalysis (UV light) has been extensively investigated in the literature, especially as an advanced oxidation process. Based on these results but with a completely different strategy, the sonophotocatalysis starts to be applied to organic reactions and could represent an innovative way to valorize biomass into fuels or platform molecules. This article discusses this opportunity and proposes some trends and outlooks for further researches in the area.