Efficient transformation of biomass to value-added chemicals and high-energy density fuels is pivotal for a more sustainable economy and carbon-neutral society. In this framework, developing potential cascade chemical processes using functionalised heterogeneous catalysts is essential because of their versatile roles towards viable biomass valorisation. Advances in materials science and catalysis have provided several innovative strategies for the design of new appealing catalytic materials with well-defined structures and special characteristics. Promising catalytic materials that have paved the way for exciting scientific breakthroughs in biomass upgrading are carbon materials, metal-organic frameworks, solid phase ionic liquids, and magnetic iron oxides. These fascinating catalysts offer unique possibilities to accommodate adequate amounts of acid-base and redox functional species, hence enabling various biomass conversion reactions in a one-pot way. This review therefore aims to provide a comprehensive account of the most significant advances in the development of functionalised heterogeneous catalysts for efficient biomass upgrading. In addition, this review highlights important progress ensued in tailoring the immobilisation of desirable functional groups on particular sites of the above-listed materials, while critically discussing the role of consequent properties on cascade reactions as well as on other vital processes within the bio-refinery. Current challenges and future opportunities towards a rational design of novel functionalised heterogeneous catalysts for sustainable biomass valorisation are also emphasized.

Metal nanoparticles (NPs) from colloidal synthesis are advantageous in fundamental catalysis research because of their precisely controlled size and morphology but unfortunately are usually contaminated with residues from the organic stabilizer essentially required in the synthesis. These residues could modify the surface property and disturb the catalysis intrinsic to "clean" NPs. Herein, polyvinylpyrrolidone (PVP)-stabilized Au NPs (4.7 ± 1.0 nm) from colloidal synthesis were immobilized on SiO 2 support and subjected to ultraviolet-ozone (UVO) treatment to remove the residues. Hydrogenation reactions of p-chloronitrobenzene (p-CNB) and cinnamaldehyde (CAL) were conducted to probe consequences of the stabilizer removal on the catalytic properties of Au NPs. Measurements by FTIR and XPS revealed a controlled removal and degradation of PVP according to the UVO-treatment duration. Careful HRTEM analysis disclosed that both the size and morphology of Au NPs remained unchanged after the UVO-treatment. Residual PVP significantly improved the activity of Au NPs for p-CNB hydrogenation but lowered the activity for CAL hydrogenation. Continued selectivity changes of CAL hydrogenation to favor the reaction at the CC bond were observed on increasing the removal degree of the residues. The UVO-cleaned Au NPs were also "restabilized" with PVP and other stabilizers by adsorption in aqueous solution. Comparison of the catalytic properties of these Au NPs involving different stabilizers with those of the UVO-cleaned ones enabled a comprehension of the stabilizer impacts on the hydrogenation catalysis of Au NPs.

A physical phenomenon has been found: in a structure of nanometal film with dielectric-medium loading, the surface polaritons excited by a uniformly moving electron bunch can be transformed into Cherenkov radiation with intensity enhancement in the medium. Based on this mechanism, the surface polariton Cherenkov light radiation source is presented and explored in the Letter. The results show that surface polariton Cherenkov light radiation source can generate radiation, from visible light to the ultraviolet frequency regime and the radiation power density can reach or even exceed 10(8) W/cm(2) depending on the beam energy and current density. It is a tunable and miniature light radiation source promising to be integrated on a chip and built into a light radiation source array.

The correlation between the structural characteristics and the wetting of anodized aluminum oxide (AAO) surfaces with large pore sizes (>100 nm) is discussed. The roughness-induced wettability is systematically examined for oxide films grown by a two-step, high-field anodization in phosphoric acid of three different concentrations using a commercial aluminum alloy. This is done for the as-synthesized AAO layers, after various degrees of pore widening by a wet chemical etching in phosphoric acid solution, and upon surface modification by either Lauric acid or a silane. The as-grown AAO films feature structurally disordered pore architectures with average pore openings in the range 140-190 nm but with similar interpore distances of about 405 nm. The formation of such AAO structures induces a transition from slightly hydrophilic to moderately hydrophobic surfaces up to film thicknesses of about 6 μm. Increased hydrophobicity is obtained by pore opening and a maximum value of the water contact angle (WCA) of about 128° is measured for AAO arrays with a surface porosity close to 60%. Higher surface porosity by prolonged wet chemical etching leads to a rapid decrease in the WCA as a result of the limited pore wall thickness and partial collapse of the dead-end pore structures. Modification of the AAO surfaces by Lauric acid results in 5-30° higher WCA's, whereas near-superhydrophobicity (WCA ~146°) is realized through silane coating. The "rose petal effect" of strongly hydrophobic wetting with high adhesive force on the produced AAO surfaces is explained by a partial penetration of water through capillary action into the dead-end pore cavities which leads to a wetting state in-between the Wenzel and Cassie states. Moreover, practical guidelines for the synthesis of rough, highly porous AAO structures with controlled wettability are provided and the possibility of forming superhydrophobic surfaces is evaluated.

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Although surface plasmon polaritons (SPPs) resonance in graphene can be tuned in the terahertz regime, transforming such SPPs into coherent terahertz radiation has not been achieved. Here, we propose a graphene-based coherent terahertz radiation source with greatly enhanced intensity. The radiation works at room temperature, it is tunable and can cover the whole terahertz regime. The radiation intensity generated with this method is 400 times stronger than that from SPPs at a conventional dielectric or semiconducting surface and is comparable to that from the most advanced photonics source such as a quantum cascade laser. The physical mechanism for this strong radiation is presented. The phase diagrams defining the parameters range for the occurrence of radiation is also shown.

Adding a small amount of fully dispersed Pt entities onto the Au surface in Au/SiO(2) catalyst is found to be an efficient approach to improve the catalytic activity of Au (up to 70-fold) for the hydrogenation of α,β-unsaturated carbonyl compounds, without alternating its selectivity towards C=O or C=C bond hydrogenation.

This contribution studies the steam-assisted dealkylation of 4-npropylphenol (4-n-PP), one of the major products derived from lignin, into phenol and propylene over several micro-and mesoporous acidic aluminosilicates in gas phase. A series of acidic zeolites with different topology (e.g., FER, TON, MFI, BEA, and FAU) are studied, of which ZSM-5 outperforms the others. The catalytic results, including zeolite topology and water stability effects, are rationalized in terms of thermodynamics and kinetics. A reaction mechanism is proposed by (i) analyzing products distribution under varying temperature and contact time conditions, (ii) investigating the dealkylation of different regio-and geometric isomers of propylphenol, and (iii) studying the reverse alkylation of phenol and propylene. The mechanism accords to the classic carbenium chemistry including isomerization, disproportionation, transalkylation, and dealkylation, as the most important reactions. The exceptional selectivity of ZSM-5 is attributed to a pore confinement, avoiding disproportionation/transalkylation as a result of a transition state shape selectivity. The presence of water maintains a surprisingly stable catalysis, especially for ZSM-5 with low acid density. The working hypothesis of this stabilization is that water precludes diphenyl ether(s) formation in the pores by reducing the lifetime of the phenolics at the active site due to the high heat of adsorption of water on H-ZSM-5, besides counteracting the equilibrium of the phenolics condensation reaction. The water effect is unique for the combination of (alkyl)phenols and ZSM-5.