In pursuit of more sustainable and competitive biorefineries, the effective valorisation of lignin is key. An alluring opportunity is the exploitation of lignin as a resource for chemicals. Three technological biorefinery aspects will determine the realisation of a successful lignin-to-chemicals valorisation chain, namely (i) lignocellulose fractionation, (ii) lignin depolymerisation, and (iii) upgrading towards targeted chemicals. This review provides a summary and perspective of the extensive research that has been devoted to each of these three interconnected biorefinery aspects, ranging from industrially well-established techniques to the latest cutting edge innovations. To navigate the reader through the overwhelming collection of literature on each topic, distinct strategies/topics were delineated and summarised in comprehensive overview figures. Upon closer inspection, conceptual principles arise that rationalise the success of certain methodologies, and more importantly, can guide future research to further expand the portfolio of promising technologies. When targeting chemicals, a key objective during the fractionation and depolymerisation stage is to minimise lignin condensation (i.e. formation of resistive carbon–carbon linkages). During fractionation, this can be achieved by either (i) preserving the (native) lignin structure or (ii) by tolerating depolymerisation of the lignin polymer but preventing condensation through chemical quenching or physical removal of reactive intermediates. The latter strategy is also commonly applied in the lignin depolymerisation stage, while an alternative approach is to augment the relative rate of depolymerisation vs. condensation by enhancing the reactivity of the lignin structure towards depolymerisation. Finally, because depolymerised lignins often consist of a complex mixture of various compounds, upgrading of the raw product mixture through convergent transformations embodies a promising approach to decrease the complexity. This particular upgrading approach is termed funneling, and includes both chemocatalytic and biological strategies.

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Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading

This review surveys recent advances in the applications of layered double hydroxides (LDHs) in heterogeneous catalysis. By virtue of the flexible tunability and uniform distribution of metal cations in the brucite-like layers and the facile exchangeability of intercalated anions, LDHs-both as directly prepared or after thermal treatment and/or reduction-have found many applications as stable and recyclable heterogeneous catalysts or catalyst supports for a variety of reactions with high industrial and academic importance. A major challenge in this rapidly growing field is to simultaneously improve the activity, selectivity and stability of these LDH-based materials by developing ways of tailoring the electronic structure of the catalysts and supports. Therefore, this Review article is mainly focused on the most recent developments in smart design strategies for LDH materials and the potential catalytic applications of the resulting materials.

Catalytic applications of layered double hydroxides: recent advances and perspectives

Carbon-based nanomaterials have been widely used as catalysts or catalyst supports in the chemical industry or for energy or environmental applications due to their fascinating properties. High surface areas, tunable porosity, and functionalization are considered to be crucial to enhance the catalytic performance of carbon-based materials. Recently, the newly emerging metal–organic frameworks (MOFs) built from metal ions and polyfunctional organic ligands have proved to be promising self-sacrificing templates and precursors for preparing various carbon-based nanomaterials, benefiting from their high BET surface areas, abundant metal/organic species, large pore volumes, and extraordinary tunability of structures and compositions. In comparison with other carbon-based catalysts, MOF-derived carbon-based nanomaterials have great advantages in terms of tailorable morphologies and hierarchical porosity and easy functionalization with other heteroatoms and metal/metal oxides, which make them highly efficient as...

Development of MOF-Derived Carbon-Based Nanomaterials for Efficient Catalysis

Core–shell nanoparticles (CSNs) are a class of nanostructured materials that have recently received increased attention owing to their interesting properties and broad range of applications in catalysis, biology, materials chemistry and sensors. By rationally tuning the cores as well as the shells of such materials, a range of core–shell nanoparticles can be produced with tailorable properties that can play important roles in various catalytic processes and offer sustainable solutions to current energy problems. Various synthetic methods for preparing different classes of CSNs, including the Stober method, solvothermal method, one-pot synthetic method involving surfactants, etc., are briefly mentioned here. The roles of various classes of CSNs are exemplified for both catalytic and electrocatalytic applications, including oxidation, reduction, coupling reactions, etc.

Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis

Ethylene glycol (EG) is an important organic compound and chemical intermediate used in a large number of industrial processes (e.g. energy, plastics, automobiles, and chemicals). Indeed, owing to its unique properties and versatile commercial applications, a variety of chemical systems (e.g., catalytic and non-catalytic) have been explored for the synthesis of EG, particularly via reaction processes derived from fossil fuels (e.g., petroleum, natural gas, and coal) and biomass-based resources. This critical review describes a broad spectrum of properties of EG and significant advances in the prevalent synthesis and applications of EG, with emphases on the catalytic reactivity and reaction mechanisms of the main synthetic methodologies and applied strategies. We also provide an overview regarding the challenges and opportunities for future research associated with EG.

Ethylene glycol: properties, synthesis, and applications

Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal–support interaction were discussed. A second approach—the promotion in the mobility of the surface oxygen—is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design of other types of heterogeneous base-metal catalysts for high temperature processes including methanation, dry reforming, and hydrocarbon combustion.

Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions

This paper describes an investigation on understanding catalytic consequences of Pt nanoparticles supported on a TiO2–Al2O3 binary oxide for propane dehydrogenation (PDH). The TiO2–Al2O3 supports were synthesized by a sol–gel method, and the Pt/TiO2–Al2O3 catalysts were prepared by an incipient wetness impregnation method. Both as-prepared and post-experiment catalysts were characterized employing N2 adsorption–desorption, X-ray diffraction, Raman spectra, H2–O2 titration, temperature-programmed desorption, thermogravimetric analysis, temperature-programmed oxidation, transmission electron microscopy, and Fourier-transform infrared spectra of chemisorbed CO. We have shown that TiO2 is highly dispersed on Al2O3, and the addition of appropriate amount of TiO2 improves propylene selectivity and catalytic stability, which is ascribed to the electron transfer from partially reduced TiOx (x < 2) to Pt atoms. The increased electron density of Pt could reduce the adsorption of propylene and facilitate the migrati...

Propane Dehydrogenation over Pt/TiO2-Al2O3 Catalysts

This paper describes an investigation of the promotional effect of Cu on the catalytic performance of Pt/Al2O3 catalysts for propane dehydrogenation. We have shown that Pt/Al2O3 catalysts possess higher propylene selectivity and lower deactivation rate as well as enhanced anti-coking ability upon Cu addition. The optimized loading content of Cu is 0.5 wt%, which increases the propylene selectivity to 90.8% with a propylene yield of 36.5%. The origin of the enhanced catalytic performance and anti-coking ability of the Pt–Cu/Al2O3 catalyst is ascribed to the intimate interaction between Pt and Cu, which is confirmed by the change of particle morphology and atomic electronic environment of the catalyst. The Pt–Cu interaction inhibits propylene adsorption and elevates the energy barrier of C–C bond rupture. The inhibited propylene adsorption diminishes the possibility of coke formation and suppresses the cracking reaction towards the formation of lighter hydrocarbons on Pt–Cu/Al2O3, while a higher energy barrier for C–C bond cleavage suppresses the methane formation.

Propane dehydrogenation over Pt–Cu bimetallic catalysts: the nature of coke deposition and the role of copper

This paper describes the sorption of carbon dioxide for enhanced steam reforming of ethanol to produce hydrogen via Ni–CaO–Al2O3 multifunctional catalysts derived from hydrotalcite-like compounds (HTlcs). The catalysts were characterized by N2 adsorption–desorption, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and thermogravimetric analysis (TGA) and tested in sorption enhanced steam reforming of ethanol (SESRE), in which products were monitored by an online mass spectrometer (MS). The Ni–CaO–Al2O3 catalysts possess uniform distribution of Ni, Ca and Al, contributing significantly to the excellent CO2 adsorbent capacity and reforming activity in SESRE. We have also examined the effect of Ca/Al ratios on Ni dispersion, CaO particle size, and catalytic reactivity; a Ca/Al of 3.0 was optimized. The Ni–CaO–Al2O3 catalysts outperform the conventional mixture of CaO adsorbents and Ni/Al2O3 catalysts for SESRE.

Sorption enhanced steam reforming of ethanol on Ni–CaO–Al2O3 multifunctional catalysts derived from hydrotalcite-like compounds

This paper describes an investigation regarding the influence of Ni precursors on catalytic performances of Ni/Al2O3 catalysts in glycerol steam reforming. A series of Ni/Al2O3 is synthesized using four different precursors, nickel nitrate, nickel chloride, nickel acetate, and nickel acetylacetonate. Characterization results based on N2 adsorption–desorption, X-ray diffraction, H2 temperature-programmed reduction, H2 chemisorption, transmission electron microscopy, and thermogravimetric analysis show that reduction degrees of nickel, nickel dispersion, and particle sizes of Ni/Al2O3 catalysts are closely dependent on the anion size and nature of the nickel precursors. Ni/Al2O3 prepared by nickel acetate possesses the moderate Ni reduction degree, high Ni dispersion, and small nickel particle size, which possesses the highest H2 yield. Reaction parameters are also examined, and 550 °C and a steam-to-carbon ratio of 3 are optimized. Moreover, coke deposition, mainly graphite species, leads to the deactivati...

Shuirong Li

Papers

Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions

Propane Dehydrogenation over Pt/TiO2-Al2O3 Catalysts

Propane dehydrogenation over Pt–Cu bimetallic catalysts: the nature of coke deposition and the role of copper

Sorption enhanced steam reforming of ethanol on Ni–CaO–Al2O3 multifunctional catalysts derived from hydrotalcite-like compounds

Hydrogen Production via Glycerol Steam Reforming over Ni/Al2O3: Influence of Nickel Precursors