Various methods of physical, chemical and combined physicochemical pre-treatments for lignocellulosic biomass waste valorisation to value-added feedstock/solid fuels for downstream processes in chemical industries have been reviewed. The relevant literature was scrutinized for lignocellulosic waste applicability in advanced thermochemical treatments for either energy or liquid fuels. By altering the overall naturally occurring bio-polymeric matrix of lignocellulosic biomass waste, individual components such as cellulose, hemicellulose and lignin can be accessed for numerous downstream processes such as pyrolysis, gasification and catalytic upgrading to value-added products such as low carbon energy. Assessing the appropriate lignocellulosic pre-treatment technology is critical to suit the downstream process of both small- and large-scale operations. The cost to operate the process (temperature, pressure or energy constraints), the physical and chemical structure of the feedstock after pre-treatment (decomposition/degradation, removal of inorganic components or organic solubilization) or the ability to scale up the pre-treating process must be considered so that the true value in the use of bio-renewable waste can be revealed.

Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.

The production of syngas (H₂ and CO)—a key building block for the manufacture of liquid energy carriers, ammonia and hydrogen—through the dry (CO2−) reforming of methane (DRM) continues to gain attention in heterogeneous catalysis, renewable energy technologies and sustainable economy. Here we report on the effects of the metal oxide support ($\mathsf{\gamma }$-Al₂O₃, alumina-ceria-zirconia (ACZ) and ceria-zirconia (CZ)) on the low-temperature (ca. 500–750 ${}^{\circ }$C) DRM activity, selectivity, resistance against carbon deposition and iridium nanoparticles sintering under oxidative thermal aging. A variety of characterization techniques were implemented to provide insight into the factors that determine iridium intrinsic DRM kinetics and stability, including metal-support interactions and physicochemical properties of materials. All Ir/$\mathsf{\gamma }$-Al₂O₃, Ir/ACZ and Ir/CZ catalysts have stable DRM performance with time-on-stream, although supports with high oxygen storage capacity (ACZ and CZ) promoted CO₂ conversion, yielding CO-enriched syngas. CZ-based supports endow Ir exceptional anti-sintering characteristics. The amount of carbon deposition was small in all catalysts, however decreasing as Ir/$\mathsf{\gamma }$-Al₂O₃ > Ir/ACZ > Ir/CZ. The experimental findings are consistent with a bifunctional reaction mechanism involving participation of oxygen vacancies on the support’s surface in CO₂ activation and carbon removal, and overall suggest that CZ-supported Ir nanoparticles are promising catalysts for low-temperature dry reforming of methane (LT-DRM).