Zirconium phosphate glycine diphosphonate nanosheets (ZPGly) have been used as support for the preparation of solid palladium nanoparticles, namely Pd@ZPGly. Thanks to the presence of carboxy-aminophosponate groups on the layer surface, ZPGly-based materials were able to stabilize a high amount of palladium (up to 22 wt %) also minimizing the amount of metal leached in the final products of representative important cross-coupling processes selected for proving the catalysts’ efficiency. The catalytic systems have been fully characterized and used in low amounts (0.1 mol %) in the Suzuki–Miyaura and Heck cross-couplings. Moreover, the protocols were optimized for the use of recoverable azeotropic mixtures (aq. EtOH 96% or aq. CH₃CN 84%, respectively) and in the flow procedure allowing one to isolate the final pure products, without any purification step, with very low residual palladium content and with a very low waste production.

A gold‐incorporated SBA‐15 catalyst was prepared by a solvent‐free ball‐milling approach. The catalyst showed high reactivity and selectivity in the reduction of a variety of nitroarenes to anilines operating in absolute EtOH with NaBH₄ as reducing agent. The catalyst was reused in batch conditions over five consecutive runs without any losses of activity or selectivity. Considering the high chemical stability and reusability of the catalytic system, a continuous‐flow protocol was also investigated and defined to minimize the generation of waste and optimize the continuous reuse of the catalyst. Benefits of flow conditions were proven by turnover numbers that increased from 47.5 to 1902 and also by the minimization of both leaching (9.5 vs. 1 ppm) and E‐factor values (8 vs. 23 in batch).

One of the primary targets for the new lignocellulosic feedstock-based biorefinery is the simultaneous valorization of holocellulose and lignin. Acidified organosolv treatment is among the most promising strategy for recovering technical lignin, water-soluble hemicellulose, and cellulose pulp with increased accessibility to hydrolytic enzymes. In this work, a design-of-experiment (DoE) approach was used to increase the cellulose recovery, digestibility, and the delignification of Cynara cardunculus L. feedstock. In the first treatment, the milled biomass was subjected to microwave-assisted extraction using an acidified GVL/water mixture to separate lignin and hemicellulose from cellulose. In the second treatment, the cellulose pulp was hydrolyzed by cellulolytic enzymes to demonstrate the enhanced digestibility. At the optimal condition (154 °C, 2.24% H₂SO₄, and 0.62 GVL/water ratio), the cellulose pulp showed a cellulose content of 87.59%, while the lignin content was lower than 8%. The cellulose recovery and digestibility were equal to 79.46% and 86.94%, respectively. About 40% of the initial hemicellulose was recovered as monosaccharides. This study demonstrated the effectiveness of the two-step organosolv treatment for biomass fractionation; however, as suggested by DoE analysis, a confirmative study at a low temperature (<154 °C) should be performed to further increase the cellulose recovery.

Cardoon (Cynara cardunculus) is a promising crop from which to obtain oilseeds and lignocellulosic biomass. Acid-catalyzed steam explosion is a thermochemical process that can efficiently pre-treat lignocellulosic biomass. The drawback is the production of a high number of carbohydrate degradation products in the liquid fraction that could inhibit microbial growth. In this work, the lignocellulosic biomass of cardoon, gathered from a dedicated field, were used as the raw material for the production of fermentable monosaccharides by employing acid-catalyzed steam explosion. The raw material was pre-soaked with a dilute 1% (w/w) sulfuric acid solution and then subjected to steam explosion under three different severity conditions. The recovered slurry was separated into solid and liquid fractions, which were individually characterized to determine total carbohydrate and inhibitor concentrations. The slurry and the washed solid fraction underwent enzymatic hydrolysis to release glucose and pentose monosaccharides. By conducting the pre-treatment at 175 °C for 35 min and hydrolyzing the obtained slurry, a yield of 33.17 g of monosaccharides/100 g of cardoon was achieved. At the same conditions, 4.39 g of inhibitors/100 g of cardoon were produced.

Lignocellulosic biomass is a nonedible matrix that can be efficiently exploited as feedstock in an integrated biorefinery after a proper pretreatment. An organosolv pretreatment using an acidified γ-valerolactone (GVL)/water solution was proposed to improve the cellulose enrichment and enzymatic saccharification of cardoon (Cynara cardunculus L.) stems. At the optimal pretreatment condition (140 °C, 0.6 GVL/water, and 2.24% H₂SO₄), xylan was efficiently removed from the cardoon, and up to 50% of its content was recovered in the aqueous fraction, while 86% of the cellulose was retained in the solid fraction. The resulting cardoon pulp showed a cellulose content of 91.5% and an enzymatic digestibility of 100%. An overall glucose production of 37.17 g/100 g raw material (90% theoretical maximum) was obtained using high solid loading (20% w/w) and a high enzyme dosage (60 FPU/g cellulose). At a low enzyme dosage, glucose concentrations of 169 g/L and 210 g/L were achieved using 10 FPU/g cellulose and 20 FPU/g cellulose, respectively. Therefore, an organosolv pretreatment can be an effective process for producing cellulose-enriched pulp with enhanced enzymatic digestibility from cardoon stems, providing a promising option for green lignocellulosic biorefineries that aim to produce high concentrations of glucose with low cellulase addition.