Catalytic refining of lignin holds promise for producing sustainable platform chemicals. In this work, a gaseous hydrogen-free catalytic hydrodeoxygenation system is developed for upgrading lignin-derived phenols to alkane chemicals. Commercially available Raney Ni and HZSM-5 are used as a combinational catalyst, with isopropanol serving as the hydrogen-donating solvent. By modifying the temperature and the ratio of Raney Ni to HZSM-5, the reaction pathways for hydrogenation and deoxygenation can be tailored to specific requirements. As a result, a 97.1% yield of alkane fuels is achieved, with 64.4% propylcyclohexane and 32.7% propylbenzene obtained in one-pot reaction from the hydrodeoxygenation of 2-methoxy-4-propylphenol using a 3:1 mass ratio of Ni to HZSM-5, further increasing the ratio of HZSM-5 leads to a selectively production of propylbenzene in 62.0% yield. Through careful regulation of the catalytic system and the design of hydrogenation–deoxygenation pathways, excellent yields of 4-propylcyclohexanol (92.2%), propylcyclohexene (93.3%), and propylcyclohexane (93.2%) are directionally achieved. The catalyst maintained a conversion rate of over 99% after five cycles, demonstrating excellent robustness. This study offers a strategic system that expedites the selective upgrading of lignin-derived chemicals, heralding a pathway toward sustainable fuels and chemicals.
The Liquid-Sunshine presents a transformative approach for converting biomass into high-value platform chemicals. However, conventional photorefineries suffer from low efficiency and excessive byproduct formation due to the inherent incompatibility between biomass and photocatalysts. Herein, we introduce an innovative tandem oxygen-reforming-photocatalysis (TORP) strategy, which first selectively reforms biomass functional groups before driving photocatalytic C–C bond cleavage to produce high-value platform chemicals (HPCs). The oxygen reforming enhances substrate–catalyst interaction and facilitates selective C–C bond activation, while the formation of a hydrogen-rich surface and associated hydrogen spillover promotes C n −1 radical quenching, thereby improving selectivity and suppressing overoxidation. This TORP strategy leads to a seven-fold increase in xylitol yield (1.3 mmol g −1 h −1 ) with 89% feedstock conversion and provides a robust and efficient approach for biomass valorization and exhibits broad applicability across organic waste and plastic substrates, offering strong potential for industrial deployment.
Engineering anodic and cathodic half-reactions with more favorable thermodynamics and techno-economics in water-splitting cells for electrorefining offers a promising approach to producing green fuels and fine chemicals. Herein, we demonstrated a coelectrolysis system integrating nitrate reduction reaction (NO3RR) and biomass oxidation reaction (BOR), where a well-designed CuNi alloy acted as the catalyst at the cathode and anode. The CuNi delivered a yield rate of 2.87 mmol h–1 cm–2 (8.44 mmol h–1 mgcat–1) at 0 V vs RHE and a FE of 95.33% (a current density of −136 mA cm–2) at −0.2 V vs RHE for ammonia synthesis from nitrate reduction. Mechanistic studies revealed that Cu centers rapidly converted NO3– to NO2–, while Ni sites promoted water dissociation, generating *H species for intermediate deoxygenation and hydrogenation via stepwise proton transfer. At the anode, the CuNi efficiently catalyzed the oxidative upgradation of biomass derivatives, with a Faradaic efficiency of >90% and a long-term stability over 240 h for formate production. In situ experiments demonstrate that Cu substantially enhances the dynamic transformation efficiency of the NiIII–O active species on CuNi catalysts. The integrated NO3RR||BOR system demonstrated an efficient and stable electrosynthesis (>120 h) of ammonia (∼3.9 mmol h–1 cm–2 or 11.47 mmol h–1 mgcat–1) and formate (∼38.3 mmol h–1 cm–2 or 112.65 mmol h–1 mgcat–1). This study emphasizes the design of a hybrid system for electrocatalytic refining of waste feedstocks into commodity chemicals.
危险品化学品经营许可证（带存储）