Green hydrogen production from methanol is a pivotal technology for energy transformation. In this work, the heterojunction structure of NiO–TiO 2 and incorporated Pd/Ir/Ru nanoparticles were successfully prepared through the utilization of sol-gel and in situ photodeposition methods. The highest yield of hydrogen from methanol is contributed by 0.5Pd–1Ni–TiO 2 showing 80.73 mmol g −1 H 2 for 4 h, which is 15.03 times higher than the H 2 yield obtained using TiO 2 . Furthermore, this work reveals that methanol adsorbs in two states: molecular CH 3 OH and dissociated CH 3 O∗, and the main adsorption modes of methanol on the surfaces of TiO 2 , 1Ni–TiO 2 and 0.5Pd–1Ni–TiO 2 exhibit similarities, with bridge adsorption being identified as the most favorable mode. The possible mechanism of the formation of main products was proposed. HCOOH is formed by oxidation of HCHO, or from desorption of formate. The two C–C coupling reactions of ·COOH + ·COOH and ·COOH + ·CH 3 produce CH 3 COOH.
Jirong Long,Yuxuan Mao,Yiwei Long,Guozhang Chang,Lungang Chen,Wenguang Zhou,Jinxing Long,Yong Liu
Hydrodeoxygenation of lignin-derived phenols into high-value cycloalkanes under mild conditions is challenging. Herein, we report a Ru NPs @HZSM-5 catalyst with a unique metal-support interactions that achieves 100 % guaiacol conversion and 99.7 % cyclohexane selectivity at 160 °C and 1 MPa H 2 . Comparative studies with single-atom and aggregated Ru catalysts reveal that well-dispersed Ru nanoparticles coupled with acid sites offer superior activity and selectivity. Kinetic analysis and in situ DRIFTS demonstrate a sequential mechanism involving rapid hydrogenation of the aromatic ring followed by rate-limiting deoxygenation steps. Characterizations and CO-DRIFTS confirm particle sizes, optimal metal-support interactions, and enhanced acidity in Ru NPs @HZSM-5. Theoretical calculations further reveal favorable electronic states and lower energy barriers for deoxygenation on Ru NPs @HZSM-5. The catalyst also shows broad substrate compatibility, efficiently converting various lignin-derived phenolics. This work provides valuable insights into the critical synergy between metal nanoparticles and acidic supports for efficient lignin upgrading.
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