Fine-Tuning of Ni/NiO over H-NbOx for Enhanced Eugenol Hydrogenation through Enhanced Oxygen Vacancies and Synergistic Participation of Active Sites.

The hydrogenation of lignin-derived phenolics to produce valuable chemicals is a promising but challenging task. This study successfully demonstrates the use of sustainable transition metal-based catalysts to hydrogenate lignin-derived phenolics. A defect-induced oxygen vacancy containing H-NbOx prepared from commercial Nb2O5 was employed as a catalyst. H-NbOx exhibited higher oxygen vacancies (158.21 µmol/g) than commercial Nb2O5 (39.01 µmol/g), evaluated from O2-TPD. Upon supporting 10 wt % Ni, a Ni/NiO interface was formed over H-NbOx, which was intrinsically active for the hydrogenation of phenolics. 10Ni/H-NbOx exhibited a two-fold increase in activity than 10Ni/Nb2O5, achieving >99% eugenol conversion and affording ∼94% 4-propyl cyclohexanol selectivity, wherein ∼63% eugenol conversion and ∼73% 4-propyl cyclohexanol selectivity were obtained over 10Ni/Nb2O5. The Ni/NiO formation was confirmed by X-ray photoelectron spectroscopy, HR-TEM, and H2-TPR analysis, while the oxygen vacancies were verified by Raman spectroscopy and O2-TPD analysis. The resulting interface enhanced the synergy between Ni and H-NbOx and facilitated hydrogen dissociation, confirmed by H2-TPD. Remarkably, 10Ni/H-NbOx maintained its catalytic activity for five tested cycles and demonstrated exceptional activity with various phenolics. Our findings highlight the potential of a sustainable transition metal catalyst for the hydrogenation of lignin-derived phenolic compounds, which could pave the path to producing valuable chemicals in an environmentally friendly manner.

Cu-Ce Bimetallic Metal-Organic Framework-Derived, Oxygen Vacancy-Boosted Visible Light-Active Cu2O-CeO2/C Heterojunction: An Efficient Photocatalyst for the Sonogashira Coupling Reaction.

The development of an economical transition metal-based catalyst for photocatalytic carbon-carbon coupling reactions is aspiring. Herein, a Cu-Ce metal-organic framework (MOF) was synthesized and carbonized to produce bimetallic Cu2O-CeO2/C, which was utilized in the Sonogashira cross-coupling reaction. The defects and oxygen vacancies in the catalyst were characterized by X-ray photoelectron spectroscopy and Raman spectroscopy, while the nature of Cu was characterized by H2-TPR analysis. The defect-induced MOF-derived Cu-Ce heterojunction created more oxygen vacancies (OV) in CeO2, revealing the high photocatalytic activity. The Cu-Ce heterojunction (Cu2O-CeO2/C) formed a Cu(I)-phenylacetylide active complex and exhibited higher catalytic activity for the visible light-induced Sonogashira cross-coupling reaction. 25%Cu2O-CeO2/C offered 93.8% phenylacetylene conversion with a 94.2% Sonogashira product selectivity by using household light-emitting diodes. No discernible activity loss was observed from the recycling of the catalyst. Based on catalytic activity, control reactions, and physicochemical and optoelectronic characterization, the structure-activity relationship was established and a reaction mechanism was proposed. Replacement of the costly Pd metal-based catalyst with a cheap Cu2O-CeO2-based catalyst for the synthesis of commercially important compounds with a sustainable visible light-induced catalytic process will be highly attractive to chemists and industrialists.

Thermal and photocatalytic cascade one-pot synthesis of secondary amine using multifunctional Pd decorated MOF-derived CeO2.

The use of a single catalyst to perform thermal and photochemical N-alkylation of amine is challenging work. Herein, Pd decorated MOF-derived CeO2 was prepared for the cascade one-pot synthesis of secondary amine by thermal and photocatalytic routes. Among the designed catalysts, Pd(0.5%)/CeO2-300 exhibited the best activity for thermal and photocatalytic one-pot secondary amine synthesis involving benzyl alcohol and aniline. The physicochemical characteristics of Pd(0.5%)/CeO2-300 suited for the oxidation of benzyl alcohol followed by condensation with aniline to form an imine. Further, reduction of imine over Pd NPs decorated on CeO2-300 took place to form secondary amine. An excellent conversion of benzyl alcohol and secondary amine selectivity was observed thermally at 100 °C in 26 h. The Pd(0.5%)/CeO2-300 exhibited excellent activity in white LED. Interestingly, more activity was achieved in sunlight. The Pd(0.5%)/CeO2-300 demonstrated excellent stability under thermal and photocatalytic conditions and was recycled 5 times without losing any significant activity. The surface area, acidity, and elemental compositions were characterized by various physicochemical techniques. The light absorption property, bandgap, charge carrier separation, and photocurrent measurements were carried out by photoelectrochemical and optoelectronic analysis. The reaction mechanism and structural activity relationship correlated with control experiments, catalytic activity data, physicochemical, and optoelectronic characterization. One catalyst affording efficient activity in conventional thermal and photocatalytic conditions, especially sunlight, would be exciting to researchers and industrial practitioners.