RESUMEN
Small-pore zeolites catalyze the methanol-to-olefins (MTO) reaction via a dual-cycle mechanism, encompassing both olefin- and aromatic-based cycles. Zeolite topology is crucial in determining both the catalytic pathway and the product selectivity of the MTO reaction. Herein, we investigate the mechanistic influence of MCM-35 zeolite on the MTO process. The structural properties of the as-synthesized MCM-35 catalyst, including its confined cages (6.19 Å), were characterized, confirming them as the catalytic centers. Then, the MTO reactions were systematically performed and investigated over a MCM-35 catalyst. Feeding pure methanol to the reactor yielded minimal MTO activity despite the formation of some aromatic species within the zeolite. The results suggest that the aromatic-based cycle is entirely suppressed in MCM-35, preventing the simultaneous occurrence of the olefin-based cycle. However, cofeeding a small amount of propene in methanol can obviously enhance the methanol conversion under the same studied reaction conditions. Thus, the exclusive operation of the olefin-based cycle in the MTO reaction, independent of the aromatic-based cycle, was demonstrated in MCM-35 zeolite.
RESUMEN
Hydrodeoxygenation (HDO) of lignin derivatives at room-temperature (RT) is still of challenge due to the lack of satisfactory activity reported in previous literature. Here, it is successfully designed a Pd/UiO-66-(COOH)2 catalyst by using UiO-66-(COOH)2 as the support with uncoordinated carboxyl groups. This catalyst, featuring a moderate Pd loading, exhibited exceptional activity in RT HDO of vanillin (VAN, a typical model lignin derivative) to 2-methoxyl-4-methylpheonol (MMP), and >99% VAN conversion with >99% MMP yield is achieved, which is the first metal-organic framework (MOF)-based catalyst realizing the goal of RT HDO of lignin derivatives, surpassing previous reports in the literature. Detailed investigations reveal a linear relationship between the amount of uncoordinated carboxyl group and MMP yield. These uncoordinated carboxyl groups accelerate the conversion of intermediate such as vanillyl alcohol (VAL), ultimately leading to a higher yield of MMP over Pd/UiO-66-(COOH)2 catalyst. Furthermore, Pd/UiO-66-(COOH)2 catalyst also exhibits exceptional reusability and excellent substrate generality, highlighting its promising potential for further biomass utilization.
RESUMEN
Facing with serious carbon emission issues, the production of green H2 from electrocatalytic hydrogen evolution reaction (HER) has received extensive research interest. Almost all kinds of noble metal phosphides (NMPs) consisting of Pt-group elements (i.e., Ru, Rh, Pd, Os, Ir and Pt) are all highly active and pH-universal electrocatalysts toward HER. In this review, the recent progress of NMP-based HER electrocatalysts is summarized. It is further take typical examples for discussing important impact factors on the HER performance of NMPs, including crystalline phase, morphology, noble metal element and doping. Moreover, the synthesis and HER application of hybrid catalysts consisting of NMPs and other materials such as transition metal phosphides, oxides, sulfides and phosphates, carbon materials and noble metals is also reviewed. Reducing the use of noble metal is the key idea for NMP-based hybrid electrocatalysts, while the expanded functionality and structure-performance relationship are also noticed in this part. At last, the potential opportunities and challenges for this kind of highly active catalyst is discussed.