Zhaopeng Liu,Youming Ni,Zhongpan Hu,Yi Fu,Xudong Fang,Qike Jiang,Zhiyang Chen,Wenliang Zhu,Zhongmin Liu
The utilization of metal oxide-zeolite catalysts in the syngas-to-olefin reaction is a promising strategy for producing C 2 –C 4 olefins from non-petroleum resources. However, the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous. Herein, typical metal oxides (ZnO/ZrO 2 ) with different crystal phases (monoclinic ( m -ZrO 2 ) and tetragonal ( t -ZrO 2 )) were employed for syngas conversion. The (ZnO/ m -ZrO 2 +SAPO-34) composite catalyst exhibited 80.5% selectivity for C 2 –C 4 olefins at a CO conversion of 27.9%, where the results are superior to those (CO conversion of 16.4% and C 2 –C 4 olefin selectivity of 76.1%) obtained over (ZnO/ t -ZrO 2 +SAPO-34). The distinct differences are ascribed to the larger number of hydroxyl groups, Lewis acid sites, and oxygen defects in ZnO/ m -ZrO 2 compared to ZnO/ t -ZrO 2 . These features result in the formation of more formate and methoxy intermediate species on the ZnO/ m -ZrO 2 oxides during syngas conversion, followed by the formation of more light olefins over SAPO-34. The present findings provide useful information for the design of highly efficient ZrO 2 -based catalysts for syngas conversion.
Pengyuan Guan,Yongjie Zhao,Yihui Wu,Weixian Li,Xiao Zhang,Xiang Gao,Xiaoxia Ou,Wai Siong Chai,Yinfeng He,Hao Nan Li
CuO–ZnO–ZrO 2 catalyst attracted significant attention for CO 2 hydrogenation to methanol. Gyroid-based triply period minimal surface lattice structures feature highly ordered porous networks, which could be used to enhance catalytic performance and efficiency. This paper presents a formulating and one-step calcination strategy that united the removal of polymer resin and calcination of catalyst precursor at one temperature. This enabled 3D printing gyroid-structured CuO–ZnO–ZrO 2 catalyst for CO 2 hydrogenation while minimizing the impact of overheating on the catalyst performance. A photocurable formulation loaded with CuO–ZnO–ZrO 2 precursor was developed. Using the optimized formulation, gyroid structures with varying pore sizes were successfully printed and calcined. The optimal lattice wall thickness that balances porosity and structural stability was identified. The results indicate that the resin used for 3D printing was successfully removed at a lower temperature and the catalytic activity of the 3D-printed structured catalyst was retained through the one-step calcination process while the gyroid lattice geometry can enhance catalytic efficiency than cylindrical structure.
The selective hydrogenation of CO 2 to methanol demands precise control of both catalyst architecture and reaction pathways. Here, we design an atomic layer deposition (ALD)-engineered Pd/ZnO/ZrO 2 ternary catalyst with atomic-scale ZnO interlayers to decouple and reconfigure active sites at dual interfaces (Pd-ZnO and ZnO-ZrO 2 ). This interfacial engineering drives a 7-fold enhancement in methanol space–time yield (0.584 vs. 0.084 g MeOH g cat −1 h −1 ) and switches the dominant reaction pathway from CO-mediated to formate-driven selectivity (methanol selectivity remarkably surges from 6 % to 64 %). Multimodal characterization and theoretical calculations reveal that ZnO interlayers orchestrate bifunctional cooperation: activating CO 2 /CO adsorption while suppressing CO/CH 4 formation through electronic effects. Long-term stability study uncovers a dynamic restructuring mechanism, where Pd-ZnO interfaces gradually evolve into PdZn β alloy phases under the reaction conditions. This work establishes ALD-mediated interface design as a generalizable strategy to manipulate reaction networks and methanol selectivity in catalytic CO 2 hydrogenation systems.
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