探索用于丙烷脱氢的聚酰胺-酰亚胺掺杂氧化锌氮碳材料

Huahua Zhao, Tingyu Ji, Yanping Wu, Huanling Song, Jianfeng Wu, L. Chou
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摘要

采用真空固化-碳化策略,以聚酰胺-酰亚胺为氮碳源,以硝酸锌为金属源,制备了一系列氧化锌含量为 5-40% 的掺氮碳材料 (xZnO-N-C),用于丙烷脱氢 (PDH)。20ZnO-N-C 具有出色的初始活性(丙烷转化率为 35.2%,丙烯产率为 24.6%),并且在 600 °C 时的失活率相对较低(0.071 h-1)。详细的表征结果表明,通过调节氧化锌的负载量,可以获得在催化剂上高度分散的小氧化锌纳米颗粒(5.5 nm)。此外,与通过无真空固化碳化制备的 20ZnO-N-C-air 相比,20ZnO-N-C 上形成了更多的氮基物种,尤其是 ZnNx 物种,这可能有助于提高 20ZnO-N-C 的产品选择性和催化稳定性。催化剂体系上 PDH 反应的活性位点被认为是 C=O 物种和 Zn2+ 物种。此外,碳沉积和 ZnO 纳米粒子的聚集是该催化剂体系活性降低的原因。
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Exploration of ZnO-Doped Nitrogen-Carbon Materials Derived from Polyamide-Imide for Propane Dehydrogenation
A series of ZnO-doped nitrogen-carbon materials (xZnO-N-C) with ZnO contents of 5–40% are prepared by a vacuum curing–carbonization strategy using polyamide-imide as the N-C source and zinc nitrate as the metal source for propane dehydrogenation (PDH). 20ZnO-N-C exhibits outstanding initial activity (propane conversion of 35.2% and propene yield of 24.6%) and a relatively low deactivation rate (0.071 h−1) at 600 °C. The results of detailed characterization show that small ZnO nanoparticles (5.5 nm) with high dispersion on the catalyst can be obtained by adjusting the ZnO loading. Moreover, more nitrogen-based species, especially ZnNx species, are formed on 20ZnO-N-C in comparison with 20ZnO-N-C-air prepared via curing carbonization without vacuum, which may contribute to the higher product selectivity and catalytic stability of 20ZnO-N-C. The active sites for the PDH reaction on the catalyst system are proposed to be C=O species and Zn2+ species. Moreover, the carbon deposition and the aggregation of ZnO nanoparticles are the causes of activity loss on this catalyst system.
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