Utilization of CO₂ as a C₁ resource for the synthesis of aromatics is of great significance and is also related to carbon recycling. However, forming an ethylated or propylated side chain at the benzene ring by this strategy is difficult, and the products reported are methylated aromatics. Here, we show the first CO₂ hydrogenation in tandem coupling with benzene alkylation to synthesize ethylbenzene and propylbenzene over a dual-bed system containing ZnZrO_x, SAPO-34, and phosphorus-modified ZSM-5 catalysts. Controlled experiments and density functional theory studies reveal that the intermediate reactive species CH_xO∗ (x = 1–3) of CO₂ hydrogenation are preferentially alkylated with benzene to give methylated aromatics, rather than to form ethylated and propylated aromatics, when the three catalysts are simply mixed. By contrast, the three catalysts with rationally spatial distribution in the dual-bed system can afford 83.5% selectivity to ethylbenzene or 64.7% to propylbenzene in total aromatics without deactivation after 100 h.

利用CO ₂作为C ₁资源合成芳烃具有重要意义，也与碳循环利用有关。然而，通过这种策略在苯环上形成乙基化或丙基化侧链是困难的，并且报道的产物是甲基化芳烃。在这里，我们展示了在含有 ZnZrO _x、SAPO-34 和磷改性 ZSM-5 催化剂的双床系统上，首次 CO _{2加氢与苯烷基化偶联合成乙苯和丙苯。}对照实验和密度泛函理论研究表明， CO _{2的中间活性物质 CH x} O∗ ( x  = 1-3)当三种催化剂简单混合时，氢化优先用苯烷基化得到甲基化芳烃，而不是形成乙基化和丙基化芳烃。相比之下，在双床体系中空间分布合理的三种催化剂在100小时后可以在总芳烃中提供83.5%的乙苯选择性或64.7%的丙苯选择性，而不会失活。