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Dynamic metal-polymer interaction for the design of chemoselective and long-lived hydrogenation catalysts

机译:用于化学选择性和长寿命氢化催化剂设计的动态金属 - 聚合物相互作用

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Metal catalysts are generally supported on hard inorganic materials because of their high thermochemical stabilities. Here, we support Pd catalysts on a thermochemically stable but “soft” engineering plastic, polyphenylene sulfide (PPS), for acetylene partial hydrogenation. Near the glass transition temperature (~353 K), the mobile PPS chains cover the entire surface of Pd particles via strong metal-polymer interactions. The Pd-PPS interface enables Hsub2/sub activation only in the presence of acetylene that has a strong binding affinity to Pd and thus can disturb the Pd-PPS interface. Once acetylene is hydrogenated to weakly binding ethylene, re-adsorption of PPS on the Pd surface repels ethylene before it is further hydrogenated to ethane. The Pd-PPS interaction enables selective partial hydrogenation of acetylene to ethylene even in an ethylene-rich stream and suppresses catalyst deactivation due to coke formation. The results manifest the unique possibility of harnessing dynamic metal-polymer interaction for designing chemoselective and long-lived catalysts.
机译:由于其高热化学稳定性,通常金属催化剂通常在硬无机材料上负载。在此,我们支持在热化学稳定但“软”工程塑料,聚苯硫醚(PPS)上的PD催化剂,用于乙炔部分氢化。在玻璃化转变温度(〜353 k)附近,移动PPS链通过强金属聚合物相互作用覆盖Pd颗粒的整个表面。 PD-PPS界面仅在存在对PD具有强粘合亲和力的乙炔的存在下仅启用H 2 激活,因此可以干扰PD-PPS界面。一旦乙炔氢化到弱结合乙烯,在Pd表面脱乙烯上再吸收PPS在进一步氢化至乙烷之前。即使在富含乙烯的流中,PD-PPS相互作用也能够选择性部分氢化乙炔在乙烯中氢化并抑制由于焦炭形成引起的催化剂失活。结果表明,利用动态金属 - 聚合物相互作用以设计化学选择性和长寿命催化剂的独特可能性。

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