Sulfur-Promoted Hydrocarboxylation of Olefins on Heterogeneous Single-Rh-Site Catalysts
Sulfur-Promoted Hydrocarboxylation of Olefins on Heterogeneous Single-Rh-Site Catalysts
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DOI：
10.1021/acscatal.1c06039
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发表时间：
2022-03
期刊：
影响因子：
12.9
通讯作者：
Qiao Yuan;Yating Gu;Siquan Feng;Xiangen Song;Jiali Mu;Bin Li;Xingju Li;Yutong Cai;Miao Jian
中科院分区：
文献类型：
--
作者：
Qiao Yuan;Yating Gu;Siquan Feng;Xiangen Song;Jiali Mu;Bin Li;Xingju Li;Yutong Cai;Miao Jian
硫中毒是工业应用中的一个严重问题，引起了基础研究的广泛兴趣。虽然已经在纳米颗粒催化剂上的许多反应中实施了一些关于抗硫性的研究，但是很少有研究关注使用非均相单金属中心催化剂（HSMSC）的羰基化反应。在此，我们提出了一个意想不到的硫促进的烯烃氢羧化反应中的单中心铑负载在多孔离子聚合物（Rh 1/PIP）催化剂上的性能与1000 ppm的H2S在CO进料中。Ex situEXAFS和原位DRIFTS揭示了烯烃氢羧化反应的三元循环机理与Rh-H配合物作为主要活性物种在纯和含H2S的原料。此外，还证明了Rh单核络合物的转化与H2S的加入。通过密度泛函理论研究验证了该反应途径的可行性，并证实了含硫配体的过渡态的能垒比正常进料中的能垒低得多，例如CO的迁移和插入的速率决定步骤降低了3.4 kcal/mol。这对于HSMSC的进一步应用可能是潜在有益的。
Sulfur poisoning is a severe problem in industrial applications, attracting broad interest in fundamental research studies. Although a number of studies about sulfur resistance have been implemented in many reactions on nanoparticle catalysts, few investigations focus on carbonylation reactions using heterogeneous single-metal-site catalysts (HSMSCs). Herein, we present an unanticipated sulfur-promoted performance in olefin hydrocarboxylation reactions on a single-Rh-site catalyst supported on porous ionic polymers (Rh1/PIPs) with 1000 ppm H2S in CO feed.Ex situEXAFS andin situDRIFTS revealed a ternary cycle mechanism of olefin hydrocarboxylation reactions with Rh–H complexes as predominant active species in both pure and H2S-containing feedstock. Moreover, the transformation of the Rh mononuclear complex with the addition of H2S was also demonstrated. Density functional theory studies were performed to verify the feasibility of the proposed pathway and confirm that the energy barriers of transition states with the sulfur ligand were much lower than those in normal feed, for example, a decline of 3.4 kcal/mol for the rate-determining step of migration and insertion of CO. This work provides a distinctive example for the insight of sulfur effect on carbonylation, which could be potentially beneficial for further applications of HSMSCs.