Efficient and Stable Co/β-Mo2C Catalyst for Hydroformylation
Efficient and Stable Co/β-Mo2C Catalyst for Hydroformylation
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DOI：
10.1021/acscatal.1c04022
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发表时间：
2021-11
期刊：
影响因子：
12.9
通讯作者：
Baiyin Wei;Xiaofang Liu;Yuchao Deng;Kaimin Hua;Junjun Chen;Hui Wang;Yuhan Sun
中科院分区：
文献类型：
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作者：
Baiyin Wei;Xiaofang Liu;Yuchao Deng;Kaimin Hua;Junjun Chen;Hui Wang;Yuhan Sun
烯烃的氢甲酰化反应是醛合成中最重要的工业过程之一，通常需要使用稀有且昂贵的铑基催化剂。因此，开发廉价的催化剂，例如具有足够高活性和稳定性的钴基催化剂对于氢甲酰化非常重要。然而，作为活性中心的传统金属钴团簇活性低，金属浸出严重。在这里，我们发现mo6c2键合的Co可以作为丙烯氢甲酰化的有效活性中心，在5个原位循环后，总周转数为3158，大约是传统金属Co簇的7.5倍。此外，开发的co6mo6c2催化剂有效抑制钴浸出，证明了其在长期测试中的稳定性。理论计算和表征分析结果表明，mo6c2键合Co的活性和稳定性的增强是由于氢甲酰化的总能垒降低和co6mo6c2晶体结构的稳定性，这源于Co与载体之间的强相互作用。
The hydroformylation of olefins is one of the most important industrial processes used for aldehyde synthesis, which commonly involves the use of scarce and expensive rhodium-based catalysts. It is therefore important to develop inexpensive catalysts, e.g., cobalt-based catalysts with sufficiently high activity and stability for hydroformylation. However, conventional metallic Co clusters, acting as active centers, suffer from low activity and severe metal leaching. Here, we show that Mo6C2-bonded Co can serve as an efficient active center for propene hydroformylation, with a total turnover number of 3158 after five in situ cycles, which is approximately 7.5 times higher than that of conventional metallic Co clusters. Furthermore, the developed Co6Mo6C2catalyst effectively suppresses cobalt leaching, demonstrating its stability in a long-lasting test. The results of theoretical calculations and characterization analyses demonstrate that the enhanced activity and stability of Mo6C2-bonded Co result from a reduction in the overall energy barrier for hydroformylation and the stability of the Co6Mo6C2crystal structure, which originates from the strong interaction between Co and the support.