Efficient Base-Free Aqueous Reforming of Methanol Homogeneously Catalyzed by Ruthenium Exhibiting a Remarkable Acceleration by Added Catalytic Thiol.
Efficient Base-Free Aqueous Reforming of Methanol Homogeneously Catalyzed by Ruthenium Exhibiting a Remarkable Acceleration by Added Catalytic Thiol.
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DOI：
10.1021/jacs.1c09007
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发表时间：
2021-10-20
影响因子：
15
通讯作者：
Milstein D
中科院分区：
文献类型：
--
作者：
Luo J;Kar S;Rauch M;Montag M;Ben-David Y;Milstein D
由于甲醇成本低、易于获得且氢含量高，通过甲醇重整生产氢气特别受关注。然而，大多数当前方法要么需要非常高的温度和压力，要么强烈依赖于大量碱的利用。在这里，我们报道了一种由吖啶基钌钳络合物均相催化的高效、无碱水相重整甲醇，其活性通过催化量的硫醇添加剂出人意料地提高。添加硫醇后，该体系的反应活性提高了近2个数量级，并且可以保持活性超过3周，总H2周转数超过130 000。在实验和计算研究的基础上，提出了一种机制，该机制涉及以硫醇盐作为辅助配体的独特钌配合物促进外球脱氢。目前的系统克服了均相甲醇重整中添加碱的需要，并且还突出了通过添加催化量的硫醇实现的金属配合物的催化活性的前所未有的加速。
Production of H2 by methanol reforming is of particular interest due the low cost, ready availability, and high hydrogen content of methanol. However, most current methods either require very high temperatures and pressures or strongly rely on the utilization of large amounts of base. Here we report an efficient, base-free aqueous-phase reforming of methanol homogeneously catalyzed by an acridine-based ruthenium pincer complex, the activity of which was unexpectedly improved by a catalytic amount of a thiol additive. The reactivity of this system is enhanced by nearly 2 orders of magnitude upon addition of the thiol, and it can maintain activity for over 3 weeks, achieving a total H2 turnover number of over 130 000. On the basis of both experimental and computational studies, a mechanism is proposed which involves outer-sphere dehydrogenations promoted by a unique ruthenium complex with thiolate as an assisting ligand. The current system overcomes the need for added base in homogeneous methanol reforming and also highlights the unprecedented acceleration of catalytic activity of metal complexes achieved by the addition of a catalytic amount of thiol.
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影响因子：
16.6
作者：
Khusnutdinova, Julia R.;Milstein, David
通讯作者：
Milstein, David
影响因子：
15
作者：
Kar, Sayan;Goeppert, Alain;Prakash, G. K. Surya
通讯作者：
Prakash, G. K. Surya
影响因子：
37.8
作者：
Kar S;Rauch M;Leitus G;Ben-David Y;Milstein D
通讯作者：
Milstein D
影响因子：
4.6
作者：
Campos, Jesus;Sharninghausen, Liam S.;Crabtree, Robert H.
通讯作者：
Crabtree, Robert H.
影响因子：
3.6
作者：
Kothandaraman, Jotheeswari;Kar, Sayan;Prakash, G. K. Surya
通讯作者：
Prakash, G. K. Surya