Wu Qingyuan, Su Wang, Huang Rui, Shen Hui, Qiao Mengfei, Qin Ruixuan, Zheng Nanfeng
New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, 361102, China.
Angew Chem Int Ed Engl. 2024 Sep 16;63(38):e202408731. doi: 10.1002/anie.202408731. Epub 2024 Aug 14.
A full selectivity control over the catalytic hydrogenation of nitroaromatics leads to the production of six possible products, i.e., nitroso, hydroxylamine, azoxy, azo, hydrazo or aniline compounds, which has however not been achieved in the field of heterogeneous catalysis. Currently, there is no sufficient evidence to support that the catalytic hydrogenation of nitroaromatics with the use of heterogeneous metal catalysts would follow the Haber's mechanistic scheme based on electrochemical reduction. We now demonstrate in this work that it is possible to fully control the catalytic hydrogenation of nitroaromatics into their all six products using a single catalytic system under various conditions. Employing SnO-supported Pt nanoparticles facilitated by the surface coordination of ethylenediamine and vanadium species enabled this unprecedented selectivity control. Through systematic investigation into the controlled production of all products and their chemical reactivities, we have constructed a detailed reaction network for the catalytic hydrogenation of nitroaromatics. Crucially, using oxygen-isolated characterization techniques is essential for identifying unstable compounds such as nitroso, hydroxylamine, hydrazo compounds. The insights gained from this research offer invaluable guidance for selectively transforming nitroaromatics into a wide array of functional N-containing compounds, both advancing fundamental understanding and fostering practical applications in various fields.
对硝基芳烃催化氢化反应实现完全的选择性控制可生成六种可能的产物，即亚硝基、羟胺、氧化偶氮、偶氮、氢化偶氮或苯胺类化合物，然而在多相催化领域尚未实现这一点。目前，没有足够的证据支持使用多相金属催化剂进行硝基芳烃的催化氢化反应会遵循基于电化学还原的哈伯机理。我们在这项工作中证明，在各种条件下使用单一催化体系能够完全控制硝基芳烃催化氢化为其所有六种产物。通过乙二胺和钒物种的表面配位作用促进的负载在SnO上的Pt纳米颗粒实现了这种前所未有的选择性控制。通过对所有产物的可控生成及其化学反应性进行系统研究，我们构建了硝基芳烃催化氢化反应的详细反应网络。至关重要的是，使用氧隔离表征技术对于鉴定不稳定化合物（如亚硝基、羟胺、氢化偶氮化合物）至关重要。这项研究获得的见解为将硝基芳烃选择性转化为各种功能性含氮化合物提供了宝贵的指导，既推进了基础理解，又促进了在各个领域的实际应用。
