The synergic effects at the molecular level in CoS2 for selective hydrogenation of nitroarenes,Green Chemistry

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The synergic effects at the molecular level in CoS2 for selective hydrogenation of nitroarenes
Green Chemistry ( IF 9.3 ) Pub Date : 2017-12-22 00:00:00 , DOI: 10.1039/c7gc03122j
Zhongzhe Wei _{1,

2,

3,

4,

5} , Shanjun Mao _{1,

2,

3,

4,

5} , Fanfei Sun _{6,

7,

8,

9,

10} , Jing Wang _{1,

2,

3,

4,

5} , Bingbao Mei _{6,

7,

8,

9,

10} , Yiqing Chen _{1,

2,

3,

4,

5} , Haoran Li _{1,

2,

3,

4,

5} , Yong Wang _{1,

2,

3,

4,

5}

Affiliation

Catalytic functionalized aniline formation from nitroarenes is a core technology in the synthesis of pharmaceuticals, agrochemicals, and fine chemicals. However, control of chemoselectivity still poses particular challenges with aromatic nitro substrates bearing one or more reducible groups. Here, we report the low-cost synthesis of a porous carbon supported CoS₂ catalyst (CoS₂/PC) and successfully apply the catalyst in the chemoselective hydrogenation of nitroarenes. For hydrogenation of 3-nitrostyrene, the catalyst furnishes a superior selectivity of 99% towards 3-aminostyrene at a conversion of >99%. Density functional theory calculations together with X-ray absorption fine structure spectroscopy reveal that terdentate and tetrahedral coordinated Co atoms in CoS₂ (labeled as Co₃ and Co₄) are possible active sites. The face to face located Co₃ and Co₄ sites make the reaction rather local, and Co₃ and Co₄ sites are occupied by substrates and H₂, respectively, which is beneficial to the superior activity and selectivity. The Co₃–Co₄ “synergic active site pair” in CoS₂ makes the investigation of the synergic effects at the molecular level a reality on heterogeneous catalysts.

中文翻译：

CoS ₂在分子水平上对硝基芳烃选择性加氢的协同作用

由硝基芳烃形成的催化功能化苯胺是制药，农用化学品和精细化学品合成中的一项核心技术。然而，对于带有一个或多个可还原基团的芳族硝基底物，化学选择性的控制仍然提出了特殊的挑战。在这里，我们报告了低成本的多孔碳负载CoS ₂催化剂（CoS ₂ / PC）的合成，并将该催化剂成功应用于硝基芳烃的化学选择性加氢。对于3-硝基苯乙烯的氢化，该催化剂对3-氨基苯乙烯具有99％的优良选择性，转化率＞ 99％。密度泛函理论计算和X射线吸收精细结构光谱显示，CoS _2中的齿状和四面体配位的Co原子（标记为Co ₃和Co ₄）可能是活性位点。面对面定位的Co ₃和Co ₄位使反应相当局限，并且Co ₃和Co ₄位分别被底物和H ₂占据，这有利于优异的活性和选择性。CoS _2中的Co ₃ -Co ₄ “协同活性位点对”使得研究分子水平上的协同效应对非均相催化剂成为现实。

更新日期：2018-02-06

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