MoO_2催化剂近室温下催化水合肼转氢还原硝基苯
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- 英文论文题名：Transfer hydrogenation of nitroarenes with hydrazine at near-room temperature catalysed by a MoO_2 catalyst
- 论文作者：张超锋 ; 吕建民 ; 王峰
- 英文论文作者：Chaofeng Zhang ; Jianmin Lu ; Feng Wang ; Dalian Institute of Chemical Physics ; Chinese Academy of Sciences ; Graduate University of Chinese Academy of Sciences
- 年：2016
- 作者机构：中科院大连化学物理研究所;中国科学院大学;
- 论文关键词：二氧化钼 ; 肼分解 ; 转氢 ; 硝基苯还原 ; DFT计算
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十七分会：纳米催化
- 语种：中文
- 分类号：O621.251
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十七分会 ; 纳米催化
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：272k
- 原文格式：D
- 会议级别：全国
摘要
我们通过实验和理论计算手段呈现出水合肼在MoO_2晶体表面的转氢过程,MoO_2独特的金属性-碱性双功能特征在催化转氢过程中起到了重要的作用。密度泛函理论(DFT)计算表明,比起N-N键的断裂,MoO_2优先催化肼分子中N-H键的选择性断裂,在Mo,O多核位点处生成异裂的H~(δ-)和H~(δ+)物种,使得MoO_2不同于其它金属氧化物。相比较于C=C,C≡C和C≡N基团,MoO_2在室温甚至0℃条件下选择性高效催化硝基还原。
We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO_2, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory(DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N–H bond rather than the N–N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO_2 shows exceptionally high chemoselectivity toward the nitro reduction over C=C, C≡C, and C≡N groups at room temperature and lower, down to 0 ℃.
We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO_2, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory(DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N–H bond rather than the N–N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO_2 shows exceptionally high chemoselectivity toward the nitro reduction over C=C, C≡C, and C≡N groups at room temperature and lower, down to 0 ℃.
引文
[1]Zhang,C.;Lu,J.;Li,M.;Wang,Y.;Zhang,Z.;Chen,H.;Wang,F.Green Chem.2016,DOI:10 .1039/c5gc02460a.