IMR OpenIR
表面暴露活性位点的MoS2纳米催化剂催化硝基化合物的非均相氢转移反应
Alternative TitleA MoS2nanocatalyst with surface‐enriched active sites for the heterogeneous transfer hydrogenation of nitroarenes
Wang Jia; Zhang Yajie; Diao Jiangyong; Zhang Jiayun; Liu Hongyang; Su Dangsheng
2018
Source Publication催化学报
ISSN0253-9837
Volume39.0Issue:1.0Pages:79-87
AbstractMoS2具有独特的二维层状结构,被广泛用于加氢脱硫过程以及HER反应,而且可以通过减少MoS2的颗粒尺寸以及层数来进一步改善其催化活性.通过剥离方法得到的MoS2纳米片虽然表现出优良的加氢脱硫活性,但容易团聚使其循环使用性能很差.如果通过引入纳米碳将单层的MoS2纳米片进行有效“隔离”,则可明显降低团聚的可能性,从而改善其催化性能和稳定性.本文通过一步水热法制备出了碳嵌入的MoS2纳米颗粒(MoS2@C),将其应用于硝基苯类化合物的氢转移反应中表现出了非常好的催化性能.进一步通过粉末X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和在线质谱检测等手段研究了层间距增加的MoS2催化剂在硝基苯类化合物的氢转移反应中催化性能提升的原因.XRD,SEM和TEM结果表明,通过引入碳材料可以明显增加MoS2的层间距,同时减小其颗粒尺寸,而且使MoS2表现出弯曲的(002)晶面.由于存在一定的曲率,这种(002)晶面也会表现出一定的催化能力.氮气物理吸附结果表明,这种MoS2@C复合物具有较高的比表面积(89m2g?1)和明显的介孔结构(~20nm),在催化反应中有利于底物扩散,进而改善催化性能.XPS结果显示,与体相的MoS2相比,MoS2@C表面暴露出更多的不饱和Mo原子(Mo/S=0.71(MoS2@C)vsMo/S=0.63(MoS2)),形成了独特的S-Mo-O结构以及缺陷结构.在硝基苯类化合物的氢转移反应中,层间距增加的MoS2@C由于暴露出更多的活性位和具有弯曲的(002)晶面,表现出了更高的催化活性(TOF=3.66s–1vs1.24s–1(MoS2)).通过质谱对反应过程的追踪发现,在只有肼存在的条件下,MoS2@C催化肼分解的主要气相产物是氨气.这说明MoS2@C能够使肼发生N?N键的断裂.而当肼和硝基苯同时存在的条件下,质谱检测的气相产物主要是氮气,表明硝基苯的存在可以诱导肼逐步发生N?H键断裂,在催化剂表面形成活性的H物种,进而转移到硝基苯上使其还原得到苯胺.使用偶氮苯和氧化偶氮苯作为反应底物,发现MoS2@C很难使其还原为苯胺,这说明在该催化体系中,硝基苯的还原过程主要是沿着直接路径(硝基苯-亚硝基苯-苯胺)进行的.
Other AbstractA highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of nitroarenes with hydrazine monohydrate as a reductant under mild reaction conditions without pressure and base,which was different from other hydrogen transfer systems that require the presence of a base(e.g.,propan‐2‐ol/KOH).The sandwiching of carbon between the MoS2nanosheets increased the distance between the layers of MoS2and exposed more Mo sites,resulting in superior catalytic performance compared with that of bulk MoS2catalyst.The active hydrogen(H*)generated from N2H4could directly transfer to the–NO2groups of nitrobenzene to form aniline followed by N2emission,which was confirmed by detecting the gas emission with mass spectrometry during the decomposition of hydrazine or the co‐existence of nitrobenzene and hydrazine.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
Keyword二硫化钼 增加的层间距 氢转移反应 硝基苯还原 无碱体系
Indexed ByCSCD
Language中文
CSCD IDCSCD:6160937
Citation statistics
Cited Times:2[CSCD]   [CSCD Record]
Document Type期刊论文
Identifierhttp://ir.imr.ac.cn/handle/321006/157350
Collection中国科学院金属研究所
Affiliation中国科学院金属研究所
Recommended Citation
GB/T 7714
Wang Jia,Zhang Yajie,Diao Jiangyong,等. 表面暴露活性位点的MoS2纳米催化剂催化硝基化合物的非均相氢转移反应[J]. 催化学报,2018,39.0(1.0):79-87.
APA Wang Jia,Zhang Yajie,Diao Jiangyong,Zhang Jiayun,Liu Hongyang,&Su Dangsheng.(2018).表面暴露活性位点的MoS2纳米催化剂催化硝基化合物的非均相氢转移反应.催化学报,39.0(1.0),79-87.
MLA Wang Jia,et al."表面暴露活性位点的MoS2纳米催化剂催化硝基化合物的非均相氢转移反应".催化学报 39.0.1.0(2018):79-87.
Files in This Item:
There are no files associated with this item.
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[Wang Jia]'s Articles
[Zhang Yajie]'s Articles
[Diao Jiangyong]'s Articles
Baidu academic
Similar articles in Baidu academic
[Wang Jia]'s Articles
[Zhang Yajie]'s Articles
[Diao Jiangyong]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[Wang Jia]'s Articles
[Zhang Yajie]'s Articles
[Diao Jiangyong]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.