Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (1): 22-29.DOI: 10.6023/A17070339 Previous Articles     Next Articles

Article

MOF热解法制备Ni/C核壳材料及其催化苯乙炔加氢性能研究

郭小玲a,b, 陈霄a, 苏党生b, 梁长海a   

  1. a 大连理工大学 化工学院 先进材料与催化工程实验室 大连 116024;
    b 中国科学院金属研究所 沈阳材料科学国家(联合)实验室 催化材料研究部 沈阳 110016
  • 收稿日期:2017-07-26 出版日期:2018-01-15 发布日期:2017-10-24
  • 通讯作者: 梁长海 E-mail:changhai@dlut.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21373038,21403026),辽宁省自然科学基金-沈阳材料科学国家(联合)实验室联合开放基金(No.2015021014)和中央高校基本科研业务费专项资金(No.DUT16RC(4)03)的资助项目.

Preparation of Ni/C Core-shell Nanoparticles through MOF Pyrolysis for Phenylacetylene Hydrogenation Reaction

Guo Xiaolinga,b, Chen Xiaoa, Su Dangshengb, Liang Changhaia   

  1. a Laboratory of Advanced Materials and Catalytic Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024;
    b Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016
  • Received:2017-07-26 Online:2018-01-15 Published:2017-10-24
  • Contact: 10.6023/A17070339 E-mail:changhai@dlut.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21373038, 21403026), the Natural Science Foundation of Liaoning Province in China (No. 2015021014), and the Fundamental Research Funds for the Central Universities (No. DUT16RC(4)03).

A series of Ni/C core-shell nano catalysts with abundant mesoporous and uniform size were prepared by Ni-MOF-74 pyrolysis. The Ni-MOF-74 was synthesized via hydrothermal method with nickel acetate and 2,5-dihydroxyterephthalic acid (DHTA) as raw materials. The pyrolysis process was carried out in a tube furnace under Argon (Ar) atmosphere with a heating rate of 2℃/min. Completed pyrolytic product Ni/C can be obtained by extending the pyrolysis time (6 h) at 400℃ or increasing the pyrolysis temperature (≥ 500℃) based on the TG result. Moreover, the particle size of Ni/C varied with pyrolysis temperature from 3 nm (500℃) to 17 nm (800℃). The TEM images and Ar ion sputtering XPS indicated a core-shell structure of the pyrolysis product. Nickel species can be stable in the form of nickel (Ni0) due to the electronic properties regulating and confinement effect of the carbon shell. Moreover, the carbon shell greatly weaken the interaction between particles, which is favorable for the dispersion of the catalyst in the reaction system. H2-TPR results show that the interaction between nickel and amorphous carbon increases with the pyrolysis temperature, which is unfavorable to the interaction between Ni species and the reactant. The phenylacetylene (PA) hydrogenation reaction was carried out with 0.2 g catalyst, 10 mL of 1 mol/L ethanolic phenylacetylene solution and 1.0 MPa H2 in a 50 mL high-pressure autoclave under 50℃. Ni/C exhibits excellent catalytic activity and recyclability in phenylacetylene (PA) hydrogenation. In addition, we compared the activity of Ni/C with several reported catalyst system and found their activity increases in the order of Ni, NiSix, supported Ni2Si, Ni/C, Pd and Pt. With an activity of up to 0.833 mmol•min-1•gcat.-1 at 50℃ (Ni/C-400-6, Ni/C-500-2), Ni/C is the most promising transition metal catalyst that can be comparable with noble metal.

Key words: MOFs pyrolysis, Ni/C nano-material, core-shell structure, heterogeneous catalysis, phenylacetylene hydrogenation