催化学报

催化学报 ›› 2020, Vol. 41 ›› Issue (2): 350-356.DOI: 10.1016/S1872-2067(19)63439-X

• 论文 • 上一篇    下一篇

镍掺杂对氧化铝纳米片负载金催化剂在CO氧化反应中的促进作用

路饶, 贺雷, 王阳, 高新芊, 李文翠   

  1. 大连理工大学化工学院精细化工国家重点实验室, 辽宁大连 116024
  • 收稿日期:2019-05-10 修回日期:2019-06-23 出版日期:2020-02-18 发布日期:2019-11-04
  • 通讯作者: 李文翠

Promotion effects of nickel-doped Al2O3-nanosheet-supported Au catalysts for CO oxidation

Rao Lu, Lei He, Yang Wang, Xin-Qian Gao, Wen-Cui Li   

  1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
  • Received:2019-05-10 Revised:2019-06-23 Online:2020-02-18 Published:2019-11-04

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摘要： 负载型金催化剂在CO氧化反应中具有良好的低温活性，受到了研究者的广泛关注，其催化性能与载体的性质密切相关.氧化铝具有廉价易得、比表面积大和热稳定性好等优点.然而，作为一种非还原性载体，氧化铝提供活性氧物种的能力差，与还原性载体相比催化剂的CO氧化活性较低.理论计算和实验结果表明，在金催化剂中引入过渡金属镍能够有效促进氧分子在催化剂表面的吸附和活化，从而提升金催化剂活性.此外，过渡金属的存在能够提高金的分散度，增加活性位数目，防止在高温预处理过程中金颗粒的烧结，从而提高催化剂的活性和稳定性.
基于上述考虑，本文在氧化铝纳米片合成过程中原位引入硝酸镍，以实现对氧化铝载体的改性，然后负载金并应用于CO氧化反应.结果表明，当载体中的Ni/Al摩尔比为0.05，金负载量为1 wt%时，采用还原性气氛对催化剂进行预处理可以得到具有CO氧化性能优良的金催化剂，20℃下CO转化率即可达100%.预处理气氛能够显著影响催化活性，采用还原性气氛预处理后催化剂活性明显优于氧化性气氛预处理.
采用X射线衍射（XRD）、高分辨透射电镜（HRTEM）、氢气程序升温还原（H2-TPR）、氧气程序升温脱附（O2-TPD）、CO吸附原位红外光谱（CO-DRIFT）和X射线光电子能谱（XPS）等表征手段进一步研究了镍掺杂对Au/Al2O3催化剂上CO氧化反应的促进作用机制.XRD测试未观察到明显的金或镍衍射峰，表明金或镍物种均为高分散.HRTEM结果进一步证实，引入镍物种后金颗粒的粒径由3.6nm减小为2.4nm，表明镍掺杂有助于提高金的分散度.而XPS结果显示，镍掺杂催化剂中金与镍存在电子转移，而镍仍以NiO为主.H2-TPR结果表明，镍掺杂的催化剂前驱体中的金物种更容易被还原.O2-TPD结果证实，镍掺杂催化剂能够引入更多的氧空位，促进氧分子的吸附和活化，从而促进CO氧化反应的进行.CO-DRIFT结果表明，相比于氧化性气氛，采用还原性气氛预处理后金物种的电子云密度增加，CO吸附增强.而对于镍掺杂的催化剂，金物种吸附CO分子的能力进一步提高，有利于CO氧化反应的进行.综上，镍掺杂能够有效提高催化剂中金的分散度，增强催化剂对CO的吸附，促进氧气分子的吸附和活化，从而提高了催化剂的CO氧化活性.

关键词: 氧化铝, 金催化剂, 镍掺杂, 一氧化碳氧化, 氧物种活化

Abstract: Supported gold catalysts show high activity toward CO oxidation, and the nature of the support significantly affects the catalytic activity. Herein, serial Ni doping of thin porous Al2O3 nanosheets was performed via a precipitation-hydrothermal method by varying the amount of Ni during the precipitation step. The prepared nanosheets were subsequently used as supports for the deposition of Au nanoparticles (NPs). The obtained Au/NixAl catalysts were studied in the context of CO oxidation to determine the effect of Ni doping on the supports. Enhanced catalytic performances were obtained for the Au/NixAl catalysts compared with those of the Au supported on bare Al2O3. The Ni content and pretreatment atmosphere were both shown to influence the catalytic activity. Pretreatment under a reducing atmosphere was beneficial for improving catalytic activity. The highest activity was observed for the catalysts with a Ni/Al molar ratio of 0.05, achieving complete CO conversion at 20℃ with a gold loading of 1 wt%. The in-situ FTIR results showed that the introduction of Ni strengthened CO adsorption on the Au NPs. The H2-TPR and O2-TPD results indicated that the introduction of Ni produced new oxygen vacancies and allowed the oxygen molecules to be adsorbed and activated more easily. The improved catalytic performance after doping Ni was attributed to the smaller size of the Au NPs and more active oxygen species.

Key words: Alumina, Gold catalyst, Nickel doping, CO oxidation, Oxygen activation