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分子氧环氧化烯烃多相催化剂PCuMo11/富氮类共价有机骨架材料的制备及应用

高文秀 吕杰琼 邢树宇 谢晖 高永平 娄大伟

高文秀, 吕杰琼, 邢树宇, 等. 分子氧环氧化烯烃多相催化剂PCuMo11/富氮类共价有机骨架材料的制备及应用[J]. 复合材料学报, 2022, 39(10): 1-8 doi: 10.13801/j.cnki.fhclxb.20211108.003
引用本文: 高文秀, 吕杰琼, 邢树宇, 等. 分子氧环氧化烯烃多相催化剂PCuMo11/富氮类共价有机骨架材料的制备及应用[J]. 复合材料学报, 2022, 39(10): 1-8 doi: 10.13801/j.cnki.fhclxb.20211108.003
Wenxiu GAO, Jieqiong LV, Shuyu XING, Hui XIE, Yongping GAO, Dawei LOU. Preparation and application of heterogeneous catalyst PCuMo11/ nitrogen rich covalent organic framework material for olefin epoxidation with molecular oxygen oxidant[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 1-8. doi: 10.13801/j.cnki.fhclxb.20211108.003
Citation: Wenxiu GAO, Jieqiong LV, Shuyu XING, Hui XIE, Yongping GAO, Dawei LOU. Preparation and application of heterogeneous catalyst PCuMo11/ nitrogen rich covalent organic framework material for olefin epoxidation with molecular oxygen oxidant[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 1-8. doi: 10.13801/j.cnki.fhclxb.20211108.003

分子氧环氧化烯烃多相催化剂PCuMo11/富氮类共价有机骨架材料的制备及应用

doi: 10.13801/j.cnki.fhclxb.20211108.003
基金项目: 吉林省科技发展计划项目(2020122373JC);吉林省产业技术研究与开发项目(No.2020C028-1);吉林省教育厅科研规划项目(JJKH20200240KJ);吉林市科技局杰出青年人才培养项目(201831757);吉林省精细化工重点实验室(20140622023JC)
详细信息
    通讯作者:

    高文秀,博士,副教授,硕士生导师,研究方向为多相催化 E-mail:gaowenxiu-0922@163.com

  • 中图分类号: O643.36

Preparation and application of heterogeneous catalyst PCuMo11/ nitrogen rich covalent organic framework material for olefin epoxidation with molecular oxygen oxidant

  • 摘要: 环氧化合物是一类重要的有机合成中间体和化工原料,主要通过烯烃环氧化反应获得。制备在分子氧环境下高效、稳定、可重复使用的烯烃环氧化反应新型催化剂是一项十分有意义的工作。以富氮类共价有机骨架材料(PC)为载体,多金属氧酸盐PCuMo11为活性物质,制备了复合材料PCuMo11/PC。通过FT-IR、N2吸附脱附、XPS、TEM及EDS等测试对材料进行了表征,并将PCuMo11/PC应用于多相催化分子氧气氛下的烯烃(苯乙烯、1-辛烯、环辛烯和环十二烯)环氧化反应中,取得了较高的催化活性和选择性,循环使用5次以上催化活性没有明显下降。实验结果显示,二维层状富氮类共价有机骨架材料的高表面积及骨架中丰富的氮元素含量,有利于均匀地分散催化活性物质多金属氧酸盐,并与其建立相对稳定的化学链接,提高复合材料的催化活性及稳定性。

     

  • 图  1  PMo12、富氮类共价有机骨架材料(PC)、PCuMo11和PCuMo11/PC的FT-IR图谱

    Figure  1.  FT-IR spectra of PMo12, nitrogen rich covalent organic framework material (PC), PCuMo11 and PCuMo11/PC

    图  2  PC和PCuMo11/PC的N2吸附-脱附等温线(a)和孔径分布曲线(b)

    Figure  2.  N2 adsorption-desorption isotherm (a) and pore size distribution curves (b) of PC and PCuMo11/PC

    图  3  PCuMo11/PC (a)、Mo3d (b)、Cu2p (c) 和N1s (d)的XPS能谱

    Figure  3.  XPS spectra of PCuMo11/PC composite (a), Mo3d (b), Cu2p (c) , N1s (d)

    图  4  PCuMo11/PC的TEM图像和EDS面扫图像

    Figure  4.  TEM and EDS images of PCuMo11/PC

    图  5  PCuMo11/PC催化苯乙烯(a)、环辛烯(b)、环十二烯(c)、 1-辛烯(d)环氧化反应的循环实验

    Figure  5.  Recycling experiments of styrene (a), cyclooctene (b), cyclododecene (c), 1-octene (d) epoxidation over PCuMo11/PC

    表  1  PC和PCuMo11/PC的物理性质

    Table  1.   Physical performance of PC and PCuMo11/PC

    SampleSBET /(m2·g−1)Mode pore size/nmPore volume/
    (cm3·g−1)
    PC 216 1.30 0.6
    PCuMo11/PC 60 1.43 0.2
    Notes: SBET—Specific surface area.
    下载: 导出CSV

    表  2  PCuMo11/PC催化不同烯烃环氧化反应的催化性能

    Table  2.   Catalytic performance of PCuMo11/PC in different olefins epoxidation

    SubstrateTime/hConversion/%Epoxide selectivity/%Yield/%
    Styrene 1 98 84 82
    Cyclooctene 1 98 ≥99 98
    Cyclododecene 1 95 ≥99 95
    1-octene 6 99 ≥99 99
    Notes:Substrate olefin 2 mmol, catalyst PCuMo11/PC 20 mg, solvent CH3CN 10 mL, IBA 6 mmol, O2 10 mL/min, temperature 60℃, unless otherwise mentioned.
    下载: 导出CSV

    表  3  PCuMo11/PC与同类催化剂催化烯烃环氧化反应性能比较

    Table  3.   Catalytic performance comparison of PCuMo11/PC with other reported catalysts for olefins epoxidation

    EntryCatalystSubstrateOxidantTime
    /h
    Conversion
    /%
    Epoxide selectivity/%TOF/(10− 3 mol·g− 1·h− 1)Ref.
    1 PCuMo11/PC Styrene O2 1 98 84 98 This work
    2 PMo11Co/SBA Styrene Air 1 89 7 89 [25]
    3 POSS-OIM8-PW Styrene H2O2 6 72 66 12 [26]
    4 CoPMA/POP-II Styrene H2O2 9 67 14 8 [27]
    5 PCuMo11/PC Cyclooctene O2 1 98 ≥ 99 98 This work
    6 POSS-OIM8-PW Cyclooctene H2O2 2 100 100 50 [26]
    7 PMo11Co/SBA Cyclooctene Air 3 98 ≥ 99 33 [25]
    8 PMA@COF-300 Cyclooctene TBHP 3 91 ≥ 99 30 [18]
    9 Fe/PMA@CIN− 1 Cyclooctene H2O2 9 88 ≥ 99 10 [28]
    10 CoPMA/POP-II Cyclooctene H2O2 9 80 ≥ 99 9 [27]
    11 PCuMo11/PC Cyclododecene O2 1 95 ≥ 99 95 This work
    12 PMA@COF-300 Cyclododecene TBHP 3 34 ≥ 99 11 [18]
    13 Fe/PMA@CIN− 1 Cyclododecene H2O2 9 58 ≥ 99 6 [28]
    14 PCuMo11/PC 1-octene O2 6 99 ≥ 99 17 This work
    15 POSS-OIM8-PW 1-octene H2O2 6 51 99 9 [26]
    16 PMA@COF-300 1-octene TBHP 9 77 ≥ 99 9 [18]
    Notes: TBHP—Tert-butyl hydroperoxide; SBA—SBA-15 (Santa barbara amorphous-15); POSS-OIM8-PW—POSS-derived mesoporous ionic copolymer-polyoxometalate (POSS—Polyhedral oligomeric silsesquioxanes, OIM8—[3-Octyl-1-vinylimidazolium]Br, PW—Phospho-tungstic acid); CoPMA/POP-II—Triphenylamine-based porous organic polymers supporting cobalt phosphomolybdate (CoPMA—Cobalt phosphomolybdate, POP-II—Triphenylamine-based porous organic polymers); PMA@COF-300—Heteropolyacid-based hybrid composite (PMA—Phosphomolybdic acid, COF-300—Covalent organic framework material); CIN—Covalent imine network;
    $ \mathrm{T}\mathrm{u}\mathrm{r}\mathrm{n}\mathrm{o}\mathrm{v}\mathrm{e}\mathrm{r}\;\;\mathrm{f}\mathrm{r}\mathrm{e}\mathrm{q}\mathrm{u}\mathrm{e}\mathrm{n}\mathrm{c}\mathrm{y}\;\;\left(\mathrm{T}\mathrm{O}\mathrm{F}\right)\;\;=\dfrac{\mathrm{m}\mathrm{o}\mathrm{l}\mathrm{e}\;\;\mathrm{o}\mathrm{f}\;\;\mathrm{c}\mathrm{o}\mathrm{n}\mathrm{v}\mathrm{e}\mathrm{r}\mathrm{t}\mathrm{e}\mathrm{d}\;\;\mathrm{s}\mathrm{u}\mathrm{b}\mathrm{s}\mathrm{t}\mathrm{r}\mathrm{a}\mathrm{t}\mathrm{e}}{\mathrm{c}\mathrm{a}\mathrm{t}\mathrm{a}\mathrm{l}\mathrm{y}\mathrm{s}\mathrm{t}\left(\mathrm{g}\right)\times\mathrm{r}\mathrm{e}\mathrm{a}\mathrm{c}\mathrm{t}\mathrm{i}\mathrm{o}\mathrm{n}\;\;\mathrm{t}\mathrm{i}\mathrm{m}\mathrm{e}\left(\mathrm{h}\right)} $
    下载: 导出CSV
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  • 收稿日期:  2021-09-09
  • 录用日期:  2021-10-31
  • 修回日期:  2021-10-16
  • 网络出版日期:  2021-11-09
  • 刊出日期:  2022-10-15

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