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高分散Co3O4对钙钛矿类LaCoO3低浓度甲烷催化燃烧性能的影响

陈雪 王雪峰 王荀 邓存宝 曹敏敏

陈雪, 王雪峰, 王荀, 邓存宝, 曹敏敏. 高分散Co3O4对钙钛矿类LaCoO3低浓度甲烷催化燃烧性能的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60051-3
引用本文: 陈雪, 王雪峰, 王荀, 邓存宝, 曹敏敏. 高分散Co3O4对钙钛矿类LaCoO3低浓度甲烷催化燃烧性能的影响[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60051-3
CHEN Xue, WANG Xue-feng, WANG Xun, DENG Cun-bao, CAO Min-min. Effect of highly dispersed Co3O4 on the catalytic performance of LaCoO3 perovskite in the combustion of lean methane[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60051-3
Citation: CHEN Xue, WANG Xue-feng, WANG Xun, DENG Cun-bao, CAO Min-min. Effect of highly dispersed Co3O4 on the catalytic performance of LaCoO3 perovskite in the combustion of lean methane[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60051-3

高分散Co3O4对钙钛矿类LaCoO3低浓度甲烷催化燃烧性能的影响

doi: 10.1016/S1872-5813(22)60051-3
基金项目: 国家自然科学基金联合基金(U1810206)和国家自然科学基金面上项目(51774172)资助
详细信息
    通讯作者:

    Tel: 13303433823,18634300787,E-mail: wangxuefeng01@tyut.edu.cn

    wangxun@tyut.edu.cn

  • 中图分类号: X959

Effect of highly dispersed Co3O4 on the catalytic performance of LaCoO3 perovskite in the combustion of lean methane

Funds: The project was supported by the NSF Joint Foundation Program (U1810206) and the NSF Facial Program (51774172)
  • 摘要: 本研究采用溶胶凝胶法,通过调变镧钴比合成了一种纳米新型钙钛矿类催化剂。利用物理吸附、ICP、XRD、H2-TPR、O2-TPD和XPS等技术对催化剂进行了表征,并对其在乏风甲烷氧化燃烧中的催化性能进行了研究。结果表明,高分散性的Co3O4纳米颗粒有利于甲烷的低温活化,且催化剂中镧钴钙钛矿体相可提供大量的晶格氧,促进高温下甲烷的催化燃烧速率和催化剂的高温稳定性。通过调变镧钴比例,可有效调变催化剂中Co3O4纳米颗粒的分散状态,进而实现催化剂低温活性和高温稳定性的有效统一。当La/Co比为0.9时,在空速为30000 mL/(gcat·h)的条件下,La0.9CoO3钙钛矿催化剂的甲烷起燃温度为382 ℃;稳定运行72 h后,甲烷转化率保持在95%以上。这些结果为今后开发低成本、高活性和高稳定性的甲烷燃烧催化剂提供了参考。
  • 图  1  (a)镧钴系列催化剂的X射线衍射图,(b)36°−38.5°的局部X射线衍射谱图

    Figure  1  (a)XRD patterns of LaxCoO3 catalysts;(b)XRD patterns of LaxCoO3 catalysts from 36° to 38.5°

    图  2  La0.9CoO3的(a)TEM和(b)HRTEM照片

    Figure  2  TEM (a) and HRTEM (b) images of La0.9CoO3

    图  3  (a)镧钴系列催化剂的Co 2p和(b) Co 2p3/2拟合谱图

    Figure  3  Co 2p spectra (a) and Co 2p3/2 fitting spectra (b) of LaxCoO3 catalysts

    图  4  镧钴系列催化剂的O 1s拟合谱图

    Figure  4  O 1s XPS spectra of various LaxCoO3 samples

    图  5  镧钴系列催化剂的O2-TPD谱图

    Figure  5  O2-TPD profiles of various LaxCoO3 samples

    图  6  镧钴系列催化剂的H2-TPR谱图

    Figure  6  H2-TPR profiles of various LaxCoO3 samples

    图  7  (a)镧钴系列催化剂的甲烷氧化活性和 (b) La0.9CoO3在640 ℃下的稳定性测试

    Figure  7  (a) Activity of various LaxCoO3 catalysts in methane oxidation; (b) Stability of various LaxCoO3 catalysts tested at 640 ℃ (0.2 g catalysts, CH4∶O2∶N2=1∶20∶79, GHSV=30000 mL/(gcat·h))

    图  8  (a)甲烷浓度和(b)氧气浓度对La0.9CoO3催化甲烷燃烧的影响

    Figure  8  Effects of methane (a) and oxygen (b) concentrations on the catalytic combustion of methane over the La0.9CoO3 catalyst (CH4∶O2∶N2=x∶20∶(80−x) or CH4∶O2∶N2=1∶y∶(99−y), GHSV=30000 mL/(gcat·h)

    表  1  镧钴系列催化剂的物性参数

    Table  1  Physical properties of various LaxCoO3 catalysts

    SampleLa/Co molar ratioSBET/
    (m2·g−1
    vpore/
    (cm3·g−1)
    dCo3O4-XRD
    /nm
    LaCoO30.9174.4360.03427.76
    La0.95CoO30.9064.3110.12127.59
    La0.9CoO30.8795.5040.03728.78
    La0.8CoO30.7815.4660.06621.05
    Co3O44.2760.05579.68
    notes: La/Co molar ratio wasdetermined by ICP; the specific surface area ( SBET ) and pore volume ( vpore) were derived from N2 sorption isotherms; the particle size ( dCo3O4 ) was calculated by Scherrer’s formula
    下载: 导出CSV

    表  2  镧钴系列催化剂的Co 2p3/2谱图拟合数据

    Table  2  Co 2p3/2 spectra fitting results of various LaxCoO3 samples

    SampleCo3 + Co2 + Co3 + /Co2 +
    BE /eVFraction /%BE /eVFraction /%
    LaCoO3779.5361 781.29391.56
    La0.95CoO3779.7660.16781.4739.841.51
    La0.9CoO3779.6747.78781.0852.220.92
    La0.8CoO3779.6143.71780.9956.290.78
    Co3O4779.5245.06781.0254.940.82
    下载: 导出CSV

    表  3  镧钴系列催化剂的O 1s谱图拟合数据

    Table  3  Fitted results of O 1s XPS spectra of various LaxCoO3 samples

    SampleOlatt OsurfOsurf/ Olatt
    BE /eVFraction /%BE /eVFraction /%
    LaCoO3528.5936.92 530.9863.081.71
    La0.95CoO3528.939.3531.2760.71.54
    La0.9CoO3528.8548.1531.351.91.08
    La0.8CoO3528.8448.49531.2551.511.06
    Co3O4529.8147.53531.1552.471.10
    下载: 导出CSV

    表  4  镧钴系列催化剂的H2-TPR拟合数据

    Table  4  Fitted H2-TPR results of various LaxCoO3 samples

    SamplePeak 1
    Co3 + →Co2 + (Co3O4
    Peak 2
    Co2 + →Co0(Co3O4
    Co3 + →Co2 + (LaCoO3
    Peak 3
    Co2 + →Co0(LaCoO3
    Co3O4/LaCoO3
    tred /℃percentage /%tred /℃percentage /%tred /℃percentage /%
    LaCoO3359.2613.39 401.5721.24 588.9465.370.0149
    La0.95CoO3353.9414.19406.8924.26599.3361.550.0623
    La0.9CoO335232.17406.57.2593.5860.630.0747
    La0.8CoO3359.2623.15409.3711.91594.2664.940.0199
    Co3O4350.5622.52447.777.48
    notes: tred refers to the temperature corresponding to the maximum value of the reduction peak and area percentage refers to the percentage of the reduction peak area to the total reduction peak area; According to the stoichiometric number, the relative content of Co3O4 and LaCoO3 is calculated by the reduction peak area in H2-TPR; that is, Co3O4/LaCoO3 = Speak-1/(0.5× Speak-3)
    下载: 导出CSV

    表  5  甲烷催化燃烧代表性催化剂性能对比

    Table  5  Comparison of representative catalysts in their performance in methane combustion

    NumberCatalystPreparation
    method
    Methane initial
    concentration /%
    GHSV /
    (mL·gcat−1·h−1)
    Temp. /℃Stability testRef.
    t10t50t90temp. (℃)-
    time (h)
    conv. /%
    1 La0.9CoO3 sol-gel method 1 30000 382 449 530 640−72 96 this work
    2 Pd/Al2O3 impregnation 1 12000 298 346 401 370−20 68 [36]
    3 BaMnAl11O19−d coprecipitation 0.5 18000 545 640 [37]
    4 Co3O4 coprecipitation 1 18000 285 373 455 360−30 80 [38]
    5 LaCoO3 template method 3 30000 370 485 578 650−70 82 [11]
    6 LaMnO3 template method 3 30000 405 480 570 650−70 98 [11]
    7 MnOx/LaMnO3 acid etching method 2.5 30000 351 441 519 [39]
    8 La0.8Sr0.2CoO3 acid etching method 1 44000 385 491 595 600−24 90 [40]
    下载: 导出CSV
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  • 收稿日期:  2022-04-23
  • 录用日期:  2022-06-21
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  • 网络出版日期:  2022-07-19

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