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Fe3O4晶体碳化过程中的晶面效应

李思琪 魏旭松 王洪 青明 索海云 吕振刚 过会闯 刘颖 于欣 杨勇 李永旺

李思琪, 魏旭松, 王洪, 青明, 索海云, 吕振刚, 过会闯, 刘颖, 于欣, 杨勇, 李永旺. Fe3O4晶体碳化过程中的晶面效应[J]. 燃料化学学报(中英文), 2023, 51(9): 1282-1290. doi: 10.19906/j.cnki.JFCT.2023017
引用本文: 李思琪, 魏旭松, 王洪, 青明, 索海云, 吕振刚, 过会闯, 刘颖, 于欣, 杨勇, 李永旺. Fe3O4晶体碳化过程中的晶面效应[J]. 燃料化学学报(中英文), 2023, 51(9): 1282-1290. doi: 10.19906/j.cnki.JFCT.2023017
LI Si-qi, WEI Xu-song, WANG Hong, QING Ming, SUO Hai-yun, LÜ Zhen-gang, GUO Hui-chuang, LIU Ying, YU Xin, YANG Yong, LI Yong-wang. The effect of crystal plane on Fe3O4 carbonization[J]. Journal of Fuel Chemistry and Technology, 2023, 51(9): 1282-1290. doi: 10.19906/j.cnki.JFCT.2023017
Citation: LI Si-qi, WEI Xu-song, WANG Hong, QING Ming, SUO Hai-yun, LÜ Zhen-gang, GUO Hui-chuang, LIU Ying, YU Xin, YANG Yong, LI Yong-wang. The effect of crystal plane on Fe3O4 carbonization[J]. Journal of Fuel Chemistry and Technology, 2023, 51(9): 1282-1290. doi: 10.19906/j.cnki.JFCT.2023017

Fe3O4晶体碳化过程中的晶面效应

doi: 10.19906/j.cnki.JFCT.2023017
基金项目: 国家自然科学基金 (21972162, 22025804)和准格尔旗科技重大专项项目(2022ZD-03) 资助
详细信息
    通讯作者:

    Tel: 18611906663

    E-mail: yyong@sxicc.ac.cn

  • 中图分类号: O643.36

The effect of crystal plane on Fe3O4 carbonization

Funds: The project was supported by the National Natural Science Foundation of China (21972162 and 22025804) and Jungar Banner Important Science & Technology Specific Projects (2022ZD-03)
  • 摘要: 在费托合成反应中,Fe基催化剂由于价格低廉、活性高、CH4选择性低等多种优势,被广泛应用于大规模煤炭间接液化工业中。催化性能与催化剂颗粒尺寸、表面结构、成分构成等性质密切相关。还原碳化是铁基催化剂活化的关键步骤,本工作通过改变晶体生长条件,制备了暴露{111}晶面的不同尺寸的Fe3O4-O,以及尺寸接近的Fe3O4-O和暴露{110}晶面的Fe3O4-RD,探究Fe3O4晶粒尺寸以及暴露晶面对碳化过程的影响。结果表明,尺寸达到微米级的Fe3O4-O晶体比50 nm的晶体更难被碳化。利用原位XRD表征尺寸均为150 nm的Fe3O4-O和Fe3O4-RD晶体在还原碳化过程中的物相组成变化,结果显示,两种晶体的碳化速率不同,且可碳化上限不同,因此,晶面取向会影响还原碳化过程。使用TEM表征暴露不同晶面的Fe3O4碳化后的晶体结构,发现两种晶体的形貌均发生改变,形成核壳结构。
  • FIG. 2671.  FIG. 2671.

    FIG. 2671.  FIG. 2671.

    图  1  微米级Fe3O4-O1的SEM照片:(a)新鲜样品;(b)对(a)中虚线区域放大;(c) 300 ℃,5%CO气氛碳化12 h;(d)对(c)中虚线区域放大;(e) 300 ℃,100%CO气氛碳化12 h;(f)对(e)中虚线区域放大

    Figure  1  SEM of micron-sized Fe3O4-O1: (a) as prepared sample; (b) zoomed-in image of marked area in (a); (c) carbonized for 12 h in 5%CO at 300 ℃; (d) zoomed-in image of marked area in (c); (e) carbonized for 12 h in 100%CO at 300 ℃; (f) zoomed-in image of marked area in (e)

    图  2  微米级Fe3O4-O1在300 ℃、100%CO气氛中碳化12 h后的XRD谱图

    Figure  2  XRD patterns of micron-sized Fe3O4-O1 carbonized at 300 ℃ in 100% CO for 12 h

    图  3  50 nm Fe3O4-O3在300 ℃、5%CO气氛中碳化不同时间的XRD谱图

    Figure  3  XRD patterns of 50 nm-sized Fe3O4-O3 with different time of carbonization in 5% CO at 300 ℃

    图  4  50 nm Fe3O4-O3碳化前后TEM照片:(a)新鲜样品的TEM;(b)新鲜样品的HRTEM;(c) 对(b)中虚线区域放大;(d)碳化样品的TEM;(e)碳化样品的HRTEM;(f)对(e)中虚线区域放大

    Figure  4  TEM images of 50 nm Fe3O4-O3: (a) TEM of fresh sample; (b) HRTEM of fresh sample; (c) zoomed-in image of marked area in (b); (d) TEM of carbonized sample; (e) HRTEM of carbonized sample; (f) zoomed-in image of marked area in (e)

    图  5  两种尺寸相近的Fe3O4晶体的SEM照片:(a)150 nm左右Fe3O4-O2;(b)对(a)中虚线区域放大;(c)150 nm左右 Fe3O4-RD; (d)对(c)中虚线区域放大

    Figure  5  SEM of Fe3O4 NPs: (a) 150 nm Fe3O4-O2; (b) zoomed-in image of marked area in (a); (c) 150 nm Fe3O4-RD; (d) zoomed-in image of marked area in (c)

    图  6  原位XRD碳化实验的分析:(a1)、(a2)Fe3O4-O2碳化中特定时间点的XRD谱图和2D热图;(b1)、(b2) Fe3O4-RD碳化中特定时间点的XRD谱图和2D热图;(c)两种晶体的Fe3O4最强峰41.3°的相对衍射强度变化;(d)气相色谱分析尾气计算出的CO转化率

    Figure  6  Analysis of in-situ XRD carbonization experiments: (a1), (a2) XRD patterns at specific time points and 2D heatmap of Fe3O4-O2 carbonization process; (b1), (b2) XRD patterns at specific time points and 2D heatmap of Fe3O4-RD carbonization process; (c) diffraction intensity change of the Fe3O4 strongest peak of two crystals at 41.3°; (d) CO conversion calculated by gas chromatographic analysis of exhaust gas

    图  7  原位XRD碳化实验结束后样品的TEM照片: (a)Fe3O4-O2碳化后的TEM;(b)Fe3O4-O2碳化后HRTEM;(d)Fe3O4-RD碳化后的TEM;(e)Fe3O4-RD碳化后的HRTEM;(c)、(f)两个样品(b)和(e)中对应区域的EDX mapping

    Figure  7  TEM images of the samples after the in-situ XRD carbonization experiments: (a) TEM of carbonized Fe3O4-O2; (b) HRTEM of carbonized Fe3O4-O2; (d)TEM of carbonized Fe3O4-RD; (e) HRTEM of carbonized Fe3O4-RD; (c), (f) EDX mapping of the corresponding regions of (b) and (e)

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出版历程
  • 收稿日期:  2022-10-28
  • 修回日期:  2022-12-11
  • 录用日期:  2022-12-13
  • 网络出版日期:  2023-01-10
  • 刊出日期:  2023-09-30

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