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γ-Mo2N/C催化剂的合成及其甲酸脱氢性能研究

路军 王美君 王志青 董立波 余钟亮 常丽萍

路军, 王美君, 王志青, 董立波, 余钟亮, 常丽萍. γ-Mo2N/C催化剂的合成及其甲酸脱氢性能研究[J]. 燃料化学学报(中英文), 2024, 52(1): 76-86. doi: 10.19906/j.cnki.JFCT.2023063
引用本文: 路军, 王美君, 王志青, 董立波, 余钟亮, 常丽萍. γ-Mo2N/C催化剂的合成及其甲酸脱氢性能研究[J]. 燃料化学学报(中英文), 2024, 52(1): 76-86. doi: 10.19906/j.cnki.JFCT.2023063
LU Jun, WANG Meijun, WANG Zhiqing, DONG Libo, YU Zhongliang, CHANG Liping. Synthesis of γ-Mo2N/C catalysts and its performance on formic acid dehydrogenation[J]. Journal of Fuel Chemistry and Technology, 2024, 52(1): 76-86. doi: 10.19906/j.cnki.JFCT.2023063
Citation: LU Jun, WANG Meijun, WANG Zhiqing, DONG Libo, YU Zhongliang, CHANG Liping. Synthesis of γ-Mo2N/C catalysts and its performance on formic acid dehydrogenation[J]. Journal of Fuel Chemistry and Technology, 2024, 52(1): 76-86. doi: 10.19906/j.cnki.JFCT.2023063

γ-Mo2N/C催化剂的合成及其甲酸脱氢性能研究

doi: 10.19906/j.cnki.JFCT.2023063
详细信息
    通讯作者:

    E-mail: wangmeijun@tyut.edu.cn

  • 中图分类号: TQ116.2

Synthesis of γ-Mo2N/C catalysts and its performance on formic acid dehydrogenation

  • 摘要: 甲酸 (FA) 因其H含量较高 (4.4%)、易产H2、可经小平台化合物合成等优势受到广泛关注,而γ-Mo2N/C对FA沿H2和CO2路径分解具有非常高的选择性,产生CO极少,显示出较高的应用价值。基于此,本研究采用对苯二胺和钼酸铵水溶液经前驱体制备γ-Mo2N/C催化剂,并对其FA分解性能进行了原位评价,采用热重分析 (TG)、X射线衍射 (XRD)、傅里叶变换红外光谱 (FT-IR)、扫描电镜 (SEM)、透射电镜 (TEM) 等表征手段对催化剂的结构和表面官能团进行了分析,利用DFT对FA在γ-Mo2N (200) 晶面的吸附构型进行了计算,在此基础上,对催化剂性能及FA在其表面的分解机理进行了研究。结果表明,γ-Mo2N/C在较低温度下即可表现出极高的催化活性,提高γ-Mo2N在C载体上的分散性能有效改善FA转化率。对苯二胺与钼酸铵的物质的量比为4∶1时,催化性能最佳,在160 ℃、100 h的FA分解实验中,催化剂性能稳定、H2选择性高(N2 40 mL/min, CO<5.0×10−5)。而DFT计算表明,FA中O−H键的H原子与γ-Mo2N/C (200) 晶面上N原子结合的可能性更大,而C=O键的O原子更有可能与γ-Mo2N/C (200) 晶面上Mo原子结合。上述结果有助于明确FA在γ-Mo2N/C作用下的分解机理,也显示出非贵金属催化剂γ-Mo2N/C在FA分解制H2方面潜在的应用前景。
  • FIG. 2882.  FIG. 2882.

    FIG. 2882.  FIG. 2882.

    图  1  不同温度下FA分解ΔG

    Figure  1  Two decomposition ΔG of FA at different temperatures

    图  2  反应器装置示意图

    Figure  2  Schematic diagram of the reactor

    图  3  γ-Mo2N/C前驱体的TG曲线

    Figure  3  TG result of γ-Mo2N/C precursor

    (a) Mass loss ration and DTG curves during γ-Mo2N/C pyrolysis at 700 ℃; (b) Transformation ratio of γ-Mo2N/C at different temperatures.

    图  4  高温合成后γ-Mo2N/C形貌

    Figure  4  γ-Mo2N/C morphology after high temperature synthesis

    图  5  不同γ-Mo2N/C的XRD谱图

    Figure  5  The XRD results of different γ-Mo2N/C (a): XRD patterns of γ-Mo2N/C synthesised by pyrolysis at different temperatures; (b): XRD patterns of C carriers synthesized at 700 ℃ and different ratios of γ-Mo2N/C after reaction with formic acid; (c): XRD patterns of C carriers and different ratios of γ-Mo2N/C at 700 ℃ after passivation with oxygen.

    图  6  700 ℃ 不同对苯二胺与钼酸铵比例合成的γ-Mo2N/C的XRD谱图

    Figure  6  The XRD results of γ-Mo2N/C synthesized at 700 ℃ with different ratios of p-phenylenediamine to ammonium molybdate

    图  7  700 ℃合成不同比例催化剂的N2 吸附-解吸等温线 (a) 和孔径分布 (b)

    Figure  7  N2 adsorption and desorption isotherms (a) and pore size distribution (b) for the synthesis of different ratios of catalysts at 700 ℃

    图  8  700 ℃合成不同比例催化剂的扫描电镜照片

    Figure  8  Scanning electron microscope images of different scales of catalysts synthesised at 700 ℃

    图  9  700 ℃合成不同比例催化剂的透射电镜照片

    Figure  9  Transmission electron microscopy images of different scales of catalysts synthesised at 700 ℃

    图  10  催化剂表面的红外光谱谱图

    Figure  10  FF-IR spectra of the catalyst surface

    图  11  700 ℃ NM-4∶1的高分辨XPS谱图

    Figure  11  High-resolution XPS spectra of NM-4∶1 at 700 ℃ (a): Survey; (b): C 1s; (c): Mo 3d; (d): N 1s.

    图  12  催化剂200晶体表面上FA的吸附状态

    Figure  12  Adsorption state of FA on the surface of Catalyst 200 crystals (a): main view; (b): side view; (c): top view.

    图  13  700 ℃下不同合成比例的γ-Mo2N/C在不同温度下分解FA的H2选择性和FA转化率及C载体的FA转化率与其XRD谱图

    Figure  13  H2 selectivity and FA conversion of different synthetic ratios on γ-Mo2N/C at 700 ℃ for the decomposition of FA at different temperatures and FA conversion of C carriers with their XRD patterns (a): FA conversion on γ-Mo2N/C; (b): H2 selectivity; (c): FA conversion over C carriers; (d): XRD spectra of C carriers.

    图  14  700 ℃ NM-4∶1在160 ℃分解FA的稳定性测试(a)和测试后的XRD谱图 (b)

    Figure  14  Stability test of NM-4∶1 at 700 ℃ for decomposition of FA at 160 ℃ (a) and XRD pattern after the test (b)

    表  1  不同温度下获得的γ-Mo2N/C的N和H含量

    Table  1  N and H contents of γ-Mo2N/C obtained at different temperatures

    Pyrolysis temperature/℃N w/%H w/%
    50014.921.80
    55012.451.50
    60010.071.35
    6507.520.92
    7005.750.65
    7502.760.58
    8002.540.44
    下载: 导出CSV

    表  2  700 ℃下不同比例催化剂Mo质量分数

    Table  2  Mo content of different ratios of catalysts at 700 ℃

    SampleMo
    (SEM-EDS, %)
    Mo
    (ICP-MS, %)
    Moδ+
    (XPS, atomic %)
    NM-1∶147.5268.160.64
    NM-2∶139.0259.210.38
    NM-3∶121.4446.480.22
    NM-4∶115.5635.800.15
    NM-5∶114.3633.200.07
    下载: 导出CSV

    表  3  不同合成比例下FA评价后与钝化后获得的γ-Mo2N/C的N和C质量分数

    Table  3  N and C contents of γ-Mo2N/C obtained after formic acid reaction and passivation at different synthesis ratios

    Composite rationN w/%C w/%
    NM-1∶1re1.2527.94
    NM-1∶1pa1.2828.27
    NM-2∶1 re1.8642.42
    NM-2∶1 pa2.1440.48
    NM-3∶1 re2.2846.37
    NM-3∶1 pa2.3446.16
    NM-4∶1re2.5354.38
    NM-4∶1pa2.7752.86
    NM-5∶1re2.9855.52
    NM-5∶1pa3.0153.70
    re: evaluation of the catalyst after testing; pa: passivated catalyst.
    下载: 导出CSV

    表  4  700 ℃合成不同比例催化剂的物理性质

    Table  4  Physical properties of catalysts for the synthesis of different ratios of catalysts at 700 ℃

    SampleSurface area/(m2·g−1)Pore volume/(cm3·g−1)Macropore ratio/
    %
    NM-1∶1 6.520.0743.28
    NM-2∶113.440.1352.44
    NM-3∶113.970.1553.08
    NM-4∶117.060.2059.20
    NM-5∶113.880.1646.86
    下载: 导出CSV

    表  5  钝化和评价后的γ-Mo2N/C的元素分析

    Table  5  Elemental content of γ-Mo2N/C after passivation and evaluation

    SampleElement abundance w /%
    NCH
    Fresh2.5453.700.77
    Long term2.7855.550.76
    下载: 导出CSV

    表  6  钝化和评价后的γ-Mo2N/C的物理特性

    Table  6  Physical properties of γ-Mo2N/C after passivation and evaluation

    SampleSurface area/(m2·g−1)Pore volume/(cm3·g−1)Macropore
    ratio/%
    Fresh17.060.2059.20
    Long term16.240.1158.00
    下载: 导出CSV
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  • 收稿日期:  2023-03-02
  • 修回日期:  2023-04-09
  • 录用日期:  2023-04-10
  • 网络出版日期:  2023-09-18
  • 刊出日期:  2024-01-09

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