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Rh/g-C3N4纳米催化剂催化水合肼分解制氢性能研究

邱小魁 孙佳丽 花俊峰 郑君宁 万超 许立信

邱小魁, 孙佳丽, 花俊峰, 郑君宁, 万超, 许立信. Rh/g-C3N4纳米催化剂催化水合肼分解制氢性能研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022093
引用本文: 邱小魁, 孙佳丽, 花俊峰, 郑君宁, 万超, 许立信. Rh/g-C3N4纳米催化剂催化水合肼分解制氢性能研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022093
QIU Xiao-kui, SUN Jia-li, HUA Jun-feng, ZHENG Jun-ning, WAN Chao, XU Li-xin. Hydrogen generation from hydrous hydrazine over Rh/g-C3N4 nanocatalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022093
Citation: QIU Xiao-kui, SUN Jia-li, HUA Jun-feng, ZHENG Jun-ning, WAN Chao, XU Li-xin. Hydrogen generation from hydrous hydrazine over Rh/g-C3N4 nanocatalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022093

Rh/g-C3N4纳米催化剂催化水合肼分解制氢性能研究

doi: 10.19906/j.cnki.JFCT.2022093
基金项目: 国家自然科学基金青年基金项目(22108238, U22A20408)、安徽省自然科学基金青年基金项目(1908085QB68)、安徽省科技重大专项(201903a05020055)、中国博士后面上项目(2019M662060)和特别资助站中项目(2020T130580, PC2022046)资助
详细信息
    通讯作者:

    E-mail: lxxu@hotmail.com

  • 中图分类号: O643.36

Hydrogen generation from hydrous hydrazine over Rh/g-C3N4 nanocatalysts

Funds: The project was supported by the National Natural Science Foundation of China (22108238, U22A20408), Anhui Provincial Natural Science Foundation (1908085QB68), Major Science and Technology Project of Anhui Province (201903a05020055), China Postdoctoral Science Foundation (2019M662060, 2020T130580,PC2022046)
  • 摘要: 水合肼(N2H4·H2O)作为一种理想的储氢材料,引起了广大研究者的关注。水合肼在室温下相对稳定,在温和条件下开发高效、高选择性的催化剂是实现水合肼分解制氢的关键。本文将三聚氰胺在静态空气中焙烧合成的g-C3N4作为载体,通过简单的浸渍还原法将Rh纳米粒子负载在g-C3N4载体上制备出Rh/g-C3N4催化剂。采用多种表征方法对催化剂的微观结构、组成成分进行研究。此外,还研究了反应温度和NaOH浓度对催化剂催化水合肼分解的影响。研究结果表明,催化剂优异的催化活性源于g-C3N4载体为金属Rh提供了锚定位点,并且载体和金属之间存在强相互作用。催化剂的催化活性随着反应温度的升高而不断提升,当NaOH浓度为0.75 mol/L时Rh/g-C3N4催化剂具有最高的催化活性。Rh/g-C3N4催化剂催化水合肼分解制氢的活化能为30.7 kJ/mol,TOF值为1466.4 h−1,在经过5次循环后,催化剂依旧保持着较好的催化活性,表明催化剂具有良好的循环稳定性。
  • 图  1  Rh/g-C3N4合成示意图

    Figure  1  The synthetic schematic illustration of Rh/g-C3N4

    图  2  不同放大倍数下Rh/g-C3N4催化剂的TEM图

    Figure  2  TEM images of Rh/g-C3N4 with different magnification

    图  3  Rh/g-C3N4催化剂的XRD谱图

    Figure  3  the X-ray diffraction (XRD) patterns of Rh/g-C3N4

    图  4  (a) Rh/g-C3N4的XPS测试全谱图,(b) Rh/g-C3N4的Rh 3d区域XPS谱图,Rh/g-C3N4和g-C3N4的 (c) C 1s区域,(d) N 1s区域XPS谱图

    Figure  4  XPS spectra of Rh/g-C3N4 sample (a) Full XPS spectrum and (b) Rh 3d, (c) the XPS of C 1s regions and (d) N 1s regions of Rh/g-C3N4 and g-C3N4

    图  5  (a) 343 K下Rh/g-C3N4在不同浓度的碱溶液中催化水合肼分解产生的气体当量;(b) 343 K下不同NaOH浓度反应对应的TOF值;(c) 不同温度下Rh/g-C3N4上水合肼分解生成气体当量体积与时间的关系;(d) Rh/g-C3N4催化剂催化水合肼分解阿伦尼乌斯曲线图

    Figure  5  (a) Plots equivalent produced by dehydrogenation of hydrous hydrazine catalyzed by Rh/g-C3N4 in alkaline solutions with different concentrations at 343 K; (b) TOF values corresponding to different NaOH concentration reactions at 343 K; (c) Relationship between volume and time of gas generated by hydrous hydrazine dehydrogenation at Rh/g-C3N4 at different temperatures; (d) Arrhenius diagram of dehydrogenation of hydrous hydrazine catalyzed by Rh/g-C3N4 catalyst

    图  6  Rh/g-C3N4催化水合肼分解产氢循前后的XRD对比图

    Figure  6  the X-ray diffraction (XRD) patterns of Rh/g-C3N4 befor and after reaction

    图  7  Rh/g-C3N4在343 K下催化水合肼产氢循环测试图

    Figure  7  The recycling performance of Rh/g-C3N4 at 343 K

    表  1  Rh/g-C3N4催化剂的ICP-AES测试结果

    Table  1  ICP-AES results of Rh/g-C3N4 catalyst

    CatalystRh (wt%)Final Metals/Catalyst
    (mmol·(100 mg)−1)
    Rh/g-C3N412.370.137
    下载: 导出CSV

    表  2  不同催化剂在水合肼产氢中的性能比较

    Table  2  Comparison performance of different catalysts for dehydrogenation of hydrous hydrazine

    CatalystT/(K)TOF/ (h−1)Ea/ (kJ·mol−1)Ref.
    Rh/g-C3N43231466.430.7This work
    Rh55Ni45/Ce(OH)CO332339538.8[19]
    Rh4Ni1@RGO29820.1/[24]
    Rh4Ni2986/[33]
    Ni0.90Pt0.05Rh0.05/La2O329866.7/[34]
    Ni66Rh34@ZIF-832314058.1[35]
    Rh47Ni18P35@MOF-74323715.449.39[21]
    Ni37Pt63/g-C3N432357036.6[29]
    Ni0.4Pt0.6/CNTs3231725.336.3[36]
    Pt0.6Ni0.4/(MnOx)2-C3N4323274948.7[37]
    下载: 导出CSV
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  • 收稿日期:  2022-09-23
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