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Cr-WO3超细纳米线用于苯乙烯选择性氧化制苯甲醛

王会香 李鹏慧 吕宝亮

王会香, 李鹏慧, 吕宝亮. Cr-WO3超细纳米线用于苯乙烯选择性氧化制苯甲醛[J]. 燃料化学学报(中英文), 2023, 51(12): 1814-1824. doi: 10.19906/j.cnki.JFCT.2023038
引用本文: 王会香, 李鹏慧, 吕宝亮. Cr-WO3超细纳米线用于苯乙烯选择性氧化制苯甲醛[J]. 燃料化学学报(中英文), 2023, 51(12): 1814-1824. doi: 10.19906/j.cnki.JFCT.2023038
WANG Hui-xiang, LI Peng-hui, LÜ Bao-liang. Selective oxidation of styrene to benzaldehyde with Cr-WO3 ultrafine nanowires[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1814-1824. doi: 10.19906/j.cnki.JFCT.2023038
Citation: WANG Hui-xiang, LI Peng-hui, LÜ Bao-liang. Selective oxidation of styrene to benzaldehyde with Cr-WO3 ultrafine nanowires[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1814-1824. doi: 10.19906/j.cnki.JFCT.2023038

Cr-WO3超细纳米线用于苯乙烯选择性氧化制苯甲醛

doi: 10.19906/j.cnki.JFCT.2023038
基金项目: 国家自然科学基金(21972158),中国科学院洁净能源创新研究院-榆林学院联合基金(2021017),煤炭与绿色化工高效利用国家重点实验室基金(2021-K10),山西省优秀博士科研启动基金(SQ2019006)和专利转化专项基金(202202093)资助。
详细信息
    通讯作者:

    E-mail: lvbl@sxnu.edu.cn

  • 中图分类号: O643

Selective oxidation of styrene to benzaldehyde with Cr-WO3 ultrafine nanowires

Funds: The project was supported by the National Natural Science Foundation of China (21972158), Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (2021017), Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2021-K10), Doctoral Research Initiation Fund of Shanxi Province (SQ2019006) and Patent Conversion Foundation of Shanxi Province (202202093)
  • 摘要: 本工作在水热法制备WO3过程中直接引入Cr3 + 作为改性剂,其在非(001)晶面的选择性吸附,实现了WO3形貌从纳米棒到[001]取向超细纳米线(UNWs)的转变,最终所得Cr-WO3 UNWs催化剂的比表面积可达297 m2/g。此外,Cr3 + 的晶格掺杂和减缓结晶作用有效增加了WO3表面氧空位(L酸位点)浓度。在苯乙烯选择性氧化制苯甲醛反应中,最佳条件下(70 ℃、r(nH2O2/n苯乙烯)=2.0、6 h、m=30 mg),Cr-WO3 UNWs分别将苯乙烯转化率和苯甲醛选择性从单一WO3纳米棒的19.0%和49.6%提升到72.0%和84.6%,其催化性能的提升归结于以下两点:第一,超大比表面积可提供充足的反应活性位点;第二,L酸位点可将H2O2活化为W-OOH活性物种,L酸位点浓度的增加有利于更多活性物种的产生。
  • FIG. 2808.  FIG. 2808.

    FIG. 2808.  FIG. 2808.

    图  1  Cr-WO3和纯WO3样品的SEM照片

    Figure  1  SEM images of ((a), (b)) Cr-WO3 and ((c), (d)) pure WO3 samples

    图  2  Cr-WO3和纯WO3的XRD谱图

    Figure  2  XRD patterns of Cr-WO3 UNWs and WO3 NRs

    图  3  Cr-WO3和WO3样品的TEM、HRTEM和SAED照片以及Cr-WO3的EDX mapping图

    Figure  3  TEM, HRTEM images and SAED patterns of ((a)−(c)) Cr-WO3 UNWs and ((d)−(f)) WO3 NRs; ((g)−(j)) EDX mapping images of Cr-WO3 UNWs

    图  4  样品的Raman谱图

    Figure  4  Raman spectra of Cr-WO3 UNWs and WO3 NRs

    图  5  Cr-WO3和WO3的XPS全谱、Cr 2p、W 4f和O 1s谱图

    Figure  5  (a) Full XPS spectra of samples; (b) Cr 2p of Cr-WO3 UNWs; (c) W 4f and (d) O 1s of Cr-WO3 UNWs and WO3 NRs

    图  6  样品在70 ℃下的Py-FTIR吸收光谱谱图

    Figure  6  Py-FTIR spectra of Cr-WO3 UNWs, WO3 NRs and Cr2WO6 NPs at 70 ℃

    图  7  样品的N2吸附-脱附曲线及孔分布

    Figure  7  N2 adsorption/desorption isotherms and corresponding pore size distributions (inset e) of (a) Cr-WO3 UNWs, (b) WO3 NRs and (c) Cr2WO6 NPs

    图  8  Cr-WO3 UNWs催化苯乙烯制苯甲醛反应的影响因素

    Figure  8  Influence factors of styrene to benzaldehyde on Cr-WO3 UNWs (a): molar ratio r of H2O2 to styrene; (b): reaction temperature; (c): reaction time; (d): catalyst dosage

    图  9  H2O2效率和不同H2O2用量下的转化率

    Figure  9  (a) H2O2 efficiency and (b) conversion increment of styrene under different H2O2 dosage

    图  10  不同样品作用下的苯乙烯转化率和苯甲醛选择性

    Figure  10  (a) Conversion of styrene and (b) selectivity of benzaldehyde under different catalysts

    图  11  10 mg用量时WO3和Cr-WO3的性能比较

    Figure  11  (a) Conversion, selectivity and (b) BD yield of WO3 NRs and Cr-WO3 UNWs with 10 mg dosage

    图  12  催化剂的循环性能

    Figure  12  The cycling performance of Cr-WO3 UNWs

    图  13  苯乙烯在催化剂上可能的反应过程

    Figure  13  The possible oxidation reaction process of styrene on the Cr-WO3 UNWs

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  • 收稿日期:  2023-04-06
  • 修回日期:  2023-04-26
  • 录用日期:  2023-04-26
  • 网络出版日期:  2023-05-06
  • 刊出日期:  2023-12-05

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