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WO3-x/CFs三相催化剂的制备及其可见光催化转化甲烷制甲醇

荣丽青 杨娟 戴俊 王大钊

荣丽青, 杨娟, 戴俊, 等. WO3-x/CFs三相催化剂的制备及其可见光催化转化甲烷制甲醇[J]. 复合材料学报, 2023, 40(5): 2709-2721. doi: 10.13801/j.cnki.fhclxb.20220627.001
引用本文: 荣丽青, 杨娟, 戴俊, 等. WO3-x/CFs三相催化剂的制备及其可见光催化转化甲烷制甲醇[J]. 复合材料学报, 2023, 40(5): 2709-2721. doi: 10.13801/j.cnki.fhclxb.20220627.001
RONG Liqing, YANG Juan, DAI Jun, et al. Preparation of WO3-x/CFs triphase catalyst and visible-light photocatalytic conversion of methane to methanol[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2709-2721. doi: 10.13801/j.cnki.fhclxb.20220627.001
Citation: RONG Liqing, YANG Juan, DAI Jun, et al. Preparation of WO3-x/CFs triphase catalyst and visible-light photocatalytic conversion of methane to methanol[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2709-2721. doi: 10.13801/j.cnki.fhclxb.20220627.001

WO3-x/CFs三相催化剂的制备及其可见光催化转化甲烷制甲醇

doi: 10.13801/j.cnki.fhclxb.20220627.001
基金项目: 国家自然科学基金(52074103;U2004194);河南省自然科学基金(202300410181);河南省科技攻关重点项目(222102320095);河南省教育厅重点科研项目(21 A440008)
详细信息
    通讯作者:

    杨娟,博士,教授,研究方向为光催化与能源化学  E-mail: yangjuan@hpu.edu.cn

  • 中图分类号: TB333

Preparation of WO3-x/CFs triphase catalyst and visible-light photocatalytic conversion of methane to methanol

Funds: National Natural Science Foundation of China (52074103; U2004194); Natural Science Foundation of Henan Province (202300410181); Key Science and Technology Project of Henan Province (222102320095); Key Scientific Research Project of Henan Province Education Department (21 A440008)
  • 摘要: 将甲烷选择性转化为平台分子甲醇是有效利用天然气资源的理想途径之一,低碳排放的光催化技术可在室温常压下活化与转化甲烷,但水相光催化体系的甲烷转化性能仍较低。采用水热法首先合成富含氧缺陷的氧化钨(WO3-x),借助聚四氟乙烯浓缩液(PTFE)将WO3-x负载至碳纤维(CFs)表面制备WO3-x/CFs三相光催化剂,改变PTFE添加量可调控WO3-x/CFs的表面浸润性,通过XRD、SEM、水接触角、电子顺磁共振波谱仪(EPR)和低温氮吸脱附等测试技术对催化剂的形貌、结构与表面特性进行系统表征。可见光催化实验结果表明:WO3-x/CFs三相体系可显著提升甲烷至甲醇的转化性能,最优催化剂WO3-x/CFs-0.3的甲烷转化量为2522.20 μmol·g−1,分别为WO3-x/氧化铟锡导电玻璃(Glas)与粉末WO3-x两相体系的1.76倍和2.48倍;相应的甲醇产生量为1918.83 μmol·g−1,分别为WO3-x/Glas与粉末WO3-x体系的2.81倍和4.69倍,同时三相体系的甲醇选择性高达76.76%。WO3-x/CFs光催化性能增强主要源于疏水性催化剂形成的气-液-固三相界面,消耗的甲烷可经CFs气体传输通道直接传质至催化界面,促进甲烷分子活化与转化。此外,三相光催化体系循环稳定性优异,WO3-x/CFs-0.3经6次循环后甲醇产生量仍可达1506.98 μmol·g−1

     

  • 图  1  粉末WO3-x (a)和WO3-x/碳纤维(CFs)三相催化剂(b)的制备示意图

    PTFE—Polytetrafluoroethylene

    Figure  1.  Schematic diagram of the synthesis for WO3-x powder (a) and WO3-x/carbon fiber (CFs) triphase catalyst (b)

    图  2  甲烷光催化转化实验装置示意图

    Figure  2.  Schematic diagram of the experimental setup for photocatalytic conversion of methane

    图  3  WO3-x (a)、空白CFs (b)、WO3-x/CFs-0 (c)、WO3-x/CFs-0.1 (d)、WO3-x/CFs-0.3 (e)和WO3-x/CFs-0.5 (f)的低倍SEM图像(图3(b)~3(f))的插图表示相应样品表面的水滴接触角);((g)~(i)) WO3-x/CFs-0.3的高倍SEM图像

    CA—Contact angle

    Figure  3.  Low magnification SEM images of WO3-x (a), blank CFs (b), WO3-x/CFs-0 (c), WO3-x/CFs-0.1 (d), WO3-x/CFs-0.3 (e) and WO3-x/CFs-0.5 (f) samples respectively (The insets of Fig.3(b)-3(f) represent water contact angle of the corresponding samples surface); ((g)-(i)) High magnification SEM images of WO3-x/CFs-0.3

    图  4  WO3-x/Glas-0.3的SEM图像(图4(a)中插图为催化层表面的水滴接触角)

    Figure  4.  SEM images of WO3-x/Glas-0.3 (The inset in Fig. 4(a) is water contact angle on the surface of catalytic layer)

    图  5  (a) WO3-x粉末、空白CFs、PTFE/CFs和不同WO3-x/CFs样品的XRD图谱;(b) WO3-x和WO3-x/CFs-0.3的紫外-可见吸收光谱图(插图为CFs的紫外-可见吸收光谱)

    Figure  5.  (a) XRD patterns of WO3-x powder, blank CFs, PTFE/CFs and different WO3-x/CFs samples; (b) UV-visible DRS of WO3-x and WO3-x/CFs-0.3 (The inset is UV-visible DRS of CFs)

    图  6  WO3-x/CFs-0、WO3-x/CFs-0.1、WO3-x/CFs-0.3和WO3-x/CFs-0.5的N2吸附-脱附等温线(a)和孔径分布曲线(b)

    Figure  6.  N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of WO3-x/CFs-0, WO3-x/CFs-0.1, WO3-x/CFs-0.3 and WO3-x/CFs-0.5

    图  7  WO3-x和WO3粉末样品的室温电子顺磁共振(EPR)光谱

    g—A factor of a free radical or unpaired electron

    Figure  7.  Room-temperature electron paramagnetic resonance (EPR) spectra of WO3-x and WO3 powder samples

    图  8  (a) WO3-x/Glas两相体系 (i)、WO3-x/CFs两相体系(通过将WO3-x/CFs完全浸入水中获得)(ii)和WO3-x/CFs三相体系示意图(iii);(b)粉末WO3-x与3种不同固载体系的甲烷转化量和甲醇产生量

    Figure  8.  (a) Schematic illustration of WO3-x/Glas diphase system (i), WO3-x/CFs diphase system (which was obtained by completely immersing WO3-x/CFs in the water) (ii) and WO3-x/CFs triphase system (iii); (b) Methane conversion and methanol production in WO3-x powder and three different supporting systems

    图  9  (a) WO3-x/CFs体系甲烷转化产物生成量及甲醇选择性;(b) H2O2浓度对甲烷转化产物生成量与甲醇选择性的影响

    Figure  9.  (a) Products yield of methane conversion and methanol selectivity in WO3-x/CFs systems; (b) Effect of H2O2 concentration on the production of methane conversion products and methanol selectivity

    图  10  (a) WO3-x负载量对甲烷转化量、甲醇产生量及其选择性的影响;(b) WO3-x/CFs三相与WO3-x/Glas两相体系在不同光照强度下的甲醇产生量

    Figure  10.  (a) Effects of WO3-x loading on methane conversion, methanol production and its selectivity; (b) Methanol production of WO3-x/CFs triphase and WO3-x/Glas diphase systems under different light intensity

    图  11  (a) WO3-x/CFs-0.3三相体系的光催化循环稳定性;循环实验前后WO3-x/CFs-0.3的XRD图谱(b)、SEM图像和水接触角(c)

    Figure  11.  (a) Photocatalytic cycling stability of WO3-x/CFs-0.3 triphase system; XRD pattern (b), SEM images and water contact angle (c) of WO3-x/CFs-0.3 before and after 6 cycles

    图  12  WO3-x/CFs、WO3-x/Glas与粉末WO3-x的瞬态光电流响应谱(a)和室温荧光发射谱(b)

    Figure  12.  Transient photocurrent response spectra (a) and room temperature fluorescence emission spectra (b) of WO3-x/CFs, WO3-x/Glas and powder WO3-x

    图  13  (a) WO3-x/CFs、WO3-x/Glas与粉末WO3-x体系DMPO/•CH3和DMPO/•OH加合物的EPR信号;(b) WO3-x/CFs光催化体系三相反应界面微环境示意图

    DMPO—5, 5-dimethyl-1-pyrroline nitrogen oxide

    Figure  13.  (a) EPR signals of DMPO/•CH3 and DMPO/•OH adducts in WO3-x/CFs, WO3-x/Glas and powder WO3-x systems; (b) Schematic diagram of triphase reaction interface microenvironment in WO3-x/CFs photocatalytic system

    表  1  WO3-x/CFs样品名及其成分配比

    Table  1.   WO3-x/CFs sample name and composition ratio

    SamplePTFE dosage/µLWO3-x dosage/mg
    WO3-x/CFs-0 0 15
    WO3-x/CFs-0.1 2.5 15
    WO3-x/CFs-0.3 7.5 15
    WO3-x/CFs-0.5 12.5 15
    WO3-x/Glas-0.3 7.5 15
    Note: Glas—Indium tin oxide conducting glass.
    下载: 导出CSV

    表  2  不同WO3-x/CFs样品的孔结构参数

    Table  2.   Pore structure parameters of different WO3-x/CFs samples

    SampleSBET/(m2·g−1)Vpore/(cm3·g−1)Pore size/nm
    WO3-x/CFs-0 8.715 0.023 10.68
    WO3-x/CFs-0.1 10.020 0.035 13.95
    WO3-x/CFs-0.3 12.173 0.042 13.72
    WO3-x/CFs-0.5 8.837 0.019 8.78
    Notes: SBET—BET specific surface area; Vpore—Pore volume.
    下载: 导出CSV

    表  3  光催化转化甲烷制甲醇的性能比较

    Table  3.   Performance comparison of photocatalytic conversion of methane to methanol

    PhotocatalystLight irradiation conditionCH3OH yield/
    (μmol·g−1)
    Selectivity of
    CH3OH/%
    Ref.
    0.33wt%FeOx/TiO2300 W xenon lamp105690[7]
    Quantum-sized BiVO4High-pressure mercury lamp110096.6[9]
    La-doped mesoporous WO3Medium-pressure mercury lamp6346[13]
    Mesoporous WO3Mercury vapor lamp11137.4[14]
    0.1wt%Au/ZnO300 W xenon lamp412063[18]
    BiVO4/NaNO2450 W medium-pressure mercury lamp1890[28]
    BiVO4 microcrystals300 W xenon lamp26885[29]
    BiVO4450 W immersion medium-pressure mercury lamp41.651[30]
    WO3-x/CFs-0.3300 W xenon lamp1918.8376.76This work
    下载: 导出CSV
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  • 收稿日期:  2022-05-09
  • 修回日期:  2022-06-12
  • 录用日期:  2022-06-18
  • 网络出版日期:  2022-06-27
  • 刊出日期:  2023-05-15

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