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光驱动的CoOx/WO3-x光热协同催化CO2还原

杨娟 田然 王大钊 戴俊 杜智华

杨娟, 田然, 王大钊, 等. 光驱动的CoOx/WO3-x光热协同催化CO2还原[J]. 复合材料学报, 2023, 40(9): 5158-5169. doi: 10.13801/j.cnki.fhclxb.20221128.001
引用本文: 杨娟, 田然, 王大钊, 等. 光驱动的CoOx/WO3-x光热协同催化CO2还原[J]. 复合材料学报, 2023, 40(9): 5158-5169. doi: 10.13801/j.cnki.fhclxb.20221128.001
YANG Juan, TIAN Ran, WANG Dazhao, et al. Light-driven photothermal synergistic catalytic CO2 reduction over CoOx/WO3-x[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5158-5169. doi: 10.13801/j.cnki.fhclxb.20221128.001
Citation: YANG Juan, TIAN Ran, WANG Dazhao, et al. Light-driven photothermal synergistic catalytic CO2 reduction over CoOx/WO3-x[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5158-5169. doi: 10.13801/j.cnki.fhclxb.20221128.001

光驱动的CoOx/WO3-x光热协同催化CO2还原

doi: 10.13801/j.cnki.fhclxb.20221128.001
基金项目: 国家自然科学基金(52074103;U2004194);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,博士生导师,研究方向为光催化与能源化学 E-mail: yangjuan@hpu.edu.cn

  • 中图分类号: O643.3

Light-driven photothermal synergistic catalytic CO2 reduction over CoOx/WO3-x

Funds: National Natural Science Foundation of China (52074103; U2004194); Key Science and Technology Project of Henan Province (222102320095); Key Scientific Research Project of Henan Province Education Department (21 A440008)
  • 摘要: 基于半导体光催化还原的人工光合成技术可在室温常压下将CO2转化为碳基燃料,被认为是同时缓解能源短缺和环境危机的理想策略,但因已有光催化剂对太阳光利用不足、光生电荷复合快,致使CO2光还原能量转换效率仍较低。采用水热法并结合表面浸渍过程首次制备出无定型CoOx/WO3-x复合光催化剂,通过XRD、TEM、XPS、EPR和紫外-可见-近红外吸收光谱等测试技术对催化剂的晶相组成、微观形貌、光吸收特性与氧空位缺陷进行系统表征。CO2光还原实验结果表明可见-近红外光照射3 h后,WO3-x为催化剂仅可检测到3.2 μmol·g−1的CH4,复合CoOx可显著提升WO3-x的CO2光催化还原性能,相同条件下最优催化剂2.5wt%CoOx/WO3-x的CO与CH4产生量分别可达78.2和19.7 μmol·g−1。引入氧空位可在WO3-x的能带结构中形成一新的中间能级,增强近红外光吸收并使催化剂表面产生局部温升;复合CoOx可在调控WO3-x导带电势的同时,增强光生电荷的分离与迁移,光热效应和CoOx助催化剂的协同作用是CO2光催化转化性能增强的主要原因。此外,复合光催化剂CoOx/WO3-x具有优异的长期催化与结构稳定性。

     

  • 图  1  CoOx/WO3-x催化剂制备过程示意图

    Figure  1.  Schematic diagram of CoOx/WO3-x catalysts preparation process

    图  2  CoOx/WO3-x样品的XRD图谱

    Figure  2.  XRD patterns of CoOx/WO3-x samples

    图  3  (a) 单一WO3-x的TEM图像;((b)~(d)) 2.5wt%CoOx/WO3-x样品的TEM与HRTEM图像

    Figure  3.  (a) TEM image of bare WO3-x; ((b)-(d)) TEM and HRTEM images of 2.5wt%CoOx/WO3-x sample

    d—Distance

    图  4  (a) 2.5wt%CoOx/WO3-x样品的HAADF-STEM图像;((b)~(d)) 对应的元素Mapping图

    Figure  4.  (a) HAADF-STEM image of 2.5wt%CoOx/WO3-x sample; ((b)-(d)) Element mapping images of 2.5wt%CoOx/WO3-x sample

    图  5  单一WO3-x与2.5wt%CoOx/WO3-x的XPS全谱 (a)、W4f高分辨XPS图谱 (b) 和O1s高分辨XPS图谱 (c)、2.5wt%CoOx/WO3-x的Co2p高分辨XPS图谱 (d)

    Figure  5.  XPS survey spectra of bare WO3-x and 2.5wt%CoOx/WO3-x (a), high-resolution W4f XPS spectra (b) and O1s XPS spectra of WO3-x and 2.5wt%CoOx/WO3-x (c), high-resolution Co2p XPS spectrum of 2.5wt%CoOx/WO3-x (d)

    图  6  WO3、WO3-x与2.5wt%CoOx/WO3-x的室温ESR谱

    Figure  6.  Room temperature ESR spectra of WO3, WO3-x and 2.5wt%CoOx/WO3-x

    g—Dimensionless factor

    图  7  WO3、WO3-x与2.5wt%CoOx/WO3-x的紫外-可见-近红外吸收光谱 (a) 及相应的(αhv)2hv曲线 ((b)~(d))

    Figure  7.  UV-Vis-NIR absorption spectra (a) and corresponding (αhv)2 vs. hv curves ((b)-(d)) of WO3, WO3-x and 2.5wt%CoOx/WO3-x

    CB—Conduction band; VB—Valence band; IEL—Intermediate energy level; h—Planck constant; v—Frequency; α—Absorptivity index

    图  8  (a) 不同反应条件下C1产物与O2生成量;可见-近红外光照射(b)和不同光源照射条件下(c)CoOx/WO3-x催化剂的C1产物生成量;(d) 可见-近红外光照射下2.5wt%CoOx/WO3-x的长期催化稳定性

    Figure  8.  (a) Generation amount of C1 products and O2 under different reaction conditions; Generation amount of C1 products on different CoOx/WO3-x under Vis-NIR light (b) and under different light source irradiation (c); (d) Long-time catalytic stability of 2.5wt%CoOx/WO3-x under Vis-NIR light

    NIR—Near infrared ray

    图  9  36 h CO2光还原实验后2.5wt%CoOx/WO3-x催化剂的XRD图谱(插图为对应的TEM图像) (a) 和Co2p高分辨XPS谱图 (b)

    Figure  9.  XRD pattern (inset is the corresponding TEM image) (a) and high-resolution Co2p XPS spectra (b) of the used 2.5wt%CoOx/WO3-x catalyst after 36 h CO2 photoreduction

    图  10  WO3-x (a) 与2.5wt%CoOx/WO3-x催化剂 (b) 的莫特-肖特基曲线

    Figure  10.  Mott-Schottky plots of WO3-x (a) and 2.5wt%CoOx/WO3-x catalysts (b)

    C-2—Reciprocal of interface capacitance squared; ECB—Conduction band potential; Efb—Flat band potential

    图  11  单一WO3-x、2.5wt%CoOx/WO3-x和4.0wt%CoOx/WO3-x样品的瞬态光电流响应谱 (a) 与电化学阻抗谱 (b)

    Figure  11.  Transient photocurrent response spectra (a) and electrochemical impedance spectra (b) of bare WO3-x, 2.5wt%CoOx/WO3-x and 4.0wt%CoOx/WO3-x samples

    图  12  光驱动的CoOx/WO3-x光热协同催化CO2还原性能增强机制示意图

    Figure  12.  Performance enhancing mechanism diagram of light driven photothermal synergistic catalytic CO2 reduction over CoOx/WO3-x

    VIS—Visible light

    表  1  CoOx/WO3-x复合催化剂中Co元素的实测含量

    Table  1.   Actual content of Co element in CoOx/WO3-x composite catalysts

    SampleAddition content
    of Co/wt%
    Measured content
    of Co/wt%
    0.8wt%CoOx/WO3-x0.80.79
    1.6wt%CoOx/WO3-x1.61.57
    2.5wt%CoOx/WO3-x2.52.48
    3.2wt%CoOx/WO3-x3.23.17
    4.0wt%CoOx/WO3-x4.03.95
    下载: 导出CSV

    表  2  CO2光催化还原产物生成速率的比较

    Table  2.   Comparison of products generation rate for CO2 photocatalytic reduction

    PhotocatalystCO yield/(μmol·g−1·h−1)CH4 yield/(μmol·g−1·h−1)Reaction conditionReference
    MoO3-x 10.3 2.08 300 W Xe lamp UV-Vis-IR [20]
    Bi2S3/UiO-66 25.6 300 W Xe lamp UV-Vis-IR [17]
    C-doped WO3-x 23.2 1.01 300 W Xe lamp an AM1.5 G filter [36]
    Bi4TaO8Cl/W18O49 23.42 180 mW/cm2 solar light, 393 K [42]
    WO3 nanosheets 1.19 300 W Xe lamp Visible light [43]
    TiO2-x(A/B)-CoOx 16.46 10.02 150 W UV lamp 393 K [44]
    WO3/LaTiO2N 2.21 0.36 300 W Xe lamp Visible light [45]
    WO3-x/g-C3N4 8.3 500 W Xe lamp [46]
    2.5wt%CoOx/WO3-x 26.1 6.57 300 W Xe lamp Vis-NIR This work
    下载: 导出CSV
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  • 收稿日期:  2022-10-10
  • 修回日期:  2022-11-06
  • 录用日期:  2022-11-12
  • 网络出版日期:  2022-11-28
  • 刊出日期:  2023-09-15

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