Fe(III)Ox/ZnO催化剂的制备及其光催化CH4氧化性能

郝英东; 刘双; 孙楠楠; 魏伟

doi:10.1016/S1872-5813(22)60016-1

Fe(III)O_x/ZnO催化剂的制备及其光催化CH₄氧化性能

doi: 10.1016/S1872-5813(22)60016-1

郝英东^{1, 2,},
刘双^{1, 2},
孙楠楠^1, ,,
魏伟^{1, 3, ,}

1.
中国科学院上海高等研究院中国科学院低碳转化科学与工程重点实验室，上海201210
2.
中国科学院大学，北京100049
3.
上海科技大学物质科学与技术学院，上海201210

基金项目: 上海市科学技术委员会（19YF1452800, 19ZR1463500）资助

详细信息

通讯作者:
E-mail：sunnn@sari.ac.cn

weiwei@sari.ac.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2022-02-09
- 修回日期: 2022-03-15
- 录用日期: 2022-04-12
- 网络出版日期: 2022-04-28
- 刊出日期: 2022-10-21

Photocatalytic oxidation of CH₄ to oxygenates on Fe(III)O_x/ZnO

HAO Ying-dong^{1, 2
,},
LIU Shuang^{1, 2},
SUN Nan-nan^{1
, ,},
WEI Wei^{1, 3
, ,}

1.
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China

Funds: The project was supported by Shanghai Science and Technology Committee (19YF1452800, 19ZR1463500)

摘要

摘要: 基于浸渍法制备了不同Fe含量的nFe(III)O_x/ZnO光催化剂，并对所得样品进行了XRD、N₂吸附-脱附、TEM、XPS、UV-vis以及PL表征。结果发现，通过改变浸渍液中Fe物种的浓度，能够实现最终样品中Fe含量的调控，在实验涉及的范围内，Fe的负载没有造成ZnO载体在晶相、形貌和孔道结构等方面的显著变化，但却改变了催化剂表面的电子状态，从而引入了更多的O空位。此外，Fe的修饰增加了光生载流子的分离效率，显著提升了样品的CH₄光催化性能。通过对溶剂体积，H₂O₂浓度以及反应时间等参数的优化，0.1Fe(III)O_x/ZnO样品表现出了最佳的性能，其液相氧化产物（CH₃OH、CH₃OOH、HCHO）的产率和选择性分别达到了5443 μmol/(g_cat·h)和99%。基于自由基捕获实验，发现H₂O₂在光生载流子的作用下形成的·${{\rm{O}}_2^-} $自由基是CH₄活化为·CH₃的关键。
- 甲烷 /
- 光催化 /
- 氧化锌 /
- 氧化 /
- 活化
Abstract: A series of nFe(III)O_x/ZnO photocatalysts with different Fe contents was prepared by impregnation method, and the samples were characterized by XRD, N₂ physisorption, TEM, XPS, UV-vis and PL. It was found that by changing the concentration of Fe species in the impregnation solution, the Fe content in the final sample could be properly adjusted. Within the scope of this work, the loading of Fe does not cause significant changes in the phase, morphology, and porous structure of the ZnO support. However, the electronic state of the catalyst surface was altered considerably, with more O-vacancies were introduced. Fe species enhanced the separation of photo-induced electron-hole pairs, which was responsible to improve the performance of photocatalytic CH₄ conversion. Through the optimization of solvent volume, H₂O₂ concentration and reaction time, the 0.1Fe(III)O_x/ZnO sample showed the best performance over which the yield and selectivity of liquid oxidation products (CH₃OH, CH₃OOH, HCHO) was 5443 μmol/(g_cat·h) and 99%, respectively. Based on radical quenching experiments, it was found that the ·${{\rm{O}}_2^-} $ radicals derived from H₂O₂ played a major role for the activation of CH₄ to ·CH₃.
- methane /
- photocatalysis /
- ZnO /
- oxidation /
- activation

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FIG. 1879. FIG. 1879.

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图 1 ZnO和nFe(III)O_x/ZnO样品的（a）XRD谱图，（b）N₂吸附-脱附等温曲线

Figure 1 (a) XRD patterns and (b) nitrogen adsorption-desorption isotherms of ZnO and nFe(III )O_x /ZnO

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图 2 （a），（b），（c）0.1Fe(III)O_x/ZnO样品的TEM照片，（d）0.1Fe(III)O_x/ZnO样品的不同元素分布

Figure 2 (a), (b) and (c) TEM images of 0.1Fe(III)O_x/ZnO, (d) EDS mapping images for various elements

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图 3 ZnO和nFe(III)O_x/ZnO的XPS谱图（a）Zn 2p，（b）Fe 2p，（c）O 1s

Figure 3 XPS profiles of ZnO and nFe(III)O_x/ZnO (a) Zn 2p, (b) Fe 2p, (c) O 1s

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图 4 ZnO和0.1Fe(III)O_x/ZnO的（a）UV-vis吸收谱图，（b）PL谱图

Figure 4 (a) Ultraviolet-visible diffusive reflectance spectra, (b) PL spectra of ZnO and 0.1Fe(III)O_x/ZnO

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图 5 ZnO和nFe(III)O_x/ZnO催化剂上的光催化CH₄氧化液相产物产率及选择性（a）不同Fe负载量，（b）不同H₂O体积，（b）不同H₂O₂浓度，（d）不同反应时间

Figure 5 Product yields and selectivity by ZnO and nFe(III)O_x/ZnO with (a) different amounts of Fe, (b) varying water amount, (c) varying H₂O₂ amount, (d) different reaction time

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图 6 （a）加入不同自由基捕获剂的光催化CH₄氧化液相产物产率及选择性，（b）反应路径

Figure 6 (a) Product yields and selectivity over ZnO and nFe(III)O_x/ZnO with different quenchers, (b) Sketch of the proposed reaction mechanism for photocatalytic CH₄ oxidation to CH₃OOH, CH₃OH, and HCHO on 0.1Fe(III)O_x/ZnO

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表 1 ZnO和nFe(III)O_x/ZnO催化剂的孔结构特性

Table 1 Pore structure characteristics of ZnO and nFe(III)O_x/ZnO catalysts

Sample	Fe loading w/%	Surface area/(m²·g⁻¹)
ZnO	−	16
0.1Fe(III)O_x/ZnO	0.08	19
0.5Fe(III)O_x/ZnO	0.50	15
1.0Fe(III)O_x/ZnO	0.99	16
2.0Fe(III)O_x/ZnO	1.55	12

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表 2 不同催化剂的CH₄光催化活性对比

Table 2 Comparison of catalytic activity in oxidation of methane to liquid oxygenates

Entry	Catalyst	Condition	Product	Reference
1	0.1Fe(III)O_x/ZnO	5 mg catalyst, 90 mL H₂O, 5 mmol/L H₂O₂, 3 MPa CH₄, 3 h, RT, 300 W Xe lamp, 320−780 nm	liquid products: CH₃OOH + CH₃OH + HCHO, total productivity: 5.44 mmol/(g_cat·h)	this work
2	q-BiVO₄	10 mg catalyst, 10 mL H₂O, 1 MPa O₂, 1 MPa CH₄, RT, 7 h, Hg lamp, 300−400 nm	liquid products: CH₃OH + C₂H₅OH + HCHO, total productivity: 2.16 mmol/(g_cat·h)	[13]
3	Au-CoO_x/TiO₂	10 mg catalyst, 100 mL H₂O, 0.1 MPa O₂, 2 MPa CH₄, 2 h, 25 ℃, Xe lamp, 300−500 nm	liquid product: CH₃OOH + CH₃OH + HCHO, total productivity: 2.5 mmol/(g_cat·h)	[12]
4	ZnO nanosheets	4 mg catalyst, 10 mL H₂O, 5 mmol/L H₂O₂, 0.1 MPa CH₄, 1h, 50 ℃, 300 W Xe lamp	liquid products: CH₃OOH + CH₃OH + HOCH₂OOH + HCOOH, total productivity: 2.21 mmol/(g_cat·h)	[23]

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