AgCl/ZnO上CH<sub>4</sub>光催化部分氧化制HCHO性能研究

王迎霄; 张春来; 郝英东; 孙楠楠; 魏伟

doi:10.12434/j.issn.2097-2547.20240082

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AgCl/ZnO上CH₄光催化部分氧化制HCHO性能研究

甲烷化工与催化转化

- AgCl/ZnO上CH₄光催化部分氧化制HCHO性能研究
  增强出版
- Study on performance of photocatalytic partial oxidation of CH₄ to HCHO on AgCl/ZnO
- 低碳化学与化工 2024, 49(8): 46-56.
- 作者机构：
  
  1.中国科学院上海高等研究院低碳转化科学与工程重点实验室，上海 201210
  2.上海科技大学物质科学与技术学院，上海 201210
  3.中国科学院大学，北京 100049
- 作者简介：
  
  王迎霄（1999—），硕士研究生，研究方向为甲烷光催化转化，E-mail：wangyx@sari.ac.cn。
  孙楠楠（1983—），博士，研究员，博士研究生导师，研究方向为温室气体减排，E-mail：sunnn@sari.ac.cn；
  魏伟（1971—），博士，研究员，博士研究生导师，研究方向为碳中和关键技术与战略，E-mail：weiwei@sari.ac.cn。
- 基金信息：
  
  国家重点研发计划“战略性科技创新”重点专项(2022YFEO208100)
- DOI：10.12434/j.issn.2097-2547.20240082
  中图分类号： TQ51
- 纸质出版日期：2024-08-25，
  
  收稿日期：2024-03-04，
  
  修回日期：2024-04-22，
- 稿件说明：
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王迎霄,张春来,郝英东等.AgCl/ZnO上CH₄光催化部分氧化制HCHO性能研究[J].低碳化学与化工,2024,49(08):46-56.

WANG Yingxiao,ZHANG Chunlai,HAO Yingdong,et al.Study on performance of photocatalytic partial oxidation of CH₄ to HCHO on AgCl/ZnO[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):46-56.
王迎霄,张春来,郝英东等.AgCl/ZnO上CH₄光催化部分氧化制HCHO性能研究[J].低碳化学与化工,2024,49(08):46-56. DOI： 10.12434/j.issn.2097-2547.20240082.

WANG Yingxiao,ZHANG Chunlai,HAO Yingdong,et al.Study on performance of photocatalytic partial oxidation of CH₄ to HCHO on AgCl/ZnO[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):46-56. DOI： 10.12434/j.issn.2097-2547.20240082.

摘要

光催化部分氧化为CH

OH、HCHO等产物是一种潜在的低能耗CH

转化路径，该转化路径存在CH

活化难度高和产物选择性低等问题，高性能催化剂的设计和制备对解决这一系列问题至关重要。使用不同Zn前驱体，通过水热法分别制备了具有块状颗粒、纳米花、纳米片和团聚纳米颗粒等不同形貌特征的ZnO-

光催化剂，发现形貌特征对ZnO-

的CH

光催化部分氧化制HCHO性能（简称“CH

光催化氧化性能”）有显著影响。采用CH

光催化氧化性能最好的ZnO-Cl为基底，进一步制备了

AgCl/ZnO-Cl光催化剂（

为AgNO

物质的量分数）。采用X射线衍射、N

吸/脱附和扫描电子显微镜等对光催化剂进行了表征，并研究了

AgCl/ZnO-Cl的CH

光催化氧化性能。结果表明，2.0%AgCl/ZnO-Cl表现出了最优的CH

光催化氧化性能。在5 mg 2.0%AgCl/ZnO-Cl作用下，当反应条件为25 ℃、0.1 MPa O

、2.9 MPa CH

、75 mL H

O、光照强度450 mW/cm

和光照2 h时，含氧液相产物（CH

OH + CH

OOH + HCHO）总产率达到10409 μmol/(g·h)，含氧液相产物总选择性为91.4%，其中主产物HCHO产率为6271 μmol/(g·h)，HCHO选择性为60.2%。自由基捕获实验结果表明，•O

和空穴是CH

活化为•CH

的关键，并且•O

与•CH

的相互作用成为了反应的主要路径，该路径得到的初级产物（CH

OOH）能够较为容易的被氧化为HCHO，从而显著提升了

AgCl/ZnO-Cl的HCHO选择性。

Abstract

The photocatalytic partial oxidation of CH

to CH

HCHO and other products is a potential low-energy CH

conversion path

which has the problems of high activation difficulty of CH

and low product selectivity. The design and preparation of high-performance catalysts are crucial to solve these problems. Based on the hydrothermal method

ZnO-

catalysts with different morphologies including granules

nano-flower

nano-flake and agglomerated nanoparticles were prepared by varying Zn precursors. It is found that the morphologies of ZnO-

has a significant effect on photocatalytic partial oxidation of CH

to HCHO (short for “CH

photocatalytic oxidation performance”). The

AgCl/ZnO-Cl photocatalysts (

is the mole fraction of AgNO

) were further prepared by using ZnO-Cl as the substrate with the best CH

photocatalytic oxidation performance. The samples were characterized by X-ray diffraction

adsorption/desorption and scanning electron microscopy

etc. The results show that 2.0%AgCl/ZnO-Cl shows the best CH

photocatalytic oxidation performance. Under the action of 5 mg 2.0%AgCl/ZnO-Cl and reaction conditions of temperature of 25 ℃

pressure of 0.1 MPa

pressure of 2.9 MPa

O volume of 75 mL

light intensity of 450 mW/cm

and illumination time of 2 h. The total yield of oxygenated liquid products (CH

OH + CH

OOH + HCHO) is 10409 μmol/(g·h)

and the total selectivity of oxygenated liquid products is 91.4%

and the main product HCHO is 6271 μmol/(g·h) with HCHO selectivity of 60.2%. Based on radical trapping experiments

it is found that the formation of •O

and the holes are the key to the activation of CH

to •CH

and more importantly

interaction of •O

and •CH

becomes the major reaction path. In such a way

the initial product (CH

OOH) can be further oxidized to HCHO

and thus leading to the promotion of HCHO selectivity of

AgCl/ZnO-Cl.

关键词

CH4光催化部分氧化ZnOHCHO

Keywords

CH4photocatalytic partial oxidationZnOHCHO

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AgCl/ZnO上CH4光催化部分氧化制HCHO性能研究

Study on performance of photocatalytic partial oxidation of CH4 to HCHO on AgCl/ZnO

DOI：10.12434/j.issn.2097-2547.20240082

摘要

Abstract

关键词

Keywords

references

AgCl/ZnO上CH₄光催化部分氧化制HCHO性能研究

Study on performance of photocatalytic partial oxidation of CH₄ to HCHO on AgCl/ZnO