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Study on performance of photocatalytic partial oxidation of CH4 to HCHO on AgCl/ZnO
增强出版- Low-carbon Chemistry and Chemical Engineering Vol. 49, Issue 8, Pages: 46-56(2024)
- 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：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240082
CLC： TQ51Published：25 August 2024，
Received：04 March 2024，
Revised：22 April 2024，
- 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
CH
4
光催化部分氧化为CH
3
OH、HCHO等产物是一种潜在的低能耗CH
4
转化路径，该转化路径存在CH
4
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-
x
光催化剂，发现形貌特征对ZnO-
x
的CH
4
光催化部分氧化制HCHO性能（简称“CH
4
光催化氧化性能”）有显著影响。采用CH
4
光催化氧化性能最好的ZnO-Cl为基底，进一步制备了
n
AgCl/ZnO-Cl光催化剂（
n
为AgNO
3
物质的量分数）。采用X射线衍射、N
2
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
n
AgCl/ZnO-Cl的CH
4
光催化氧化性能。结果表明，2.0%AgCl/ZnO-Cl表现出了最优的CH
4
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
、2.9 MPa CH
4
、75 mL H
2
O、光照强度450 mW/cm
2
和光照2 h时，含氧液相产物（CH
3
OH + CH
3
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
2
-
和空穴是CH
4
活化为•CH
3
的关键，并且•O
2
-
与•CH
3
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
3
OOH）能够较为容易的被氧化为HCHO，从而显著提升了
n
AgCl/ZnO-Cl的HCHO选择性。
Abstract
The photocatalytic partial oxidation of CH
4
to CH
3
OH
HCHO and other products is a potential low-energy CH
4
conversion path
which has the problems of high activation difficulty of CH
4
and low product selectivity. The design and preparation of high-performance catalysts are crucial to solve these problems. Based on the hydrothermal method
ZnO-
x
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-
x
has a significant effect on photocatalytic partial oxidation of CH
4
to HCHO (short for “CH
4
photocatalytic oxidation performance”). The
n
AgCl/ZnO-Cl photocatalysts (
n
is the mole fraction of AgNO
3
) were further prepared by using ZnO-Cl as the substrate with the best CH
4
photocatalytic oxidation performance. The samples were characterized by X-ray diffraction
N
2
adsorption/desorption and scanning electron microscopy
etc. The results show that 2.0%AgCl/ZnO-Cl shows the best CH
4
photocatalytic oxidation performance. Under the action of 5 mg 2.0%AgCl/ZnO-Cl and reaction conditions of temperature of 25 ℃
O
2
pressure of 0.1 MPa
CH
4
pressure of 2.9 MPa
H
2
O volume of 75 mL
light intensity of 450 mW/cm
2
and illumination time of 2 h. The total yield of oxygenated liquid products (CH
3
OH + CH
3
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
2
-
and the holes are the key to the activation of CH
4
to •CH
3
and more importantly
interaction of •O
2
-
and •CH
3
becomes the major reaction path. In such a way
the initial product (CH
3
OOH) can be further oxidized to HCHO
and thus leading to the promotion of HCHO selectivity of
n
AgCl/ZnO-Cl.
关键词
CH4光催化部分氧化ZnOHCHO
Keywords
CH4photocatalytic partial oxidationZnOHCHO
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