Cu掺杂MnO<italic style="font-style: italic"><sub>x</sub></italic>低温催化氧化甲苯性能研究： Cu-Mn协同作用

刘雪平; 韩太宇; 陈潘; 朱少燃; 高洪润; 李海洋; 宋忠贤

doi:10.12434/j.issn.2097-2547.20250267

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Cu掺杂MnO_x低温催化氧化甲苯性能研究： Cu-Mn协同作用

分离材料与净化技术 | 更新时间：2025-10-22

- Cu掺杂MnO_x低温催化氧化甲苯性能研究： Cu-Mn协同作用
- Study on low-temperature catalytic oxidation of toluene by Cu-doped MnO_x: Synergetic effect of Cu-Mn
- 低碳化学与化工 2025, 50(10): 100-107.
- 作者机构：
  
  1.河南城建学院市政与环境工程学院，河南平顶山 467036
  2.西南化工研究设计院有限公司，四川成都 610225
- 作者简介：
  
  刘雪平（1973—），博士，副教授，研究方向为新型环境功能材料制备与应用，E-mail：xuepingliu1@126.com。
  宋忠贤（1986—），博士，副教授，研究方向为大气污染控制工程，E-mail：songzhongxian@126.com。
- 基金信息：
  
  河南省重点研发项目(231111320400);河南省骨干青年教师(2023GGJS140);河南省科技攻关项目(252102231040);河南省研究生教育改革与质量提升工程精品教学案例项目(YJS2024AL144)
- DOI：10.12434/j.issn.2097-2547.20250267
  中图分类号： TQ426;TQ13;X511
- 收稿：2025-06-10，
  
  修回：2025-08-07，
  
  纸质出版：2025-10-25
- 稿件说明：
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刘雪平,韩太宇,陈潘等.Cu掺杂MnO_x低温催化氧化甲苯性能研究： Cu-Mn协同作用[J].低碳化学与化工,2025,50(10):100-107.

LIU Xueping,HAN Taiyu,CHEN Pan,et al.Study on low-temperature catalytic oxidation of toluene by Cu-doped MnO_x: Synergetic effect of Cu-Mn[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(10):100-107.
刘雪平,韩太宇,陈潘等.Cu掺杂MnO_x低温催化氧化甲苯性能研究： Cu-Mn协同作用[J].低碳化学与化工,2025,50(10):100-107. DOI： 10.12434/j.issn.2097-2547.20250267.

LIU Xueping,HAN Taiyu,CHEN Pan,et al.Study on low-temperature catalytic oxidation of toluene by Cu-doped MnO_x: Synergetic effect of Cu-Mn[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(10):100-107. DOI： 10.12434/j.issn.2097-2547.20250267.

摘要

挥发性有机化合物（VOCs）排放引发的环境污染问题日益严重，开发具有低温催化活性的催化剂进行VOCs治理已成为催化净化领域的研究重点。针对MnO

催化剂在低温条件下对甲苯氧化催化活性不足的问题，可通过Cu掺杂调控其结构与表面性质，并构建

Mn-O

-Cu（O

代表氧空位）协同活性位点。采用水热法制备了一系列Cu掺杂MnO

催化剂，采用XRD、FT-IR和XPS等表征了催化剂的物相组成、官能团、表面组成及化学状态等。以MnO

和CuO

为对照组，研究了催化剂的甲苯催化氧化性能。结果表明，Cu掺杂可促进Cu-Mn固溶体形成，降低催化剂结晶度，增大比表面积和结构缺陷数量，从而有利于催化剂活性位点暴露与反应物吸附。其中，

(Cu):

(Mn) = 1:9的催化剂1Cu9MnO

的表面吸附氧在表面氧物种中的占比（物质的量分数）为32.5%。在反应气主要组分为甲苯（物质的量分数为5 × 10

-4

）和空气（O

体积分数为20%）、反应气总流量为100 mL/min及空速为60000 h

-1

的条件下，1Cu9MnO

在230  °C下的甲苯转化率为90%，优于MnO

和CuO

。

Abstract

The environmental pollution caused by emission of volatile organic compounds (VOCs) has become increasingly severe

and the development of catalysts with low-temperature catalytic activity for VOCs treatment has become a research focus in the field of catalytic purification. To address the insufficient low-temperature activity of MnO

catalysts in toluene oxidation

the Cu-doping strategy was employed to regulate the structural and surface properties of MnO

and construct Mn-O

-Cu (O

represents oxygen vacancies) synergistic active sites. A series of Cu-doped MnO

catalysts were synthesized via hydrothermal method

and their phase compositions

functional groups

surface compositions and chemical states were characterized using XRD

FT-IR

XPS and so on. The catalytic oxidation performances of the catalysts were studied using MnO

and CuO

as control groups. The results show that Cu-doping can promote the formation of Cu-Mn solid solutions

reduce the crystallinities of catalysts

increase the specific surface areas and the numbers of structural defect

thereby facilitating the exposure of active sites and the adsorption of reactants. Amo

ng the catalysts

for the catalyst with

(Cu):

(Mn) of 1:9 (1Cu9MnO

)

the proportion (molar fraction) of surface adsorbed oxygen in surface oxygen species is 32.5%. Under the conditions of toluene (mole fraction of 5 × 10

-4

) and air (O

volume fraction of 20%) as main components in reaction gas

the total flow rate of reaction gas of 100 mL/min and space velocity of 60000 h

-1

the toluene conversion rate of 1Cu9MnO

at 230 ℃ is 90%

which is superior to that of MnO

and CuO

关键词

Keywords

references

LI H Y , SONG Z X , ZHANG Z F , et al . Catalytic combustion of toluene performance over MnO x catalysts: Effect of KMnO 4 content [J ] . Applied Organometallic Chemistry , 2024 , 38 ( 4 ): 7388 .

GONG P J , HE F , XIE J L , et al . Catalytic removal of toluene using MnO 2 -based catalysts: A review [J ] . Chemosphere , 2023 , 318 : 137938 .

SU Z , LI X S , SI W Z , et al . Probing the actual role and activity of oxygen vacancies in toluene catalytic oxidation: Evidence from in situ XPS/NEXAFS and DFT + U calculation [J ] . ACS Catalysis , 2023 , 13 ( 6 ): 3444 - 3455 .

ZHAO Z Y , MA S T , GAO B , et al . A systematic review of intermediates and their characterization methods in VOCs degradation by different catalytic technologies [J ] . Separation and Purification Technology , 2023 , 314 : 123510 .

FAN Y H , SONG Z X , GAO H R , et al . Adjustment mechanism of Co 3+ performance in Co 3 O 4 -LaO x catalyst for high-efficiency catalytic combustion of toluene [J ] . Separation and Purification Technology , 2025 , 354 : 128941 .

张立欣 , 东渴言 , 李飞跃 , 等 . Cu-Mn-CeO x 催化剂制备及其对甲苯催化燃烧性能的探究 [J ] . 化工新型材料 , 2024 , 52 ( 11 ): 198 - 202 .

ZHANG L X , DONG K Y , LI Y F , et al . Preparation of Cu-Mn-CeO x catalysts and investigation of their performance in catalytic combustion of toluene [J ] . New Chemical Materials , 2024 , 52 ( 11 ): 198 - 202 .

樊洁 , 李炳炫 , 毛璐涛 , 等 . 制备方法对Pt/CeO 2 催化氧化甲苯性能的影响 [J ] . 低碳化学与化工 , 2025 , 50 ( 6 ): 113 - 120 .

FAN J , LI B X , MAO L T , et al . Effects of preparation methods on catalytic performances of Pt/CeO 2 for toluene oxidation [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 6 ): 113 - 120 .

XIAO M L , HAN D W , YANG X Q , et al . Ni-doping-induced oxygen vacancy in Pt-CeO 2 catalyst for toluene oxidation: Enhanced catalytic activity, water-resistance, and SO 2 -tolerance [J ] . Applied Catalysis B: Environmental , 2023 , 323 : 122173 .

LI H Y , SONG Z , MAO Y L , et al . Degradation mechanism of toluene over Ce-M (Cu, Co and Fe) catalysts: Effect of oxygen vacancies on reaction intermediates [J ] . Applied Surface Science , 2024 , 652 : 159272 .

任思达 , 潘文 , 梁文俊 , 等 . Mn-Ce复合金属氧化物催化氧化甲苯性能 [J ] . 环境工程学报 , 2023 , 17 ( 8 ): 2615 - 2623 .

REN S D , PAN W , LIANG W J , et al . Catalytic oxidation of toluene over Mn-Ce composite metal oxide catalyst [J ] . Chinese Journal of Environmental Engineering , 2023 , 17 ( 8 ): 2615 - 2623 .

CHEN X , LIU S C , FENG Y , et al . Establishing efficient toluene elimination over cobalt-manganese bimetallic oxides via constructing strong Co-Mn interaction [J ] . Chemosphere , 2024 , 352 : 141346 .

CHEN L Z , LIU Y J , FANG X , et al . Simple strategy for the construction of oxygen vacancies on α -MnO 2 catalyst to improve toluene catalytic oxidation [J ] . Journal of Hazardous Materials , 2021 , 409 : 125020 .

REN Q M , MO S P , FAN J , et al . Enhancing catalytic toluene oxidation over MnO 2 @Co 3 O 4 by constructing a coupled interface [J ] . Chinese Journal of Catalysis , 2020 , 41 ( 12 ): 1873 - 1883 .

ZHONG J P , ZENG Y K , ZHANG M Y , et al . Toluene oxidation process and proper mechanism over Co 3 O 4 nanotubes: Investigation through in-situ DRIFTS combined with PTR-TOF-MS and quasi in-situ XPS [J ] . Chemical Engineering Journal , 2020 , 397 : 125375 .

RONG S P , ZHANG P Y , LIU F , et al . Engineering crystal facet of α -MnO 2 nanowire for highly efficient catalytic oxidation of carcinogenic airborne formaldehyde [J ] . ACS Catalysis , 2018 , 8 ( 4 ): 3435 - 3446 .

LI J J , WENG B , CAI S C , et al . Efficient promotion of charge transfer and separation in hydrogenated TiO 2 /WO 3 with rich surface-oxygen-vacancies for photodecomposition of gaseous toluene [J ] . Journal of Hazardous Materials , 2018 , 342 : 661 - 669 .

XING X , LI Z , WANG Y X , et al . Synergistic catalytic degradation of benzene and toluene on spinel MMn 2 O 4 (M: Co, Ni, Cu) catalysts [J ] . Journal of Environmental Sciences , 2025 , 154 : 238 - 251 .

DONG C , QU Z P , JIANG X , et al . Tuning oxygen vacancy concentration of MnO 2 through metal doping for improved toluene oxidation [J ] . Journal of Hazardous Materials , 2020 , 391 : 122181 .

GAN S , HUANG Z W , LIAN X L , et al . Enhancing catalytic oxidation of benzene with Cu-doped MnO 2 : Insights into structural defects and electronic modifications [J ] . Fuel , 2025 , 381 : 133327 .

ZHENG Y T , DENG J , LIU C C , et al . Catalytic oxidation of toluene by Mn-based Cu-Mn composite oxides at low temperature [J ] . Journal of Alloys and Compounds , 2025 : 181033 .

DU J P , QU Z P , DONG C , et al . Low-temperature abatement of toluene over Mn-Ce oxides catalysts synthesized by a modified hydrothermal approach [J ] . Applied Surface Science , 2018 , 433 : 1025 - 1035 .

HU Y S , PAN D , ZHANG Z , et al . Preparation of Cu n Co 1 O x catalysts by co-precipitation method for catalytic oxidation of toluene [J ] . Journal of Molecular Structure , 2025 , 1326 : 141139 .

BI F K , FENG X B , ZHOU Z X , et al . Mn-based catalysts derived from the non-thermal treatment of Mn-MIL-100 to enhance its water-resistance for toluene oxidation: Mechanism study [J ] . Chemical Engineering Journal , 2024 , 485 : 149776 .

WANG X X , YANG S , SONG Z X , et al . Constructing oxygen vacancies in Cu-doped MnO 2 by a quenching strategy for boosting the catalytic oxidation of toluene [J ] . Journal of Hazardous Materials , 2025 , 488 : 137297 .

LIU J Y , LI H F , LEI W J , et al . A high nucleus Cu-incorporated giant phosphotungstate with photocatalytic oxidation C—H of toluene [J ] . Inorganic Chemistry , 2024 , 63 ( 23 ): 10603 - 10610 .

ZHANG R Q , HE H Z , TANG Y N , et al . A review on Fe 2 O 3 -based catalysts for toluene oxidation: Catalysts design and optimization with the formation of abundant oxygen vacancies [J ] . Chemical Catalysis Chemistry , 2024 , 16 ( 18 ): e202400396 .

XIAO Z , YANG J S , REN R , et al . Facile synthesis of homogeneous hollow microsphere Cu-Mn based catalysts for catalytic oxidation of toluene [J ] . Chemosphere , 2020 , 247 : 125812 .

LI M Y , ZHANG W L , ZHANG X W , et al . Influences of different surface oxygen species on oxidation of toluene and/or benzene and their reaction pathways over Cu-Mn metal oxides [J ] . Journal of Colloid and Interface Science , 2023 , 630 : 301 - 316 .

XU C R , DONG S W , CHEN T H , et al . Low-temperature catalytic performance of toluene oxidation over Cu-Mn oxide catalysts derived from LDH precursor [J ] . Fuel , 2023 , 347 : 128401 .

CHEN X , GENG J X , FENG Y , et al . Identifying the distinct influences and mechanisms of chelating agents on CoCe bimetallic oxides towards robust toluene purification [J ] . Separation and Purification Technology , 2025 , 367 : 132861 .

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Cu掺杂MnOx低温催化氧化甲苯性能研究： Cu-Mn协同作用

Study on low-temperature catalytic oxidation of toluene by Cu-doped MnOx: Synergetic effect of Cu-Mn

DOI：10.12434/j.issn.2097-2547.20250267

摘要

Abstract

关键词

Keywords

references

Cu掺杂MnO_x低温催化氧化甲苯性能研究： Cu-Mn协同作用

Study on low-temperature catalytic oxidation of toluene by Cu-doped MnO_x: Synergetic effect of Cu-Mn