一步水热法合成Mn3O4/CuMnO2及其光芬顿反应性能的研究

doi:10.12422/j.issn.1006-396X.2024.03.010

摘要/Abstract

摘要：

以二水合氯化铜、四水合氯化锰为原料，通过一步水热法制备了Mn₃O₄/CuMnO₂异质结构催化剂CMO-A（A为水热合成温度）；通过X射线粉末衍射仪对不同合成温度下制备的样品进行了组成分析；以汞灯为光源，50 mg/L罗丹明B(RhB)溶液作为污染物模型，对所制备CMO-A样品的光芬顿反应性能进行了测试；向反应体系中加入牺牲剂，结合对照实验探究了反应机理。结果表明，在反应温度为150 ℃时合成的样品CMO-150对RhB溶液的降解效果最好，降解时间为15 min时降解率可达98.01%；0.2 mol/L H₂O₂、50 mg CMO-150催化剂、50 mg/L RhB溶液、pH=3.0为最佳反应条件；经过5次循环后，降解时间为15 min时降解率仅下降22.24%；反应的主要活性物种为羟基自由基(·OH)；结合对照实验，对反应机理进行了探究。

关键词: 水热法, CuMnO₂, 异质结, 光芬顿反应, 罗丹明B

Abstract:

Heterogeneous Mn₃O₄/CuMnO₂ catalyst CMO-A is prepared by a one-step hydrothermal method using cupric chloride dihydrate and manganese chloride tetrahydrate as raw materials.The composition of the samples prepared at different temperatures is analyzed by X-ray diffraction analysis.Using mercury lamp as light source and 50 mg/L Rhodamine B(RhB) solution as contaminant model,the photo-Fenton reaction performance of the prepared CMO-A sample is tested.The results show that CMO-150 has the best degradation effect on RhB solution when the reaction temperature is 150 ℃,and the degradation rate reaches 98.01% when the reaction time is 15 min.The optimal reaction conditions and cyclic stability of CMO-150 catalyst are investigated.The experimental results show that the optimal reaction conditions are 0.2 mol/L H₂O₂,50 mg CMO-150 catalyst,50 mg/L RhB solution and pH=3.0.After 5 cycles,the degradation rate only decreases by 22.24% at 15 min.The main active species in the reaction is hydroxyl radical (·OH) through the sacrificial agent experiment,and the reaction mechanism is explored by combining with the control experiment.

Key words: Hydrothermal method, CuMnO₂, Heterojunction, Photo-Fenton reaction, Rhodamine B

中图分类号:

TQ131.2

李哲, 王芳芳, 陈常东. 一步水热法合成Mn₃O₄/CuMnO₂及其光芬顿反应性能的研究[J]. 石油化工高等学校学报, 2024, 37(3): 73-80.

Zhe LI, Fangfang WANG, Changdong CHEN. Synthesis of Mn₃O₄/CuMnO₂ by One-Step Hydrothermal Method and Its Photo-Fenton Reaction Performance[J]. Journal of Petrochemical Universities, 2024, 37(3): 73-80.

图/表 13

图1 CMO-A的XRD谱图

Fig.1 XRD pattern of CMO-A

图2 CMO-A的降解图及降解速率常数图

Fig.2 Degradation rate and degradation rate constant of CMO-A

表1 光芬顿反应中不同催化剂对污染物降解性能对比

Table 1 Comparison of pollutant degradation performance of different catalysts in photo-Fenton reaction

催化剂	污染物	ρ（污染物）/ （mg $⋅$ L^-1）	降解速率常数/min^-1	降解率/%	降解时间/min	来源
CMO-150	RhB	50	0.240	98.01	15	本文
CuFeO₂–MW	活性红141	50	0.110	98.00	30	[9]
CuFeO₂	活性红141	50	0.010	84.00	150	[9]
Cu-Fe LDHs/Bi₂WO₆	RhB	50	0.006	98.00	60	[21]
Mn₃O₄	亚甲基蓝	40	-	99.00	60	[22]

表1 光芬顿反应中不同催化剂对污染物降解性能对比

Table 1 Comparison of pollutant degradation performance of different catalysts in photo-Fenton reaction

催化剂	污染物	ρ（污染物）/ （mg $⋅$ L^-1）	降解速率常数/min^-1	降解率/%	降解时间/min	来源
CMO-150	RhB	50	0.240	98.01	15	本文
CuFeO₂–MW	活性红141	50	0.110	98.00	30	[9]
CuFeO₂	活性红141	50	0.010	84.00	150	[9]
Cu-Fe LDHs/Bi₂WO₆	RhB	50	0.006	98.00	60	[21]
Mn₃O₄	亚甲基蓝	40	-	99.00	60	[22]

图3 H2O2浓度对RhB降解率和降解速率常数的影响

Fig.3 Effect of H2O2 concentration on the degradation rate and degradation rate constant of RhB

图4 催化剂质量对RhB降解率和降解速率常数的影响

Fig.4 Effect of catalyst mass on the degradation rate and degradation rate constant of RhB

图5 RhB的质量浓度对RhB降解率和降解速率常数的影响

Fig.5 Effect of RhB mass concentration on the degradation rate and degradation rate constant of RhB

图6 溶液pH对RhB降解率和降解速率常数的影响

Fig.6 Effect of solution pH on the degradation rate and degradation rate constant of RhB

图7 反应温度对RhB降解率的影响及CMO-150的活化能拟合图

Fig.7 Effect of reaction temperature on degradation rate of RhB and fitting of activation energy of CMO-150

图8 CMO-150循环5次的光芬顿反应降解曲线

Fig.8 Degradation curve of CMO-150 photo-Fentonreaction after 5 cycles

图9 循环前CMO-150与循环5次后CMO-150的XRD谱图

Fig.9 XRD pattern of CMO-150 and CMO-150 after5 cycles

图10 对照实验降解率及降解速率常数对比

Fig.10 Comparison of degradation rate and degradation rate constant in control experiment

图11 牺牲剂实验结果

Fig.11 Sacrificial agent experiment

图12 反应机理

Fig.12 Reaction mechanism diagram

参考文献 26

1	KOČÍ K，RELI M，TROPPOVÁ I，et al.Degradation of ammonia from gas stream by advanced oxidation processes［J］.Journal of Environmental Science and Health，Part A，2020，55（4）：433-437.
2	汪筱迪，李丽华，张金生，等.MnFe₂O₄/TiO₂的制备及其类芬顿光催化性能［J］.辽宁石油化工大学学报，2021，41（2）：32-36.
	WANG X D，LI L H，ZHANG J S，et al.Preparation of MnFe₂O₄/TiO₂ and its Fenton-like photocatalytic properties［J］.Journal of Liaoning Petrochemical University，2021，41（2）：32-36.
3	KOUTAHZADEH N，ESFAHANI M R，ARCE P E.Removal of acid black 1 from water by the pulsed corona discharge advanced oxidation method［J］.Journal of Water Process Engineering，2016，10：1-8.
4	GASMI I，HAMDAOUI O，FERKOUS H，et al.Sonochemical advanced oxidation process for the degradation of furosemide in water：Effects of sonication's conditions and scavengers［J］.Ultrasonics Sonochemistry，2023，95：106361.
5	YANG Y，ZHEN W Q，ZHAO T T，et al.Engineering low-valence Moδ ⁺（0<δ<4） sites on MoS₂ surface：Accelerating Fe³⁺/Fe²⁺ cycle，maximizing H₂O₂ activation efficiency，and extending applicable pH range in photo-Fenton reaction［J］.Journal of Cleaner Production，2023，404：136918.
6	ZHAO M C，MA X D，LI R X，et al.In-situ slow production of Fe²⁺ to motivate electro-Fenton oxidation of bisphenol A in a flow through dual-anode reactor using current distribution strategy：Advantages，CFD and toxicity assessment［J］.Electrochimica Acta，2022，411：140059.
7	WANG L P，LIU G H，ZHANG M Y，et al.Reduced graphene oxide-coated CuFeO₂ with Fenton-like catalytic degradation performance for terramycin［J］.Nanomaterials，2022，12（24）：4391.
8	LIU Q L，ZHAO Z Y，ZHAO R D，et al.Fundamental properties of delafossite CuFeO₂ as photocatalyst for solar energy conversion［J］.Journal of Alloys and Compounds，2020，819：153032.
9	SCHMACHTENBERG N，SILVESTRI S，DA SILVEIRA SALLA J，et al.Preparation of delafossite–type CuFeO₂ powders by conventional and microwave–assisted hydrothermal routes for use as photo–Fenton catalysts［J］.Journal of Environmental Chemical Engineering，2019，7（2）：102954.
10	YIN C K，ZHOU S J，ZHANG K Y，et al.Crednerite CuMnO₂ as highly efficient Fenton-like catalysts for p-nitrophenol removal：Synergism between Cu（Ⅰ） and Mn （Ⅲ）［J］.Journal of Cleaner Production，2021，319：128640.
11	CHEN H，ZHANG X Y，ZHAO Y，et al.Highly efficient catalyst of crednerite CuMnO₂ for PMS activation：Synthesis，performance and mechanism［J］.Surfaces and Interfaces，2023，42（Part B）：103522.
12	DONG X Y，WANG J X，YANG J D，et al.CuMnO₂ nanoflakes as cathode catalyst for oxygen reduction reaction in magnesium-air battery［J］.Journal of the Electrochemical Society，2021，168（10）：100502.
13	YANG Y Y，YANG L，CAO G Q，et al.Monolithic CuMnO₂-nanosheet-based catalysts in situ grown on stainless steel mesh for selective catalytic reduction of NO with CO［J］.ACS Applied Nano Materials，2023，6（6）：4803-4811.
14	WANG L，ARIF M，DUAN G R，et al.A high performance quasi-solid-state supercapacitor based on CuMnO₂ nanoparticles［J］.Journal of Power Sources，2017，355：53-61.
15	BENREGUIA N，BARNABÉ A，TRARI M.Preparation and characterization of the semiconductor CuMnO₂ by sol-gel route［J］.Materials Science in Semiconductor Processing，2016，56：14-19.
16	熊德华，邓砚文，杜子娟，等.CuMnO₂/TiO₂复合光催化剂增效催化降解亚甲基蓝［J］.材料导报，2019，33（8）：1262-1267.
	XIONG D H，DENG Y W，DU Z J，et al.CuMnO₂/TiO₂ composite photocatalyst with synergistic photocatalytic activity used for methylene blue degradation［J］.Materials Review，2019，33（8）：1262-1267.
17	DAI C，TIAN X K，NIE Y L，et al.Enhanced radical generation and utilization efficiency by interfacial enrichment and electronic regulation of CuMnO₂/CeO₂：Processes and mechanism［J］.Separation and Purification Technology，2022，303：122231.
18	YANG Z M，KANG M L，CHEN L，et al.Interfacial engineering over tungsten oxide by constructing Z-scheme interatomic junction for efficient photocatalytic tetrachlorophenol degradation［J］.Applied Surface Science，2023，609：155306.
19	SHUKLA K K，SHAHI P，S.G，et al.Magnetic and optical properties of Fe doped crednerite CuMnO₂［J］.RSC Advances，2015，5（101）：83504-83511.
20	WANG F F，CHEN C D，WANG W，et al.Internal field engineering of WO₃ by ion channel migration with enhanced photocatalytic oxygen evolution ability［J］.Journal of Materials Chemistry A，2021，9（3）：1678-1691.
21	JI Y，SONG Z L，XU Y，et al.Cu-Fe LDHs/Bi₂WO₆ composite for superior photo-Fenton rhodamine B removal through combination of photogenerated electrons and multivalent bimetal redox for accelerating Fe³⁺/Fe²⁺ cycles［J］.Journal of Alloys and Compounds，2022，925：166655.
22	CHEN R Q，YAN Y K，WEN G D，et al.Controllable synthesis of Mn₃O₄ nanoparticles through in situ reduction reaction via PVA hydrogel template for Fenton-like degradation［J］.Journal of Materials Science，2022，57（40）：18770-18786.
23	CHEN Y，YANG G W.Light-mediated modulation of enzyme-mimetic activity of CuMnO₂ nanosheets［J］.The Journal of Physical Chemistry Letters，2022，13（50）：11770-11777.
24	ZHAO J G，LI C T，YU Q，et al.Interface engineering of Mn₃O₄/Co₃O₄ S-scheme heterojunctions to enhance the photothermal catalytic degradation of toluene［J］.Journal of Hazardous Materials，2023，452：131249.
25	WANG F F，YANG Z M，YANG Z X，et al.Graphene triggered hole activation strategy for 2D/2D-layered （001）/（100）WO₃ facet junction towards enhanced photocatalytic water oxidation kinetics［J］.Chemical Engineering Journal，2022，450（Part 2）：138166.
26	LI J，XIAO C，WANG K，et al.Enhanced generation of reactive oxygen species under visible light irradiation by adjusting the exposed facet of FeWO₄ nanosheets to activate oxalic acid for organic pollutant removal and Cr（Ⅵ） reduction［J］.Environmental Science & Technology，2019，53（18）：11023-11030.

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一步水热法合成Mn₃O₄/CuMnO₂及其光芬顿反应性能的研究

Synthesis of Mn₃O₄/CuMnO₂ by One-Step Hydrothermal Method and Its Photo-Fenton Reaction Performance

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