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Introduction

Graphite carbon nitride (g-C3N4) composite manganese cobalt based prussian blue (MnCoPBA/g-C3N4) catalyst was prepared by a self-assembly method, a coprecipitation method and a high-temperature annealing method. The catalyst prepared was used to analyze the catalytic degradation of rhodamine B (RhB) in the SR Photo Fenton like system. The MnCoPBA/g-C3N4 catalyst has a degradation efficiency of 96% for RhB within 10 minutes and exhibits a good cyclic stability. The catalyst also has a good catalytic degradation performance for RhB at pH values of 1-9, indicating a superior applicability in acidic, neutral, and weakly alkaline environments.

Methods

Catalytic performance test is an important indicator for evaluating MnCoPBA/g-C3N4 catalysts. A certain amount of MnCoPBA/g-C3N4 (0.05-0.20 g/L) catalyst was added into 100 mL of RhB (5-20 mg/L) solution. The suspension was stirred magnetically for 30 min to achieve adsorption-desorption equilibrium. Subsequently, 3 mL of suspension was taken and centrifuged to add the supernatant to a colorimetric dish. The data were recorded using a UV spectrophotometer. Subsequently, in a xenon lamp (350 W, >420 nm), a certain amount of PMS (5-60 mg/L) was added and 3 mL of suspension was treated by centrifugal force every 5 minutes to obtain the supernatant. The data were recorded in a UV spectrophotometer until the solution become colorless and the UV absorption spectrum data unchanged.

The cyclic stability of catalysts is an important indicator for evaluating their practical application. To reduce the possible experimental errors caused by catalyst loss in the cyclic experiment, the cyclic experiment was designed as a parallel experiment, where each cyclic experiment was conducted independently. Sampling was no longer conducted during the n-1st cycle before the n-th cycle experiment, and sampling was conducted again during the n-th cycle experiment. The experimental operation was the same as the catalytic experiment. The waste liquid was collected and centrifuged, and the product was washed and dried with deionized water and ethanol. The UV spectrophotometer was used to test the data and collect records.

Results and discussion

Based on the analysis of the results, a possible catalytic degradation mechanism for the Photo-Fenton like system was proposed. The photocatalytic excitation of g-C3N4 semiconductor material in the Photo-Fenton like system generates photo- generated electrons and hole pairs, which are captured by metal ions in MnCoPBA and undergo a reduction reaction, achieving an effective separation of photo-generated carriers in the photocatalytic system and overcoming the defect of high photo-generated carrier recombination efficiency in g-C3N4 photocatalytic system. Simultaneously achieving a closed loop cycle of Fe(Ⅲ)/Fe(Ⅱ), Mn(Ⅲ)/Mn(Ⅱ) and Co(Ⅲ)/Co(Ⅱ) ions in the Fenton like system is obtained. An energy support for the Fenton like system is provided. The rate limiting step is broken through, and the defect of ion deficiency in the Fenton like system is overcome. Also, photo-generated electrons can directly activate PMS to generate SO4·-, triggering chain reactions to produce ·OH, and reacting with O2 to form ·O2-. Various strong oxidizing radicals efficiently degrade RhB, thus improving the catalytic degradation performance.

Conclusions

MnCoPBA/g-C3N4 catalyst was prepared by a coprecipitation method combined with a high-temperature calcination method. The effect of catalytic condition on the catalytic degradation performance of RhB was investigated. The results indicated that when MnCoPBA/g-C3N4-2.5 had the optimal catalytic degradation efficiency for RhB under the optimum condition (i.e., the catalyst dosage of 0.1 g/L, RhB concentration of 10 mg/L, PMS dosage of 0.15 g/L, and pH values of 1-9). The catalytic degradation mechanism indicated that Mn and Co metal ions in MnCoPBA acted as mediators for photocatalytic and the Fenton like connections, capturing photo-generated electrons to slow down the rate of photo generated electron hole recombination. Also, the reduced metal ions could promote the Fenton like reaction to decompose PMS, producing the more intense oxidizing free radicals and accelerating the catalytic degradation of RhB. The catalytic degradation efficiency of RhB was 90% within 2 min, and 96% within 10 min. In addition, the catalyst also exhibited a good cycling stability.

, authors=Jiahong ZHENG, Xiaopeng LIN, Xin ZHENG, authorsList=Jiahong ZHENG, Xiaopeng LIN, Xin ZHENG, authorCompany=null, correspAuthors=null, authorNote=

ZHENG Jiahong (1983-), female, Ph.D., Associate Professor. E-mail:

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罗丹明B(RhB)作为工业废水中广泛存在的有机染料,对生物体危害极大。由于RhB结构稳定,传统的污水处理方法对其去除效果并不明显,因此对RhB的降解性能的研究成为研究者广泛研究的热点。通过自组装法与共沉淀法结合高温退火法制备了石墨氮化碳(g-C3N4)复合锰钴基普鲁斯蓝(MnCoPBA/g-C3N4)催化剂,用于研究硫酸根光类芬顿(SR-Photo-Fenton-like)体系下RhB的催化降解性能。MnCoPBA/g-C3N4催化剂在10 min内对RhB的降解效率为96%,具有良好的循环稳定性;并且在pH=1~9的范围内对RhB具有良好的催化降解性能,表明该催化剂在酸性、中性和弱碱性环境均具有良好的环境适用性。

, authors=郑佳红, 蔺小朋, 郑馨, authorsList=郑佳红, 蔺小朋, 郑馨, authorCompany=null, correspAuthors=null, authorNote=

郑佳红(1983—),女,博士,副教授。

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MnCoPBA/g-C3N4催化剂的制备及光类芬顿降解RhB
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郑佳红 , 蔺小朋 , 郑馨
硅酸盐学报 | 研究论文 2024,52(1): 89-97
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硅酸盐学报 |研究论文 2024 , 52 (1) : 89 -97
MnCoPBA/g-C3N4催化剂的制备及光类芬顿降解RhB
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郑佳红 , 蔺小朋, 郑馨
作者信息
  • 长安大学材料科学与工程学院,西安 710021
作者简介:

郑佳红(1983—),女,博士,副教授。

Preparation of MnCoPBA/g-C3N4 Catalyst and Photo-Fenton-Like Degradation of RhB
Jiahong ZHENG , Xiaopeng LIN, Xin ZHENG
Affiliations
  • School of Materials Science and Engineering, Chang'an University, Xi'an 710061, China
  • ZHENG Jiahong (1983-), female, Ph.D., Associate Professor. E-mail:

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230320
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罗丹明B(RhB)作为工业废水中广泛存在的有机染料,对生物体危害极大。由于RhB结构稳定,传统的污水处理方法对其去除效果并不明显,因此对RhB的降解性能的研究成为研究者广泛研究的热点。通过自组装法与共沉淀法结合高温退火法制备了石墨氮化碳(g-C3N4)复合锰钴基普鲁斯蓝(MnCoPBA/g-C3N4)催化剂,用于研究硫酸根光类芬顿(SR-Photo-Fenton-like)体系下RhB的催化降解性能。MnCoPBA/g-C3N4催化剂在10 min内对RhB的降解效率为96%,具有良好的循环稳定性;并且在pH=1~9的范围内对RhB具有良好的催化降解性能,表明该催化剂在酸性、中性和弱碱性环境均具有良好的环境适用性。

氮化碳  /  光类芬顿  /  罗丹明B  /  过硫酸氢钾
Introduction

Graphite carbon nitride (g-C3N4) composite manganese cobalt based prussian blue (MnCoPBA/g-C3N4) catalyst was prepared by a self-assembly method, a coprecipitation method and a high-temperature annealing method. The catalyst prepared was used to analyze the catalytic degradation of rhodamine B (RhB) in the SR Photo Fenton like system. The MnCoPBA/g-C3N4 catalyst has a degradation efficiency of 96% for RhB within 10 minutes and exhibits a good cyclic stability. The catalyst also has a good catalytic degradation performance for RhB at pH values of 1-9, indicating a superior applicability in acidic, neutral, and weakly alkaline environments.

Methods

Catalytic performance test is an important indicator for evaluating MnCoPBA/g-C3N4 catalysts. A certain amount of MnCoPBA/g-C3N4 (0.05-0.20 g/L) catalyst was added into 100 mL of RhB (5-20 mg/L) solution. The suspension was stirred magnetically for 30 min to achieve adsorption-desorption equilibrium. Subsequently, 3 mL of suspension was taken and centrifuged to add the supernatant to a colorimetric dish. The data were recorded using a UV spectrophotometer. Subsequently, in a xenon lamp (350 W, >420 nm), a certain amount of PMS (5-60 mg/L) was added and 3 mL of suspension was treated by centrifugal force every 5 minutes to obtain the supernatant. The data were recorded in a UV spectrophotometer until the solution become colorless and the UV absorption spectrum data unchanged.

The cyclic stability of catalysts is an important indicator for evaluating their practical application. To reduce the possible experimental errors caused by catalyst loss in the cyclic experiment, the cyclic experiment was designed as a parallel experiment, where each cyclic experiment was conducted independently. Sampling was no longer conducted during the n-1st cycle before the n-th cycle experiment, and sampling was conducted again during the n-th cycle experiment. The experimental operation was the same as the catalytic experiment. The waste liquid was collected and centrifuged, and the product was washed and dried with deionized water and ethanol. The UV spectrophotometer was used to test the data and collect records.

Results and discussion

Based on the analysis of the results, a possible catalytic degradation mechanism for the Photo-Fenton like system was proposed. The photocatalytic excitation of g-C3N4 semiconductor material in the Photo-Fenton like system generates photo- generated electrons and hole pairs, which are captured by metal ions in MnCoPBA and undergo a reduction reaction, achieving an effective separation of photo-generated carriers in the photocatalytic system and overcoming the defect of high photo-generated carrier recombination efficiency in g-C3N4 photocatalytic system. Simultaneously achieving a closed loop cycle of Fe(Ⅲ)/Fe(Ⅱ), Mn(Ⅲ)/Mn(Ⅱ) and Co(Ⅲ)/Co(Ⅱ) ions in the Fenton like system is obtained. An energy support for the Fenton like system is provided. The rate limiting step is broken through, and the defect of ion deficiency in the Fenton like system is overcome. Also, photo-generated electrons can directly activate PMS to generate SO4·-, triggering chain reactions to produce ·OH, and reacting with O2 to form ·O2-. Various strong oxidizing radicals efficiently degrade RhB, thus improving the catalytic degradation performance.

Conclusions

MnCoPBA/g-C3N4 catalyst was prepared by a coprecipitation method combined with a high-temperature calcination method. The effect of catalytic condition on the catalytic degradation performance of RhB was investigated. The results indicated that when MnCoPBA/g-C3N4-2.5 had the optimal catalytic degradation efficiency for RhB under the optimum condition (i.e., the catalyst dosage of 0.1 g/L, RhB concentration of 10 mg/L, PMS dosage of 0.15 g/L, and pH values of 1-9). The catalytic degradation mechanism indicated that Mn and Co metal ions in MnCoPBA acted as mediators for photocatalytic and the Fenton like connections, capturing photo-generated electrons to slow down the rate of photo generated electron hole recombination. Also, the reduced metal ions could promote the Fenton like reaction to decompose PMS, producing the more intense oxidizing free radicals and accelerating the catalytic degradation of RhB. The catalytic degradation efficiency of RhB was 90% within 2 min, and 96% within 10 min. In addition, the catalyst also exhibited a good cycling stability.

carbon nitride  /  photo-fenton-like  /  rhodamine B  /  potassium monopersulfate
郑佳红, 蔺小朋, 郑馨. MnCoPBA/g-C3N4催化剂的制备及光类芬顿降解RhB. 硅酸盐学报, 2024 , 52 (1) : 89 -97 . DOI: 10.14062/j.issn.0454-5648.20230320
Jiahong ZHENG, Xiaopeng LIN, Xin ZHENG. Preparation of MnCoPBA/g-C3N4 Catalyst and Photo-Fenton-Like Degradation of RhB[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (1) : 89 -97 . DOI: 10.14062/j.issn.0454-5648.20230320
  • 陕西省自然科学专项基金(2020JM-221)
  • 陕西省重点研发项目(2022GY-358)
  • 长安大学中央高校基本科研业务费专项资金资助(300102310203; 300102311405; 300102312405; 300102312406)
  • 大学生创新创业训练计划项目(S202310710271; X202310710415)
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2024年第52卷第1期
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doi: 10.14062/j.issn.0454-5648.20230320
  • 接收时间:2023-05-11
  • 首发时间:2026-10-22
  • 出版时间:2024-01-20
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  • 收稿日期:2023-05-11
  • 修回日期:2023-06-11
基金
陕西省自然科学专项基金(2020JM-221)
陕西省重点研发项目(2022GY-358)
长安大学中央高校基本科研业务费专项资金资助(300102310203; 300102311405; 300102312405; 300102312406)
大学生创新创业训练计划项目(S202310710271; X202310710415)
作者信息
    长安大学材料科学与工程学院,西安 710021
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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230320
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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