介孔CuCo/FeCeOx催化剂协同催化类Fenton反应

硅酸盐通报 ›› 2023, Vol. 42 ›› Issue (8): 2985-2993.

介孔CuCo/FeCeO_x催化剂协同催化类Fenton反应

陈濛濛, 宋亚坤, 崔佳乐, 曹君营, 李冰, 刘军辉, 刘振

河南科技大学化学化工学院,洛阳 471000

收稿日期:2023-04-03 修订日期:2023-04-23 发布日期:2023-08-18
通信作者: 宋亚坤,博士,讲师。E-mail:songyakun@haust.edu.cn
刘振,博士,教授。E-mail:liuz@haust.edu.cn
作者简介:陈濛濛(1998—),女,硕士研究生。主要从事多相催化和水处理方面的研究。E-mail:2271948443@qq.com
基金资助:
国家自然科学基金(21908043);河南省科技攻关项目(232102230148,232102240006)

Synergistic Catalytic Fenton-Like Reaction by Mesoporous CuCo/FeCeO_x Catalyst

CHEN Mengmeng, SONG Yakun, CUI Jiale, CAO Junying, LI Bing, LIU Junhui, LIU Zhen

School of Chemistry and Chemical Engineering, Henan University of Science and Technology, Luoyang 471000, China

Received:2023-04-03 Revised:2023-04-23 Published:2023-08-18

摘要/Abstract

摘要： 类Fenton反应是降解水中有机污染物的有效方法之一,开发高效的非均相催化剂至关重要。通过硬模板法制备了Fe掺杂的具有有序介孔结构的FeCeO_x材料,以此为载体通过浸渍法负载Cu和Co后,构建了具有多金属活性位点的催化剂。催化剂在亚甲基蓝降解反应中表现出优异的催化性能,在45 min内可将亚甲基蓝完全降解,且具有良好的循环使用性能,使用5次后亚甲基蓝降解率仍达到93.3%。催化剂的介孔结构有利于吸附亚甲基蓝,暴露更多的活性位点,多金属之间的协同作用促进了催化剂上的电子转移,从而提高H₂O₂的活化效率和促进·OH的产生。

关键词: 类Fenton反应, 介孔结构, 催化剂, 协同作用, 非均相催化

Abstract: The Fenton-like reaction is one of the most effective methods for decomposing organic pollutants in water. Designing efficient heterogeneous catalysts is crucial in this industry. The hard template method was used to construct FeCeO_x materials with Fe-doped ordered mesoporous structures, and the impregnation method was employed to create multi-metallic active sites after loading Cu and Co as the carrier. Methylene blue could be entirely eliminated in 45 min by using an as-prepared catalyst with strong recycling capacity. After 5 runs, methylene blue degradation could still reach 93.3%. The porous structure of the catalyst is conducive to enhancing methylene blue absorption, exposing more active spots, and the synergistic effects of multi-metals promote electron transport, thus boosting the activation efficiency of H₂O₂ and the formation of ·OH.

Key words: fenton-like reaction, mesoporous structure, catalyst, synergistic effect, heterogeneous catalysis

中图分类号:

TQ426.82

陈濛濛, 宋亚坤, 崔佳乐, 曹君营, 李冰, 刘军辉, 刘振. 介孔CuCo/FeCeO_x催化剂协同催化类Fenton反应[J]. 硅酸盐通报, 2023, 42(8): 2985-2993.

CHEN Mengmeng, SONG Yakun, CUI Jiale, CAO Junying, LI Bing, LIU Junhui, LIU Zhen. Synergistic Catalytic Fenton-Like Reaction by Mesoporous CuCo/FeCeO_x Catalyst[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(8): 2985-2993.

参考文献

[1] DIAS E M, PETIT C. Towards the use of metal-organic frameworks for water reuse: a review of the recent advances in the field of organic pollutants removal and degradation and the next steps in the field[J]. Journal of Materials Chemistry A, 2015, 3(45): 22484-22506.
[2] 王建芳, 王君, 杨和平, 等. Fe₃O₄/δ-MnO₂纳米片的制备及其对亚甲基蓝的吸附研究[J]. 无机盐工业, 2019, 51(10): 93-96.
WANG J F, WANG J, YANG H P, et al. Preparation of Fe₃O₄/δ-MnO₂ nanosheet and its adsorption property of methylene blue[J]. Inorganic Chemicals Industry, 2019, 51(10): 93-96 (in Chinese).
[3] PASTRANA-MARTÍNEZ L M, PEREIRA N, RUI L M, et al. Degradation of diphenhydramine by photo-Fenton using magnetically recoverable iron oxide nanoparticles as catalyst[J]. Chemical Engineering Journal, 2015, 261: 45-52.
[4] 宋瑾, 吴凤龙, 王岳俊. 不同负载方式Fe/改性MCM-41催化剂的制备及其降解亚甲基蓝性能研究[J]. 无机盐工业, 2021, 53(11): 122-128.
SONG J, WU F L, WANG Y J. Study on preparation of Fe/modified MCM-41 catalyst with different loading methods and degradation of methylene blue[J]. Inorganic Chemicals Industry, 2021, 53(11): 122-128 (in Chinese).
[5] SUN Y, YANG Z X, TIAN P F, et al. Oxidative degradation of nitrobenzene by a fenton-like reaction with Fe-Cu bimetallic catalysts[J]. Applied Catalysis B: Environmental, 2019, 244: 1-10.
[6] LI J Y, PHAM A N, DAI R B, et al. Recent advances in Cu-Fenton systems for the treatment of industrial wastewaters: role of Cu complexes and Cu composites[J]. Journal of Hazardous Materials, 2020, 392: 122261.
[7] 许乃才, 史丹丹. 不同晶型纳米二氧化锰制备及对亚甲基蓝吸附性能[J]. 无机盐工业, 2021, 53(3): 44-47.
XU N C, SHI D D. Preparation of manganese dioxide nanomaterials with different crystalline and their adsorption properties to methylene blue[J]. Inorganic Chemicals Industry, 2021, 53(3): 44-47 (in Chinese).
[8] GUO X X, HU B, WANG K, et al. Cu embedded Co oxides and its fenton-like activity for metronidazole degradation over a wide pH range: active sites of Cu doped Co₃O₄ with {1 1 2} exposed facet[J]. Chemical Engineering Journal, 2022, 435: 132910.
[9] 赵永琴. Fe₃O₄复合材料的制备及其催化类-Fenton反应性能研究[D]. 大连: 大连理工大学, 2017.
ZHAO Y Q. Preparation of magnetite composites and their Fenton-like catalytic performance[D]. Dalian: Dalian University of Technology, 2017 (in Chinese).
[10] 杨权成, 张开永, 郭德, 等. 介孔硅酸钙吸附亚甲基蓝性能研究[J]. 无机盐工业, 2021, 53(10): 86-91.
YANG Q C, ZHANG K Y, GUO D, et al. Research on adsorption properties of methylene blue by mesoporous calcium silicate[J]. Inorganic Chemicals Industry, 2021, 53(10): 86-91 (in Chinese).
[11] MONTINI T, MELCHIONNA M, MONAI M, et al. Fundamentals and catalytic applications of CeO₂-based materials[J]. Chemical Reviews, 2016, 116(10): 5987-6041.
[12] GOGOI A, NAVGIRE M, SARMA K C, et al. Fe₃O₄-CeO₂ metal oxide nanocomposite as a Fenton-like heterogeneous catalyst for degradation of catechol[J]. Chemical Engineering Journal, 2017, 311: 153-162.
[13] NIU L J, WEI T, LI Q G, et al. Ce-based catalysts used in advanced oxidation processes for organic wastewater treatment: a review[J]. Journal of Environmental Sciences, 2020, 96: 109-116.
[14] 吴春笃, 陈婷婷, 陈闪闪, 等. 类Fenton催化剂氢氧化钴制备及其降解甲基橙的研究[J]. 印染助剂, 2022, 39(9): 29-32+45.
WU C D, CHEN T T, CHEN S S, et al. Preparation of Fenton-like catalyst cobalt hydroxide and its degradation of methyl orange[J]. Textile Auxiliaries, 2022, 39(9): 29-32+45 (in Chinese).
[15] AN K, ALAYOGLU S, MUSSELWHITE N, et al. Enhanced CO oxidation rates at the interface of mesoporous oxides and Pt nanoparticles[J]. Journal of the American Chemical Society, 2013, 135(44): 16689-16696.
[16] KLEITZ F, CHOI S H, RYOO R. Cubic Ia3d large mesoporous silica: synthesis and replication to platinum nanowires, carbon nanorods and carbon nanotubes[J]. Chemical Communications, 2003(17): 2136-2137.
[17] ZHA S X, CHENG Y, GAO Y, et al. Nanoscale zero-valent iron as a catalyst for heterogeneous Fenton oxidation of amoxicillin[J]. Chemical Engineering Journal, 2014, 255: 141-148.
[18] CHO J M, LEE S R, SUN J, et al. Highly ordered mesoporous Fe₂O₃-ZrO₂ bimetal oxides for an enhanced CO hydrogenation activity to hydrocarbons with their structural stability[J]. ACS Catalysis, 2017, 7(9): 5955-5964.
[19] GONG J L, YUE H R, ZHAO Y J, et al. Synthesis of ethanol via syngas on Cu/SiO₂ catalysts with balanced Cu⁰-Cu⁺ sites[J]. Journal of the American Chemical Society, 2012, 134(34): 13922-13925.
[20] LIU J H, ZHANG Z A, LIU B B, et al. Enhanced catalytic performance of Fenton-like reaction: dependence on meso-structure and Cu-Ce interaction[J]. Catalysis Letters, 2022, 152(10): 2947-2955.
[21] DOU R Y, CHENG H, MA J F, et al. Manganese doped magnetic cobalt ferrite nanoparticles for dye degradation via a novel heterogeneous chemical catalysis[J]. Materials Chemistry and Physics, 2020, 240: 122181.