Dual-reaction-center catalytic process continues Fenton’s story

Highlights

• Dual-reaction-center (DRC) system breaks through bottleneck of Fenton reaction.

• Utilization of intrinsic electrons of pollutants is realized in DRC system.

• DRC catalytic process well continues Fenton’s story.

Abstract

Triggered by global water quality safety issues, the research on wastewater treatment and water purification technology has been greatly developed in recent years. The Fenton technology is particularly powerful due to the rapid attack on pollutants by the generated hydroxyl radicals (•OH). However, both heterogeneous and homogeneous Fenton/Fenton-like technologies follow the classical reaction mechanism, which depends on the oxidation and reduction of the transition metal ions at single sites. So even after a century of development, this reaction still suffers from its inherent bottlenecks in practical application. In recent years, our group has been focusing on studying a novel heterogeneous Fenton catalytic process, and we developed the dual-reaction-center (DRC) system for the first time. In the DRC system, H₂O₂ and O₂ can be efficiently reduced to reactive oxygen species (ROS) in electron-rich centers, while pollutants are captured and oxidized by the electron-deficient centers. The obtained electrons from pollutants are diverted to the electron-rich centers through bonding bridges. This process breaks through the classic Fenton mechanism, and improves the performance and efficiency of pollutant removal in a wide pH range. Here, we provide a brief overview of Fenton’s story and focus on combing the discovery and development of the DRC technology and mechanism in recent years. The construction of the DRC and its performance in the pollutant degradation and interfacial reaction process are described in detail. We look forward to bringing a new perspective to continue Fenton’s story through research and development of DRC technology.

Graphical abstract

Keywords

Dual reaction centers / Fenton / Pollutant utilization / Electron transfer

References

[1] Bui V K H, Pham T N, Lee Y C (2019). One-pot synthesis of magnesium aminoclay-iron oxide nanocomposites for improved photo-Fenton catalytic performance. Journal of Nanoscience and Nanotechnology, 19(2): 1069–1073

[2] Cao W R, Han M E, Lyu L, Hu C, Xiao F (2019). Efficient Fenton-like process induced by fortified electron-rich O microcenter on the reduction state Cu-doped CNO polymer. ACS Applied Materials & Interfaces, 11(18): 16496–16505

[3] Cao W R, Lyu L, Deng K L, Lu C, Hu C (2020). ι-ascorbic acid oxygen-induced micro-electronic fields over metal-free polyimide for peroxymonosulfate activation to realize efficient multi-pathway destruction of contaminants. Journal of Materials Chemistry. A, 8(2): 810–819

[4] Eisenhauer H R (1964). Oxidation of phenolic wastes. Journal-Water Pollution Control Federation, 36(9): 1116–1128

[5] Fenton H J H (1876). On a new reaction of tartaric acid. Chemistry News, 33: 190–195

[6] Fenton H J H (1894). LXXIII.—Oxidation of tartaric acid in presence of iron. Journal of the Chemical Society Transactions, 65: 899–910

[7] Fenton H J H (1896). XLI.—The constitution of a new dibasic acid, resulting from the oxidation of tartaric acid. Journal of the Chemical Society Transactions, 69: 546–562

[8] Fenton H J H, Jones H O (1900). VII.—The oxidation of organic acids in presence of ferrous iron. Part I. Journal of the Chemical Society Transactions, 77: 69–76

[9] Gao Y W, Li T, Zhu Y, Chen Z H, Liang J Y, Zeng Q Y, Lyu L, Hu C (2019). Highly nitrogen-doped porous carbon transformed from graphitic carbon nitride for efficient metal-free catalysis. Journal of Hazardous Materials, 393: 121280

[10] Gao Y W, Zhu Y, Lyu L, Zeng Q Y, Xing X C, Hu C (2018). Electronic structure modulation of graphitic carbon nitride by oxygen doping for enhanced catalytic degradation of organic pollutants through peroxymonosulfate activation. Environmental Science & Technology, 52(24): 14371–14380

[11] Haber F, Weiss J (1932). Über die katalyse des hydroperoxydes. Naturwissenschaften, 20(51): 948–950

[12] Han M E, Lyu L, Huang Y M, Liang J R, Xue M M, Wu T, Li J Y, Chen M P, Hu C (2019). In situ generation and efficient activation of H₂O₂ for pollutant degradation over CoMoS₂ nanosphere-embedded rGO nanosheets and its interfacial reaction mechanism. Journal of Colloid and Interface Science, 543: 214–224

[13] Huang L Z, Zhu M T, Liu Z Z, Wang Z P, Hansen H C B (2019). Single sheet iron oxide: An efficient heterogeneous electro-Fenton catalyst at neutral pH. Journal of Hazardous Materials, 364: 39–47

[14] Lagutschenkov A, Sinha R K, Maitre P, Dopfer O (2010). Structure and infrared spectrum of the Ag⁺-Phenol ionic complex. Journal of Physical Chemistry A, 114(42): 11053–11059

[15] Lu Y B, He S L, Yu G F, Wang D T, Luo S Y, Liu A P, Luo H P,Liu G L,Zhang R D(2018). A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4-Dichlorophenoxyacetic acid degradation. Frontiers of Environmental Science & Engineering, 12(5): 9

[16] Lyu L, Cao W R, Yu G F, Yan D B, Deng K L, Lu C, Hu C (2020). Enhanced polarization of electron-poor/rich micro-centers over nZVCu-Cu(II)-rGO for pollutant removal with H₂O₂. Journal of Hazardous Materials, 383: 121182

[17] Lyu L, Han M E, Cao W R, Gao Y W, Zeng Q Y, Yu G F, Huang X, Hu C (2019). Efficient Fenton-like process for organic pollutant degradation on Cu-doped mesoporous polyimide nanocomposites. Environmental Science. Nano, 6(3): 798–808

[18] Lyu L, Yan D B, Yu G F, Cao W R, Hu C (2018a). Efficient destruction of pollutants in water by a dual-reaction center Fenton-like process over carbon nitride compounds-complexed Cu(II)-CuAlO₂. Environmental Science & Technology, 52(7): 4294–4304

[19] Lyu L, Yu G F, Zhang L L, Hu C, Sun Y (2018b). 4-phenoxyphenol-functionalized reduced graphene oxide nanosheets: A metal-free Fenton-like catalyst for pollutant destruction. Environmental Science & Technology, 52(2): 747–756

[20] Lyu L, Zhang L L, He G Z, He H, Hu C (2017). Selective H₂O₂ conversion to hydroxyl radicals in the electron-rich area of hydroxylated C-g-C₃N₄/CuCo-Al₂O₃. Journal of Materials Chemistry. A, 5(15): 7153–7164

[21] Lyu L, Zhang L L, Hu C (2015a). Enhanced Fenton-like degradation of pharmaceuticals over framework copper species in copper-doped mesoporous silica microspheres. Chemical Engineering Journal, 274: 298–306

[22] Lyu L, Zhang L L, Hu C (2016a). Galvanic-like cells produced by negative charge nonuniformity of lattice oxygen on d-TiCuAl-SiO₂ nanospheres for enhancement of Fenton-catalytic efficiency. Environmental Science. Nano, 3(6): 1483–1492

[23] Lyu L, Zhang L L, Hu C, Yang M (2016b). Enhanced Fenton-catalytic efficiency by highly accessible active sites on dandelion-like copper-aluminum-silica nanospheres for water purification. Journal of Materials Chemistry. A, 4(22): 8610–8619

[24] Lyu L, Zhang L L, Wang Q Y, Nie Y L, Hu C (2015b). Enhanced Fenton catalytic efficiency of gamma-Cu-Al₂O₃ by sigma-Cu²⁺-Ligand complexes from aromatic pollutant degradation. Environmental Science & Technology, 49(14): 8639–8647

[25] Navalon S, De Miguel M, Martin R, Alvaro M, Garcia H (2011). Enhancement of the catalytic activity of supported gold nanoparticles for the Fenton reaction by light. Journal of the American Chemical Society, 133(7): 2218–2226

[26] Ou X X, He S L, Yan J F, Zhang F J, Zhang C H(2018). Accelerated degradation of orange G over a wide pH range in the presence of FeVO₄. Frontiers of Environmental Science & Engineering, 12(1): 7

[27] Saleh R, Taufik A (2019). Degradation of methylene blue and congo-red dyes using Fenton, photo-Fenton, sono-Fenton, and sonophoto-Fenton methods in the presence of iron (II,III) oxide/zinc oxide/graphene (Fe₃O₄/ZnO/graphene) composites. Separation and Purification Technology, 210: 563–573

[28] Shi J G, Ai Z H, Zhang L Z (2014). Fe@Fe₂O₃ core-shell nanowires enhanced Fenton oxidation by accelerating the Fe(III)/Fe(II) cycles. Water Research, 59: 145–153

[29] Tušar N N, Maucec D, Rangus M, Arcon I, Mazaj M, Cotman M, Pintar A, Kaucic V (2012). Manganese functionalized silicate nanoparticles as a Fenton-type catalyst for water purification by advanced oxidation processes (AOP). Advanced Functional Materials, 22(4): 820–826

[30] Wang L, Huang X, Han M E, Lyu L, Li T, Gao Y W, Zeng Q Y, Hu C (2019). Efficient inhibition of photogenerated electron-hole recombination through persulfate activation and dual-pathway degradation of micropollutants over iron molybdate. Applied Catalysis B: Environmental, 257: 117904

[31] Wang L, Yan D B A, Lyu L, Hu C, Jiang N, Zhang L L (2018). Notable light-free catalytic activity for pollutant destruction over flower-like BiOI microspheres by a dual-reaction-center Fenton-like process. Journal of Colloid and Interface Science, 527: 251–259

[32] Xie Z Q, Zhou J L, Wang J N, Francois-Xavier C P, Wintgens T (2019). Novel Fenton-like catalyst gamma-Cu-Al₂O₃-Bi₁₂O₁₅Cl₆ with electron-poor Cu centre and electron-rich Bi centre for enhancement of phenolic compounds degradation and H₂O₂ utilization: The synergistic effects of sigma-Cu-ligand, dual-reaction centres and oxygen vacancies. Applied Catalysis B: Environmental, 253: 28–40

[33] Xu S Q, Zhu H X, Cao W R, Wen Z B, Wang J N, Francois-Xavier C P, Wintgens T (2018). Cu-Al₂O₃-g-C₃N₄ and Cu-Al₂O₃-C-dots with dual-reaction centres for simultaneous enhancement of Fenton-like catalytic activity and selective H₂O₂ conversion to hydroxyl radicals. Applied Catalysis B: Environmental, 234: 223–233

[34] Yoo S H, Jang D, Joh H I, Lee S (2017). Iron oxide/porous carbon as a heterogeneous Fenton catalyst for fast decomposition of hydrogen peroxide and efficient removal of methylene blue. Journal of Materials Chemistry. A, 5(2): 748–755

[35] Zhang L L, Lyu L, Nie Y L, Hu C (2016). Cu-doped Bi₂O₃/Bi-0 composite as an efficient Fenton-like catalyst for degradation of 2-chlorophenol. Separation and Purification Technology, 157: 203–208

[36] Zhang L L, Nie Y L, Hu C, Qu J H (2012). Enhanced Fenton degradation of rhodamine B over nanoscaled Cu-doped LaTiO₃ perovskite. Applied Catalysis B: Environmental, 125: 418–424

[37] Zhang L L, Xu D A, Hu C, Shi Y L (2017). Framework Cu-doped A1PO₄ as an effective Fenton-like catalyst for bisphenol A degradation. Applied Catalysis B: Environmental, 207: 9–16

[38] Zhuang Y, Liu Q Z, Kong Y, Shen C C, Hao H T, Dionysiou D D, Shi B Y (2019a). Enhanced antibiotic removal through a dual-reaction-center Fenton-like process in 3D graphene based hydrogels. Environmental Science. Nano, 6(2): 388–398

[39] Zhuang Y, Wang X C, Zhang L L, Dionysiou D D, Shi B Y (2019b). Fe-Chelated polymer templated graphene aerogel with enhanced Fenton-like efficiency for water treatment. Environmental Science. Nano, 6(11): 3232–3241

Acknowledgements

The related work was financially supported by the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (Young Scholar), the Introduced Innovative R&D Team Project under the “Pearl River Talent Recruitment Program” of Guangdong Province (No. 2019ZT08L387), the Natural Science Foundation of Guangdong Province (No. 2018A030313487), the National Natural Science Foundation of China (Grant Nos. 51808140, 51838005 and 51538013) and the Young Innovative Talent Project in Higher Education of Guangdong Province (No. 2017KQNCX150).

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