Advancements in Copper-Based Catalysts for Efficient Generation of Reactive Oxygen Species from Peroxymonosulfate
Abstract
:1. Introduction
2. Cu-Based Catalyst-Activated PMS Processes
2.1. Zero-Valent Copper
2.2. Copper Oxide
2.3. Magnetic Copper Ferrite
2.4. Cu-Based Designed Catalyst Materials
2.4.1. Cu-Based MOFs
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- Solvothermal synthesis: This is the most widely used method to produce Cu-MOFs. In this technique, the copper salts and organic linkers are dissolved in a solvent and heated in a sealed container (often an autoclave) at elevated temperatures, typically in the range of 80° C to 220° C. The solvothermal conditions facilitate the self-assembly of the metal ions and organic linkers into the desired structural structure [106]. This method allows for precise control over the size, morphology, and crystallinity of the MOFs by adjusting parameters such as temperature, reaction time, and solvent type.
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- MW-assisted synthesis: This offers a fast and energy-efficient approach to producing Cu-MOFs. This method involves the use of MW radiation to heat the reaction mixture, significantly reducing the synthesis time compared to conventional solvothermal methods. MW-assisted synthesis can improve the nucleation and growth rates of MOFs, leading to high-quality crystalline materials with uniform particle sizes [107]. The rapid heating and cooling cycles provided by MW irradiation also help to minimize the formation of defects within the MOF structure.
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- Electrochemical synthesis: This is an emerging technique for producing Cu-MOFs, where an electric current is applied to drive the assembly of the framework. In this method, a copper anode is dissolved to release copper ions in an electrolyte solution containing organic linkers. The electric field promotes the interaction between the copper ions and the linkers, which results in the formation of the MOF on the electrode surface [108]. Electrochemical synthesis is advantageous for producing thin films of MOF directly on conductive substrates, which makes it suitable for applications in sensors and electronic devices.
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- Sonochemical synthesis: This uses ultrasonic waves to induce chemical reactions and facilitate the formation of copper MOFs. The ultrasonic waves generate high temperatures and localized pressures within the reaction mixture, improving the reaction kinetics and promoting the formation of the MOF structure [109]. This method is known for its simplicity, fast reaction times, and ability to produce MOFs with unique morphologies and improved surface areas.
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- Mechanochemical synthesis: This involves the use of mechanical force to induce chemical reactions between copper salts and organic linkers. This technique typically employs grinding or ball milling to physically mix and activate the reactants, leading to the formation of the MOF structure without the need for solvents or high temperatures [110]. Mechanochemical synthesis is environmentally friendly and scalable, which makes it a promising approach for the large-scale production of Cu-MOFs.
2.4.2. Cu-Based LDHs
Catalyst | Contaminant | Reactive Species | Efficiency and Reusability | Ref. |
---|---|---|---|---|
HKUST-1 | Saccharomyces cerevisiae (>105 CFU·mL−1) Geotrichum candidum (>105 CFU·mL−1) | - | 100% in 25 h >79% in 25 h | [123] |
HKUST-1 | E. coli (1010 CFU·mL−1) | , | 100% in 30 min 4 cycles, 100% | [124] |
FeCu-MOF | Methylene blue (0.2 mM) | 100% in 30 min 3 cycles, 87.1% | [125] | |
CuCo-MOF | Nimesulide (20 mg·L−1) | , | 100% in 25 min | [126] |
CuCo-MOF-74 | Methylene blue (0.2 mM) | 100% in 30 min 5 cycles, 76.4% | [116] | |
Co1Cu1-MOF | Tetracycline (20 mg·L−1) | , 1, | 98.17% in 30 min 4 cycles, 71.26% | [101] |
NH2–Fe2.4Cu1-MOF in polyacrylonitrile spheres | RhB (10 mg·L−1) | , | 80.92% in 90 min 5 cycles, >77% | [127] |
Co2Cu1-LDH | Lomefloxacin (10 mg·L−1) | , | 96.2% in 30 min 10 cycles, >95% | [102] |
MgCuFe-LDH | RhB (5 mg·L−1) Acetaminophen (5 mg·L−1) | , | 97.6% in 25 min 93% in 20 min | [128] |
Cu-Co-Fe-LDH | Nitrobenzene (2 mg·L−1) | at pH < 7 at pH > 9 | 100% in 6 min 5 cycles, >87% | [129] |
CuMn-LDH | BPA (5 mg·L−1) | 1, | 100% 90 min 4 cycles, >95% | [130] |
CoCu-LDH | Sulfamethoxazole (10 mg·L−1) | , | 86.6% in 60 min | [131] |
CoCu-LDH@polyvinylidene fluoride (PVDF) | Sulfamethoxazole Sulfacetamide Lomefloxacin Carbamazepine (each 10 mg·L−1) | , | 92.8% in 60 min 89.6% in 60 min 97.1% in 60 min 91.8% in 60 min | [131] |
CuCoFe-LDH coated on biochar | Phenanthrene (1 mg·L−1) | , | 96.5% in 15 min 4 cycles, >80% | [132] |
CuCoFe-LDH | Glyphosate (100 mg·L−1) | 99.54% in 5 min 5 cycles, 90.34% | [133] | |
CuO nanoparticles–DES (DL-menthol/Fenchyl alcohol) | RhB (20 mg·L−1) | , | 98% in 18 min | [134] |
Cu-BDC * MOF-DES (Choline chloride/urea) | AO7 (30 mg·L−1) | - | 99% in 120 min | [135] |
2.4.3. Cu-Based DESs
3. Investigative Methodologies for Assessing PMS Activation with Copper-Based Catalysts
3.1. EPR and ESR Methods
3.2. Radical Quenching
4. Factors Influencing Reactivity
4.1. Impact of pH on PMS Activation
4.2. Impact of PMS and Catalyst Concentrations
4.3. Anions
4.4. Natural Organic Matter
5. Coupling Copper-Based Catalyst/PMS Systems with Other Advanced Oxidation Techniques
6. Mechanisms for PMS Activation by Copper-Based Catalysts
6.1. Radical Pathways
6.2. Non-Radical Pathways
7. Toxicity Assessment after PMS-Based Processes
8. Conclusions and Outlooks
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- Future research directions: Continued research should focus on enhancing the stability and reusability of Cu-based catalysts, particularly through innovative catalyst design and the exploration of new materials such as bimetallic MOFs and advanced LDHs. Further investigation into the mechanisms of PMS activation, especially under real-world conditions, will be critical for optimizing these systems.
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- Real applications: The translation of laboratory findings into large-scale industrial applications remains a key objective. This includes scaling up the synthesis of Cu-based catalysts and integrating them into existing wastewater treatment infrastructure. The potential for coupling Cu-based catalysts with other AOPs offers exciting opportunities for developing more efficient and comprehensive treatment systems.
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- Sustainability considerations: As environmental regulations become more stringent, the demand for sustainable water treatment technologies will continue to grow. Cu-based catalysts, with their low toxicity and high efficiency, are well-positioned to meet this demand. Future developments should prioritize minimizing the environmental footprint of these catalysts, ensuring they contribute to a circular economy by enabling the recovery and reuse of resources.
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Catalyst | Contaminant | Reactive Species | Efficiency | Ref. |
---|---|---|---|---|
ZVCu | ||||
Nanoscale ZVCu | Benzoic acid (BA) | , | 100% in 10 min | [27] |
ZVCu | 2,4-DCP | , | 56.7% of TOC in 120 min. | [28] |
ZVCu | NPX | , | 91.0% in 30 min | [29] |
Copper oxide | ||||
CuO | Iopamidol | , | 100% in 15 min | [30] |
CuO | Phenol | , | 65% in 60 min | [31] |
CuO | BPA | 1, | 100% in 20 min | [32] |
BPA | Surface-activated PMS | 100% in 120 min | [33] | |
CuO | AO7 | , | 95.38% in 15 min | [34] |
Spongelike porous CuO | AO7 | 85% in 60 min | [35] | |
Copper ferrite | ||||
TBBPA | , | 99% in 30 min | [36] | |
ATZ | , | >98% in 15 min | [37] | |
BPA | , | 95.2% in 60 min | [38] | |
Norfloxacin | , | >90% in 120 min | [39] | |
Iopromide | , | ~100% in 10 min | [40] | |
Sulfadiazine (SDZ) | , | 86% in 12 min | [41] | |
Orange I | , | 77.8–79.3% in 30 min | [42] |
Scavenging Agents | Specific ROS | Kinetic Constants (M−1s−1) | Determination of ROS | Ref. |
---|---|---|---|---|
MeOH | 3.2 × 106 | , | [36] | |
9.7 × 108 | ||||
EtOH | 1.6–7.7 × 107 | , | [155] | |
1.2–2.8 × 108 | ||||
TBA | 4–9.1 × 105 | [158] | ||
3.8–7.6 × 108 | ||||
p-BQ | 1.0 × 109 | [166] | ||
FFA | 1 | 3.2 × 107 | 1 | [160] |
NaN3 | 1 | 1.2 × 108 | 1 | [162] |
Phenol | 8.8 × 109 | , | [165] | |
6.6 × 109 |
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Bouzayani, B.; Lomba-Fernández, B.; Fdez-Sanromán, A.; Elaoud, S.C.; Sanromán, M.Á. Advancements in Copper-Based Catalysts for Efficient Generation of Reactive Oxygen Species from Peroxymonosulfate. Appl. Sci. 2024, 14, 8075. https://doi.org/10.3390/app14178075
Bouzayani B, Lomba-Fernández B, Fdez-Sanromán A, Elaoud SC, Sanromán MÁ. Advancements in Copper-Based Catalysts for Efficient Generation of Reactive Oxygen Species from Peroxymonosulfate. Applied Sciences. 2024; 14(17):8075. https://doi.org/10.3390/app14178075
Chicago/Turabian StyleBouzayani, Bakhta, Bárbara Lomba-Fernández, Antía Fdez-Sanromán, Sourour Chaâbane Elaoud, and Maria Ángeles Sanromán. 2024. "Advancements in Copper-Based Catalysts for Efficient Generation of Reactive Oxygen Species from Peroxymonosulfate" Applied Sciences 14, no. 17: 8075. https://doi.org/10.3390/app14178075