Hypercrosslinked Polymers Research Articles

Highly selective adsorption of dyes by functional hypercrosslinked-polymers prepared in a facile and chemically stable manner

One of the challenges in water pollution control is the design of adsorbents aimed at achieving low cost, ultrafast, and selective adsorption of pollutants. Hypercrosslinked-polymers (HCPs) possess abundant microporous structures and advantages such as the ability to manipulate the framework structure, making them highly valuable in the field of adsorption. Three HCPs namely polythiophene (Th-1), polypyrrole (Py-1), and polyfuran (Fu-1) were synthesized through a Friedel's alkylation reaction utilizing different functional monomers (thiophene, pyrrole, and furan) employing a knitting strategy. The HCPs exhibit a heterocyclic structure (C-S-C, C-N-C, C-O-C) with remarkable charge selectivity as well as strong resistance to acids and alkalis. The HCPs, with varying functional monomers, demonstrate selective adsorption of dyes based on their charges and release of dyes dependent on solvent and pH conditions. The ease of synthesis, cost-effectiveness, and high reusability render these HCPs suitable for further design optimization through the utilization of diverse functional monomers to achieve efficient adsorption and removal of environmental pollutants from water.

Sulfonated hypercrosslinked polymer enhanced structural composite supercapacitors

Structural supercapacitors are multifunctional devices able to bear mechanical load while storing electrical energy. Carbon fibres can be used as a bifunctional component within structural supercapacitors, acting both as current collector and mechanical reinforcement. A promising route to such devices is to increase the surface area of carbon fibres, which can be achieved by the deposition of active materials, and embed them into a structural electrolyte. A highly sulfonated, high porosity hypercrosslinked polymer was deposited onto carbon fibres by electrophoretic deposition from an aqueous suspension. We investigated the effect of polymer and binder concentration in the deposition suspension on the electrochemical properties of the coated carbon fibre electrodes. Multifunctional structural composite supercapacitors had a fibre volume fraction of only 21% and possessed a tensile strength and Young's modulus of 495 MPa and 49 GPa, respectively. A specific capacitance of 1.2 F/g was reached, comparable to graphene coated carbon fibre electrodes. At room temperature and ambient humidity an energy density of 39 mWh/kg and a power density of 15 W/kg were measured. We demonstrate that moisture plays a major role in the energy storage mechanism in these SCs.

Application progress of hypercrosslinked porous organic polymers in cartridge-based solid phase extraction

Hypercrosslinked porous organic polymers (HCPs), a novel type of porous materials synthesized via the Friedel-Crafts reaction, are widely used in gas storage, heterogeneous catalysis, chromatographic separation, and organic pollutant capture. HCPs have the advantages of a wide monomer source, low cost, mild synthesis conditions, and easy functionalization. In recent years, HCPs have shown great application potential in solid phase extraction. Given their high specific surface area, excellent adsorption properties, diverse chemical structures, and easy chemical modification, HCPs have been successfully applied to the extraction of different types of analytes with efficient extraction performance. Based on the chemical structure of HCPs, their target analytes, and the adsorption mechanism, HCPs can be classified as hydrophobic, hydrophilic, and ionic species. Hydrophobic HCPs are usually constructed as extended conjugated structures by overcrosslinking aromatic compounds as monomers. Common monomers include ferrocene, triphenylamine, triphenylphosphine, etc. This type of HCPs shows good adsorption effects on nonpolar analytes such as benzuron herbicides and phthalates through strong π-π and hydrophobic interactions. Hydrophilic HCPs are prepared by introducing polar monomers or crosslinking agents, or by modifying polar functional groups. This type of adsorbent is commonly used to extract polar analytes such as nitroimidazole, chlorophenol, tetracycline, etc. In addition to hydrophobic forces, polar interactions, such as hydrogen-bonding and dipole-dipole interactions, also occur between the adsorbent and analyte. Ionic HCPs are mixed-mode solid phase extraction materials formed by introducing ionic functional groups into the polymer. Mixed-mode adsorbents usually have a dual reversed-phase/ion-exchange retention mechanism, which helps control the retention behavior of the adsorbent by adjusting the elution strength of the eluting solvent. In addition, the extraction mode can be switched by controlling the pH of the sample solution and eluting solvent. In this manner, matrix interferences can be removed while the target analytes are enriched. Ionic HCPs present a unique advantage in the extraction of acid-base drugs in water. The combination of new HCP extraction materials with modern analytical techniques, such as chromatography and mass spectrometry, has been widely used in environmental monitoring, food safety, and biochemical analyses. In this review, the characteristics and synthesis methods of HCPs are briefly introduced, and the application progress of different types of HCPs in cartridge-based solid phase extraction is described. Finally, the future outlook of HCP applications is discussed.

Tailoring hypercrosslinked ionic polymers with high ionic density for rapid conversion of CO2 into cyclic carbonates at low pressure

Designing and preparing hypercrosslinked ionic polymers (HIPs) with high ionic density for CO2 conversion is a significant challenge in materials science. Herein, the simple Friedel-Crafts alkylation synthesized a series of imidazolium-based HIPs with different ionic densities and porosities. Among these HIPs, [HBIM-6]Br-DCX(3) with high ionic content (2.31 mmol g−1) was prepared through Friedel-Crafts alkylation of alpha'-Dichloro-p-xylene with a monomer [BIM-6]Br, in which [BIM-6]Br produced from the reaction of 1,2,3,4,5,6-hexakis(bromomethyl)benzene with 1-benzylimidazole. What's more, in the absence of co-catalysts, solvents and additives, the metal-free catalyst [HBIM-6]Br-DCX(3) exhibited excellent catalytic activity for the conversion of CO2 with various epoxides into corresponding cyclic carbonates at atmospheric pressure in the ultrashort reaction time because its high ionic density provides abundant imidazolium cations and bromide anions as active sites, and 99% yield and 99% selectivity were achieved for cycloaddition of CO2 with epichlorohydrin and epibromohydrin within 1 h. The reaction time is shorter than most reported porous ionic polymer catalysts under the same conditions (styrene oxide, 120 ℃, 4 h, 99% yield; 100 ℃, 10 h, 97% yield). Notably, styrene oxide (SO) was converted into styrene carbonate (SC) with 90% yield under simulated flue gas (1 bar, 15% CO2 and 85 % N2) in 15 h. Furthermore, the catalyst was easily separable and maintained high reusability and stability after running five times. This work provides a new strategy to synthesize HIPs with high ionic density and the obtained HIPs can be used as efficient catalysts for rapidly converting CO2 with epoxides into cyclic carbonates at low pressure.

The influence of cross-linking density on the efficiency of post-synthetic sulfonation of hyper-cross-linked polymers and their adsorption capacity for antibiotic pollutants

Hyper-cross-linked polymers (HCPs) attract increasing attention as promising adsorbents for removal of organic pollutants from water. The present work reveals for the first time that the efficiency of the post-synthetic sulfonation of HCPs-based adsorbents and their reactivity in removal of selected polar antibiotic pollutants can be simply controlled by adjusting the cross-linking density of the polymer network. The study included both the evaluation of the mechanism and kinetics of the adsorption process over sulfonated HCPs, as well as the determination of their stability, recyclability, and affinity toward various antibiotics. The latter was established based on adsorption tests using mono- and multicomponent mixtures of different structure antibiotics (ciprofloxacin, tetracycline, sulfamethoxazole and amoxicillin). The adsorption capacity of all sulfonated polymers was found to be directly proportional to the concentration of -SO3H functions and inversely proportional to the cross-linking density of the parent HCPs. The most promising sulfonated polymer had approximately 4 times higher adsorption capacity toward ciprofloxacin than commercial carbon-based adsorbent Norit (427.5 vs. 110.5 mg/g, respectively). The main adsorption mechanism over sulfonated HCPs was chemisorption of the antibiotics via ionic interactions with surface -SO3H groups. Spent adsorbent could be successfully recycled ten times without any loss in its efficiency.

Construction of silsesquioxane and phosphinum‐based ionic porous hypercrosslinked polymers for efficient heterogeneous catalytic CO2 cycloaddition

AbstractIn this work, we reported a facile one‐pot route to construct polyhedral oligomeric silsesquioxane (POSS) and phosphonium‐based ionic porous hypercrosslinked polymers (denoted as P‐iPHCPs) with multiple catalytic active sites, which could be regarded as efficient heterogeneous catalysts for the conversion of carbon dioxide (CO2) to highly value‐added cyclic carbonates. The targeted polymers P‐iPHCPs were prepared from a rigid building block octavinylsilsesquioxane (VPOSS) and a low‐cost commercially available organic ionic salt methyltriphenylphosphonium bromide ([Ph3PMe]Br) by the AlCl3‐catalyzed Friedel‐Crafts reaction. The series of polymers P‐iPHCPs that synthesized by different molar ratios of VPOSS to [Ph3PMe]Br possess hierarchical micro/mesoporous structures with high surface areas ranging from 376 to 429 m2 g−1 and behave the flower‐like nano‐morphology. Especially, the desired multiple active sites involved the mixed anions including free Cl−, Br− anions and the in‐situ formed metal‐halogen complex anion [AlCl3Br]− within phosphonium segments, and the enriched POSS‐derived SiOH hydrogen bond donor (HBD) groups that derived from the breakage of POSS cages during the synthetic process. The typical polymer P‐iPHCP‐14 has the aforementioned nucleophilic‐electrophilic multiple catalytic active sites, which was regarded as an efficient recyclable heterogeneous catalyst for synergistic catalytic conversion of CO2 with various epoxides into cyclic carbonates under mild conditions.

Facile Synthesis Hyper-Crosslinked PdFe Bimetallic Polymer as Highly Active Catalyst for Ullmann Coupling Reaction of Chlorobenzene.

The synthesis of efficient and sustainable heterogeneous Pd-based catalysts has been an active field of research due to their crucial role in carbon-carbon coupling reactions. In this study, we developed a facile and eco-friendly in situ assembly technique to produce a PdFe bimetallic hyper-crosslinked polymer (HCP@Pd/Fe) to use as a highly active and durable catalyst in the Ullmann reaction. The HCP@Pd/Fe catalyst exhibits a hierarchical pore structure, high specific surface area, and uniform distribution of active sites, which promote catalytic activity and stability. Under mild conditions, the HCP@Pd/Fe catalyst is capable of efficiently catalyzing the Ullmann reaction of aryl chlorides in aqueous media. The exceptional catalytic performance of HCP@Pd/Fe is attributed to its robust absorption capability, high dispersion, and strong interaction between Fe and Pd, as confirmed by various material characterizations and control experiments. Furthermore, the coated structure of a hyper-crosslinked polymer enables easy recycling and reuse of the catalyst for at least 10 cycles without any significant loss of activity.

Advancing hyper-crosslinked materials with high efficiency and reusability for oil spill response

Developing materials with high efficiency for recovering oil to mitigate the environmental impact of oil spills has always been a challenging task. A commercial melamine formaldehyde sponge was coated with an optimised superhydrophobic/superoleophilic hyper-crosslinked polymer and applied to the removal of crude oil from oil-in-water emulsions for the improvement of oil spill clean-up processes. The high surface area, porosity, hydrophobicity, and selectivity of oil over water made the hyper-crosslinked polymer coated sponge (HPCS) an ideal sorbent for efficient oil/water separation. The system was able to strip crude oil from water emulsions of 1000 ppm to a negligible level of 2 ppm oil with minimal amounts of the HPCS material. More importantly, the HPCS material could be reused via a simple mechanical compression process, and the uptake capacity was retained over ten cycles. For five cycles of oil adsorption/mechanical compression the HPCS was able to provide water filtrate with oil concentrations of under 15 ppm. This is an effective and economical recovery system, removing the need for consistent solvent washing and drying processes. These results suggest that the HPCS is a promising material for oil/water separation and recovery under challenging conditions.

Hyper-crosslinked polymer derived porous Co@CN catalyst for selective hydrogenation of quinoline

A benzotrizole-based hyper-crosslinked polymer (HCP) was employed to load cobalt and prepare a novel metal-containing nitrogen-doped carbon catalyst for the selective hydrogenation of quinoline. The high porosity, large surface area and nitrogen-containing monomer of HCP made a positive contribution to metal loading. Owing to the excellent thermostability of HCP, the original porous texture of HCP was partially reserved during pyrolysis, which resulted in highly dispersive Co species in the N-doped carbon material. The remaining mesopores in Co@CN catalyst during thermal decomposition provided available diffusion channels for substrates, which facilitated their full contact with catalytic active sites and their effective conversion. The prepared Co@CN catalyst achieved a conversion rate of 100% and a selectivity of 100% in the hydrogenation of quinoline into 1, 2, 3, 4-tetra-hydroquinoline in water at 100 °C under 3 MPa H2. The as-synthesized catalyst had good reuse performance, exhibiting >95% conversion rate and >99% selectivity even after 12 cycles. Moreover, the catalyst could also be applied to the selective hydrogenation of a serial of quinoline derivatives. The study provided a useful strategy for constructing metal-doped carbon materials which might be applicable for other metals and other reactions.

Fabrication of the hyper-crosslinked polymers chemically functionalized by 8-hydroxyquinoline and their efficient adsorptive removal of 2-naphthol from water

Hyper-crosslinked polymers (HCPs) chemically functionalized with plentiful heteroatoms are of great importance for the adsorptive removal of polar aromatic substances from water, while their facile fabrication is of great challenge, and the adsorptive removal of the 2-naphthol from water remains a bottleneck. Herein, 8-hydroxyquinoline (HQ) was employed as the chemical modifier and firstly uploaded on the polymers according to the nucleophilic substitution, thereafter several external crosslinking agents were employed and the Friedel-Crafts alkylation was performed for the intermediate polymer, and hence the HCPs chemically functionalized by HQ, namely, PS-HQ-HCPs, were successfully fabricated. The nucleophilic substitution supplied the intermediate polymer with plentiful ether oxygen (O, 4.81%) and pyridine nitrogen (N, 6.39%). The Friedel-Crafts alkylation constructed predominant micro-porosity and meso-porosity for the final polymers with high Brunauer-Emmett-Teller (BET) surface area (SBET, 384–618 m2/g) and pore volume (Vtotal, 0.36–0.63 cm3/g). 2-Naphthol was utilized as the adsorbate to investigate the batch adsorption, and the predicted maximum capacity (qmax) on the final polymer, namely, PS-HQ-DCX was 828 mg/g at 318 K, higher than most synthetic materials. Meanwhile, the adsorption attained the equilibrium within 360 min, and the kinetic data can be described by the micro-pore diffusion model. As the initial 39.5 mg/L of 2-naphthol was fed for the adsorption, the final concentration reduced to 1.9 mg/L, less than the discharge standard in China (GB 8978–19962, mg/L). The dynamic adsorption revealed that the saturated capacity was 632 mg/g, approaching to the fitted qmax (688 mg/g) by the Langmuir model, and 232 mL anhydrous ethanol completely desorbed 2-naphthol from the polymers. This universal synthetic protocol is of great importance for the fabrication of some other functionalized HCPs, and this strategy was universal for some other phenolic compounds and external cross-linking agents.

Amine functionalized benzene based hypercrosslinked polymer as an adsorbent for CO2/N2 adsorption

In this work, benzene based hypercrosslinked polymer (HCP) as an adsorbent was modified using amine group to enhance CO2 uptake capability and selectivity. Based on BET analysis result, the HCP and the modified HCP provide surface area of 806 (m2 g−1) and micropore volume of 453 (m2 g−1) and 0.19 (cm3 g−1) and 0.14 (cm3 g−1), respectively. The CO2 and N2 gases adsorption were performed in a laboratory scale reactor at a temperature between 298 and 328 K and pressure up to 9 bar. The experimental data were evaluated using isotherm, kinetic and thermodynamic models to identify the absorbent behavior. The maximum CO2 adsorption capacity at 298 K and 9 bar was obtained 301.67 (mg g−1) for HCP and 414.41 (mg g−1) for amine modified HCP. The CO2 adsorption thermodynamic parameters assessment including enthalpy changes, entropy changes, and Gibbs free energy changes at 298 K were resulted − 14.852 (kJ mol−1), − 0.024 (kJ mol−1 K−1), − 7.597 (kJ mol−1) for HCP and − 17.498 (kJ mol−1), − 0.029(kJ mol−1 K−1), − 8.9 (kJ mol−1) for amine functionalized HCP, respectively. Finally, the selectivity of the samples were calculated at a CO2/N2 composition of 15:85 (v/v) and 43% enhancement in adsorption selectivity at 298 K was obtained for amine modified HCP.

Analyzing Environmental Impacts of Hypercrosslinked Polymers Produced from Continuous Flow Synthesis for Water Treatment

Analyzing Environmental Impacts of Hypercrosslinked Polymers Produced from Continuous Flow Synthesis for Water Treatment

High-performance asymmetric supercapacitors utilizing manganese oxide nanoparticles grafted graphitic carbon nitride nanosheets as the cathode and hypercross-linked polymer derived activated carbon as the anode

Herein, we demonstrated the inexpensive construction of a high-performance asymmetric supercapacitor (ASC) that was combined with manganese oxide nanoparticles grafted graphitic carbon nitride nanosheets (Mn3O4@GCN-NS) as the cathode and nitrogen doped hypercross-linked polymer derived activated carbon (NHCP-AC) as the anode with 6.0 M aqueous KOH electrolyte. In the beginning, Mn3O4@GCN-NS was successfully prepared via a single-step pyrolysis assisted method and the NHCP-AC was synthesized via Friedel-Crafts reaction. The as-synthesized nanocomposites exhibited higher specific capacitance of 436.2 at 0.5 A g−1 in three-electrode cell configuration. Furthermore, the ASC device was fabricated by integrating Mn3O4@GCN-NS with NHCP-AC, which demonstrated considerable energy density of 22.2 Wh/kg at 400 W/kg power density together with remarkable cyclability (93.5 % capacitive retention even after 5000 cycles of charge and discharge). The light emitting diode (5 mm dia.) was powered for about 15 min using two ASC devices coupled in series, demonstrating the effectiveness of its power source. Thus, the results demonstrated that the ASC devices have enormous potential for investigating cutting-edge applications in the field of advanced energy storage.

A Concise Review on Hypercrosslinked Polymers with Catalytic Applications

A Concise Review on Hypercrosslinked Polymers with Catalytic Applications

Magnetic amino-rich hyper-crosslinked polymers for fat-rich foodstuffs pretreatment in nontargeted analysis of chemical hazards

Nontargeted analysis for chemical hazards is highly desirable in controlling food safety to ensure human health. As the dominating interference in fat-rich foodstuffs, lipids removal is a great challenge in sample pretreatment. Herein, diverse lipids from both animal and vegetable oils are effectively removed and 565 chemical hazards with various physicochemical properties are used for method validation. These benefits are from the designed magnetic amino-rich hyper-crosslinked core–shell polymeric composites (Fe3O4@poly(MAAM-co-EGDMA)) and the application of an auto extraction system. Among them, the amino groups are the key factors for lipid removal. Theoretical calculations, isothermal titration calorimetry (ITC), and functional monomer replacement demonstrated that the mechanisms to universally capture free fatty acids (FFAs) and triglycerides (TGs) are electrostatic interaction and supplemented by hydrogen bonding. Overall, this work highlights the great application potentials of polymeric adsorbents as sample pretreatment materials for nontargeted analysis in food safety.

Dispersive solid-phase extraction of alkaloids and polyphenols using borate hypercrosslinked polymers.

In this study, a borate hyper-crosslinked polymer was synthesized by crosslinking 1-naphthalene boric acid and dimethoxymethane via the Friedel-Crafts reaction. The prepared polymer exhibits excellent adsorption performance toward alkaloids and polyphenols with maximum adsorption capacities ranging from 25.07 to 39.60mg/g. Adsorption kinetics and isotherms model results indicated the adsorption was a monolayer and chemical process. Under the optimal extraction conditions, a sensitive method was established for the simultaneous quantification of alkaloids and polyphenols in green tea and Coptis chinensis by coupling with the proposed sorbent and ultra-high performance liquid chromatography detection. The proposed method exhibited a wide linear range of 5.0-5000.0ng/ml with R2 ≥ 0.99, a low limit of detection (0.66-11.25ng/ml), and satisfactory recoveries (81.2%-117.4%). This work provides a simple and convenient candidate for the sensitive determination of alkaloids and polyphenols in green tea and complex herbal products.

Hyper-Cross-Linked Polymers with Sulfur-Based Functionalities for the Prevention of Aging Effects in PIM-1 Mixed Matrix Membranes

The instability of gas permeation rates over time in PIM-1-based membranes is one of the obstacles preventing the implementation of this technology on larger scales. The addition of porous materials to the PIM-1 matrix is a known process to reduce aging effects in PIM-1-based membranes. Many porous solids of various chemical natures have been tested, ranging from inorganic to inorganic–organic hybrids to completely organic materials. Here, we report on the synthesis of two hyper-cross-linked polymers (HCPs) based on the diphenyl sulfide monomer, synthesized in either dichloromethane at 35 °C or dichloroethane at 78 °C. Two mixed matrix membranes (MMMs) were obtained from the addition of 3 wt % of either filler to PIM-1. Both the CO2 permeation rates and the CO2/N2 selectivity were measured for the pure PIM-1 membrane and for the two MMMs over a period of 400 days. PIM-1 exhibits a classic aging behavior with an 85% drop in the CO2 permeation rate with respect to the initial value. For the two MMMs, a retention of 50% of the initial CO2 permeability was instead observed after more than 400 days of aging. Despite the low surface area and low pore volume of the fillers, we show that diphenyl sulfide-based HCPs can reduce the aging rate in PIM-1 membranes.

Investigation on Regulating Porous Polymers with Suitable Porosities and/or N-Doping for Enhanced CO2 Capture

Various cost-effective polycyclic aromatic hydrocarbons (PAHs) were used to fabricate hyper-cross-linked polymers (HCLPs) via an external cross-linker knitting method (ECLKM) followed by N-source impregnation modification. Multiple characterization techniques and thorough tests confirmed that the resultant thermally stable materials featured large specific surface areas (up to 2870 m2 g–1), narrow pore distributions (<0.70 nm), and high pore volumes (up to 1.09 cm3/g). Effects of porosities and N-doping modification ways on HCLPs’ CO2 capture capacities have been fully studied via controlling experiments. Remarkably, HCLP 1 prepared using naphthalene without further modification possessed the highest CO2 uptake capacity (up to 3.8 mmol g–1), indicating that porosities dominated the CO2 uptake process of HCLPs compared with N-doping modification. This study offers a facile strategy to construct HCLPs with great CO2 capture performances using PAHs via a simple one-pot ECLKM.

Phosphorylated calix[4]arene/balsa wood copolymers for selective uranyl extraction from wastewater and seawater

Hyper-crosslinked polymers are frequently used to recover specific guest molecules due to their high porosities, excellent chemical properties, and structural stability. However, the recovery of powder adsorbents poses a significant challenge in the extraction of uranyl from aqueous solutions, which limits their practical application. A phosphorylated calix[4]arene/balsa wood copolymer (C4-W-P) was successfully synthesized and utilized for the extraction of uranyl from radioactive wastewater and seawater. Compared to previously reported adsorbents, C4-W-P demonstrated rapid uranyl capture kinetics, with adsorption equilibrium achieved within 150 min. The material exhibited a monolayer saturation adsorption capacity of 473.9 mg·g−1 at pH 5. Thermodynamic studies confirmed the spontaneous and endothermic nature of the adsorption process. Furthermore, C4-W-P exhibited exceptional structural stability, with only a 9.7 % reduction in adsorption capacity after six adsorption–desorption cycles. Additionally, C4-W-P demonstrated excellent selectivity in simulated wastewater containing 16 rare metal ions and simulated seawater containing an additional five metal ions. The KdU values were recorded to be 1817.2 and 33,265.3 mL·g−1, respectively, for these conditions. These results demonstrate the high-efficiency uranium removal capabilities of C4-W-P under realistic conditions. The abundant phosphate groups (∼1.69 mmol·g−1) on the material surface were identified as the primary adsorption contributors. Overall, this study provides a promising strategy for uranyl extraction with high selectivity and ease of preparation, contributing to environmental protection and economic development.

Conjugated cross-linked phosphine as broadband light or sunlight-driven photocatalyst for large-scale atom transfer radical polymerization

The use of light to regulate photocatalyzed reversible deactivation radical polymerization (RDRP) under mild conditions, especially driven by broadband light or sunlight directly, is highly desired. But the development of a suitable photocatalyzed polymerization system for large-scale production of polymers, especially block copolymers, has remained a big challenge. Herein, we report the development of a phosphine-based conjugated hypercrosslinked polymer (PPh3-CHCP) photocatalyst for an efficient large-scale photoinduced copper-catalyzed atom transfer radical polymerization (Cu-ATRP). Monomers including acrylates and methyl acrylates can achieve near-quantitative conversions under a wide range (450–940 nm) of radiations or sunlight directly. The photocatalyst could be easily recycled and reused. The sunlight-driven Cu-ATRP allowed the synthesis of homopolymers at 200 mL from various monomers, and monomer conversions approached 99% in clouds intermittency with good control over polydispersity. In addition, block copolymers at 400 mL scale can also be obtained, which demonstrates its great potential for industrial applications.