Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance

Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance Tao He, Wei-Wei Fang, Zi-Hui Fan, Bin Xia, Yi-Xing Liu, Fan Zhang, and 9 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6691883/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Reversible-deactivation radical polymerization (RDRP) is a cornerstone of polymer industry. Normally, RDRPs are highly sensitive to oxygen and inhibitors, which hamper their industrial applications. Present methods cannot achieve facile polymerization in presence of both oxygen and inhibitors, particularly for large-scale production. Herein, we report development of phenanthroline-based conjugated hypercrosslinked polymer (Phen-CHCP) as a photocatalyst for photoinduced copper-catalyzed atom transfer radical polymerization (Cu-ATRP) with both high oxygen and inhibitors tolerance. Investigation of a new catalytic mechanism indicated that heterogeneous properties accelerate the diffusion of oxygen and inhibitors towards the Phen-CHCP interface. The ATRP initiator dominates the photoreduction process, not only accelerates the Cu-catalyzed redox cycle but also stabilizes the phenol inhibitor. As a result, various monomers achieved > 95% conversions under broadband lights irradiation. This development strongly encourages the large-scale polymerizations, and we typically synthesized block copolymer of poly((2-methoxyethyl) acrylate-block-n-butyl acrylate) in situ at 20 L scale (conversion 96%, Đ = 1.26), which highlight the strong potential for industrial applications. Physical sciences/Chemistry/Polymer chemistry/Polymer synthesis Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Chemistry/Catalysis/Photocatalysis Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Reversible-deactivation radical polymerization (RDRP) relies on a dynamic equilibrium between active and dormant species, effectively minimizing the concentration of propagating centers and reducing bimolecular termination 1 , 2 . This characteristic enables the synthesis of polymers with precise control over molecular weight, dispersity, functionality, end-group fidelity, sequences, and architectures-attributes, which could not easily be achieved through conventional free radical polymerization (CRP) 3 – 9 . RDRP has become one of the most important methods for preparing functional polymers up to present 10 . Normally, most CRPs could be conducted under mild conditions in presence of oxygen and inhibitors. As a contrast, RDRPs need the deoxygenation and removal of inhibitor of monomers before polymerizations, which make them difficult to be performed as convenient as CRPs. These are the top challenges limiting the related industrial applications. Typically, Oxygen irreversibly reacts with propagating radicals, and also deactivate the copper catalyst in copper-catalyzed atom transfer radical polymerization (Cu-ATRP) 11 , 12 . Consequently, oxygen leads to polymer chain termination and halts the polymerization process. To mitigate this, most RDRPs require rigorous deoxygenation, which is costly and time-consuming 13 . Various strategies have been explored to enable oxygen-tolerant RDRPs through sacrificial reagents that in situ consume oxygen 14 . In most approaches, oxygen acts as an undesirable component, and extensive chain terminations and side reactions cannot be fully avoided 15 – 26 . Recent progresses introduced the use of oxygen as a reagent in reversible addition-fragmentation chain transfer (RAFT) polymerization and Cu-ATRP, where oxygen served as co-initiator or facilitated the activation of chain transfer agents and the regeneration of Cu(I) activators 27 – 34 . In these cases, oxygen contributes positively to the polymerizations, but the polymerization efficiency together with the polymer chain control ( eg. molecular weight or dispersity) were deteriorated in scale-up production, particularly when air remaining in the reactor headspace. This may because that the employment of large-scale reactor leads to decreasing in area/volume (S/V) ratio 35 , and the mass transport of the reactants is limited (Fig. 1 a), subsequently reduce the oxygen removal efficiency and prolong the oxygen scavenging time. These could result in inevitable accumulation of dead chains and decreasing of production efficiency. As such, simultaneous chemical and physical oxygen removal were still required when polymerization scale up to L level and above. It was reported that photocatalytic conversion represents a promising deoxygenation strategy. However, this method can’t be applied in large-scale production of photocatalyzed RDRPs at present. The scale-up processes applying batch reactors inevitably reduce the S/V ratio and result in light attenuation 36 , and polymerization reactors are spatially inhomogeneous 37 . These effects establish spatial heterogeneity in oxygen concentration profiles within the reaction system. Such physicochemical heterogeneity propagates to radical distributions, which generate regional disparities in chain growth rates that ultimately compromise the polymerization control. Meanwhile, some literature reported the applications of long-wavelength photocatalysts, which could avoid competitive overlap with reactant while exhibiting superior light penetration capabilities 38 . However, photocatalyzed oxygen conversion depended on photoinduced electron transfer processes. Even when long-wavelength light was applied, the attenuation of light still couldn’t be fully ruled out for large-scale batch reaction. An alternative solution is to employ photo flow chemical devices as they provide increased S/V. However, a typical challenge is the relatively poor reproducibility of optimized reaction outcomes when scaling up from bench-scale reactors to large-scale reactors 39 . Monomers normally need to remove phenolic inhibitors prior to RDRPs, leading to multi-step purifications and potential monomer loss 40 . Only few RDRPs can tolerate inhibitors, where the inhibitors were either stabilized by reagents or served as reductants to reduce high-valent copper complexes 41 , 42 . However, these polymerizations were generally not viable with oxygen and difficult to be performed at ambient temperature. Although few studies reported polymerizations in the presence of both inhibitors and oxygen at elevated temperatures ( e.g. , 80°C), the polymerization rate was significantly reduced (only 1/3 to 1/4 of that seen with purified, deoxygenated monomers) 43 . From perspective of industrial applications, the development of RDRPs with new catalytic process that are tolerant to both oxygen and inhibitors in large-scale synthesis at ambient temperature would significantly simplify production and increase throughput, and performing RDRP could be as convenient as CRPs. The rational design of heterogeneous catalysts with elaborate porous architectures was demonstrated as an effective strategy to enhance photocatalytic reaction kinetics 44 . Previous investigations indicated that heterogeneous photocatalyst designed by introducing suitable functional groups could benefit to metal and oxygen enrichment, which could promote oxygen conversion reactions such as photocatalytic H 2 O 2 generation 45 , 46 . We hypothesize a new catalytic mechanism that through introducing suitable chelation site, the porous materials could be expected to simultaneously facilitate the diffusion of reaction substrates including Cu catalyst and oxygen. As a result, the porous material could accelerate oxygen scavenging and reduce the adverse effects of limited diffusion in large-scale RDRP. As such, we herein report the phenanthroline-based conjugated hyper-crosslinked polymer (Phen-CHCP) photocatalyst enabled large-scale Cu-ATRP in presence of both high content of oxygen and inhibitors, driven by broadband lights and sunlight at room temperature. In the detailed catalytic process, in addition to converting oxygen into singlet oxygen ( 1 O 2 ), the excited-state Phen-CHCP exhibited promising comparable reaction rates with both R-X initiator and high-valent copper catalyst (Fig. 1 b). As such, Phen-CHCP mainly served as highly efficient supplementary activator to accelerate the cleavage of C-X bonds, generate R • and promote Cu catalyzed cycle for oxygen conversion. (Fig. 1 c) Meanwhile, X − generated from organophotocatalyzed activation process could stabilize phenol type inhibitors. This catalytic process allowed rapid photocatalyzed Cu-ATRPs to be successfully performed at high air content (up to 80% v/v) and monomer inhibitors (up to 5000 ppm) under various lights irradiation, yielding near-quantitative monomer conversions with good control over polymer dispersity. This system is very suitable for large-scale production. In practical applications, as large as 20 L scale polymerization was performed, which produced block copolymer of poly((2-methoxyethyl) acrylate-block-n-butyl acrylate) (PMEA- b -PBA) with 96% conversion and good control over dispersity ( Đ = 1.26). This is the largest scale of photo-RDRP to date. This development should represent significant catalytic advances in green and sustainable RDRPs, with substantial potential for industrial applications. Results Synthesis of Phen-CHCP In the synthesis, 4,7- diphenyl-1,10-phenanthroline was applied to construct crosslinked networks, as it provides chelation sites for Cu catalyst and pyridine rings were beneficial for oxygen enrichment 47 . Phen-HCP was synthesized via an iron (III) chloride catalyzed Friedel-Crafts alkylation reaction using 4,7-diphenyl-1,10-phenanthroline and dimethoxybenzene, followed by treating with NaBH 4 to improve dispersibility (offering Phen-CHCP, Supplementary Figs. 1–5; Supplementary Table 1). Related pore size distribution analysis and morphology characterizations revealed that Phen-CHCP possessed a microporous and mesoporous structure (Supplementary Fig. 6). Cyclic voltammetry (CV) experiments suggested that the Phen-CHCP dispersion had a stronger Cu reduction peak than that of pure solution (Supplementary Fig. 7), indicating that Phen-CHCP was beneficial to the enrichment of Cu ions. Next, the photocatalytic properties and oxygen conversion capability of Phen-CHCP were evaluated. Solid-state diffuse reflectance ultraviolet/visible/near-infrared (UV-Vis-NIR) spectra showed strong absorption across a wide range (200–900 nm), indicating its potential as an efficient broadband light harvester (Supplementary Fig. 8a-c). Notably, Phen-CHCP exhibited a nanosecond fluorescence lifetime of 1.46 ns and low quantum yields ( Φ F = 0.0056, λ em = 500 nm) (Supplementary Table 2; Supplementary Fig. 8d,e), which may enhance electron transfer efficiency 48 . Phen-CHCP displayed a photocurrent response under visible light irradiation, demonstrating effective charge transfer and separation abilities (Supplementary Fig. 8f). UV-Vis results suggested that molecular oxygen converted to 1 O 2 in the presence of Phen-CHCP under light irradiation (Supplementary Fig. 9), when 9,10-dimethylanthracene was used as internal standard 49 . These investigations suggest that Phen-CHCP is a promising broadband photocatalyst for oxygen-tolerant photocatalyzed Cu-ATRP. Photocatalyzed Cu-ATRPs using Phen-CHCP with oxygen tolerance The oxygen tolerance of the Photo-ATRPs was investigated through varying air content during polymerizations, which were conducted under green light irradiation (Supplementary Fig. 10). Methyl acrylate (MA) was used as a model monomer, and polymerization results were listed in Table 1 . Near-quantitative conversions were achieved within 6 hours when the air volume content was approximately 50% ( v/v ). However, with the air content increasing, conversions gradually declined, indicating that the generation of propagating radicals was suppressed (Supplementary Fig. 11 and Supplementary Table 3). Despite this, by extending the reaction time to 9 hours and increasing the ligand ratio (0.4 equiv to initiator), high monomer conversion (91%) could still be obtained at 80% air content ( v/v ) (entry 13, Supplementary Table 3). For subsequent experiments, the air volume content was maintained at 50% ( v/v ), as this condition required less ligand and reaction time, while still yielding efficient polymerizations. Next, oxygen-tolerant photocatalyzed Cu-ATRP of MA using Phen-CHCP was conducted under varied conditions, and the results are summarized in Table 1 . The polymerization did not proceed when the CuBr/tris[2-(dimethylamino)ethyl]amine (Me 6 TREN) ratio was 1:1 (entry 1, Table 1 ), suggesting that an excess of the amine electron donor (Me 6 TREN) was necessary to initiate the reaction. Increasing the ligand concentration resulted in near-quantitative conversions, producing well-defined polymers with low dispersity ( Đ < 1.10) and controlled molecular weights (entries 1–5, Table 1 ; Supplementary Fig. 12). In contrast, under dark conditions with Phen-CHCP, low conversion (~ 21%, entry 6, Table 1 ) was observed, and this indicated that the concentration of [Cu I /L] + activator, being generated via the activators regenerated by electron transfer (ARGET)-ATRP pathway, was insufficient to sustain significant chain growth. Notably, no polymerization occurred in the absence of Phen-CHCP (entry 7, 9, 15, and 17, Table 1 ), highlighting the essential role of the photocatalyst in regenerating the activating species. Under 50% air content ( v/v ), when conditions varied, such as using lower amounts of Phen-CHCP (Supplementary Fig. 13 and Supplementary Table 4), reduced amount of CuBr (Supplementary Fig. 14 and Supplementary Table 4), different ligands and solvents (Table 1 and Supplementary Fig. 15), and varying degrees of polymerization (targeting from 50 to 1000, Supplementary Fig. 16 and Supplementary Table 5), promising polymerizations with high monomer conversions and polymers with low dispersity were still achieved. Kinetic studies being performed in both DMSO and N,N-dimethylformamide (DMF) (Fig. 2 and Supplementary Fig. 17) indicated a living polymerization process in all cases (Fig. 2 a, b). The oxygen tolerant polymerizations also exhibited temporal control, responding effectively to green light on/off cycles (Fig. 2 C and D; Supplementary Fig. 18). When the dark period was extended to 12 hours, negligible monomer conversion was observed (Supplementary Fig. 19), suggesting that active radicals were not efficiently generated due to the continuous diffusion of oxygen from the air, which oxidized the Cu I /L activator to its inactive state. In the context of preparing block copolymers with oxygen tolerance, it is critical to investigate polymer chain-end fidelity. Good chain-end fidelity was confirmed by 1 H nuclear magnetic resonance (NMR) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) analysis (Supplementary Figs. 20 and 21). In situ oxygen-tolerant chain extension was also successful. For example, a PMA sample (conversion ~ 96%, M n = 17,300, Đ = 1.05) synthesized under green light irradiation (50% air, v/v ) was fed with MEA and followed by continuous polymerization. This resulted in a well-defined diblock copolymer ( M n = 34,300, Đ = 1.08) with 90% conversion (Fig. 3 ). Oxygen-tolerant Phen-CHCP/Cu-catalyzed photo-ATRP was successfully applied to a range of monomers, including acrylates, methyl acrylates, and styrene (St). High conversions (> 95%), along with polymers possessing controlled molecular weights and low dispersity, were consistently achieved (Supplementary Fig. 22 and Supplementary Table 6). These results strongly demonstrate the high flexibility and efficiency of oxygen-tolerant Cu-ATRP in the presence of Phen-CHCP. Furthermore, Phen-CHCP could be easily separated from the reaction mixture, and reused across multiple ATRP cycles while maintaining high photocatalytic efficiency with high oxygen tolerance (Supplementary Figs. 23–25). The high oxygen tolerance polymerizations could be performed from UV to NIR region. Results from both MA and methyl methacrylate (MMA) are summarized in Supplementary Table 7. Near-quantitative monomer conversions were achieved (Fig. 3 a), and the polymers exhibited excellent control over dispersity, with values of less than 1.08 for PMA and 1.13 for PMMA. Size-exclusion chromatography (SEC) analyses demonstrated monomodal and symmetric curves (Fig. 3 b,c). Meanwhile, linear semilogarithmic kinetic plots were obtained for polymerizations under various light wavelengths, including blue, green, red, and 940 nm light (Fig. 3 d,e and Supplementary Fig. 26). These results confirmed the living nature of oxygen tolerant photoinduced Cu-ATRP under broadband light conditions. It is notable to highlight that very low irradiation intensities were used in these polymerizations. Specifically, the light intensities were 0.9, 0.9, 2, and 15 mW/cm² for blue, green, red, and 940 nm light, respectively. The low irradiation intensity may offer significant advantages such as reduced energy consumption and minimized photocatalyst degradation, which is critical for scaling up the polymerization process (Supplementary Fig. 27). The high oxygen tolerant polymerizations could also be performed under barrier. In NIR-driven polymerizations, reaction vessels were wrapped in opaque paper (approximately 0.4 mm thick) to serve as light barriers. Remarkably, high monomer conversions (> 94%) and close agreement of the theoretical and experimental molecular weight were obtained (Supplementary Fig. 28 and Supplementary Table 8). The deep penetration of NIR light presents an opportunity for scale-up of Cu-ATRP using Phen-CHCP, applicable to both batch processes and microfluidic devices. It’s important to point out that Phen-CHCP is a suitable photocatalyst for sunlight-induced oxygen tolerant Cu-ATRP. For instance, polymerization of MA or MMA achieved over 97% conversion within 5 hours under natural sunlight (entry 11 and 22, Supplementary Table 7). The resulting polymers exhibited low dispersity values, with Đ = 1.05 for PMA and Đ = 1.19 for PMMA. This method represents a green and sustainable approach to synthesizing well-defined polymers. Inhibitor tolerant polymerizations in presence of oxygen Furthermore, our study demonstrated that Phen-CHCP-catalyzed photopolymerization could be easily performed from unpurified monomer (with inhibitor) in presence of significant amounts of oxygen. To evaluate inhibitor tolerance performance under air (50%, v/v ), unpurified monomers containing 4-methoxyphenol (MEHQ) were used. High monomer conversions (> 95%) were achieved, with dispersity values of 1.08 and 1.14 for MA and MMA respectively (Table 1 ; table S11). Additionally, the polymerization of St with 4-tert-butylcatechol as an inhibitor resulted in 60% monomer conversion and a dispersity of 1.10 (Supplementary Fig. 29). The relatively lower conversion may be attributed to the lower O-H bond dissociation energy of 4-tert-butylcatechol compared to MEHQ 42 . The oxygen and inhibitor tolerant polymerization kinetics indicated living characteristics and a reaction rate comparable to that of purified MA (Supplementary Fig. 30). MALDI-ToF-MS and 1 H NMR analyses of the resulting PMA (target DP: 100, conversion ~ 98%, M n,SEC = 8200, Đ = 1.07) confirmed good retention of chain-end fidelity (Supplementary Figs. 31 and 32). Control experiments revealed that polymerization did not proceed in the absence of Phen-CHCP or without light, highlighting the essential role of the photocatalyst (Supplementary Table 9). When using stronger inhibitors, such as 500 ppm of catechol or butylated hydroxytoluene (BHT), MA conversion reached 93% within 6 hours. Extending the reaction time to 8 hours resulted in 99% conversion (Supplementary Table 10). When the concentration of catechol or BHT was increased to 5000 ppm, the polymerization rate decreased, but high conversions of 82% and 94% were still achieved for catechol and BHT respectively. The lower conversion with catechol might be due to its higher affinity for the copper catalyst, leading to a more rapid decline in the concentration of the Cu I /L activator compared to BHT. To further assess the capability of synthesizing block copolymers directly from unpurified monomers with oxygen tolerance, chain extension experiments were conducted. A PMA macroinitiator (conversion ~ 96%, M n = 16,600, Đ = 1.06) was sequentially fed with unpurified MEA, followed by polymerization at room temperature. The resulting well-defined diblock copolymer, PMA- b -PMEA, exhibited a molecular weight of M n = 31,200, dispersity of 1.09, and 91% conversion of MEA (Supplementary Fig. 33). Oxygen and inhibitor tolerance mechanism These results underscore the promising inhibitor and oxygen tolerance of Phen-CHCP/Cu-catalyzed photo-ATRP, providing a viable approach for more straightforward and cost-effective polymerization processes. In reported Cu-ATRP with oxygen tolerance, molecular oxygen could generate singlet oxygen ( 1 O 2 ) or O 2 •− , which didn’t participate the polymerization 50 , 51 . Besides, in the photocatalytic cross-coupling of phenols, the deprotonation of phenol radical cations may be triggered by O 2 • − 52,53 . Based on this, we propose that if the reactive oxygen species (ROS) generated during RDRP process can be harnessed to promote both the formation of propagating radicals and elimination of phenolic inhibitor, it could pave the way for Cu-ATRP with both enhanced oxygen and inhibitor tolerance. Our results suggest that the Cu I /L complex may react with continuous generated 1 O 2 in presence of excess oxygen, which facilitate the formation O 2 -Cu II /L species in the presence of Phen-CHCP 33 , and excess ligands do not rapidly reduce these species (Supplementary Fig. 34a,b). Meanwhile, ligands, DMSO, or Phen-CHCP lack the capability to reduce O 2 -Cu II /L species rapidly back to Cu I /L, implying that the initiator should participate in this reduction process. There were no O 2 -Cu II /L peaks being observed within 4 hours, after adding the initiator to a solution containing CuBr/DMSO/Me 6 TREN (Supplementary Fig. 34c). This suggested that the initiator (in significant excess relative to Cu I /L) could quickly oxidize Cu I /L to X-Cu II /L (Supplementary Fig. 35), while the other components of the system lack the capability to reduce this species. Meanwhile, in the presence of Phen-CHCP, the absorption intensity of the superoxide species increased rapidly from 30 min to 3 hours before plateauing (Supplementary Fig. 34d), indicating the fast regeneration of Cu I /L. To gain further understanding of the Phen-CHCP/Cu-catalyzed photo-ATRP, we conducted amperometric i-t analysis of these photoredox reaction. Upon adding the initiator EBiB to a solution containing Cu I /L and O 2 -Cu II /L species, the current dropped sharply from positive to negative, stabilizing thereafter, indicating rapid conversion to X-Cu II /L and negligible photo-reduction of X-Cu II /L (Supplementary Fig. 36a). In contrast, in the presence of Phen-CHCP, the current decreased gradually, signifying continuous diffusion-driven reduction reactions (Supplementary Fig. 36b). Similar results were observed when X-Cu II /L was the initial catalyst (Supplementary Fig. 36c). These results indicate that the reduction of X-Cu II /L is mediated by photo-reduction of the initiator, which, in turn, reduces the transition state or final product in the presence of Phen-CHCP. Without the copper catalyst, the current initially dropped from positive to negative, then gradually increased (Supplementary Fig. 36d), suggesting rapid photo-reduction of EBiB, although the product was unstable. Cyclic voltammetry curves of Phen-CHCP exhibited reduction potential of ( E ox * = -0.88 V) (Supplementary Fig. 37), indicating that excited states of Phen-CHCP were highly reducing to reduce EBiB ( E red = − 0.74 V). In order to further ascertain the reducing ability of excited Phen-CHCP, spectroscopic analyses were carried out. We choose EBiB, CuBr 2 /Me 6 TREN, and Me 6 TREN as the quencher (Supplementary Fig. 38). The linear relationship between I 0 / I and quencher concentration ( I 0 and I were the fluorescence intensities before and after adding quencher) demonstrated that this was a dynamic quenching process involving a photoinduced electron transfer. In this process, the quenching rate ( k q ) of EBiB, CuBr 2 /Me 6 TREN, Me 6 TREN and dissolved O 2 toward the excited state Phen-CHCP were estimated to be 0.85×10 12 M − 1 S − 1 , 1.22×10 12 M − 1 S − 1 , 3.65×10 10 M − 1 S − 1 , and 10 12 M − 1 S − 1 , respectively (Fig. 4 a). The k q was much higher than reactant diffusity in solvent (estimated as 10 8 -10 9 M − 1 S − 1 , according to Einstein relation), indicating that the heterogeneous porous structure promoted the adsorption of reactants on the surface. In addition, considering the comparable magnitude of k q among diverse quenchers (particularly EBiB and CuBr 2 /Me 6 TREN), the photoinduced electron transfer processes should predominantly govern by the initial quencher concentration. Therefore, Phen-CHCP/Cu-catalyzed photoATRP exhibited a distinct electron-transfer pathway (compared to previous dual photoinduced Cu-ATRP), whereas the photogenerated electrons preferentially transfer to the R-X (1 equiv.) rather than copper complexes (0.02 equiv.). As such, the overall proposed mechanism is shown in Fig. 1 c. Photoexcitation of Phen-CHCP generates the excited state Phen-CHCP * . Both charge separation and energy transfer occur on the surface of Phen-CHCP * . In the case of charge separation, an electron is transferred to alkyl bromides, generating R • , X − and oxidized Phen-CHCP (Phen-CHCP •+ ) (Stage 1). Regarding the energy transfer, 1 O 2 is generated by transferring energy to molecular oxygen. Meanwhile, hole transfer to an amine donor (D) forms an amine radical cation (D •+ ), regenerating the ground state Phen-CHCP photocatalyst. The R • species reduce X-Cu II /L, forming Cu I /L and R-X (Stage 2). Partial Cu I /L is then oxidized by 1 O 2 to produce O 2 -Cu II /L species (Stage 3). The superoxido complex undergoes rapid reduction by Phen-CHCP * , yielding Cu I /L and O 2 (Stage 3). Notably, the high diffusivity drives spontaneous accumulation of reactants at the liquid-solid interface of the Phen-CHCP, effectively reducing the oxygen concentration in non-interfacial regions. Simultaneously, surface-adsorbed oxygen undergoes indirect conversion via a Cu-mediated pathway, bypassing direct photocatalyst mediated conversion. This dual mechanism allows the intrinsic oxygen tolerance under scaled-up reaction. Since the reversible redox equilibrium between Cu(I) and Cu(II) complexes is mediated by photoelectron transfer being induced supplementary activation of R-X, partial R-X ultimately participates the Cu(II) reduction process rather than initiating polymerization. Consequently, the proportion of unreacted R-X increases (Supplementary Fig. 39), and the molecular weight of polymers deviates from theoretical values with increasing air content (Supplementary Table 3). Besides, these unreacted R-X were stable after long time irradiation in our system (Supplementary Table 11). The proposed mechanism for Phen-CHCP/Cu-catalyzed photo-ATRP in DMF was similar to that of DMSO (Supplementary Figs. 40–42). To further explore whether photocatalytic cross-coupling occurred, we irradiated Phen-CHCP solutions in DMSO containing MEHQ, EBiB, and Me 6 TREN with green light. As expected, no significant changes happened from the 1 H NMR result of phenolic hydroxyl group (Supplementary Fig. 43), indicating that O 2 •− didn’t trigger a coupling reaction. However, the phenolic hydroxyl peak broadened significantly upon addition of EBiB, suggesting the formation of hydrogen bonds (Fig. 4 b). The current further decreased upon addition of MEHQ according to i-t analysis (Supplementary Fig. 36b). Since MEHQ remained stable throughout the reaction, this suggests that MEHQ may facilitating the reduction of R-X. Therefore, we believe that the generated X − might stabilize the phenolic inhibitor underpins the observed inhibitor tolerance. The phenolic hydroxyl bond dissociation energies (BDE) of three phenolic compounds in the presence and absence of bromide ions were evaluated. Results indicated that the BDE of phenolic hydroxyl groups underwent enhancement in the presence of bromide ions (Fig. 4 c), which was attributed to hydrogen-bonding interactions between Br⁻ and the hydroxyl moieties (Supplementary Fig. 44). Furthermore, confocal Raman spectra were applied to investigate these organocatalyzed activation-induced phenol stabilization in the presence of Phen-CHCP. A blue shift of the Raman signal representing the phenolic hydroxyl group was observed instantaneously under 532nm laser light irradiation (Fig. 4 d), which was consistent with the increasement of BDE of the phenolic hydroxyl bond. Consequently, the synergistic interplay between bromide-ion-stabilized phenolic inhibitors (generated through auxiliary activation processes) and catalyst-mediated rapid reactant diffusion collectively endowed this catalytic system with exceptional tolerance of inhibitors. Therefore, attenuation of supplementary activation processes would compromise the inherent inhibitor tolerance of the system. This infer was supported by the fact that ~ 0% monomer conversion was observed in the PPh 3 -CHCP system at 5000 ppm catechol inhibitor (Supplementary Table 12), where the k q of EBiB and CuBr 2 /Me 6 TREN toward the excited state PPh 3 -CHCP * were estimated as 0.81×10 12 M − 1 S − 1 and 4.37×10 12 M − 1 S − 1 (Supplementary Fig. 45). Scale-up production The above mechanism encouraged large-scale photo-ATRP for synthesizing both of the homopolymer and block copolymer. Photopolymerization of MA (10 L scale in 20 L reactor, 50% in DMSO) was performed in a 20 L photoreactor with Phen-CHCP (air 50%, v/v ) within 4 h under white light irradiation (Supplementary Fig. 46), producing PMA with dispersity of 1.07 (conversion ~ 97%, M n = 8,600) (Supplementary Fig. 47a). Furthermore, we prepared 10 L polymerization of PMEA macroinitiator (50% in DMSO) (conversion ~ 90%, M n = 11,300, Đ = 1.26). Subsequently, 10 L of unpurified n-BA solution (50% n-BA) was fed into the reactor for the in situ block copolymerization (Fig. 1 d). n-BA approached 96% conversion, and well-defined diblock copolymer was obtained ( Đ : 1.26, Supplementary Fig. 47b). To the best of our knowledge, this represents the largest example of photocatalyzed RDRP using unpurified monomer in presence of air (Supplementary Table 13). Conclusion We developed a Cu-catalyzed photo-ATRP system using phenanthroline-based hyper-crosslinked polymers (Phen-CHCP) as the photocatalyst, together with investigation of a new catalytic process. The photoinduced electron transfer process, governed by reactant concentration, indirectly facilitates the conversion of oxygen while generating bromide anions that stabilize phenolic inhibitors. The heterogeneous Phen-CHCP facilitates spontaneous diffusion of reactants to the catalyst interface, resulting in relatively low oxygen and inhibitor concentrations in non-interfacial regions of the reaction system. The synergistic interplay of these dual mechanisms confers upon the Phen-CHCP/Cu-catalyzed photo-ATRP system with the capacity to maintain high oxygen and inhibitor tolerance under scaled-up production. As a result, various acrylates and methacrylates could be polymerized in the presence of 50%-80% air, yielding well-defined polymers with low dispersity under broadband light irradiation. The Phen-CHCP/Cu-catalyzed photo-ATRP system demonstrates exceptional tolerance to both oxygen and inhibitors, enabling the synthesis of homo- and block copolymers with low dispersity (scaling up to 20 L). This methodology offers a robust platform for large-scale RDRP production without the need for tedious deoxygenation or monomer purification steps. Declarations Competing interests The authors declare no competing interests. Author Contributions T.H., B.E.T., and W.W.F. conceived the idea; T.H. and B.E.T guided the project and wrote the manuscript; Z.H.F., W.W.F., B.X. and Y.X.L. performed the experiments; L.X., X.L.H., F.Z., N.C., X.Z., T.C.S., B.X., X.Y.H. and H.G. supported and participated the acquisition of data; B.H. guided scale-up experiment; and T.H., B.E.T., W.W.F., and X.Z. analyzed the data and participated in the preparation of the manuscript. Acknowledgements This work was financially supported by National Natural Science Foundation of China (22171067, 22101275, 22475076, 22473104), the Postdoctoral Fellowship Program of CPSF under Grant Number GZC20240536, and the Fundamental Research Funds for the Central Universities of China (Grant No.PA2023GDSK0074). We also expressed our sincere gratitude to Jiangsu Bud Polyurethane Co., Ltd. and Shanghai 3S Technology Co., Ltd. for their support and assistance in scale-up experiments. References N. Corrigan, K. Jung, G. Moad, C. J. Hawker, K. Matyjaszewski, C. Boyer, Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications. Prog. Polym. Sci. 111, 101311 (2020). F. Lorandi, M. Fantin, K. Matyjaszewski, Atom transfer radical polymerization: A mechanistic perspective. J. Am. Chem. Soc. 144, 15413–15430 (2022). K. Parkatzidis, H. S. Wang, N. P. Truong, A. Anastasaki, Recent developments and future challenges in controlled radical polymerization: A 2020 update. Chem 6, 1575–1588 (2020). M.-N. Antonopoulou, R. Whitfield, N. P. Truong, D. Wyers, S. Harrisson, T. Junkers, A. Anastasaki, Concurrent control over sequence and dispersity in multiblock copolymers. Nat. Chem. 14, 304–312 (2021). Y. Zhao, Y. Chen, H. Zhou, Y. Zhou, K. Chen, Y. Gu, M. Chen, Controlled radical copolymerization of fluoroalkenes by using light-driven redox-relay catalysis. Nat. Synth. 2, 653–662 (2023). K. Kapil, G. Szczepaniak, M. R. Martinez, H. Murata, A. M. Jazani, J. Jeong, S. R. Das, K. Matyjaszewski, Visible-light‐mediated controlled radical branching polymerization in water. Angew. Chem. Int. Ed. 62, e202217658 (2023). R. Yin, J. Tarnsangpradit, A. Gul, J. Jeong, X. Hu, Y. Zhao, H. Wu, Q.Li, G. Fytas, A. Karim, M. R. Bockstaller, K. Matyjaszewski, Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP. Proc. Natl. Acad. Sci. U. S. A. 121, e2406337121 (2024). G. Szczepaniak, K. Kapil, S. Adida, K. Kim, T.-C. Lin, G. Yilmaz, H. Murata and K. Matyjaszewski, Solid-phase synthesis of well-defined multiblock copolymers by atom transfer radical polymerization. J. Am. Chem. Soc. 146, 22247–22256 (2024). G. K. K. Clothier, T. R. Guimarães, S. W. Thompson, S. C. Howard, B. W. Muir, G. Moad, P. B. Zetterlund, Streamlining the generation of advanced polymer materials through the marriage of automation and multiblock copolymer synthesis in emulsion. Angew. Chem. Int. Ed. 63, e202320154 (2024). N. P. Truong, G. R. Jones, K. G. E. Bradford, D. Konkolewicz, A. Anastasaki, A comparison of RAFT and ATRP methods for controlled radical polymerization. Nat. Rev. Chem. 5, 859–869 (2021). G. Szczepaniak, L. Fu, H. Jafari, K. Kapil, K. Matyjaszewski, Making ATRP more practical: Oxygen tolerance. Acc. Chem. Res. 54, 1779–1790 (2021). G. Ng, S. W. Prescott, A. Postma, G. Moad, C. J. Hawker, C. Boyer, Strategies for achieving oxygen tolerance in reversible addition-fragmentation chain transfer polymerization. Macromol. Chem. Phys. 224, 2300132 (2023). M. Destarac, Industrial development of reversible-deactivation radical polymerization: is the induction period over? Polym. Chem. 9, 4947–4967 (2018). J. Yeow, R. Chapman, A. J. Gormley, C. Boyer, Up in the air: Oxygen tolerance in controlled/living radical polymerisation. Chem. Soc. Rev. 47, 4357–4387 (2018). A. Layadi, B. Kessel, W. Yan, M. Romio, N. D. Spencer, M. Zenobi-Wong, K. Matyjaszewski, E. M. Benetti, Oxygen tolerant and cytocompatible iron(0)-mediated atrp enables the controlled growth of polymer brushes from mammalian cell cultures. J. Am. Chem. Soc. 142, 3158–3164 (2020). G. Szczepaniak, M. Łagodzińska, S. Dadashi-Silab, A. Gorczyński, K. Matyjaszewski, Fully oxygen-tolerant atom transfer radical polymerization triggered by sodium pyruvate. Chem. Sci. 11, 8809–8816 (2020). W. Li, W. Sheng, B. Li, R. Jordan, Surface grafting "band-aid" for "everyone": filter paper-assisted surface-initiated polymerization in the presence of air. Angew. Chem. Int. Ed. 60, 13621–13625 (2021). F. De Bon, R. G. Fonseca, F. Lorandi, A. C. Serra, A. A. Isse, K. Matyjaszewski, J. F. J. Coelho, The scale-up of electrochemically mediated atom transfer radical polymerization without deoxygenation. Chem. Eng. J. 445, 136690 (2022). J. Jeong, X. Hu, H. Murata, G. Szczepaniak, M. Rachwalak, A. Kietrys, S. R. Das, K. Matyjaszewski, RNA-Polymer hybrids via direct and site-selective acylation with the atrp initiator and photoinduced polymerization. J. Am. Chem. Soc. 145, 14435–14445 (2023). E. Liarou, R. Whitfield, A. Anastasaki, N. G. Engelis, G. R. Jones, K. Velonia, D. M. Haddleton, Copper-Mediated polymerization without external deoxygenation or oxygen scavengers. Angew. Chem. Int. Ed. 57, 8998–9002 (2018). A. Theodorou, E. Liarou, D. M. Haddleton, I. G. Stavrakaki, P. Skordalidis, R. Whitfield, A. Anastasaki, K. Velonia, Protein-polymer bioconjugates via a versatile oxygen tolerant photoinduced controlled radical polymerization approach. Nat. Commun. 11, 1486 (2020). R. Li, S. Zhang, Q. Li, G. G. Qiao, Z. An, An atom-economic enzymatic cascade catalysis for high-throughput raft synthesis of ultrahigh molecular weight polymers. Angew. Chem. Int. Ed. 61, e202213396 (2022). K. Kapil, A. M. Jazani, G. Szczepaniak, H. Murata, M. Olszewski, K. Matyjaszewski, Fully oxygen-tolerant visible-light-induced atrp of acrylates in water: toward synthesis of protein-polymer hybrids. Macromolecules 56, 2017–2026 (2023). T. Zhang, Z. Wu, G. Ng, C. Boyer, Design of an oxygen-tolerant photo-RAFT system for protein-polymer conjugation achieving high bioactivity. Angew. Chem. Int. Ed. 62, e202309582 (2023). H. I. Coskun, F. De Luca Bossa, X. Hu, S. Jockusch, J. Sobieski, G. Yilmaz, K. Matyjaszewski, ATRP with ppb concentrations of photocatalysts. J. Am. Chem. Soc. 146, 28994–29005 (2024). A. M. Jazani, A Yilmaz, M. Baumer, J. Sobieski, S. Bernhard, K. Matyjaszewski, Unraveling the roles of amines in atom transfer radical polymerization in the dark. J. Am. Chem. Soc. 147, 12562–12573 (2025). Y. Lee, C. Boyer, M. S. Kwon, Photocontrolled RAFT polymerization: past, present, and future. Chem. Soc. Rev. 52, 3035–3097 (2023). C. Lv, C. He, X. Pan, Oxygen-Initiated and regulated controlled radical polymerization under ambient conditions. Angew. Chem. Int. Ed. 57, 9430–9433 (2018). H. Feng, Z. Chen, L. Li, X. Shao, W. Fan, C. Wang, L. Song, K. Matyjaszewski, X. Pan, Z. Wang, Aerobic mechanochemical reversible-deactivation radical polymerization. Nat. Commun. 15, 6179 (2024). L. Zhang, C. Wu, K. Jung, Y. H. Ng, C. Boyer, An oxygen paradox: catalytic use of oxygen in radical photopolymerization. Angew. Chem. Int. Ed. 58, 16811–16814 (2019). C. Wu, K. Jung, Y. Ma, W. Liu, C. Boyer, Unravelling an oxygen-mediated reductive quenching pathway for photopolymerisation under long wavelengths. Nat. Commun. 12, 478 (2021). Y. Lee, Y. Kwon, Y. Kim, C. Yu, S. Feng, J. Park, J. Doh, R. Wannemacher, B. Koo, J. Gierschner, M. S. Kwon, A water-soluble organic photocatalyst discovered for highly efficient additive‐free visible‐light‐driven grafting of polymers from proteins at ambient and aqueous environments. Adv. Mater. 34, 2108446 (2022). K. Parkatzidis, N. P. Truong, R. Whitfield, C. E. Campi, B. Grimm-Lebsanft, S. Buchenau, M. A. Rübhausen, S. Harrisson, D. Konkolewicz, S. Schindler, A. Anastasaki, Oxygen-Enhanced atom transfer radical polymerization through the formation of a copper superoxido complex. J. Am. Chem. Soc. 145, 1906–1915 (2023). Y. Du, Z. Chen, Z. Xie, S. Yi, K. Matyjaszewski, X. Pan, Oxygen-driven atom transfer radical polymerization. J. Am. Chem. Soc. 147, 3662–3669 (2025). F. Maestri, F. Petrella, R. Rota, Kinetic-free sizing criterion for the thermally controlled scale-up of batch fine-chemical processes. Chem. Eng. J. 499, 156120 (2024). L. Buglioni, F. Raymenants, A. Slattery, S. D. A. Zondag, T. Noël, Technological innovations in photochemistry for organic synthesis: Flow chemistry, high-throughput experimentation, scale-up, and photoelectrochemistry. Chem. Rev. 122, 2752–2906 (2022). Y.-N. Zhou, J.-J. Li, T.-T. Wang, Y.-Y. Wu, Z.-H. Luo, Precision polymer synthesis by controlled radical polymerization: Fusing the progress from polymer chemistry and reaction engineering. Prog. Polym. Sci. 130, 101555 (2022). Wu, Z. et al. Photo-RAFT polymerization for hydrogel synthesis through barriers and development of light-regulated healable hydrogels under NIR irradiation. Angew. Chem. Int. Ed. 62, e202302451 (2023). S. Cañellas, M. Nuño, E. Speckmeier, Improving reproducibility of photocatalytic reactions-how to facilitate broad application of new methods. Nat. Commun. 15, 307 (2024). F. Tüdős, T. Földes-Berezsnich, Free-radical polymerization: Inhibition and retardation. Prog. Polym. Sci. 14, 717–761 (1989). Q. Yang, J. Lalevée, J. Poly, Development of a robust photocatalyzed ATRP mechanism exhibiting good tolerance to oxygen and inhibitors. Macromolecules 49, 7653–7666 (2016). Q. Wang, F.-Y. Bai, Y. Wang, F. Niu, Y. Zhang, Q. Mi, K. Hu, X. Pan, Photoinduced ion-pair inner-sphere electron transfer-reversible addition-fragmentation chain transfer polymerization. J. Am. Chem. Soc. 144, 19942–19952 (2022). K. Matyjaszewski, S. Coca, S. G. Gaynor, M.Wei, B. E. Woodworth, Controlled radical polymerization in the presence of oxygen. Macromolecules 31, 5967–5969 (1998). J. Zhang, F. Xue, Z. Wang, N-Phenylphenothiazine-based hyper-cross-linked polymers for recyclable, heterogeneous photocatalysis of organic transformations: A strategy to access 6-difluoromethyl-phenanthridines. Org. Lett. 27, 1136–1141 (2025). J. Zhang, F. Xue, Z. Wang, Terpyridine- and quarterpyridine‐based cationic covalent organic frameworks for visible‐light‐catalytic H 2 O 2 synthesis. Angew. Chem. Int. Ed. 137, e202425617 (2025). C. Feng, J. Alharbi, M. Hu, S. Zuo, J. Luo, H. S. A. Qahtani, M.Rueping, K. W. Huang, H. Zhang, Ultrafast charge transfer on Ru-Cu atomic units for enhanced photocatalytic H 2 O 2 production. Adv. Mater. 37, 2406748 (2025). W. Wu, et al. Pyridine-based covalent organic frameworks with pyridyl-imine structures for boosting photocatalytic H 2 O 2 production via one-step 2e – oxygen reduction. Angew. Chem. Int. Ed. 63, e202404563 (2024). M. Vanga, A. Sahoo, R. A. Lalancette, F. Jäkle, Linear extension of anthracene via B←N lewis pair formation: effects on optoelectronic properties and singlet O 2 sensitization. Angew. Chem. Int. Ed. 61, e202113075 (2021). J. Jiang, G. Ye, F. Lorandi, Z. Liu, Y. Liu, T. Hu, J. Chen, Y. Lu, K. Matyjaszewski, Localized surface plasmon resonance meets controlled/living radical polymerization: An adaptable strategy for broadband light-regulated macromolecular synthesis. Angew. Chem. Int. Ed. 58, 12096–12101 (2019). X. Hu, R. Yin, J. Jeong, K. Matyjaszewski, Robust miniemulsion photoATRP driven by red and near-infrared light. J. Am. Chem. Soc. 146, 13417–13426 (2024). X. Hu, G. Szczepaniak, A. Lewandowska-Andralojc, J. Jeong, B. Li, H. Murata, R. Yin, A.M. Jazani, S.R. Das, K. Matyjaszewski, Red-Light-Driven atom transfer radical polymerization for high-throughput polymer synthesis in open air. J. Am. Chem. Soc. 145, 24315–24327 (2023). K. A. Niederer, P. H. Gilmartin, M. C. Kozlowski, Oxidative photocatalytic homo- and cross-coupling of phenols: Nonenzymatic, catalytic method for coupling tyrosine. ACS Catal. 10, 14615–14623 (2020). J. Wu, M. C. Kozlowski, Visible-Light-Induced oxidative coupling of phenols and alkenylphenols with a recyclable, solid photocatalyst. Org. Lett. 25, 907–911 (2023). Additional Declarations There is NO Competing Interest. Supplementary Files SupplementaryInformation.doc Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance Table1.docx Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6691883","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":470918372,"identity":"164b2a4a-1627-48bc-b6cf-38fea7bf3a7e","order_by":0,"name":"Tao 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Cu\u003csup\u003eII\u003c/sup\u003e/L-X photoreduction rate under light irradiation in the presence of Phen-CHCP. \u003cstrong\u003ec\u003c/strong\u003e, The proposed mechanism of Phen-CHCP/Cu-catalyzed photo-ATRP in DMSO.\u003cstrong\u003e d\u003c/strong\u003e, Large scale Phen-CHCP/Cu-catalyzed photo-ATRP in the presence of air from unpurified monomers (inserted photo: 20L reaction scale of PMEA-\u003cem\u003eb\u003c/em\u003e-PBA).\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/fc03ef1d0b3729330df40348.png"},{"id":85988641,"identity":"c47dc824-42c0-4010-84b7-353c36b26c30","added_by":"auto","created_at":"2025-07-04 04:15:42","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":95598,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eResults for the polymerization of MA using Phen-CHCP with high oxygen tolerance.\u003c/strong\u003e (\u003cstrong\u003ea\u003c/strong\u003e) Kinetics and (\u003cstrong\u003eb\u003c/strong\u003e) evolution of molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e, filled points) and dispersity (\u003cem\u003eĐ\u003c/em\u003e, empty points) of the polymers as a function of monomer conversion for Phen-CHCP/Cu-catalyzed photo-ATRP of MA under green light irradiation in DMSO and DMF respectively. (\u003cstrong\u003ec\u003c/strong\u003e) Plot of monomer conversion versus time and (\u003cstrong\u003ed\u003c/strong\u003e) plot of \u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e and \u003cem\u003eĐ\u003c/em\u003e (solid symbols and open symbols indicated after irradiation and dark period respectively) versus monomer conversions, using Phen-CHCP as the photocatalyst in DMF during pulsed light irradiation. Reaction conditions: [MA]/[EBiB]/[CuBr]/[Me\u003csub\u003e6\u003c/sub\u003eTREN] = 200/1/0.02/0.2 in 50 vol % solvent, \u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003eair\u003c/em\u003e\u003c/sub\u003e/\u003cem\u003eV\u003c/em\u003e\u003csub\u003e\u003cem\u003ebottle\u003c/em\u003e\u003c/sub\u003e = 0.5, Phen-CHCP = 0.5 mg/mL, irradiated under green LEDs (0.9 mW/cm\u003csup\u003e2\u003c/sup\u003e).\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/2ce909cb2eab307292c6d54e.png"},{"id":85987929,"identity":"ca8c6987-6156-40c7-bdb8-558ce20a23b7","added_by":"auto","created_at":"2025-07-04 04:07:40","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":158478,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eResults for Phen-CHCP/Cu-catalyzed photo-ATRP under broadband light and sunlight with high oxygen tolerance (50% air, v/v). \u003c/strong\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Monomer conversions of MA and MMA using Phen-CHCP as photocatalysts under blue, green, orange, red, white, 730 nm, 760 nm, 800 nm, 850 nm, 940 nm, and sunlight irradiation respectively. SEC traces of synthesized (\u003cstrong\u003eb\u003c/strong\u003e) PMA and (\u003cstrong\u003ec\u003c/strong\u003e) PMMA using Phen-CHCP under series light irradiation. (\u003cstrong\u003ed\u003c/strong\u003e) Kinetics and (\u003cstrong\u003ee\u003c/strong\u003e) evolution of molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e, filled points) and dispersity (\u003cem\u003eĐ\u003c/em\u003e, empty points) of the polymers as a function of monomer conversion for Phen-CHCP/Cu-catalyzed photo-ATRP of MA in DMSO under blue, green, red and 940 nm light irradiation respectively.(\u003cstrong\u003ef\u003c/strong\u003e) SEC traces of PMA macroinitiator (in blue) and PMA\u003csub\u003e200\u003c/sub\u003e-\u003cem\u003eb\u003c/em\u003e-PMEA\u003csub\u003e136 \u003c/sub\u003ecopolymer (in red) upon \u003cem\u003ein situ \u003c/em\u003echain extension showing high chain-end fidelity and successful chain extension.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/377df420c68bc1549e8f2bbc.png"},{"id":85988636,"identity":"a502dce7-aa21-478a-a80d-11df5659f3ea","added_by":"auto","created_at":"2025-07-04 04:15:40","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":214897,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eThe effect of activation process in Phen-CHCP/Cu-catalyzed photo-ATRP. a\u003c/strong\u003e,\u003cstrong\u003e \u003c/strong\u003eThe Stern-Volmer plot for Phen-CHCP in the presence of EBiB, CuBr\u003csub\u003e2\u003c/sub\u003e/Me\u003csub\u003e6\u003c/sub\u003eTREN, and O\u003csub\u003e2\u003c/sub\u003e-CuBr/Me\u003csub\u003e6\u003c/sub\u003eTREN (1/1) as quenchers (Q) in non-deoxygenated DMSO. \u003cstrong\u003eb\u003c/strong\u003e, Monitoring of MEHQ over time by \u003csup\u003e1\u003c/sup\u003eH NMR as formed in the presence of Phen-CHCP, Me\u003csub\u003e6\u003c/sub\u003eTREN and EBiB in DMSO. \u003cstrong\u003ec\u003c/strong\u003e,\u003cstrong\u003e \u003c/strong\u003eBond dissociation energies (BDEs) of O-H bonds with and without Br\u003csup\u003e- \u003c/sup\u003eand C-H bonds in polymers. Calculated O-H and C-H dissociation BDEs were listed in unit of kcal/mol. \u003cstrong\u003ed\u003c/strong\u003e,\u003cstrong\u003e \u003c/strong\u003eConfocal Raman spectra over MEHQ in DMSO (containing Phen-CHCP, Me\u003csub\u003e6\u003c/sub\u003eTREN and EBiB) with light and without light irradiation. The Phen-CHCP was fixed using optical tweezers, and then Raman spectra were collected the interface of the Phen-CHCP surface.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/14075fd08ef94a9e6154b8fc.png"},{"id":85988642,"identity":"7e6145c9-161f-45fe-b577-6ddf5fc1b8b5","added_by":"auto","created_at":"2025-07-04 04:15:51","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2128998,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/1ded4b04-0612-4b52-b2d8-765fc56df32e.pdf"},{"id":85987933,"identity":"934bd16f-b022-446b-8c65-f289109b5541","added_by":"auto","created_at":"2025-07-04 04:07:40","extension":"doc","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":14175232,"visible":true,"origin":"","legend":"Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance","description":"","filename":"SupplementaryInformation.doc","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/3fcbd0cc4ff68ea324369ea8.doc"},{"id":85987931,"identity":"5cd5bf0a-a86d-469e-ba49-542c8c51548a","added_by":"auto","created_at":"2025-07-04 04:07:40","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":132731,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-6691883/v1/dc1e67d77ccdc6de8798b97a.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance","fulltext":[{"header":"Introduction","content":"\u003cp\u003eReversible-deactivation radical polymerization (RDRP) relies on a dynamic equilibrium between active and dormant species, effectively minimizing the concentration of propagating centers and reducing bimolecular termination\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. This characteristic enables the synthesis of polymers with precise control over molecular weight, dispersity, functionality, end-group fidelity, sequences, and architectures-attributes, which could not easily be achieved through conventional free radical polymerization (CRP)\u003csup\u003e\u003cem\u003e\u003cspan additionalcitationids=\"CR4 CR5 CR6 CR7 CR8\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. RDRP has become one of the most important methods for preparing functional polymers up to present\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eNormally, most CRPs could be conducted under mild conditions in presence of oxygen and inhibitors. As a contrast, RDRPs need the deoxygenation and removal of inhibitor of monomers before polymerizations, which make them difficult to be performed as convenient as CRPs. These are the top challenges limiting the related industrial applications. Typically, Oxygen irreversibly reacts with propagating radicals, and also deactivate the copper catalyst in copper-catalyzed atom transfer radical polymerization (Cu-ATRP)\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Consequently, oxygen leads to polymer chain termination and halts the polymerization process. To mitigate this, most RDRPs require rigorous deoxygenation, which is costly and time-consuming\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Various strategies have been explored to enable oxygen-tolerant RDRPs through sacrificial reagents that in situ consume oxygen\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. In most approaches, oxygen acts as an undesirable component, and extensive chain terminations and side reactions cannot be fully avoided \u003csup\u003e\u003cem\u003e\u003cspan additionalcitationids=\"CR16 CR17 CR18 CR19 CR20 CR21 CR22 CR23 CR24 CR25\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Recent progresses introduced the use of oxygen as a reagent in reversible addition-fragmentation chain transfer (RAFT) polymerization and Cu-ATRP, where oxygen served as co-initiator or facilitated the activation of chain transfer agents and the regeneration of Cu(I) activators\u003csup\u003e\u003cem\u003e\u003cspan additionalcitationids=\"CR28 CR29 CR30 CR31 CR32 CR33\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. In these cases, oxygen contributes positively to the polymerizations, but the polymerization efficiency together with the polymer chain control (\u003cem\u003eeg.\u003c/em\u003e molecular weight or dispersity) were deteriorated in scale-up production, particularly when air remaining in the reactor headspace. This may because that the employment of large-scale reactor leads to decreasing in area/volume (S/V) ratio\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e, and the mass transport of the reactants is limited (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea), subsequently reduce the oxygen removal efficiency and prolong the oxygen scavenging time. These could result in inevitable accumulation of dead chains and decreasing of production efficiency. As such, simultaneous chemical and physical oxygen removal were still required when polymerization scale up to L level and above.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIt was reported that photocatalytic conversion represents a promising deoxygenation strategy. However, this method can\u0026rsquo;t be applied in large-scale production of photocatalyzed RDRPs at present. The scale-up processes applying batch reactors inevitably reduce the S/V ratio and result in light attenuation\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e, and polymerization reactors are spatially inhomogeneous\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. These effects establish spatial heterogeneity in oxygen concentration profiles within the reaction system. Such physicochemical heterogeneity propagates to radical distributions, which generate regional disparities in chain growth rates that ultimately compromise the polymerization control. Meanwhile, some literature reported the applications of long-wavelength photocatalysts, which could avoid competitive overlap with reactant while exhibiting superior light penetration capabilities\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. However, photocatalyzed oxygen conversion depended on photoinduced electron transfer processes. Even when long-wavelength light was applied, the attenuation of light still couldn\u0026rsquo;t be fully ruled out for large-scale batch reaction. An alternative solution is to employ photo flow chemical devices as they provide increased S/V. However, a typical challenge is the relatively poor reproducibility of optimized reaction outcomes when scaling up from bench-scale reactors to large-scale reactors\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eMonomers normally need to remove phenolic inhibitors prior to RDRPs, leading to multi-step purifications and potential monomer loss\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Only few RDRPs can tolerate inhibitors, where the inhibitors were either stabilized by reagents or served as reductants to reduce high-valent copper complexes\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e,\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. However, these polymerizations were generally not viable with oxygen and difficult to be performed at ambient temperature. Although few studies reported polymerizations in the presence of both inhibitors and oxygen at elevated temperatures (\u003cem\u003ee.g.\u003c/em\u003e, 80\u0026deg;C), the polymerization rate was significantly reduced (only 1/3 to 1/4 of that seen with purified, deoxygenated monomers)\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. From perspective of industrial applications, the development of RDRPs with new catalytic process that are tolerant to both oxygen and inhibitors in large-scale synthesis at ambient temperature would significantly simplify production and increase throughput, and performing RDRP could be as convenient as CRPs.\u003c/p\u003e \u003cp\u003eThe rational design of heterogeneous catalysts with elaborate porous architectures was demonstrated as an effective strategy to enhance photocatalytic reaction kinetics\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Previous investigations indicated that heterogeneous photocatalyst designed by introducing suitable functional groups could benefit to metal and oxygen enrichment, which could promote oxygen conversion reactions such as photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e generation\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e,\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. We hypothesize a new catalytic mechanism that through introducing suitable chelation site, the porous materials could be expected to simultaneously facilitate the diffusion of reaction substrates including Cu catalyst and oxygen. As a result, the porous material could accelerate oxygen scavenging and reduce the adverse effects of limited diffusion in large-scale RDRP. As such, we herein report the phenanthroline-based conjugated hyper-crosslinked polymer (Phen-CHCP) photocatalyst enabled large-scale Cu-ATRP in presence of both high content of oxygen and inhibitors, driven by broadband lights and sunlight at room temperature. In the detailed catalytic process, in addition to converting oxygen into singlet oxygen (\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e), the excited-state Phen-CHCP exhibited promising comparable reaction rates with both R-X initiator and high-valent copper catalyst (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). As such, Phen-CHCP mainly served as highly efficient supplementary activator to accelerate the cleavage of C-X bonds, generate R\u003csup\u003e\u0026bull;\u003c/sup\u003e and promote Cu catalyzed cycle for oxygen conversion. (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec) Meanwhile, X\u003csup\u003e\u0026minus;\u003c/sup\u003e generated from organophotocatalyzed activation process could stabilize phenol type inhibitors. This catalytic process allowed rapid photocatalyzed Cu-ATRPs to be successfully performed at high air content (up to 80% v/v) and monomer inhibitors (up to 5000 ppm) under various lights irradiation, yielding near-quantitative monomer conversions with good control over polymer dispersity. This system is very suitable for large-scale production. In practical applications, as large as 20 L scale polymerization was performed, which produced block copolymer of poly((2-methoxyethyl) acrylate-block-n-butyl acrylate) (PMEA-\u003cem\u003eb\u003c/em\u003e-PBA) with 96% conversion and good control over dispersity (\u003cem\u003eĐ\u003c/em\u003e = 1.26). This is the largest scale of photo-RDRP to date. This development should represent significant catalytic advances in green and sustainable RDRPs, with substantial potential for industrial applications.\u003c/p\u003e"},{"header":"Results","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis of Phen-CHCP\u003c/h2\u003e \u003cp\u003eIn the synthesis, 4,7- diphenyl-1,10-phenanthroline was applied to construct crosslinked networks, as it provides chelation sites for Cu catalyst and pyridine rings were beneficial for oxygen enrichment\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Phen-HCP was synthesized \u003cem\u003evia\u003c/em\u003e an iron (III) chloride catalyzed Friedel-Crafts alkylation reaction using 4,7-diphenyl-1,10-phenanthroline and dimethoxybenzene, followed by treating with NaBH\u003csub\u003e4\u003c/sub\u003e to improve dispersibility (offering Phen-CHCP, Supplementary Figs.\u0026nbsp;1\u0026ndash;5; Supplementary Table\u0026nbsp;1). Related pore size distribution analysis and morphology characterizations revealed that Phen-CHCP possessed a microporous and mesoporous structure (Supplementary Fig.\u0026nbsp;6). Cyclic voltammetry (CV) experiments suggested that the Phen-CHCP dispersion had a stronger Cu reduction peak than that of pure solution (Supplementary Fig.\u0026nbsp;7), indicating that Phen-CHCP was beneficial to the enrichment of Cu ions.\u003c/p\u003e \u003cp\u003eNext, the photocatalytic properties and oxygen conversion capability of Phen-CHCP were evaluated. Solid-state diffuse reflectance ultraviolet/visible/near-infrared (UV-Vis-NIR) spectra showed strong absorption across a wide range (200\u0026ndash;900 nm), indicating its potential as an efficient broadband light harvester (Supplementary Fig.\u0026nbsp;8a-c). Notably, Phen-CHCP exhibited a nanosecond fluorescence lifetime of 1.46 ns and low quantum yields (\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003eF\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0056, \u003cem\u003eλ\u003c/em\u003e\u003csub\u003eem\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;500 nm) (Supplementary Table\u0026nbsp;2; Supplementary Fig.\u0026nbsp;8d,e), which may enhance electron transfer efficiency\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003ePhen-CHCP displayed a photocurrent response under visible light irradiation, demonstrating effective charge transfer and separation abilities (Supplementary Fig.\u0026nbsp;8f). UV-Vis results suggested that molecular oxygen converted to \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e in the presence of Phen-CHCP under light irradiation (Supplementary Fig.\u0026nbsp;9), when 9,10-dimethylanthracene was used as internal standard\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. These investigations suggest that Phen-CHCP is a promising broadband photocatalyst for oxygen-tolerant photocatalyzed Cu-ATRP.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003ePhotocatalyzed Cu-ATRPs using Phen-CHCP with oxygen tolerance\u003c/h3\u003e\n\u003cp\u003eThe oxygen tolerance of the Photo-ATRPs was investigated through varying air content during polymerizations, which were conducted under green light irradiation (Supplementary Fig.\u0026nbsp;10). Methyl acrylate (MA) was used as a model monomer, and polymerization results were listed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Near-quantitative conversions were achieved within 6 hours when the air volume content was approximately 50% (\u003cem\u003ev/v\u003c/em\u003e). However, with the air content increasing, conversions gradually declined, indicating that the generation of propagating radicals was suppressed (Supplementary Fig.\u0026nbsp;11 and Supplementary Table\u0026nbsp;3). Despite this, by extending the reaction time to 9 hours and increasing the ligand ratio (0.4 equiv to initiator), high monomer conversion (91%) could still be obtained at 80% air content (\u003cem\u003ev/v\u003c/em\u003e) (entry 13, Supplementary Table\u0026nbsp;3). For subsequent experiments, the air volume content was maintained at 50% (\u003cem\u003ev/v\u003c/em\u003e), as this condition required less ligand and reaction time, while still yielding efficient polymerizations.\u003c/p\u003e \u003cp\u003eNext, oxygen-tolerant photocatalyzed Cu-ATRP of MA using Phen-CHCP was conducted under varied conditions, and the results are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The polymerization did not proceed when the CuBr/tris[2-(dimethylamino)ethyl]amine (Me\u003csub\u003e6\u003c/sub\u003eTREN) ratio was 1:1 (entry 1, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), suggesting that an excess of the amine electron donor (Me\u003csub\u003e6\u003c/sub\u003eTREN) was necessary to initiate the reaction. Increasing the ligand concentration resulted in near-quantitative conversions, producing well-defined polymers with low dispersity (\u003cem\u003eĐ\u003c/em\u003e \u0026lt; 1.10) and controlled molecular weights (entries 1\u0026ndash;5, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e; Supplementary Fig.\u0026nbsp;12). In contrast, under dark conditions with Phen-CHCP, low conversion (~\u0026thinsp;21%, entry 6, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) was observed, and this indicated that the concentration of [Cu\u003csup\u003eI\u003c/sup\u003e/L]\u003csup\u003e+\u003c/sup\u003e activator, being generated \u003cem\u003evia\u003c/em\u003e the activators regenerated by electron transfer (ARGET)-ATRP pathway, was insufficient to sustain significant chain growth. Notably, no polymerization occurred in the absence of Phen-CHCP (entry 7, 9, 15, and 17, Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), highlighting the essential role of the photocatalyst in regenerating the activating species.\u003c/p\u003e \u003cp\u003eUnder 50% air content (\u003cem\u003ev/v\u003c/em\u003e), when conditions varied, such as using lower amounts of Phen-CHCP (Supplementary Fig.\u0026nbsp;13 and Supplementary Table\u0026nbsp;4), reduced amount of CuBr (Supplementary Fig.\u0026nbsp;14 and Supplementary Table\u0026nbsp;4), different ligands and solvents (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Supplementary Fig.\u0026nbsp;15), and varying degrees of polymerization (targeting from 50 to 1000, Supplementary Fig.\u0026nbsp;16 and Supplementary Table\u0026nbsp;5), promising polymerizations with high monomer conversions and polymers with low dispersity were still achieved. Kinetic studies being performed in both DMSO and N,N-dimethylformamide (DMF) (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Supplementary Fig.\u0026nbsp;17) indicated a living polymerization process in all cases (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, b). The oxygen tolerant polymerizations also exhibited temporal control, responding effectively to green light on/off cycles (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC and D; Supplementary Fig.\u0026nbsp;18). When the dark period was extended to 12 hours, negligible monomer conversion was observed (Supplementary Fig.\u0026nbsp;19), suggesting that active radicals were not efficiently generated due to the continuous diffusion of oxygen from the air, which oxidized the Cu\u003csup\u003eI\u003c/sup\u003e/L activator to its inactive state.\u003c/p\u003e \u003cp\u003eIn the context of preparing block copolymers with oxygen tolerance, it is critical to investigate polymer chain-end fidelity. Good chain-end fidelity was confirmed by \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH nuclear magnetic resonance (NMR) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) analysis (Supplementary Figs.\u0026nbsp;20 and 21). \u003cem\u003eIn situ\u003c/em\u003e oxygen-tolerant chain extension was also successful. For example, a PMA sample (conversion\u0026thinsp;~\u0026thinsp;96%, \u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e = 17,300, \u003cem\u003eĐ\u003c/em\u003e = 1.05) synthesized under green light irradiation (50% air, \u003cem\u003ev/v\u003c/em\u003e) was fed with MEA and followed by continuous polymerization. This resulted in a well-defined diblock copolymer (\u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e = 34,300, \u003cem\u003eĐ\u003c/em\u003e = 1.08) with 90% conversion (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eOxygen-tolerant Phen-CHCP/Cu-catalyzed photo-ATRP was successfully applied to a range of monomers, including acrylates, methyl acrylates, and styrene (St). High conversions (\u0026gt;\u0026thinsp;95%), along with polymers possessing controlled molecular weights and low dispersity, were consistently achieved (Supplementary Fig.\u0026nbsp;22 and Supplementary Table\u0026nbsp;6). These results strongly demonstrate the high flexibility and efficiency of oxygen-tolerant Cu-ATRP in the presence of Phen-CHCP. Furthermore, Phen-CHCP could be easily separated from the reaction mixture, and reused across multiple ATRP cycles while maintaining high photocatalytic efficiency with high oxygen tolerance (Supplementary Figs.\u0026nbsp;23\u0026ndash;25).\u003c/p\u003e \u003cp\u003eThe high oxygen tolerance polymerizations could be performed from UV to NIR region. Results from both MA and methyl methacrylate (MMA) are summarized in Supplementary Table\u0026nbsp;7. Near-quantitative monomer conversions were achieved (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea), and the polymers exhibited excellent control over dispersity, with values of less than 1.08 for PMA and 1.13 for PMMA. Size-exclusion chromatography (SEC) analyses demonstrated monomodal and symmetric curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb,c). Meanwhile, linear semilogarithmic kinetic plots were obtained for polymerizations under various light wavelengths, including blue, green, red, and 940 nm light (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed,e and Supplementary Fig.\u0026nbsp;26). These results confirmed the living nature of oxygen tolerant photoinduced Cu-ATRP under broadband light conditions.\u003c/p\u003e \u003cp\u003eIt is notable to highlight that very low irradiation intensities were used in these polymerizations. Specifically, the light intensities were 0.9, 0.9, 2, and 15 mW/cm\u0026sup2; for blue, green, red, and 940 nm light, respectively. The low irradiation intensity may offer significant advantages such as reduced energy consumption and minimized photocatalyst degradation, which is critical for scaling up the polymerization process (Supplementary Fig.\u0026nbsp;27).\u003c/p\u003e \u003cp\u003eThe high oxygen tolerant polymerizations could also be performed under barrier. In NIR-driven polymerizations, reaction vessels were wrapped in opaque paper (approximately 0.4 mm thick) to serve as light barriers. Remarkably, high monomer conversions (\u0026gt;\u0026thinsp;94%) and close agreement of the theoretical and experimental molecular weight were obtained (Supplementary Fig.\u0026nbsp;28 and Supplementary Table\u0026nbsp;8). The deep penetration of NIR light presents an opportunity for scale-up of Cu-ATRP using Phen-CHCP, applicable to both batch processes and microfluidic devices.\u003c/p\u003e \u003cp\u003eIt\u0026rsquo;s important to point out that Phen-CHCP is a suitable photocatalyst for sunlight-induced oxygen tolerant Cu-ATRP. For instance, polymerization of MA or MMA achieved over 97% conversion within 5 hours under natural sunlight (entry 11 and 22, Supplementary Table\u0026nbsp;7). The resulting polymers exhibited low dispersity values, with \u003cem\u003eĐ\u003c/em\u003e = 1.05 for PMA and \u003cem\u003eĐ\u003c/em\u003e = 1.19 for PMMA. This method represents a green and sustainable approach to synthesizing well-defined polymers.\u003c/p\u003e\n\u003ch3\u003eInhibitor tolerant polymerizations in presence of oxygen\u003c/h3\u003e\n\u003cp\u003eFurthermore, our study demonstrated that Phen-CHCP-catalyzed photopolymerization could be easily performed from unpurified monomer (with inhibitor) in presence of significant amounts of oxygen. To evaluate inhibitor tolerance performance under air (50%, \u003cem\u003ev/v\u003c/em\u003e), unpurified monomers containing 4-methoxyphenol (MEHQ) were used. High monomer conversions (\u0026gt;\u0026thinsp;95%) were achieved, with dispersity values of 1.08 and 1.14 for MA and MMA respectively (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e; table S11). Additionally, the polymerization of St with 4-tert-butylcatechol as an inhibitor resulted in 60% monomer conversion and a dispersity of 1.10 (Supplementary Fig.\u0026nbsp;29). The relatively lower conversion may be attributed to the lower O-H bond dissociation energy of 4-tert-butylcatechol compared to MEHQ\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. The oxygen and inhibitor tolerant polymerization kinetics indicated living characteristics and a reaction rate comparable to that of purified MA (Supplementary Fig.\u0026nbsp;30). MALDI-ToF-MS and \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR analyses of the resulting PMA (target DP: 100, conversion\u0026thinsp;~\u0026thinsp;98%, \u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en,SEC\u003c/em\u003e\u003c/sub\u003e = 8200, \u003cem\u003eĐ\u003c/em\u003e = 1.07) confirmed good retention of chain-end fidelity (Supplementary Figs.\u0026nbsp;31 and 32).\u003c/p\u003e \u003cp\u003eControl experiments revealed that polymerization did not proceed in the absence of Phen-CHCP or without light, highlighting the essential role of the photocatalyst (Supplementary Table\u0026nbsp;9). When using stronger inhibitors, such as 500 ppm of catechol or butylated hydroxytoluene (BHT), MA conversion reached 93% within 6 hours. Extending the reaction time to 8 hours resulted in 99% conversion (Supplementary Table\u0026nbsp;10). When the concentration of catechol or BHT was increased to 5000 ppm, the polymerization rate decreased, but high conversions of 82% and 94% were still achieved for catechol and BHT respectively. The lower conversion with catechol might be due to its higher affinity for the copper catalyst, leading to a more rapid decline in the concentration of the Cu\u003csup\u003eI\u003c/sup\u003e/L activator compared to BHT.\u003c/p\u003e \u003cp\u003eTo further assess the capability of synthesizing block copolymers directly from unpurified monomers with oxygen tolerance, chain extension experiments were conducted. A PMA macroinitiator (conversion\u0026thinsp;~\u0026thinsp;96%, \u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e = 16,600, \u003cem\u003eĐ\u003c/em\u003e = 1.06) was sequentially fed with unpurified MEA, followed by polymerization at room temperature. The resulting well-defined diblock copolymer, PMA-\u003cem\u003eb\u003c/em\u003e-PMEA, exhibited a molecular weight of \u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e = 31,200, dispersity of 1.09, and 91% conversion of MEA (Supplementary Fig.\u0026nbsp;33).\u003c/p\u003e\n\u003ch3\u003eOxygen and inhibitor tolerance mechanism\u003c/h3\u003e\n\u003cp\u003eThese results underscore the promising inhibitor and oxygen tolerance of Phen-CHCP/Cu-catalyzed photo-ATRP, providing a viable approach for more straightforward and cost-effective polymerization processes. In reported Cu-ATRP with oxygen tolerance, molecular oxygen could generate singlet oxygen (\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e) or O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e, which didn\u0026rsquo;t participate the polymerization\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e. Besides, in the photocatalytic cross-coupling of phenols, the deprotonation of phenol radical cations may be triggered by O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026thinsp;\u0026minus;\u0026thinsp;\u003cem\u003e52,53\u003c/em\u003e\u003c/sup\u003e. Based on this, we propose that if the reactive oxygen species (ROS) generated during RDRP process can be harnessed to promote both the formation of propagating radicals and elimination of phenolic inhibitor, it could pave the way for Cu-ATRP with both enhanced oxygen and inhibitor tolerance.\u003c/p\u003e \u003cp\u003eOur results suggest that the Cu\u003csup\u003eI\u003c/sup\u003e/L complex may react with continuous generated \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e in presence of excess oxygen, which facilitate the formation O\u003csub\u003e2\u003c/sub\u003e-Cu\u003csup\u003eII\u003c/sup\u003e/L species in the presence of Phen-CHCP\u003csup\u003e\u003cem\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/em\u003e\u003c/sup\u003e, and excess ligands do not rapidly reduce these species (Supplementary Fig.\u0026nbsp;34a,b). Meanwhile, ligands, DMSO, or Phen-CHCP lack the capability to reduce O\u003csub\u003e2\u003c/sub\u003e-Cu\u003csup\u003eII\u003c/sup\u003e/L species rapidly back to Cu\u003csup\u003eI\u003c/sup\u003e/L, implying that the initiator should participate in this reduction process. There were no O\u003csub\u003e2\u003c/sub\u003e-Cu\u003csup\u003eII\u003c/sup\u003e/L peaks being observed within 4 hours, after adding the initiator to a solution containing CuBr/DMSO/Me\u003csub\u003e6\u003c/sub\u003eTREN (Supplementary Fig.\u0026nbsp;34c). This suggested that the initiator (in significant excess relative to Cu\u003csup\u003eI\u003c/sup\u003e/L) could quickly oxidize Cu\u003csup\u003eI\u003c/sup\u003e/L to X-Cu\u003csup\u003eII\u003c/sup\u003e/L (Supplementary Fig.\u0026nbsp;35), while the other components of the system lack the capability to reduce this species. Meanwhile, in the presence of Phen-CHCP, the absorption intensity of the superoxide species increased rapidly from 30 min to 3 hours before plateauing (Supplementary Fig.\u0026nbsp;34d), indicating the fast regeneration of Cu\u003csup\u003eI\u003c/sup\u003e/L.\u003c/p\u003e \u003cp\u003eTo gain further understanding of the Phen-CHCP/Cu-catalyzed photo-ATRP, we conducted amperometric \u003cem\u003ei-t\u003c/em\u003e analysis of these photoredox reaction. Upon adding the initiator EBiB to a solution containing Cu\u003csup\u003eI\u003c/sup\u003e/L and O\u003csub\u003e2\u003c/sub\u003e-Cu\u003csup\u003eII\u003c/sup\u003e/L species, the current dropped sharply from positive to negative, stabilizing thereafter, indicating rapid conversion to X-Cu\u003csup\u003eII\u003c/sup\u003e/L and negligible photo-reduction of X-Cu\u003csup\u003eII\u003c/sup\u003e/L (Supplementary Fig.\u0026nbsp;36a). In contrast, in the presence of Phen-CHCP, the current decreased gradually, signifying continuous diffusion-driven reduction reactions (Supplementary Fig.\u0026nbsp;36b). Similar results were observed when X-Cu\u003csup\u003eII\u003c/sup\u003e/L was the initial catalyst (Supplementary Fig.\u0026nbsp;36c). These results indicate that the reduction of X-Cu\u003csup\u003eII\u003c/sup\u003e/L is mediated by photo-reduction of the initiator, which, in turn, reduces the transition state or final product in the presence of Phen-CHCP. Without the copper catalyst, the current initially dropped from positive to negative, then gradually increased (Supplementary Fig.\u0026nbsp;36d), suggesting rapid photo-reduction of EBiB, although the product was unstable. Cyclic voltammetry curves of Phen-CHCP exhibited reduction potential of (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eox\u003c/sub\u003e\u003csup\u003e*\u003c/sup\u003e = -0.88 V) (Supplementary Fig.\u0026nbsp;37), indicating that excited states of Phen-CHCP were highly reducing to reduce EBiB (\u003cem\u003eE\u003c/em\u003e\u003csub\u003ered\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;\u0026minus;\u0026thinsp;0.74 V). In order to further ascertain the reducing ability of excited Phen-CHCP, spectroscopic analyses were carried out. We choose EBiB, CuBr\u003csub\u003e2\u003c/sub\u003e/Me\u003csub\u003e6\u003c/sub\u003eTREN, and Me\u003csub\u003e6\u003c/sub\u003eTREN as the quencher (Supplementary Fig.\u0026nbsp;38). The linear relationship between \u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e/\u003cem\u003eI\u003c/em\u003e and quencher concentration (\u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e and \u003cem\u003eI\u003c/em\u003e were the fluorescence intensities before and after adding quencher) demonstrated that this was a dynamic quenching process involving a photoinduced electron transfer. In this process, the quenching rate (\u003cem\u003ek\u003c/em\u003e\u003csub\u003e\u003cem\u003eq\u003c/em\u003e\u003c/sub\u003e) of EBiB, CuBr\u003csub\u003e2\u003c/sub\u003e/Me\u003csub\u003e6\u003c/sub\u003eTREN, Me\u003csub\u003e6\u003c/sub\u003eTREN and dissolved O\u003csub\u003e2\u003c/sub\u003e toward the excited state Phen-CHCP were estimated to be 0.85\u0026times;10\u003csup\u003e12\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1.22\u0026times;10\u003csup\u003e12\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 3.65\u0026times;10\u003csup\u003e10\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 10\u003csup\u003e12\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). The \u003cem\u003ek\u003c/em\u003e\u003csub\u003e\u003cem\u003eq\u003c/em\u003e\u003c/sub\u003e was much higher than reactant diffusity in solvent (estimated as 10\u003csup\u003e8\u003c/sup\u003e-10\u003csup\u003e9\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, according to Einstein relation), indicating that the heterogeneous porous structure promoted the adsorption of reactants on the surface. In addition, considering the comparable magnitude of \u003cem\u003ek\u003c/em\u003e\u003csub\u003e\u003cem\u003eq\u003c/em\u003e\u003c/sub\u003e among diverse quenchers (particularly EBiB and CuBr\u003csub\u003e2\u003c/sub\u003e/Me\u003csub\u003e6\u003c/sub\u003eTREN), the photoinduced electron transfer processes should predominantly govern by the initial quencher concentration. Therefore, Phen-CHCP/Cu-catalyzed photoATRP exhibited a distinct electron-transfer pathway (compared to previous dual photoinduced Cu-ATRP), whereas the photogenerated electrons preferentially transfer to the R-X (1 equiv.) rather than copper complexes (0.02 equiv.).\u003c/p\u003e \u003cp\u003eAs such, the overall proposed mechanism is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec. Photoexcitation of Phen-CHCP generates the excited state Phen-CHCP\u003csup\u003e*\u003c/sup\u003e. Both charge separation and energy transfer occur on the surface of Phen-CHCP\u003csup\u003e*\u003c/sup\u003e. In the case of charge separation, an electron is transferred to alkyl bromides, generating R\u003csup\u003e\u0026bull;\u003c/sup\u003e, X\u003csup\u003e\u0026minus;\u003c/sup\u003e and oxidized Phen-CHCP (Phen-CHCP\u003csup\u003e\u0026bull;+\u003c/sup\u003e) (Stage 1). Regarding the energy transfer, \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e is generated by transferring energy to molecular oxygen. Meanwhile, hole transfer to an amine donor (D) forms an amine radical cation (D\u003csup\u003e\u0026bull;+\u003c/sup\u003e), regenerating the ground state Phen-CHCP photocatalyst. The R\u003csup\u003e\u0026bull;\u003c/sup\u003e species reduce X-Cu\u003csup\u003eII\u003c/sup\u003e/L, forming Cu\u003csup\u003eI\u003c/sup\u003e/L and R-X (Stage 2). Partial Cu\u003csup\u003eI\u003c/sup\u003e/L is then oxidized by \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e to produce O\u003csub\u003e2\u003c/sub\u003e-Cu\u003csup\u003eII\u003c/sup\u003e/L species (Stage 3). The superoxido complex undergoes rapid reduction by Phen-CHCP\u003csup\u003e*\u003c/sup\u003e, yielding Cu\u003csup\u003eI\u003c/sup\u003e/L and O\u003csub\u003e2\u003c/sub\u003e (Stage 3). Notably, the high diffusivity drives spontaneous accumulation of reactants at the liquid-solid interface of the Phen-CHCP, effectively reducing the oxygen concentration in non-interfacial regions. Simultaneously, surface-adsorbed oxygen undergoes indirect conversion via a Cu-mediated pathway, bypassing direct photocatalyst mediated conversion. This dual mechanism allows the intrinsic oxygen tolerance under scaled-up reaction.\u003c/p\u003e \u003cp\u003eSince the reversible redox equilibrium between Cu(I) and Cu(II) complexes is mediated by photoelectron transfer being induced supplementary activation of R-X, partial R-X ultimately participates the Cu(II) reduction process rather than initiating polymerization. Consequently, the proportion of unreacted R-X increases (Supplementary Fig.\u0026nbsp;39), and the molecular weight of polymers deviates from theoretical values with increasing air content (Supplementary Table\u0026nbsp;3). Besides, these unreacted R-X were stable after long time irradiation in our system (Supplementary Table\u0026nbsp;11). The proposed mechanism for Phen-CHCP/Cu-catalyzed photo-ATRP in DMF was similar to that of DMSO (Supplementary Figs.\u0026nbsp;40\u0026ndash;42).\u003c/p\u003e \u003cp\u003eTo further explore whether photocatalytic cross-coupling occurred, we irradiated Phen-CHCP solutions in DMSO containing MEHQ, EBiB, and Me\u003csub\u003e6\u003c/sub\u003eTREN with green light. As expected, no significant changes happened from the \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR result of phenolic hydroxyl group (Supplementary Fig.\u0026nbsp;43), indicating that O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e didn\u0026rsquo;t trigger a coupling reaction. However, the phenolic hydroxyl peak broadened significantly upon addition of EBiB, suggesting the formation of hydrogen bonds (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb). The current further decreased upon addition of MEHQ according to \u003cem\u003ei-t\u003c/em\u003e analysis (Supplementary Fig.\u0026nbsp;36b). Since MEHQ remained stable throughout the reaction, this suggests that MEHQ may facilitating the reduction of R-X. Therefore, we believe that the generated X\u003csup\u003e\u0026minus;\u003c/sup\u003e might stabilize the phenolic inhibitor underpins the observed inhibitor tolerance. The phenolic hydroxyl bond dissociation energies (BDE) of three phenolic compounds in the presence and absence of bromide ions were evaluated. Results indicated that the BDE of phenolic hydroxyl groups underwent enhancement in the presence of bromide ions (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec), which was attributed to hydrogen-bonding interactions between Br⁻ and the hydroxyl moieties (Supplementary Fig.\u0026nbsp;44). Furthermore, confocal Raman spectra were applied to investigate these organocatalyzed activation-induced phenol stabilization in the presence of Phen-CHCP. A blue shift of the Raman signal representing the phenolic hydroxyl group was observed instantaneously under 532nm laser light irradiation (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed), which was consistent with the increasement of BDE of the phenolic hydroxyl bond. Consequently, the synergistic interplay between bromide-ion-stabilized phenolic inhibitors (generated through auxiliary activation processes) and catalyst-mediated rapid reactant diffusion collectively endowed this catalytic system with exceptional tolerance of inhibitors. Therefore, attenuation of supplementary activation processes would compromise the inherent inhibitor tolerance of the system. This infer was supported by the fact that ~\u0026thinsp;0% monomer conversion was observed in the PPh\u003csub\u003e3\u003c/sub\u003e-CHCP system at 5000 ppm catechol inhibitor (Supplementary Table\u0026nbsp;12), where the \u003cem\u003ek\u003c/em\u003e\u003csub\u003e\u003cem\u003eq\u003c/em\u003e\u003c/sub\u003e of EBiB and CuBr\u003csub\u003e2\u003c/sub\u003e/Me\u003csub\u003e6\u003c/sub\u003eTREN toward the excited state PPh\u003csub\u003e3\u003c/sub\u003e-CHCP\u003csup\u003e*\u003c/sup\u003ewere estimated as 0.81\u0026times;10\u003csup\u003e12\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eand 4.37\u0026times;10\u003csup\u003e12\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e S\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Supplementary Fig.\u0026nbsp;45).\u003c/p\u003e\n\u003ch3\u003eScale-up production\u003c/h3\u003e\n\u003cp\u003eThe above mechanism encouraged large-scale photo-ATRP for synthesizing both of the homopolymer and block copolymer. Photopolymerization of MA (10 L scale in 20 L reactor, 50% in DMSO) was performed in a 20 L photoreactor with Phen-CHCP (air 50%, \u003cem\u003ev/v\u003c/em\u003e) within 4 h under white light irradiation (Supplementary Fig.\u0026nbsp;46), producing PMA with dispersity of 1.07 (conversion\u0026thinsp;~\u0026thinsp;97%, \u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e = 8,600) (Supplementary Fig.\u0026nbsp;47a). Furthermore, we prepared 10 L polymerization of PMEA macroinitiator (50% in DMSO) (conversion\u0026thinsp;~\u0026thinsp;90%, \u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e = 11,300, \u003cem\u003eĐ\u003c/em\u003e = 1.26). Subsequently, 10 L of unpurified n-BA solution (50% n-BA) was fed into the reactor for the \u003cem\u003ein situ\u003c/em\u003e block copolymerization (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed). n-BA approached 96% conversion, and well-defined diblock copolymer was obtained (\u003cem\u003eĐ\u003c/em\u003e: 1.26, Supplementary Fig.\u0026nbsp;47b). To the best of our knowledge, this represents the largest example of photocatalyzed RDRP using unpurified monomer in presence of air (Supplementary Table\u0026nbsp;13).\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eWe developed a Cu-catalyzed photo-ATRP system using phenanthroline-based hyper-crosslinked polymers (Phen-CHCP) as the photocatalyst, together with investigation of a new catalytic process. The photoinduced electron transfer process, governed by reactant concentration, indirectly facilitates the conversion of oxygen while generating bromide anions that stabilize phenolic inhibitors. The heterogeneous Phen-CHCP facilitates spontaneous diffusion of reactants to the catalyst interface, resulting in relatively low oxygen and inhibitor concentrations in non-interfacial regions of the reaction system. The synergistic interplay of these dual mechanisms confers upon the Phen-CHCP/Cu-catalyzed photo-ATRP system with the capacity to maintain high oxygen and inhibitor tolerance under scaled-up production. As a result, various acrylates and methacrylates could be polymerized in the presence of 50%-80% air, yielding well-defined polymers with low dispersity under broadband light irradiation. The Phen-CHCP/Cu-catalyzed photo-ATRP system demonstrates exceptional tolerance to both oxygen and inhibitors, enabling the synthesis of homo- and block copolymers with low dispersity (scaling up to 20 L). This methodology offers a robust platform for large-scale RDRP production without the need for tedious deoxygenation or monomer purification steps.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eCompeting interests\u003c/h2\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003ch2\u003eAuthor Contributions\u003c/h2\u003e \u003cp\u003eT.H., B.E.T., and W.W.F. conceived the idea; T.H. and B.E.T guided the project and wrote the manuscript; Z.H.F., W.W.F., B.X. and Y.X.L. performed the experiments; L.X., X.L.H., F.Z., N.C., X.Z., T.C.S., B.X., X.Y.H. and H.G. supported and participated the acquisition of data; B.H. guided scale-up experiment; and T.H., B.E.T., W.W.F., and X.Z. analyzed the data and participated in the preparation of the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThis work was financially supported by National Natural Science Foundation of China (22171067, 22101275, 22475076, 22473104), the Postdoctoral Fellowship Program of CPSF under Grant Number GZC20240536, and the Fundamental Research Funds for the Central Universities of China (Grant No.PA2023GDSK0074). We also expressed our sincere gratitude to Jiangsu Bud Polyurethane Co., Ltd. and Shanghai 3S Technology Co., Ltd. for their support and assistance in scale-up experiments.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eN. Corrigan, K. Jung, G. Moad, C. J. Hawker, K. Matyjaszewski, C. Boyer, Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications. \u003cem\u003eProg. Polym. Sci.\u003c/em\u003e 111, 101311 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eF. Lorandi, M. Fantin, K. Matyjaszewski, Atom transfer radical polymerization: A mechanistic perspective. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 144, 15413\u0026ndash;15430 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. Parkatzidis, H. S. Wang, N. P. Truong, A. Anastasaki, Recent developments and future challenges in controlled radical polymerization: A 2020 update. \u003cem\u003eChem\u003c/em\u003e 6, 1575\u0026ndash;1588 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM.-N. Antonopoulou, R. Whitfield, N. P. Truong, D. Wyers, S. Harrisson, T. Junkers, A. Anastasaki, Concurrent control over sequence and dispersity in multiblock copolymers. \u003cem\u003eNat. Chem.\u003c/em\u003e 14, 304\u0026ndash;312 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY. Zhao, Y. Chen, H. Zhou, Y. Zhou, K. Chen, Y. Gu, M. Chen, Controlled radical copolymerization of fluoroalkenes by using light-driven redox-relay catalysis. \u003cem\u003eNat. Synth.\u003c/em\u003e 2, 653\u0026ndash;662 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. Kapil, G. Szczepaniak, M. R. Martinez, H. Murata, A. M. Jazani, J. Jeong, S. R. Das, K. Matyjaszewski, Visible-light‐mediated controlled radical branching polymerization in water. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 62, e202217658 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eR. Yin, J. Tarnsangpradit, A. Gul, J. Jeong, X. Hu, Y. Zhao, H. Wu, Q.Li, G. Fytas, A. Karim, M. R. Bockstaller, K. Matyjaszewski, Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP. \u003cem\u003eProc. Natl. Acad. Sci. U. S. A.\u003c/em\u003e 121, e2406337121 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG. Szczepaniak, K. Kapil, S. Adida, K. Kim, T.-C. Lin, G. Yilmaz, H. Murata and K. Matyjaszewski, Solid-phase synthesis of well-defined multiblock copolymers by atom transfer radical polymerization. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 146, 22247\u0026ndash;22256 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG. K. K. Clothier, T. R. Guimar\u0026atilde;es, S. W. Thompson, S. C. Howard, B. W. Muir, G. Moad, P. B. Zetterlund, Streamlining the generation of advanced polymer materials through the marriage of automation and multiblock copolymer synthesis in emulsion. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 63, e202320154 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eN. P. Truong, G. R. Jones, K. G. E. Bradford, D. Konkolewicz, A. Anastasaki, A comparison of RAFT and ATRP methods for controlled radical polymerization. \u003cem\u003eNat. Rev. Chem.\u003c/em\u003e 5, 859\u0026ndash;869 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG. Szczepaniak, L. Fu, H. Jafari, K. Kapil, K. Matyjaszewski, Making ATRP more practical: Oxygen tolerance. \u003cem\u003eAcc. Chem. Res.\u003c/em\u003e 54, 1779\u0026ndash;1790 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG. Ng, S. W. Prescott, A. Postma, G. Moad, C. J. Hawker, C. Boyer, Strategies for achieving oxygen tolerance in reversible addition-fragmentation chain transfer polymerization. \u003cem\u003eMacromol. Chem. Phys.\u003c/em\u003e 224, 2300132 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM. Destarac, Industrial development of reversible-deactivation radical polymerization: is the induction period over? \u003cem\u003ePolym. Chem.\u003c/em\u003e 9, 4947\u0026ndash;4967 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Yeow, R. Chapman, A. J. Gormley, C. Boyer, Up in the air: Oxygen tolerance in controlled/living radical polymerisation. \u003cem\u003eChem. Soc. Rev.\u003c/em\u003e 47, 4357\u0026ndash;4387 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Layadi, B. Kessel, W. Yan, M. Romio, N. D. Spencer, M. Zenobi-Wong, K. Matyjaszewski, E. M. Benetti, Oxygen tolerant and cytocompatible iron(0)-mediated atrp enables the controlled growth of polymer brushes from mammalian cell cultures. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 142, 3158\u0026ndash;3164 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG. Szczepaniak, M. Łagodzińska, S. Dadashi-Silab, A. Gorczyński, K. Matyjaszewski, Fully oxygen-tolerant atom transfer radical polymerization triggered by sodium pyruvate. \u003cem\u003eChem. Sci.\u003c/em\u003e 11, 8809\u0026ndash;8816 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eW. Li, W. Sheng, B. Li, R. Jordan, Surface grafting \"band-aid\" for \"everyone\": filter paper-assisted surface-initiated polymerization in the presence of air. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 60, 13621\u0026ndash;13625 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eF. De Bon, R. G. Fonseca, F. Lorandi, A. C. Serra, A. A. Isse, K. Matyjaszewski, J. F. J. Coelho, The scale-up of electrochemically mediated atom transfer radical polymerization without deoxygenation. \u003cem\u003eChem. Eng. J.\u003c/em\u003e 445, 136690 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Jeong, X. Hu, H. Murata, G. Szczepaniak, M. Rachwalak, A. Kietrys, S. R. Das, K. Matyjaszewski, RNA-Polymer hybrids via direct and site-selective acylation with the atrp initiator and photoinduced polymerization. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 145, 14435\u0026ndash;14445 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eE. Liarou, R. Whitfield, A. Anastasaki, N. G. Engelis, G. R. Jones, K. Velonia, D. M. Haddleton, Copper-Mediated polymerization without external deoxygenation or oxygen scavengers. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 57, 8998\u0026ndash;9002 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. Theodorou, E. Liarou, D. M. Haddleton, I. G. Stavrakaki, P. Skordalidis, R. Whitfield, A. Anastasaki, K. Velonia, Protein-polymer bioconjugates via a versatile oxygen tolerant photoinduced controlled radical polymerization approach. \u003cem\u003eNat. Commun.\u003c/em\u003e 11, 1486 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eR. Li, S. Zhang, Q. Li, G. G. Qiao, Z. An, An atom-economic enzymatic cascade catalysis for high-throughput raft synthesis of ultrahigh molecular weight polymers. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 61, e202213396 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. Kapil, A. M. Jazani, G. Szczepaniak, H. Murata, M. Olszewski, K. Matyjaszewski, Fully oxygen-tolerant visible-light-induced atrp of acrylates in water: toward synthesis of protein-polymer hybrids. \u003cem\u003eMacromolecules\u003c/em\u003e 56, 2017\u0026ndash;2026 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eT. Zhang, Z. Wu, G. Ng, C. Boyer, Design of an oxygen-tolerant photo-RAFT system for protein-polymer conjugation achieving high bioactivity. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 62, e202309582 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. I. Coskun, F. De Luca Bossa, X. Hu, S. Jockusch, J. Sobieski, G. Yilmaz, K. Matyjaszewski, ATRP with ppb concentrations of photocatalysts. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 146, 28994\u0026ndash;29005 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eA. M. Jazani, A Yilmaz, M. Baumer, J. Sobieski, S. Bernhard, K. Matyjaszewski, Unraveling the roles of amines in atom transfer radical polymerization in the dark. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 147, 12562\u0026ndash;12573 (2025).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY. Lee, C. Boyer, M. S. Kwon, Photocontrolled RAFT polymerization: past, present, and future. \u003cem\u003eChem. Soc. Rev.\u003c/em\u003e 52, 3035\u0026ndash;3097 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC. Lv, C. He, X. Pan, Oxygen-Initiated and regulated controlled radical polymerization under ambient conditions. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 57, 9430\u0026ndash;9433 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eH. Feng, Z. Chen, L. Li, X. Shao, W. Fan, C. Wang, L. Song, K. Matyjaszewski, X. Pan, Z. Wang, Aerobic mechanochemical reversible-deactivation radical polymerization. \u003cem\u003eNat. Commun.\u003c/em\u003e 15, 6179 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL. Zhang, C. Wu, K. Jung, Y. H. Ng, C. Boyer, An oxygen paradox: catalytic use of oxygen in radical photopolymerization. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 58, 16811\u0026ndash;16814 (2019).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC. Wu, K. Jung, Y. Ma, W. Liu, C. Boyer, Unravelling an oxygen-mediated reductive quenching pathway for photopolymerisation under long wavelengths. \u003cem\u003eNat. Commun.\u003c/em\u003e 12, 478 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY. Lee, Y. Kwon, Y. Kim, C. Yu, S. Feng, J. Park, J. Doh, R. Wannemacher, B. Koo, J. Gierschner, M. S. Kwon, A water-soluble organic photocatalyst discovered for highly efficient additive‐free visible‐light‐driven grafting of polymers from proteins at ambient and aqueous environments. \u003cem\u003eAdv. Mater.\u003c/em\u003e 34, 2108446 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. Parkatzidis, N. P. Truong, R. Whitfield, C. E. Campi, B. Grimm-Lebsanft, S. Buchenau, M. A. R\u0026uuml;bhausen, S. Harrisson, D. Konkolewicz, S. Schindler, A. Anastasaki, Oxygen-Enhanced atom transfer radical polymerization through the formation of a copper superoxido complex. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 145, 1906\u0026ndash;1915 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY. Du, Z. Chen, Z. Xie, S. Yi, K. Matyjaszewski, X. Pan, Oxygen-driven atom transfer radical polymerization. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 147, 3662\u0026ndash;3669 (2025).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eF. Maestri, F. Petrella, R. Rota, Kinetic-free sizing criterion for the thermally controlled scale-up of batch fine-chemical processes. \u003cem\u003eChem. Eng. J.\u003c/em\u003e 499, 156120 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL. Buglioni, F. Raymenants, A. Slattery, S. D. A. Zondag, T. No\u0026euml;l, Technological innovations in photochemistry for organic synthesis: Flow chemistry, high-throughput experimentation, scale-up, and photoelectrochemistry. \u003cem\u003eChem. Rev.\u003c/em\u003e 122, 2752\u0026ndash;2906 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eY.-N. Zhou, J.-J. Li, T.-T. Wang, Y.-Y. Wu, Z.-H. Luo, Precision polymer synthesis by controlled radical polymerization: Fusing the progress from polymer chemistry and reaction engineering. \u003cem\u003eProg. Polym. Sci.\u003c/em\u003e 130, 101555 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWu, Z. et al. Photo-RAFT polymerization for hydrogel synthesis through barriers and development of light-regulated healable hydrogels under NIR irradiation. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 62, e202302451 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS. Ca\u0026ntilde;ellas, M. Nu\u0026ntilde;o, E. Speckmeier, Improving reproducibility of photocatalytic reactions-how to facilitate broad application of new methods. \u003cem\u003eNat. Commun.\u003c/em\u003e 15, 307 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eF. T\u0026uuml;dős, T. F\u0026ouml;ldes-Berezsnich, Free-radical polymerization: Inhibition and retardation. \u003cem\u003eProg. Polym. Sci.\u003c/em\u003e 14, 717\u0026ndash;761 (1989).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQ. Yang, J. Lalev\u0026eacute;e, J. Poly, Development of a robust photocatalyzed ATRP mechanism exhibiting good tolerance to oxygen and inhibitors. \u003cem\u003eMacromolecules\u003c/em\u003e 49, 7653\u0026ndash;7666 (2016).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQ. Wang, F.-Y. Bai, Y. Wang, F. Niu, Y. Zhang, Q. Mi, K. Hu, X. Pan, Photoinduced ion-pair inner-sphere electron transfer-reversible addition-fragmentation chain transfer polymerization. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 144, 19942\u0026ndash;19952 (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. Matyjaszewski, S. Coca, S. G. Gaynor, M.Wei, B. E. Woodworth, Controlled radical polymerization in the presence of oxygen. \u003cem\u003eMacromolecules\u003c/em\u003e 31, 5967\u0026ndash;5969 (1998).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Zhang, F. Xue, Z. Wang, N-Phenylphenothiazine-based hyper-cross-linked polymers for recyclable, heterogeneous photocatalysis of organic transformations: A strategy to access 6-difluoromethyl-phenanthridines. \u003cem\u003eOrg. Lett.\u003c/em\u003e 27, 1136\u0026ndash;1141 (2025).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Zhang, F. Xue, Z. Wang, Terpyridine- and quarterpyridine‐based cationic covalent organic frameworks for visible‐light‐catalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e synthesis. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 137, e202425617 (2025).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC. Feng, J. Alharbi, M. Hu, S. Zuo, J. Luo, H. S. A. Qahtani, M.Rueping, K. W. Huang, H. Zhang, Ultrafast charge transfer on Ru-Cu atomic units for enhanced photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e production. \u003cem\u003eAdv. Mater.\u003c/em\u003e 37, 2406748 (2025).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eW. Wu, et al. Pyridine-based covalent organic frameworks with pyridyl-imine structures for boosting photocatalytic H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e production via one-step 2e\u003csup\u003e\u0026ndash;\u003c/sup\u003e oxygen reduction. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 63, e202404563 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eM. Vanga, A. Sahoo, R. A. Lalancette, F. J\u0026auml;kle, Linear extension of anthracene via B\u0026larr;N lewis pair formation: effects on optoelectronic properties and singlet O\u003csub\u003e2\u003c/sub\u003e sensitization. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 61, e202113075 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Jiang, G. Ye, F. Lorandi, Z. Liu, Y. Liu, T. Hu, J. Chen, Y. Lu, K. Matyjaszewski, Localized surface plasmon resonance meets controlled/living radical polymerization: An adaptable strategy for broadband light-regulated macromolecular synthesis. \u003cem\u003eAngew. Chem. Int. Ed.\u003c/em\u003e 58, 12096\u0026ndash;12101 (2019).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX. Hu, R. Yin, J. Jeong, K. Matyjaszewski, Robust miniemulsion photoATRP driven by red and near-infrared light. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 146, 13417\u0026ndash;13426 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eX. Hu, G. Szczepaniak, A. Lewandowska-Andralojc, J. Jeong, B. Li, H. Murata, R. Yin, A.M. Jazani, S.R. Das, K. Matyjaszewski, Red-Light-Driven atom transfer radical polymerization for high-throughput polymer synthesis in open air. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 145, 24315\u0026ndash;24327 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eK. A. Niederer, P. H. Gilmartin, M. C. Kozlowski, Oxidative photocatalytic homo- and cross-coupling of phenols: Nonenzymatic, catalytic method for coupling tyrosine. \u003cem\u003eACS Catal.\u003c/em\u003e 10, 14615\u0026ndash;14623 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJ. Wu, M. C. Kozlowski, Visible-Light-Induced oxidative coupling of phenols and alkenylphenols with a recyclable, solid photocatalyst. \u003cem\u003eOrg. Lett.\u003c/em\u003e 25, 907\u0026ndash;911 (2023).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6691883/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6691883/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eReversible-deactivation radical polymerization (RDRP) is a cornerstone of polymer industry. Normally, RDRPs are highly sensitive to oxygen and inhibitors, which hamper their industrial applications. Present methods cannot achieve facile polymerization in presence of both oxygen and inhibitors, particularly for large-scale production. Herein, we report development of phenanthroline-based conjugated hypercrosslinked polymer (Phen-CHCP) as a photocatalyst for photoinduced copper-catalyzed atom transfer radical polymerization (Cu-ATRP) with both high oxygen and inhibitors tolerance. Investigation of a new catalytic mechanism indicated that heterogeneous properties accelerate the diffusion of oxygen and inhibitors towards the Phen-CHCP interface. The ATRP initiator dominates the photoreduction process, not only accelerates the Cu-catalyzed redox cycle but also stabilizes the phenol inhibitor. As a result, various monomers achieved\u0026thinsp;\u0026gt;\u0026thinsp;95% conversions under broadband lights irradiation. This development strongly encourages the large-scale polymerizations, and we typically synthesized block copolymer of poly((2-methoxyethyl) acrylate-block-n-butyl acrylate) \u003cem\u003ein situ\u003c/em\u003e at 20 L scale (conversion 96%, \u003cem\u003eĐ\u003c/em\u003e = 1.26), which highlight the strong potential for industrial applications.\u003c/p\u003e","manuscriptTitle":"Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-07-04 04:07:34","doi":"10.21203/rs.3.rs-6691883/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"2d0675a0-302c-408d-9794-ce9d97ee09d4","owner":[],"postedDate":"July 4th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":50012639,"name":"Physical sciences/Chemistry/Polymer chemistry/Polymer synthesis"},{"id":50012640,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"},{"id":50012641,"name":"Physical sciences/Chemistry/Catalysis/Photocatalysis"}],"tags":[],"updatedAt":"2025-07-04T04:07:34+00:00","versionOfRecord":[],"versionCreatedAt":"2025-07-04 04:07:34","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6691883","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6691883","identity":"rs-6691883","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}