A novel methodology for photoinduced metal-free Atom Transfer Radical Polymerization (ATRP) by using conventional Type II photoinitiators such as benzophenone, thioxanthone, isopropyl thioxanthone and camphorquinone as sensitizers is presented.

Photoinduced atom transfer radical polymerization has recently been the center of intensive research in synthetic polymer chemistry because of the unique possibility of topological and temporal control in addition to precise control of macromolecular structure offered by conventional ATRP.

Photomediated Atom Transfer Radical Polymerization (photoATRP) is an activator regeneration method, which allows for the controlled synthesis of well‐defined polymers via light irradiation. Traditional photoATRP is often limited by the need for high‐energy ultraviolet or violet light. These could negatively affect the control and selectivity of the polymerization, promote side reactions, and may not be applicable to biologically relevant systems. This drawback can be circumvented by an introduction of the catalytic amount of photocatalysts, which absorb visible and/or NIR light and, therefore, controlled, regenerative ATRP can be performed with the dual‐catalytic cycle. Herein, a critical summary of recent developments in the field of dual‐catalysis concerning Cu‐catalyzed ATRP is provided. Contributions of involved species are examined mechanistically, followed by challenges and future directions towards the next generation of advanced functional macromolecular materials.

There is an urgent demand worldwide for the development of highly selective adsorbents and sensors of heavy metal ions and other organic pollutants. Within these environmental and public health frameworks, we are combining the salient features of clays and chelatant polymers to design selective metal ion adsorbents. Towards this end, the ion imprinting approach has been used to develop a novel nanohybrid material for the selective separation of Cu²⁺ ions in an aqueous solution. The Cu²⁺-imprinted polymer/montmorillonite (IIP/Mt) and non-imprinted polymer/montmorillonite (NIP/Mt) nanocomposites were prepared by a radical photopolymerization process in visible light. The ion imprinting step was indeed important as the recognition of copper ions by IIP/Mt was significantly superior to that of NIP/Mt, i.e., the reference nanocomposite synthesized in the same way but in the absence of Cu²⁺ ions. The adsorption process as batch study was investigated under the experimental condition affecting same parameters such as contact time, concentration of metal ions, and pH. The adsorption capacity of Cu²⁺ ions is maximized at pH 5. Removal of Cu²⁺ ion achieved equilibrium within 15 min; the results obtained were found to be fitted by the pseudo-second-order kinetics model. The equilibrium process was well described by the Langmuir isothermal model and the maximum adsorption capacity was found to be 23.6 mg/g. This is the first report on the design of imprinted polymer nanocomposites using Type II radical initiators under visible light in the presence of clay intercalated with hydrogen donor diazonium. The method is original, simple and efficient; it opens up new horizons in the general domain of clay/polymer nanocomposites.

Carbon nanomaterials, specifically carbon dots and carbon nitrides, play a crucial role as heterogeneous photoinitiators in both radical and cationic polymerization processes. These recently introduced materials offer promising solutions to the limitations of current homogeneous systems, presenting a novel approach to photopolymerization. This review highlights the preparation and photocatalytic performance of these nanomaterials, emphasizing their application in various polymerization techniques, including photoinduced i) free radical, ii) RAFT, iii) ATRP, and iv) cationic photopolymerization. Additionally, it discusses their potential in addressing contemporary challenges and explores prospects in this field. Moreover, carbon nitrides, in particular, exhibit exceptional oxygen tolerance, underscoring their significance in radical polymerization processes and allowing their applications such as 3D printing, surface modification of coatings, and hydrogel engineering.