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The present study reports on the development of a new binary filler system for rubber composites, SiO2@Al2O3, where Al2O3 sheets are grown onto SiO2 nanoparticles aggregates by a sustainable water-based soft-chemistry approach. The aim is to synergistically integrate the intrinsic thermal conductivity properties of Al2O3 with the peculiar reinforcement ability of SiO2 in an easy one-pot solution, which has been exploited to prepare polybutadiene (PB) model composites by a simple solvent casting technique. More in detail, the binary filler was used as-prepared or suitably surface functionalized with 3-(Trimethoxysilyl)propylmethacrylate (TMSPM). The filler compatibilization and interplay with the polymeric matrix have been inspected by solid state NMR in conjunction with scanning electron microscopy. These investigations highlighted that the presence of alumina in the binary filler does not undermine the capability of silica in generating polymer chains stiffening and indicated a significant effect of the silanization in providing better filler networking and interaction with the PB host ensuring, in principle, an enhanced thermal transport. Accordingly, thermal conductivity measurements revealed that SiO2@Al2O3 introduction in PB induces a remarkable upgrade of the heat transfer, which becomes much more relevant upon surface modification with TMSPM. These results appear encouraging, paving the possibility of applying SiO2@Al2O3 model system to more complex case studies, where both improved thermal conductivity and enhanced reinforcement are required, such as tires tread formulations. Highlights: A new SiO2@Al2O3 binary filler system was proposed following a soft-chemistry approach. The binary filler was functionalized to enhance its compatibilization. Fillers were dispersed in polybutadiene by a simple solvent casting technique. Thermal conductivity measurements revealed a remarkable upgrade of the heat transfer ability.

Cu-substituted Ni ferrite systems are produced following a hydrothermal synthetic route carried out at relatively mild conditions (i.e., below 200 °C). Different degrees of substitution were investigated, ranging from bare Ni ferrite to a complete Cu-substituted system (by replacing 100% of Ni with Cu). Morphological and structural characterisations point out that the introduction of Cu in the Ni ferrite (below 50% substitution) causes a gradual reduction of the average diameter of the ferrite polyhedral nanoparticles maintaining the Ni ferrite structure. At higher content of Cu, instead, the morphology evolves toward the co-presence of iron oxides (magnetite and hematite) and copper oxide (tenorite), without the formation of bare Cu ferrite. The partially substituted Ni ferrite nanomaterials exhibit a mostly superparamagnetic behaviour in all samples, registering a reduction of the values of magnetisation saturation by increasing the Cu content. Transmission Mössbauer spectroscopy performed on these nanomaterials evidenced a gradual lowering of the Fe fraction occupying the octahedral sites and a consequent increment of the Fe fraction in the tetrahedral sites. Quantitative analysis confirms the gradual reduction of the Ni content within the ferrite samples, coupled with the opposite increment of the Cu content, whereas the Fe content is lower in the case of Ni75-Cu25 sample. This particular behaviour can be associated with the influence of Cu substitution in the Ni ferrite structure, with preferential replacement of Fe from the octahedral B-sites toward the tetrahedral A-sites.

The ability of modifying the surface of a given substrate to confer novel “smart” properties only at the surface level is an extremely powerful approach as it allows to introduce specific physical, chemical, or biological characteristics able to favour an increment of the performances compared to the starting substrate. This is particularly true in the case of textiles and fibres, which are largely adopted not only in the textile field, but also in many innovative applications where the surface functionalisation plays a key role [1]. In this context, the first part of the talk will provide an overview over the use of textiles in surgical operations for the hernia care, with a focus on the possibility of using surface treatments to modify non-absorbable synthetic polymeric meshes to confer advanced features. In particular, the introduction of bioresorbable coatings able to exert an in situ antibacterial action is a very promising and widely investigated route to follow as one of the main issues related to the use of fully-absorbable fibres is their poor mechanical properties, which can be overcome by the presence of a bioinert non-absorbable skeletal materials, thus making the combination of both novel absorbable coatings and standard bioinert fibres a better compromise [2-3]. Another (often underestimated) concern related to hernioplasty is the shrinking of the prosthesis after implantation, with consequent collapse of the anchoring sutures through the hernia defect margin. Even here, the possibility of introducing a functional coating able to increase the adhesion ability of the prosthesis to the human tissue is a very promising technological solution alternative to the deposition of biocompatible glue on the meshes during the surgical intervention [4-5]. In the second part of the talk, a brief survey of representative case studies involving the surface modification of textiles for different applications will be discussed, including the modification of natural fibr

Sepiolite (Sep) is a powerful and promising filler, alternative to the. synthetic shape-controlled silica filler for many industrial applications. It possesses unusual structure, producing a “checkerboard” type pattern, where the sheets are covalently bonded, so they cannot be exfoliated. For this, the breaking down of Sep fibres aggregate is still a challenge to take advantage of the peculiar sepiolite shape for designing nanostructured materials. In this context, soft-chemistry methods, and the use of functionalizing molecules, often enables the generation of tailored inorganic-organic hybrid interfaces, making Sep fibres exploitable as active component in many formulation products with unique properties. In the last decade, we are focused on the different possibility to modulate sepiolite bulk properties including surface chemistry and morphology, particle size, shape, and porosity, to design systems employed in several applications, such as polymer nanocomposites (NCs), catalysis, photoresponsive materials and biomedical products.1 The talk will present some examples of the modification and applications of Sep based materials, with some more hints on those which have now reached a quite mature stage of development and for which marketable solutions are currently or shortly available, such as the “SmartNET TM Technology”2 and the “next generation double function fillers”,3 industrially developed in Pirelli Tyre laboratories. Limits and perspectives will be addressed, especially in the light of the challenging opportunity to control and tuning hybrid interfaces of Sep clay filler with organic species and macromolecular matrix.

In this study, an alternative mixed hydro-solvothermal route has been investigated for the synthesis of magnetic iron oxide nanoparticles with anisotropic shape. The synthesis was performed at mild conditions (150 °C) in a water/2-propanol environment, using poly(ethylene glycol) (PEG400) as structure directing agent, sodium thiosulfate as reducing agent, and NaOH as precipitating agent. The resulting systems were characterized by combining morphological, structural, and magnetic techniques. Experimental results clearly demonstrate that magnetite/maghemite nanorods are preferentially obtained in water/PEG400 environment, whereas 2-propanol/PEG400 environment promotes the growth of magnetite/maghemite polyhedral systems. Interestingly, synthesis performed in a mixed hydro-solvothermal (i.e., water/2-propanol) environment favors the preferential growth of hematite phase.

Ladder-like polysilsesquioxanes (LPSQs) are characterized by a double-stranded siloxane backbone, whose chemical and structural properties depend on both the synthesis parameters and the nature of the organic side-chains. In the case of ladder-like (methacryloxypropyl) polysilsesquioxanes (LPMASQ), polymer matrices can be produced by exploiting the presence of photocurable methacrylate groups. Consequently, they can be used to prepare functional nanocomposites (NCs), either by blending with organic polymers such as polybutadiene or exploiting the inorganic fillers’ dispersion. Since the properties of LPMASQ-based NCs are strongly related to their structure, the structural changes of polymerized LPMASQ were investigated upon addition of low loadings of TiO2 nanoparticles (up to 3 wt%) by solid state nuclear magnetic resonance and X-ray diffraction. The filler addition leads to the reduction of the polymerization capacity of the LPMASQ organic side-chains. Moreover, a different organization of ladder chains has been highlighted, ascribable to the increase in fully condensed linear ladder units at the expenses of folded chains and defective structures. The methodological approach here adopted can be extended to other composite systems and may help to describe the properties at the filler-matrix interface, offering valuable hints for a better design of these materials.

ZnO nanoparticles grown on highly porous silica with spherical and rod-like morphology were investigated by radioluminescence and photoluminescence measurements to assess the influence of intrinsic defectiveness on the optical properties. Spectroscopic analysis of ZnO/SiO2 systems unveils defect-related luminescence and a very weak excitonic emission. The samples display peculiar optical properties with unlike intensity and energy emissions, disclosing the occurrence of inequivalent defect centers in ZnO nanoparticles supported onto silica with different morphology.

The localization of the rubber vulcanization reaction close to the silica filler surface was investigated in isoprene rubber composites (IR NCs): the main goal was to highlight the role of curing agents’ dispersion and filler surface features on the spatial propagation of the rubber cross-links and the resulting mechanical behavior of the material. The study was realized by tailoring the morphology of the curing activator, i.e. by vulcanizing IR NCs with Zn@SiO2 double function filler, composed of Zn(II) single sites anchored on SiO2 filler, in comparison to silica filled IR NCs vulcanized with microcrystalline ZnO. The microscopic cross-links distribution was measured by Transmission Electron Microscopy for network visualization (NVTEM) and Time Domain Nuclear Magnetic Resonance (TD-NMR). Besides the NCs mechanical behavior was characterized both at small strain and at fracture. In the presence of Zn@SiO2, higher cross-link density in proximity to SiO2 particles was evidenced, which gradually spreads from the filler surface to the bulk, induced by localization of the Zn(II) centers. IR NCs with Zn@SiO2 resulted stiffer (+45%) and with a lower fracture toughness (less than one third), compared to m-ZnO based NCs, which shows a quite homogeneous structure of the rubber cross-links network. The results highlighted the correlation between the composites structural features and their macroscopic behavior, paving the way to modulating the mechanical properties of elastomeric materials by tuning the nature of the curing agents.

Hybrid silica-based nanofillers were synthesised by grafting short chains of poly(ethylene glycol) (PEG) with different molecular weight on the surface of SiO2 porous nanoparticles. Based on this approach, homogeneous poly(ethylene oxide) (PEO)-based ceramic-in-polymer solid-state electrolytes with SiO2 loadings up to 23 wt% were obtained, thanks to the high compatibility between the two phases endowed by the grafted PEG chains. These electrolytes showed satisfying ionic conductivity and excellent resistance against dendrite piercing that enabled long operation, for more than 350 h, under continuous stripping/plating of lithium in symmetric Li/electrolyte/Li cells. Additionally, the operating life of these devices was improved by the self-healing reaction between Li dendrites and silica fillers, being able to reinstate the cycling after short circuit. Finally, a lithium metal full cell, equipped with LiFePO4 positive material and the solid-state electrolyte containing 18 wt% of SiO2, demonstrated high stability against dendrite penetration and discharge capacity at 70 °C comparable to cells based on liquid analogues.

In recent years, significant efforts have been made in view of a transition from a linear to a circular economy, where the value of products, materials, resources, and waste is maintained as long as possible in the economy. The re-utilization of industrial and agricultural waste into value-added products, such as nanostructured siliceous materials, has become a challenging topic as an effective strategy in waste management and a sustainable model aimed to limit the use of landfill, conserve natural resources, and reduce the use of harmful substances. In light of these considerations, nanoporous silica has attracted attention in various applications owing to the tunable pore dimensions, high specific surface areas, tailorable structure, and facile post-functionalization. In this review, recent progress on the synthesis of siliceous materials from different types of waste is presented, analyzing the factors influencing the size and morphology of the final product, alongside different synthetic methods used to impart specific porosity. Applications in the fields of wastewater/gas treatment and catalysis are discussed, focusing on process feasibility in large-scale productions.

One of the main relevant limitations of the use of polymer-based materials in modern technological applications (e.g., electronics and optoelectronics, photonics, automotive) is their intrinsic low thermal conductivity that does not allow polymers to counteract the occurrence of the thermal degradation due to the in-service overheating phenomenon. To overcome this thermal constraint, polymer-based materials containing highly thermally conductive fillers are receiving great attention as they show an improved heat dissipation ability. However, recent studies report that a significant improvement of thermal conductivity in polymeric nanocomposites can be achieved only at high filler loadings, but this negatively affects both the mechanical behavior and density of the materials. Moreover, to achieve an efficient heat management, a continuous network of thermally conductive fillers crossing the entire composite is mandatory. In this context, interfacial phenomena play a major role as they favor the homogeneous distribution of the conductive fillers within the polymer matrix. In a previous study, it has been already verified that the surface functionalization of inorganic fillers (i.e., silica) with Polyhedral Oligosilsesquioxane (POSS) units, a family of hybrid inorganic-organic systems composed of an inorganic core of cage-like silicon oxide and several organic functional groups, significantly improved the dispersion and compatibilization of the inorganic fillers in the polymer matrix. Hence, the present contribution reports on the recent results obtained by introducing different types of alumina-based hybrid fillers decorated at the surface with either metacrylate silane or octa-methacryl-POSS units at low filler loadings in a polybutadiene polymer matrix. Even if displaying a modest intrinsic thermal conductivity, alumina can represent a valid and appealing thermally conductive filler, due to its low cost, stable chemical performance and negligible toxicity. The promi

The incorporation of silica nanoparticles (Si-NPs) into the polymer matrix is a growing area of interest research to produce high-performance polymer nanocomposites (NCs) across a wide range of nanotechnology applications. This improvement is due to the Si-NPs capability to self-assembly giving rise to specific well-organized structures with both short- and long-range order across a hierarchy of spatial scales, determined by both NP-NP and NP-matrix interactions, involving a careful balance among attractive driving forces, repulsive forces, and directional forces. Respect to this, the aim of the present paper is to systematically review the use of Si-NPs in polymer NCs and on the role of NPs self-assembly in determining the final material properties. Firstly, we explored the synthesis and modification of both isotropic and anisotropic Si-NPs in relation with use in NC materials, focusing on NPs dispersion and distribution, as well as on the functionalization strategies of Si-NPs. Besides Si-NPs functionalization with conventional small organic molecules, a large section is devoted to an emerging class of functionalized Si-NPs with macromolecules, namely silica hairy NPs (Si-HNPs), able to give rise a rich variety of complex assemblies and materials with new structures and functionalities. Successively, NCs materials containing Si-NPs and Si-HNPs have been explored in terms of synthetic preparation and properties. The self-organization of Si-NPs and Si-HNPs in polymer matrices has been reported and its effect on the functional materials properties have been evaluated with a critical point of view on the results, limits, and future perspectives. Our review can be considered a tutorial work, aiming at providing useful insights to researchers in the field of nanotechnology and nanoscience, taking into consideration the fundamental role of NPs self-assembly processes in determining the functional material properties.

The present study reports on the development and exploitation of an original filler system, based on alumina nanoparticles (NPs) and polyhedral silsesquioxane (POSS) units, namely Al2O3@POSS, where the remarkable compatibilization and thermomechanical features imparted by the silsesquioxane cage units “makes an alliance” with the enhanced thermal conductivity of Al2O3 NPs. The target is to supply rubber nanocomposites with improved heat transport and mechanical properties potentially applicable in tires formulation. The hybrid filler was prepared by a double-step approach consisting of a first silanization of Al2O3 with a methacrylate silane and subsequent grafting of OctaMethacrylPOSS through a radical reaction mediated by dicumyl peroxide as radical initiator. The material was characterized in depth in terms of structure, surface, and morphology and then used for producing, by solvent-casting technique, polybutadiene composites. The idea is to supply and test a model alumina-rubber based system which allows to better unveil the role played by the silsesquioxane units, thanks to the absence of other components (i.e. rubber polymers, vulcanization curatives and filler) usually included in real rubber formulations for tires. The comprehensive thermomechanical and morphological characterization of the nanocomposites highlighted the key role played by POSS units decorating the alumina surface, which assure both the compatibility between filler and polymer host, and an homogeneous distribution and continuous networking of the alumina NPs. This positively influences not only the heat transport, providing thermal conductive pathways that raise the thermal diffusivity even at low filler loadings (+60–70% with respect to composite enclosing bare alumina at a concentration of 15–10 v/v %) but also the storage modulus, paving the way toward a potential exploitation of Al2O3@POSS hybrid filler in large-scale formulations of rubber composites, namely those employed for tires.

The interaction between activators (ZnO) and co-activators (stearic acid, SA) represents a key step in the vulcanization process, to generate Zn(II) intermediate complexes that enhance the reaction kinetic and promote the shortening of sulfur bridges, leading to highly cross-linked materials. To understand the influence of the structural, morphological and surface properties of ZnO in the reactivity with SA, in this work, pure ZnO nanoparticles (NPs) and ZnO NPs anchored on SiO2 (ZnO/SiO2) were prepared through soft chemistry techniques. Tailoring of morphology and surface features was accomplished through a fine control of the synthetic parameters, as demonstrated by the careful characterization of the activators. Then, the interaction of pure ZnO and ZnO/SiO2 activators with SA in the absence of rubber was investigated by using Differential Scanning Calorimetry (DSC). The occurrence of Zn(II)-SA complexes with different thermal stability and structural properties was assessed by a comprehensive thermogravimetric and spectroscopic survey. The generation and the chemical structure of these specific vulcanization intermediates was related to the peculiar characteristics of the ZnO/SiO2 systems and, in turn, to their ability in imparting faster kinetics and higher curing efficiency to isoprene rubber nanocomposites, compared to bare ZnO. These results, besides proposing a valid benchmark for achieving further insights on the interaction of stearic acid with activators, pave the way to provide specific protocols for a better design and implementation of ZnO-based materials able to effectively enhance the rubber vulcanization process, with significant economic and environmental advantages.

The development of effective thermally conductive rubber nanocomposites for heat management represents a tricky point for several modern technologies, ranging from electronic devices to the tire industry. Since rubber materials generally exhibit poor thermal transfer, the addition of high loadings of different carbon‐based or inorganic thermally conductive fillers is mandatory to achieve satisfactory heat dissipation performance. However, this dramatically alters the mechanical behavior of the final materials, representing a real limitation to their application. Moreover, upon fillers’ incorporation into the polymer matrix, interfacial thermal resistance arises due to differences between the phonon spectra and scattering at the hybrid interface between the phases. Thus, a suitable filler functionalization is required to avoid discontinuities in the thermal transfer. In this challenging scenario, the present review aims at summarizing the most recent efforts to improve the thermal conductivity of rubber nanocomposites by exploiting, in particular, inorganic and hybrid filler systems, focusing on those that may guarantee a viable transfer of lab-scale formulations to technological applicable solutions. The intrinsic relationship among the filler’s loading, structure, morphology, and interfacial features and the heat transfer in the rubber matrix will be explored in depth, with the ambition of providing some methodological tools for a more profitable design of thermally conductive rubber nanocomposites, especially those for the formulation of tires.

Ladder-like silsesquioxanes (SSQs) and TiO2 have been functionalized with methacryloyloxypropyl chains and embedded in a polybutadiene (PB) matrix giving rise to hybrid (organic–inorganic) nanocomposites (NCs) capable of acting as oxygen scavenging materials. The joint use of infrared spectroscopy, small-angle X-ray scattering, and permittivity measurements highlighted that the presence of TiO2, regardless of its modification, does not significantly alter the structure of the NCs, but just reduces the crosslinking degree and induces a local disorganization of the ladder-like SSQ stacks. The introduction of an optimum amount (0.5 wt%) of modified TiO2 within the polymeric matrix enhanced the oxygen uptake rate of ca. 70% with respect to the sole polymeric material. Moreover, the uptake kinetics changes from the first to second order with respect to the PB amount, clearly indicating different oxidation mechanisms. NCs containing modified TiO2 showed an oxygen uptake rate ranging from 30 to 60% higher than that achievable in the presence of bare TiO2. The superior activity of the materials containing modified TiO2 has been related to mechanistic aspects. Fluorescence and electron spin resonance spectroscopies allowed to underline the role of singlet oxygen within the polymeric matrix, although the known photochemical oxidation of PB and the TiO2 induced hydroxyl radical mediated oxidation cannot be excluded. These results open the route to highly efficient flexible oxygen scavenging materials for the protection of electronic devices such as organic based light emitting diodes, solar cells, and liquid crystal displays, which require high targets of protection from oxygen and water.

This study addresses the relationship between material morphology (size, growth parameters and interfaces) and optical emissions in ZnO through an experimental approach, including the effect of different material dimensions from bulk to nano-size, and different excitations, from optical sources to ionizing radiation. Silica supported ZnO nanoparticles and ligand capped ZnO nanoparticles are synthesized through a sol–gel process and hot injection method, respectively. Their optical properties are investigated by radioluminescence, steady-state and time-resolved photoluminescence, and compared to those of commercial micrometric powders and of a bulk single crystal. The Gaussian spectral reconstruction of all emission spectra highlights the occurrence of the same emission bands for all samples, comprising one ultraviolet excitonic peak and four visible defect-related components, whose relative intensities and time dynamics vary with the material parameters and the measurement conditions. The results demonstrate that a wide range of color outputs can be obtained by tuning synthesis conditions and size of pure ZnO nanoparticles, with favorable consequences for the engineering of optical devices based on this material.

Latex compounding technique is an economic and ecosustainable alternative to melt mixing for preparing nanocomposites in which fillers are directly mixed with natural rubber in the latex aqueous dispersion. Clay minerals are excellent potential fillers to be used in masterbatches prepared exploiting this technique, but their presence is associated to the occurrence of oxidative degradation phenomena of natural rubber. In this work, by exploiting a combination of high- and low-resolution 13C and 1H Solid State Nuclear Magnetic Resonance techniques, with the support of Fourier Transform Infrared spectroscopy and thermal analyses, we characterized for the first time the oxidation phenomena occurring in sepiolite/natural rubber masterbatches obtained by the latex compounding technique. Oxidized species were identified and quantified and the dynamic properties, molecular weight and thermal stability of the rubber were characterized. Moreover, the dependence of degradation phenomena on the filler treatment and on the masterbatch work-up procedure was assessed, identifying freeze-drying as the method able to effectively protect the rubber from oxidation.

The occurrence of uncontrolled electrostatic discharge (ESD) is among the major causes of damage in unprotected electronic components during industrial processes. To counteract this undesired phenomenon, ESD composites showing static-dissipative and antistatic responses are developed. In particular, static-dissipative materials are able to slow down the flow of electric charges, whereas antistatic materials directly suppress the initial charges induced by undesired charging by properly dispersing conductive fillers within an insulant matrix and thus forming a conductive filler network. In this context, the purpose of this review is to provide a useful resume of the main fundamentals of the technology necessary for facing electrostatic charging. The formation mechanisms of electrostatic charges at the material surface were described, providing a classification of ESD composites and useful characterization methods. Furthermore, we reported a deep analysis of the role of conductive fillers in the formation of filler networks to allow electric charge movements, along with an overview of the different classes of inorganic conductive fillers exploitable in ESD composites, evidencing pros/cons and criticalities of each category of inorganic fillers.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.

The development of hybrid nanoscintillators is hunted for the implementation of modern detection technologies, like in high energy physics, homeland security, radioactive gas sensing, and medical imaging, as well as of the established therapies in radiation oncology, such as in X-ray activated photodynamic therapy. Engineering of the physico-chemical properties of nanoparticles (NPs) enables the manufacture of hybrids in which the conjugation of inorganic/organic components leads to increased multifunctionality and performance. However, the optimization of the properties of nanoparticles in combination with the use of ionizing radiation is not trivial: a complete knowledge on the structure, composition, physico-chemical features, and scintillation property relationships in hybrid nanomaterials is pivotal for any applications exploiting X-rays. In this paper, the design of hybrid nanoscintillators based on ZnO grown onto porous SiO2 substrates (ZnO/SiO2) has been performed in the view to create nanosystems potentially suitable in X-ray activated photodynamic therapy. Indeed, cytotoxic porphyrin dyes with increasing concentrations have been anchored on ZnO/SiO2 nanoparticles through amino-silane moieties. Chemical and structural analyses correlated with photoluminescence reveal that radiative energy transfer between ZnO and porphyrins is the principal mechanism prompting the excitation of photosensitizers. The use of soft X-ray excitation results in a further sensitization of the porphyrin emission, due to augmented energy deposition promoted by ZnO in the surroundings of the chemically bound porphyrin. This finding unveils the cruciality of the design of hybrid nanoparticles in ruling the efficacy of the interaction between ionizing radiation and inorganic/organic moieties, and thus of the final nanomaterial performances towards the foreseen application.