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Solar light can be used by semiconductor nanocrystals as a free and largely available source of energy to transform air pollutants into non-volatile less harmful chemicals. The efficiency of this process can be enhanced by doping the semiconductor with carbon-based materials, such as graphene. Nevertheless, such an increased activity has been reported (i) for nanocomposite photocatalysts produced on the research laboratory scale, (ii) analyzing their performance as self-standing photocatalysts and not after incorporation into “real” matrixes (e.g. building materials) and (iii) typically using model target pollutants instead of “real” hazardous ones. Here we describe the large-scale preparation of two series of carbon based photocatalysts starting from commercial materials and we demonstrate their superior photocatalytic activity in degrading important air pollutants as nitrogen oxides, compared to undoped photocatalysts. The photocatalytic activity was evaluated by NOx abatement adopting the continuous flow procedure and the apparatus reported in the Italian standard UNI 11,247. Best performing materials were incorporated into two different inorganic matrixes (cement and lime). In both cases, the superior photocatalytic performances were maintained. An improvement up to 42±7% of the photocatalytic activity was measured in the case of a cement sample for a carbon-doped photocatalyst with respect to bare TiO2 . The materials were characterized by UV-Vis spectroscopy, high resolution powder X-ray diffraction (HR-PXRD), high-resolution scanning electron microscopy (HR-SEM) energy-dispersive X-ray spectroscopy (EDS) and micro-Raman.

We investigate the photocatalytic performance of composites prepared in a one-step process by liquid-phase exfoliation of graphite in the presence of TiO

Item does not contain fulltext We investigate the photocatalytic performance of composites prepared in a one-step process by liquid-phase exfoliation of graphite in the presence of TiO2 nanoparticles (NPs) at atmospheric pressure and in water, without heating or adding any surfactant, and starting from low-cost commercial reagents. These show enhanced photocatalytic activity, degrading up to 40% more pollutants with respect to the starting TiO2-NPs, in the case of a model dye target, and up to 70% more pollutants in the case of nitrogen oxides. In order to understand the photo-physical mechanisms underlying this enhancement, we investigate the photo-generation of reactive species (trapped holes and electrons) by ultrafast transient absorption spectroscopy. We observe an electron transfer process from TiO2 to the graphite flakes within the first picoseconds of the relaxation dynamics, which causes the decrease of the charge recombination rate, and increases the efficiency of the reactive species photo-production.

The cement hydration delay is due to comb-polymers (PCP), used as dispersant agent during the preparation of the cement paste. In order to evaluate the role of the PCP structure on hydration, the comb-polymer is separated in two main parts: the backbone (PAA) and the dispersing chain. A linear polymer made up of PEO, Mw = 1000, with a carboxylic head suitable to link the inorganic surface, was synthesized to simulate the effect of the dispersing-side chain. The hydration delay of C-S-H formation induced by comb-polymer on CEM I and C3S phase was analyzed by conduction calorimetry and the morphology of the crystalline structure in growth by SEM, specially studying the relation between structure and hydration time. The results show that the hydration delay is mainly ascribable to the comb-shaped structure as a whole, where PEO chain, as from considerations on energy, might assume conformations able to modify the salt concentration near the cement surface. The different hydration rates are tentatively related to the crystal growth and the surface texture observed by SEM.

The rheology of cement pastes can be controlled by polymeric dispersants such as branched polyelectrolytes that adsorb on the surfaces of silicate particles. In the present work, we analyze the adsorption behavior of ad hoc-prepared end-carboxylated poly(ethylene glycol), or PEG, on CaCO(3) particles as a model of cement in an early hydration stage. The experimental adsorption isotherms form the base of a theoretical study aimed at unraveling polymer conformational aspects of adsorption. The study was carried out with Monte Carlo simulations using a coarse-grained bead-and-spring model of linear end-charged polymer chains adsorbing on a flat, continuous, uniformly charged surface. The adsorption driving force was introduced by a Debye-Hückel electrostatic screened potential to describe the interaction between the negatively charged end group of PEG and the positively charged CaCO(3) surface empirically. With a suitable length-scale conversion between real PEG and the coarse-grained model, the calculated and experimental adsorption isotherms can be semiquantitatively compared. The theoretical results reproduce the fundamental aspects of polymer adsorption, in essential agreement with analytical approaches relating the isotherm shape to the polymer conformational properties. The conformational transition mushroom-brush of the adsorbed polymer is located on the isotherm and is related to the molecular shape. The solvent quality effect and the solution ionic strength are also considered, and their implications on the isotherms are discussed.

Comb polyelectrolytes (CPs) having neutral hydrophilic teeth, similar to double hydrophilic block copolymers, are a powerful tool to modify the chemical-physical properties of inorganic crystalline materials. One of their main applications is in concrete technology, where they work as superplasticizers, particle-dispersing agents. Here, CPs, having the same poly(acrylic acid) (PAA) backbone chain and differing in the grafting with methoxy poly(ethylene glycol) chains (MPEG) of two molecular weights, were used to investigate the influence of tooth chains in polymer aggregation and in control on morphology and aggregation of calcite particles. These polymers aggregate, forming interpolymer hydrogen bonds between carboxylic groups and ether oxygen functionalities. The presence of calcium ions in solution further enhances aggregation. Crystallization experiments of calcite in the presence of CPs show that the specificity of interactions between polymers and crystal planes and control on aggregation and size of particles is a function of the content and chain length of the MPEG in the PAA backbone. These parameters limit and can make specific the electrostatic interactions with ionic crystalline planes. Moreover, the mechanism of crystallization, classical or nonclassical, is addressed by the CP structure and concentration. These findings have implications in the understanding of the complex chemical processes associated to concrete superplasticizers action and in the study of the biomineralization processes, where biological comb polyelectrolytes, the acidic glycoproteins, govern formation of calcitic structures.

Comb-like polymers have an important application in cement industries, where they are referred to as polymeric admixtures/superplasticizers. They are used to increase the workability of fresh cementitious mixtures as well as to improve the strength and durability of the hardened state. So far, the interaction of polymer/Portland-limestone cement particles has been poorly investigated. This paper describes the overgrowth of calcite on Portland-limestone cement particles, a mixture of ground clinker and calcite, in the presence of comb-like polymers. The morphological and aggregational variation of overgrown calcite crystals is used as a model to evaluate the interaction occurring between cement particles and polymeric admixtures. Rhombohedral, spherulitic, microtrumpet, or fibrous calcite crystals were observed as a function of the kind of cement particles and comb-like polymers used. These results suggest that comb-like polymers may assume diverse conformations when associated with the different particles that constitute Portland-limestone cement.

In the cement industries the use of plasticizer additives, referred to as admixtures, to increase the material workability is of growing interest. Polymeric admixtures are sulfonate or carboxylate polyelectrolytes, the last had been recently also grafted with methoxy poly(ethylene glycol) chains. Their structure and chemical composition recall the acidic macromolecules hosted by several mineralized tissues. The mechanism of action of the polymeric admixtures on cement hydration and carbonation is still poorly understood. Here, we report a study on the variations in the calcium carbonate morphology and polymorphism induced by the presence of commercial polymeric admixtures, since calcium carbonate is one of the products of cement carbonation. We found that the conformation of the polymeric admixtures, the kind of charged functional groups and the presence of grafted chains are the crucial parameters for the specific control of the calcite crystals size and morphology. The formation of crystalline faces already observed in biogenic calcites, as function of the presence of carboxylate or sulfonate groups in the polymeric chain, was obtained. This work evidences an analogy between the polymeric admixtures and the acid macromolecules with respect to calcium carbonate crystallization and the gained information are of interest both for the cement industries and to the understanding of the biomineralization processes.