This review provides an up-to-date overview on silver nanoparticles-based materials suitable as optical sensors for water pollutants. The topic is really hot considering the implications for human health and environment due to water pollutants. In fact, the pollutants present in the water disturb the spontaneity of life-related mechanisms, such as the synthesis of cellular constituents and the transport of nutrients into cells, and this causes long / short-term diseases. For this reason, research continuously tends to develop always innovative, selective and efficient processes / technologies to remove pollutants from water. In this paper we will report on the silver nanoparticles synthesis, paying attention to the stabilizers and mostly used ligands, to the characterizations, to the properties and applications as colorimetric sensors for water pollutants. As water pollutants our attention will be focused on several heavy metals ions, such as Hg(II), Ni(II),Cu(II), Fe(III), Mn(II), Cr(III/V) Co(II) Cd(II), Pb(II), due to their dangerous effects on human health. In addition, several systems based on silver nanoparticles employed as pesticides colorimetric sensors in water will be also discussed. All of this with the aim to provide to readers a guide about recent advanced silver nanomaterials, used as colorimetric sensors in water.

In this work, hydrophilic silver nanoparticles (AgNPs), bifunctionalized with citrate (Cit) and L-cysteine (L-cys), were synthesized. The typical local surface plasmon resonance (LSPR) at λ _max = 400 nm together with Dynamic Light Scattering (DLS) measurements ( = 8 ± 1 nm) and TEM studies (Ø = 5 ± 2 nm) confirmed the system nanodimension and the stability in water. Molecular and electronic structures of AgNPs were investigated by FTIR, SR-XPS, and NEXAFS techniques. We tested the system as plasmonic sensor in water with 16 different metal ions, finding sensitivity to Hg²⁺ in the range 1–10 ppm. After this first screening, the molecular and electronic structure of the AgNPs-Hg²⁺ conjugated system was deeply investigated by SR-XPS. Moreover, in view of AgNPs application as sensors in real water systems, environmental safety assessment (ecosafety) was performed by using standardized ecotoxicity bioassay as algal growth inhibition tests (OECD 201, ISO 10253:2006), coupled with determination of Ag⁺ release from the nanoparticles in fresh and marine aqueous exposure media, by means of ICP-MS. These latest studies confirmed low toxicity and low Ag⁺ release. Therefore, these ecosafe AgNPs demonstrate a great potential in selective detection of environmental Hg²⁺, which may attract a great interest for several biological research fields.

In this work, the electronic and molecular structure, as well as the morphology, of innovative nanostructured materials whose optical properties respond to the presence of heavy metals in water samples was investigated. In particular, the here discussed silver nanoparticles (NPs) stabilized by a hydrophilic ligand (sodium 3-mercapto-1-propanesulfonate, 3MPS) are able to reveal the presence of mercury ions at ppm levels. The sensitivity of the proposed nanosensor to Hg(II) in 1–5 ppm range was ascertained by optical tests; then, the local chemistry and electronic structure of the nanostructured coordination compounds made of functionalized silver nanoparticles (NPs) and metal ions, and their correlation with the resulting nanoaggregates’ shape and morphology, were investigated by state-of-the-art synchrotron radiation (SR)-induced spectroscopies and transmission electron microscopy (TEM). In particular, SR-induced X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements allowed us to gather complementary information about the silver–mercury interaction, which is only partially mediated by the negatively charged 3MPS ligand, different from what was observed for analogous nanosensors applied to other bivalent heavy metal ions, for example, Co(II) and Ni(II). TEM morphological analysis sheds light on the structure of the AgNP-3MPS/Hg aggregates, revealing the formation of Ag/Hg alloy nanoparticles.

Silver nanoparticles capped with 3-mercapto-1propanesulfonic acid sodium salt (AgNPs-3MPS), able to interact with Ni²⁺ or Co²⁺, have been prepared to detect these heavy metal ions in water. This system works as an optical sensor and it is based on the change of the intensity and shape of optical absorption peak due to the surface plasmon resonance (SPR) when the AgNPs-3MPS are in presence of metals ions in a water solution. We obtain a specific sensitivity to Ni²⁺ and Co²⁺ up to 500 ppb (part per billion). For a concentration of 1 ppm (part per million), the change in the optical absorption is strong enough to produce a colorimetric effect on the solution, easily visible with the naked eye. In addition to the UV-VIS characterizations, morphological and dimensional studies were carried out by transmission electron microscopy (TEM). Moreover, the systems were investigated by means of dynamic light scattering (DLS), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and high-resolution X-ray photoelectron spectroscopy (HR-XPS). On the basis of the results, the mechanism responsible for the AgNPs-3MPS interaction with Ni²⁺ and Co²⁺ (in the range of 0.5–2.0 ppm) looks like based on the coordination compounds formation.

Ion exchange polymers were used for mercury and lead ions removal in water. The heavy metal ion concentration was analyzed by two independent methods: inductively coupled plasma–optical emission spectroscopy (ICP-OES) and gravimetry. The studied cation exchange polymer (CEP) was sulfonated poly(ether ether ketone) (SPEEK), and the anion exchange polymer (AEP) was poly(sulfone trimethylammonium) chloride (PSU-TMA). The removal capacity was connected with the ion exchange capacity (IEC) equal to 1.6 meq/g for both polymers. The concentration ranges were 0.15–0.006 mM for Hg²⁺ and 10.8–1.0 mM for Pb²⁺. SPEEK achieved 100% removal efficiency for mercury and lead if the concentration was below the maximum sorption capacity (Q_max), which was about 210 mg/g for Pb²⁺ with SPEEK. For PSU-TMA, the surprising removal efficiency of 100% for Hg²⁺, which seemed incompatible with ion exchange, was related to the formation of very stable complex anions that can be sorbed by an AEP. Langmuir adsorption theory was applied for the thermodynamic description of lead removal by SPEEK. A second-order law was effective to describe the kinetics of the process.