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Dr. Valdés-Morales, Héctor
Research Outputs
Simple devising of N-doped carbon dots (N-CDs) as a low-cost probe for selective environmental toxin detection and security applications
2023, Dr. Valdés-Morales, Héctor, Annamalai, Kumaresan, Annamalai, Arun, Ravichandran, Ramya, Jeevarathinam, Anandhavalli, Annamalai, Padmanaban, Elumalai, Sundaravadivel
Nitrogen-doped carbon dots (N-CDs) possess outstanding photostability and interesting physicochemical and photochemical properties. Herein, we present cyan-emitting N-CDs that were fabricated through the treatment of salicylic acid with ethylene diamine using a simple microwave-assisted method. It was observed that the reaction produced N-CDs that strongly emitted cyan light with a quantum yield (QY) of 33%. The N-CDs were examined with the assistance of HR-TEM, XPS, XRD, FTIR, PL, and UV measurements. Due to the fluorescence enrichment effect caused by the N atoms in carbon dots, these N-CDs can be used as a fluorescent material for the detection of nitro-explosives and toxic metal cations. The addition of picric acid resulted in splendid quenching of the N-CDs, with a limit of detection (LOD) value of approximately 82.9 nM that was ascribed to the Fo ¨rster resonance energy transfer between the N-CDs and the nitro-aromatics. Furthermore, the powerful coordination between oxygen-rich moieties and N-CDs for the detection of Fe3+ and Hg2+ cations induced fluorescence quenching through photo-induced electron transfer and the inner-filter effect pathway, leading to the effective recognition of metal ions. The sensor probe exhibited a wide-ranging linear response with an LOD of approximately 30 nM for Fe3+ and 160 nM for Hg2+ ions. Thus, the as-prepared N-CDs can function as a fluorescence sensor, a secure portable information device, and a paper-based probe for detection in biological systems.
The effect of visible light on the postharvest life of tomatoes (Solanum lycopersicum L.)
2023, de Bruijn, Johannes, Fuentes, Nicole, Solar, Víctor, Valdebenito, Ana, Vidal, Leslie, Melín, Pedro, Fagundes, Francis, Dr. Valdés-Morales, Héctor
Tomatoes (Solanum lycopersicum L.) are widely cultivated and consumed, but ripening should be carried out in controlled storage conditions to extend their shelf life and avoid economic losses. The aim of this study was to investigate the effects of visible artificial light on the ripening and quality of fresh market tomatoes stored at a low temperature and high humidity. The postharvest performance with respect to the ripening of organically grown tomatoes in the Toscano cultivar, with a long storage life, was studied in the presence and the absence of visible LED light. The maturation kinetics of the tomatoes was modeled using the Power Law equation. Results showed that tomatoes stored in the presence of light exhibited an increased respiration rate and a faster preclimacteric phase. Lycopene content, total soluble solids, and maturity index increased in the presence of light. Hence, light increased the postharvest ripening of tomatoes, affecting their shelf life.
Synergistic impact of nanoarchitectured GQDs-AgNCs(APTS) modified glassy carbon electrode in the electrochemical detection of guanine and adenine
2023, Dr. Valdés-Morales, Héctor, Vinoth, Victor, Kaimal, Reshma, Selvamani, Muthamizh, Michael, Rubina, Pugazhenthiran, Nalandhiran, Viswanathan-Mangalaraja, Ramalinga, Anandan, Sambandam
In this work, a facile green approach for the synthesis of graphene quantum dots (GQDs) embedded on silicate network silver nanocrystals (GQDs-AgNCs(APTS)) is reported. Moreover, glassy carbon-GC electrodes were modified with the prepared nanocomposite containing graphene quantum dots supported on silver nanocrystals (GQDs-AgNCs(APTS)) and applied for simultaneous detection of guanine (GA) and adenine (AD). The chemically modified electrode was assessed during the determination of purine bases by cyclic voltammetry-CV and differential pulse voltammetry-DPV. The incorporation of GQDs-AgNCs(APTS) nanocomposites over the surface of the GC electrode considerably enhances the anodic peak currents and decreases the adenine and guanine peak potentials. Compared to other electrodes, GQDs-AgNCs(APTS)/GC improved the electrochemical behavior towards the detection of adenine and guanine. At optimal conditions, calibration curves were obtained by DPV being linear in the range of 0.1–6.0 μM and 0.1–5.0 μM for guanine and adenine, respectively. The detection limits of both guanine and adenine were estimated as 0.1 μM. Additionally, interferences analyses were performed on the existence of other interferent compounds. Furthermore, the method developed for the identification of GA and AD was proved using fish sperm DNA samples.
Graphene modified “black {0 0 1}TiO2” nanosheets for photocatalytic oxidation of ethylene: The implications of chemical surface characteristics in the reaction mechanism
2022, Dr. Valdés-Morales, Héctor, Pugazhenthiran, Nalandhiran, Mangalaraja, Ramalinga, Sathishkumar, Panneerselvam, Murugesan, Sepperumal
In this work, crystal facets, bandgap, size and shape of reduced graphene oxide (rGO) modified anatase {001} black TiO2 nanosheets (rGO-B-TiO2 NSTs) were tailored for the photocatalytic oxidation of ethylene under high humidity content. XRD, Raman and HR-TEM analyses confirm that rGO-B-TiO2 NSTs have a 94 % of exposed {001} facets with high number of oxygen vacancies. In addition, rGO-B-TiO2 NSTs exhibit increased values of surface area and porosity compared to its pristine form. A 48 and 34 μmol g− 1 of ethylene are adsorbed at the surface of rGO-B-TiO2 NSTs in the absence and in the presence of humidity, respectively. In addition, operando DRIFTS analyses provide the insight of surface interactions between ethylene molecules and adsorption sites of rGO-B-TiO2 NSTs. The photocatalytic removal efficiencies of the synthesized materials under both UV and visible light irradiation proceed as follows: rGO-B-TiO2 NSTs > B-TiO2 NSTs > TiO2 NSTs > commercial TiO2 NPs. Further, ethylene is very quickly photocatalytic oxidized when rGO-B-TiO2 NSTs is applied under UV light irradiation, having a 72 and 92 % ethylene removal in the absence and in the presence of humidity, respectively. Moreover, a 48 and 58 % of ethylene removal takes place in the absence and presence of humidity under visible light irradiation, respectively. Results indicate that rGO-B-TiO2 NSTs boost the photocatalytic activity through their virtue of visible-light absorption properties (Bandgap = 2.61 eV) and the rapid electron-hole separation at the rGO {001} black TiO2 NSTs interfaces. Such findings are confirmed through UV-visible diffused reflectance, photoelectrochemical and photoluminescence analyses. Nanosheets made of rGO modified {001} black TiO2 could be used as an effective photocatalyst for the removal of ethylene from large volume fruit storage areas by exploiting a simple light source in the presence of high content of humidity.
Silver nanoparticles modified ZnO nanocatalysts for effective degradation of ceftiofur sodium under UV-vis light illumination
2023, Pugazhenthiran, N., Sathishkumar, P., Albormani, Omeer, Murugesan, S., Kandasamy, M., Selvaraj, M., Suresh, S., Karthick-Kumar, S., Contreras, D., Dr. Valdés-Morales, Héctor, Mangalaraja, R.V.
Light-induced photocatalytic degradation of ceftiofur sodium (CFS) has been assessed in the presence of plasmonic zinc oxide nanostructures (ZnONSTs), like, ZnO nanoparticles, ZnO nanorods (ZnONRs) and ZnO nanoflowers (ZnONFs). Silver nanoparticles (Ag NPs) loaded ZnO nanostructures (Ag-ZnONSTs) are obtained through seed-assisted chemical reaction followed by chemical reduction of silver. The surface modification of ZnO nanostructures by Ag NPs effectually altered their optical properties. Further, the surface plasmonic effect of Ag NPs facilitates visible light absorption by ZnONSTs and improved the photogenerated electron and hole separation, which makes the ZnONSTs a more active photocatalyst than TiO2 (P25) nanoparticles. Especially, Ag-ZnONRs showed higher CFS oxidation rate constant (k' = 4.6 × 10−4 s−1) when compared to Ag-ZnONFs (k' = 2.8 × 10−4 s−1) and Ag-ZnONPs (k' = 2.5 × 10−4 s−1), owing to their high aspect ratio (60:1). The unidirectional transport of photogenerated charge carriers on the Ag-ZnONRs may be accountable for the observed high photocatalytic oxidation of CFS. The photocatalytic oxidation of CFS mainly proceeds through •OH radicals generated on the Ag-ZnONRs surface under light illumination. In addition, heterogeneous activation of peroxymonosulfate by Ag-ZnONRs accelerates the rate of photocatalytic mineralization of CFS. The quantification of oxidative radicals supports the proposed CFS oxidation mechanism. Stability studies of plasmonic Ag-ZnONSTs strongly suggests that it could be useful to clean large volume of pharmaceutical wastewater under direct solar light irradiation.
Influence of fuel in the bismuth oxide photocatalytic performance for the degradation of acid blue-25 under visible light
2023, Aswini, Ravi, Padmanaban, Annamalai, Acchutharaman, K.R., Sivaraj, Durairaj, Vigneshwaran, Sankar, Dr. Valdés-Morales, Héctor, Vadivu-Arunachalam, Saravana
In this work, we prepared bismuth oxide (Bi2O3) nanoparticles with and without fuels (citric acid and urea) using a one-pot solid-state combustion method at 400 °C for visible light photocatalytic degradation of acid blue 25 (AB). The nanoparticle prepared with fuel greatly influences the Bi2O3 properties such as morphology, chemical, structural, and optical properties. Bi2O3 prepared with citric acid as fuel act as an effective photocatalyst for the breakdown of acid blue 25 within 60 min under visible light irradiation. The enhanced photocatalytic property of Bi2O3 is due to the narrow band gap, high crystallinity, flower-like morphology with high active sites, and light stability of the material. Furthermore, an effective photogenerated charge separation, high charge transfer, and lower band gap, improved the absorbing capacity in the visible region of Bi2O3 (1) and enhanced its photocatalytic ability. In the photocatalytic process, the superoxide radicals (O2·) anion played a significant role during the degradation of acid blue 25. The Bi2O3 (1) maintained its effectiveness after three reaction cycles without suffering any appreciable change in structural and functional stability. These findings demonstrated an easy method for treating the hazardous effluents into non-toxic small molecules, which can be potentially applied to purify the various textile effluent.
Evidence of synergy effects between zinc and copper oxides with acidic sites on natural zeolite during photocatalytic oxidation of ethylene using operando DRIFTS studies
2023, Abreu, Norberto J, Dr. Valdés-Morales, Héctor, Zaror, Claudio A., Ferreira- de Oliveira, Tatianne, Azzolina-Jury, Federico, Thibault-Starzyk, Frédéric
In this article, the role of surface sites of modified zeolites with semiconductor nanoparticles as alternative photocatalyts for protecting post-harvest foodstuff from the detrimental effects of ethylene is addressed. Two single and one double catalyst based on zinc and copper oxides supported over modified zeolite samples were prepared. Physical, chemical, and surface properties of prepared materials were studied by several characterization methods. UV-Vis absorption spectra show that the applied modification procedures increase the optical absorption of light in the UV and visible regions, suggesting that an increase in the photocatalytic activity could take place mainly in the obtained co-impregnated catalyst. An ethylene conversion around 50% was achieved when the parent natural zeolite support was modified with both transition metal oxides, obtaining higher removal efficiency in comparison to single oxide catalysts. Adsorption and photocatalytic oxidation experiments were also performed using single and double catalysts supported over fumed silica, attaining lower ethylene conversion and thus highlighting the role of zeolite surfaces as adsorption sites for ethylene during photocatalytic reactions. Operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies reveal that a synergistic mechanism occurs, involving ethylene adsorption at acidic sites of zeolite and its photocatalytic oxidation due to the generation of radicals by the light activation of nanoparticles of zinc and copper oxides.
Goethite (α-FeOOH) nanoparticles wrapped on reduced graphene oxide nanosheet for sensitive electrochemical detection of arsenic(III)
2023, Dr. Valdés-Morales, Héctor, Vinoth, Victor, Shanmugaraj, Krishnamoorthy, Pugazhenthiran, Nalandhiran, Salvo, Christopher, Anandan, Sambandam, Mangalaraja, Ramalinga
The goethite (α-FeOOH) nanoparticles were wrapped on the reduced graphene oxide (rGO) to synthesize the α-FeOOH/rGO nanocomposites. The nanocomposites (NCs) were initially examined for their optical, structural, and morphological properties. The XRD data obtained the crystallite size of the α-FeOOH, showed that the average crystal size for pristine α-FeOOH and α-FeOOH/rGO nanocomposites were about 85 and 90 nm, respectively. The transmission electron microscope confirmed the nanoparticles (NPs) were evenly distributed throughout the reduced graphene oxide sheets. The nanocomposites improved glassy carbon electrodes (GCE), making them efficient sensors for detecting the arsenic(III) (As+3) in a pH 5 phosphate buffer solution with an Ag/AgCl reference electrode. The detection limit for As+3 was 0.07 μgL−1 and the resulting sensitivity was 0.39 μA−1 μgL−1 in the linear dynamic range of 0.1–10 μgL−1. The α-FeOOH/rGO/GCE was more sensitive than its original and showed a synergistic effect due to the influence of α-FeOOH on the properties of rGO. The α-FeOOH/rGO NCs-modified GCE electrode performed as a promising sensor, by separating the common interfering ions. Moreover, the modified electrode exhibited remarkable stability, repeatability, and potential real-time application towards the detection of arsenic(III). Additionally, the proposed approach has been successfully applied to the detection of As+3 in the real water sample.
Enhanced photocatalytic degradation of ZnTiO3/Polycarbazole (PCz) composite towards toxic azo dye
2023, Jeffrey Joseph John Jeya Kamaraj, Padmanaban,Annamalai, Lawrence Daniel Stephen Tamil, Senthil Pandian Muthu, Ramasamy Perumalsamy, Dr. Valdés-Morales, Héctor
The ZnTiO3 material was synthesized by sol–gel method with the assistance of ethanol as solvent. The oxidative polymerization method was used to synthesize polycarbazole (PCz). The ball milling technique was employed to synthesize the mechanically composited nanoparticles—ZnTiO3/PCz nanocomposite. The synthesized composites were analysed using powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectrum (XPS), UV–Vis absorption spectrum (UV–Vis), scanning electron microscope (SEM), and high-resolution transmission electron microscope (HRTEM). The degradation of crystal violet (CV) in water under visible-light irradiation was used to assess the photocatalytic behaviour of the synthesized catalyst. The result shows that the ZnTiO3/PCz composites exhibit greater photocatalytic activity than other materials. Polycarbazole in composite material acts as an electron reservoir, actively trapping the photogenerated electrons which considerably lowers the probability of recombination and increases the degrading effect of the catalyst.
Ferrihydrite − Graphene oxide foams as an efficient adsorbent for Arsenic(III) removal from an aqueous solution
2023, Dr. Valdés-Morales, Héctor, Shanmugaraj, Krishnamoorthy, Vinoth, Victor, Pugazhenthiran, Nalandhiran, Salvo, Christopher, Sepúlveda, Erwin, Viswanathan-Mangalaraja, Ramalinga
We report the synthesis of a new range of ferrihydrite-graphene oxide (FH-GO) foams using chitosan as cross linker, with varying iron content (5 wt%, 10 wt%, and 20 wt% of FH) as highly efficient adsorbents for the removal of arsenic (III) (As(III)) in an aqueous solution. The sonochemical methods were adopted to synthesize various FH-GO foams and were further characterized by XRD, SEM, TEM, FTIR, Raman, and XPS techniques. The synthesized materials were used for the removal of As(III) in both batch and fixed bed absorbent column methods. The adsorption isotherm results showed that the 10 wt% of FH-GO foams demonstrated a superior adsorbent for the As(III) with high adsorption capacities than that of the other two FH-GO foams (5 wt% and 20 wt% of FH). Moreover, 10 wt% of FH-GO foams was also demonstrated to be nearly a complete (>98.4%) removal of As(III) ions at neutral pH 7. The adsorption isotherm fitted very well with the Langmuir model with the highest accuracy data for all the synthesized adsorbent materials. In addition, the fixed bed absorbent column method was also adopted for the removal of As(III) ions in the water sample, which showed > 99.2% of removal efficiency. The outstanding adsorption capabilities, along with their easy and low-cost synthesis, make these kinds of adsorbents extremely capable for commercial applications in wastewater treatment and drinking water purification.