Electrochemical, theoretical, and analytical investigation of the phenylurea herbicide fluometuron at a glassy carbon electrode

Sousa, Kelline Alaide Pereira; Morawski, Franciele de Matos; Campos, Carlos Eduardo Maduro de; Parreira, Renato L.T.; Piotrowski, Maurício J.; Nagurniak, Glaucio Régis; Jost, Cristiane Luisa

doi:10.1016/j.electacta.2022.139945

Cited by 16 publications

(17 citation statements)

References 55 publications

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“…and O 2 ). For all mol/clu systems, we have calculated the binding and adsorption energies considering an alternative way presented in our previous works, [75][76][77] where the usual expressions based on the total energies from individual constituents are written equivalently considering the relaxation energies from the molecular adsorption and the interaction energy between mol and clu upon relaxation, that is, taking into account the magnitude of the mol-clu interplay. Thus, the interaction energy per molecule (ΔE int ) is given by:…”

Section: Structural and Energetic Analysesmentioning

confidence: 99%

“…In that case, we have a situation where the reactant interacts very strongly with the catalyst surface and leads to a low reaction rate due to reactant poisoning, which can lead to a possible molecular dissociation represented by higher distortion energy magnitudes. 77 In our case, it would be equivalent to considering that the metal metal bond (from catalystcluster) or X Y bond (from adsorbatemolecule) has a smaller interaction magnitude than the metal-X interaction (X = C, N, O), compromising the nanocluster and/or molecule integrity after molecular interaction and making the desorption process unfeasible (effectively inhibiting further reactions).…”

Section: Energetic Analysismentioning

confidence: 99%

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Molecular adsorption on coinage metal subnanoclusters: ADFT+D3investigation

et al. 2022

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Gold and silver subnanoclusters with few atoms are prominent candidates for catalysis‐related applications, primarily because of the large fraction of lower‐coordinated atoms exposed and ready to interact with external chemical species. However, an in‐depth energetic analysis is necessary to characterize the relevant terms within the molecular adsorption process that can frame the interactions within the Sabatier principle. Herein, we investigate the interaction between Agn and Aun subnanoclusters (clu, n = 2–7) and N2, NO, CO, and O2 molecules, using scalar‐relativistic density functional theory calculations within van der Waals D3 corrections. The onefold top site is preferred for all chemisorption cases, with a predominance of linear (≈180°) and bent (≈120°) molecular geometries. A larger magnitude of adsorption energy is correlated with smaller distances between molecules and clusters and with the weakening of the adsorbates bond strength represented by the increase of the equilibrium distances and decrease of molecular stretching frequencies. From the energetic decomposition, the interaction energy term was established as an excellent descriptor to classify subnanoclusters in the adsorption/desorption process concomitant with the Sabatier principle. The limiting cases: (i) weak molecular adsorption on the subnanoclusters, which may compromise the reaction activation, where an interaction energy magnitude close to 0 eV is observed (e.g., physisorption in N2/Ag6); and (ii) strong molecular interactions with the subnanoclusters, given the interaction energy magnitude is larger than at least one of the individual fragment binding energies (e.g., strong chemisorption in CO/Au4 and NO/Au4), conferring a decrease in the desorption rate and an increase in the possible poisoning rate. However, the intermediate cases are promising by involving interaction energy magnitudes between zero and fragment binding energies. Following the molecular closed‐shell (open‐shell) electronic configuration, we find a predominant electrostatic (covalent) nature of the physical interactions for N2 ⋯clu and CO ⋯clu (O2⋯clu and NO⋯clu), except in the physisorption case (N2/Ag6) where dispersive interaction is dominant. Our results clarify questions about the molecular adsorption on subnanoclusters as a relevant mechanistic step present in nanocatalytic reactions.

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Section: Structural and Energetic Analysesmentioning

confidence: 99%

Section: Energetic Analysismentioning

confidence: 99%

Molecular adsorption on coinage metal subnanoclusters: ADFT+D3investigation

et al. 2022

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“…Moreover, the square root of the scan rate ( ν 1/2 ) and I pa had a good linear relationship (Figure B). The linear equation could be expressed as I pa (μA) = 2.27 ν 1/2 – 11.9 ( R 2 = 0.995), proving that the kinetic reaction mechanism was mainly controlled by a diffusion process …”

Section: Resultsmentioning

confidence: 99%

“…The linear equation could be expressed as I pa (μA) = 2.27 ν 1/2 − 11.9 (R 2 = 0.995), proving that the kinetic reaction mechanism was mainly controlled by a diffusion process. 44 Furthermore, the anodic peak potential (E pa ) was proportional to the natural logarithm of scan rate (In ν) (Figure 4C), and the linear equation was E pa (V) = 0.035 In ν + 1.05 (R 2 = 0.996). According to Lavilon's approach, 45 α is generally defined to be 0.5 in the irreversible redox reaction, and the electron transfer number (n) for the DU redox reaction is estimated to be 2.…”

Section: Verification Of the Feasibility Of The Du-mip-ec Sensormentioning

confidence: 99%

Molecularly Imprinted Electrochemical Sensor Based on the Self-Assembly of Cage-like Gold Nanoparticles and Amino-Functionalized rGO for the Detection of Diuron in Cotton Defoliant

He,

Bi,

Liu

et al. 2024

ACS Agric. Sci. Technol.

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Diuron (DU) is a kind of cotton defoliant with high toxicity and strong persistence that poses a serious environmental threat. DU has electroactive inertness and oxidation resistance, and there are only a few types of recognition elements, making its sensitive and specific detection critical. Herein, a novel molecularly imprinted polymer-based electrochemical (MIP-EC) sensor was developed by combing gold nanocages (AuNCs) with hollow-interior and porous walls with amino-functionalized reduced graphene oxide nanosheets (NH2-rGO) with a large surface area and excellent conductivity. Then, DU-MIP was directly grown on the modified electrode by electropolymerization, while it displayed a high imprinted factor (6.91) and high reusability (at least 5 times). Significantly, the NH2-rGO/AuNC nanocomposite could also enhance the recognition efficiency of DU-MIP, improving the analytical performances of the MIP-EC sensor, with the detection limit down to 4.3 ng/mL. In addition, this sensor exhibited high selectivity and rapid elution/recombination, and a simple construction process was utilized to detect DU in cotton and soil.

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“…The latter exhibits symmetry reduction, with one of the C−C distances (1.98 Å) being smaller than the other two (2.55 Å), accompanied by m T = 1.5 μ B , in excellent agreement with previous studies. 44,60 From the MVG substrate, we constructed ODG and NDG configurations, where O and N atoms were adsorbed near the vacancy region. The most stable results were obtained when O and N atoms became substitutional, occupying the removed C atom position.…”

Section: Theoretical Results 311 Analyte and Substratesmentioning

confidence: 99%

Quantum Simulations and Experimental Insights into Glyphosate Adsorption Using Graphene-Based Nanomaterials

S. Araújo,

Caldeira Rêgo,

Guedes-Sobrinho

et al. 2024

ACS Appl. Mater. Interfaces

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The increasing global demand for food and agrarian development brings to light a dual issue concerning the use of substances that are crucial for increasing productivity yet can be harmful to human health and the environment when misused. Herein, we combine insights from high-level quantum simulations and experimental findings to elucidate the fundamental physicochemical mechanisms behind developing graphene-based nanomaterials for the adsorption of emerging contaminants, with a specific focus on pesticide glyphosate (GLY). We conducted a comprehensive theoretical and experimental investigation of graphene-based supports as promising candidates for detecting, sensing, capturing, and removing GLY applications. By combining ab initio molecular dynamics and density functional theory calculations, we explored several chemical environments encountered by GLY during its interaction with graphene-based substrates, including pristine and punctual defect regions. Our results unveiled distinct interaction behaviors: physisorption in pristine and doped graphene regions, chemisorption leading to molecular dissociation in vacancy-type defect regions, and complex transformations involving the capture of N and O atoms from impurity-adsorbed graphene, resulting in the formation of new GLY-derived compounds. The theoretical findings were substantiated by FTIR and Raman spectroscopy, which proposed a mechanism explaining GLY adsorption in graphene-based nanomaterials. The comprehensive evaluation of adsorption energies and associated properties provides valuable insights into the intricate nature of these interactions, shedding light on potential applications and guiding future experimental investigations of graphene-based nanofilters for water decontamination.

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Electrochemical, theoretical, and analytical investigation of the phenylurea herbicide fluometuron at a glassy carbon electrode

Cited by 16 publications

References 55 publications

Molecular adsorption on coinage metal subnanoclusters: ADFT+D3investigation

Molecular adsorption on coinage metal subnanoclusters: ADFT+D3investigation

Molecularly Imprinted Electrochemical Sensor Based on the Self-Assembly of Cage-like Gold Nanoparticles and Amino-Functionalized rGO for the Detection of Diuron in Cotton Defoliant

Quantum Simulations and Experimental Insights into Glyphosate Adsorption Using Graphene-Based Nanomaterials

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