Project description:The photoreduction for hazardous Cr(VI) in industrial wastewater has been considered a "green" approach with low-cost and easy-to-go operation. SnS2 is a promising narrow bandgap photocatalyst, but its low charge carrier separation efficiency should be solved first. In this work, N-doped carbon quantum dots (CQDs) were prepared and loaded onto SnS2 nanoparticles via an in situ method. The resulting composite samples (NC@SnS2) were characterized, and their photocatalytic performance was discussed. SnS2 nanoparticles were obtained as hexagonal ones with a bandgap of 2.19 eV. The optimal doping level for NC@SnS2 was citric acid: urea:SnS2 = 1.2 mmol:1.8 mmol:3.0 mmol. It showed an average diameter of 40 nm and improved photocatalytic performance, compared to pure SnS2, following a pseudo-first-order reaction with a kinetic rate constant of 0.1144 min-1. Over 97% of Cr(VI) was photo-reduced after 30 min. It was confirmed that modification of SnS2 with CQDs can not only improve the light-harvesting ability but also stimulate the charge separation, which therefore can enhance the photoreactivity of SnS2 toward Cr(VI) reduction. The excellent stability of NC@SnS2 indicates that it is promising to be practically used in industrial wastewater purification.
Project description:The Maillard reaction involves a series of complex reactions; fluorescent compounds have been considered as vital intermediate products of the reaction. In this article, carbon dots (CDs) based on the Maillard reaction (MR-CDs) were prepared with L-tryptophan and D-glucose, and they had excellent photoluminescence stability. MR-CDs showed stable pH-dependence behavior and exhibited an excellent linear response to pH in the range of 4.0-7.5 and 7.5-13.0, respectively. Under the masking effect of sodium fluoride for Fe(III), MR-CDs showed excellent selectivity and sensitivity for Cr (VI). The linear range of Cr(VI) was 0.2-50 μM and the limit of detection was 20 nM. (S/N ≥ 3). Furthermore, MR-CDs were used to detect Cr(VI) in tap water samples. The recoveries were between 95.8% and 98.94%, and RSDs were less than 3.17%.
Project description:Hexavalent chromium is a contaminant of concern and is found in drinking water supplies. Electrochemical methods are well-suited to accomplish the reduction of toxic Cr(VI) to Cr(III). However, high overpotentials and plating of Cr(III) products on electrodes have stymied the development of efficacious purification methods. The Cr(VI) reduction reaction necessitates the transfer of multiple protons and electrons, which is accompanied by a high kinetic barrier. Following recent advances in the electrocatalytic energy storage community, we report that the use of [Fe(CN)6]3- as a small molecular electrocatalyst not only diminishes the overpotential for Cr(VI) reduction on carbon electrodes by 0.575 V, but also prevents electrode fouling by mediating solution-phase homogeneous electron transfers.
Project description:In recent years, carbon dots (CDs) are promising fluorescence probes for ions detection. In this paper, the CDs which are with an average diameter of 5.5 nm were synthesized through a simple one-step hydrothermal carbonization of ethylene diamine tetraacetic acid (EDTA) salt. The CDs have strong yellow photoluminescence (PL) with a maximum emission intensity at 550 nm under an excitation wavelength of 450 nm. As the electron transfer will occur between Cr (VI) and the CDs, yellow fluorescence was quenched after adding the Cr (VI) ions. The CDs probe allows the detection of Cr (VI) ions over a concentration range from 0 to 0.1 M (R 2 = 0.987) and the lower detection limit is 10-5 M. Simultaneously, the CDs show highly selectivity and stability toward the detection of Cr (VI) ions.
Project description:Although density functional theory (DFT) calculations have been crucial in our understanding of colloidal quantum dots (QDs), simulations are commonly carried out on QD models that are significantly smaller than those generally found experimentally. While smaller models allow for efficient study of local surface configurations, increasing the size of the QD model will increase the size or number of facets, which can in turn influence the energetics and characteristics of trap formation. Moreover, core-shell structures can only be studied with QD models that are large enough to accommodate the different layers with the correct thickness. Here, we use DFT calculations to study the electronic properties of QDs as a function of size, up to a diameter of ∼4.5 nm. We show that increasing the size of QD models traditionally used in DFT studies leads to a disappearance of the band gap and localization of the HOMO and LUMO levels on facet-specific regions of the QD surface. We attribute this to the lateral coupling of surface orbitals and the formation of surface bands. The introduction of surface vacancies and their a posteriori refilling with Z-type ligands leads to surface reconstructions that widen the band gap and delocalize both the HOMO and LUMO. These results show that the surface geometry of the facets plays a pivotal role in defining the electronic properties of the QD.
Project description:The development of stable fluorescent sensors for toxic pollutants and drugs is meaningful to the environment and public health. In this work, nitrogen-doped graphene quantum dots (N-GQDs) were facially synthesized by a one-step hydrothermal method using soluble starch and l-arginine as carbon and nitrogen sources in pure water at 190 °C for 4 h. The as-synthesized N-GQDs were well characterized and displayed blue fluorescence emission at 445 nm with excellent pH stability, salt tolerance, thermostability, photobleaching resistance and reproducibility. Moreover, N-GQDs could serve as an "on-off" sensor for selective detection of Cr(vi) and folic acid with low detection limit (0.80 and 2.1 μM), good linear correlation over wide linear range (0-50 μM and 0-200 μM) as well as short response time (<10 s). The practical applications of N-GQDs for Cr(vi) and folic acid detection in actual samples were further investigated and showed acceptable recoveries (92-105%) with relative standard deviations less than 5%. These results indicated that this N-GQDs-based sensor could be a potential alternative for Cr(vi) and folic acid detection in the fields of environmental monitoring and drug analysis.
Project description:The development of a fluorescent sensor has attracted much attention for the detection of various toxic pollutants in the environment. In this work, fluorescent carbon dots (N,Zn-CDs) doped with nitrogen and zinc were synthesized using citric acid monohydrate and 4-pyridinecarboxyaldehyde as carbon and nitrogen sources, respectively. The synthesized N,Zn-CDs served as an “off” fluorescence detector for the rapid and sensitive detection of hexavalent chromium ions (Cr(VI)). The zinc metal integrated into the heteroatomic fluorescent carbon dot played a functional role by creating a coordination site for the hydrogen ions that were displaced after the addition of Cr to the solution matrix. The stepwise addition of Cr(VI) effectively quenched the fluorescence intensity of the N,Zn-CDs, and this phenomenon was attributed to the internal filter effect. A low detection limit of 0.47 nmol/L for Cr(VI) was achieved in the fluorescence experiments. Real water samples were used to evaluate the practical application of N,Zn-CDs for the quantification of Cr(VI). The results show acceptable recoveries and agreement with ion chromatography-ultraviolet spectrometry results. These good recoveries indicate that the fluorescence probe is very well suited for environmental measurements.
Project description:Due to its lethal effect on the human body and other creatures, Cr(VI) ions have attained widespread public attention, and an effective adsorbent for removing Cr(VI) ions is vital. Chitosan (CS)/cellulose nanocrystals grafted with carbon dots (CNCD) composite hydrogel with strong sorption ability and sensitive detection ability for Cr(VI) was formed. The cellulose nanocrystals (CN) offered a natural skeleton for assembling 3D porous structures, and then improved the sorption ability for Cr(VI); moreover, carbon dots (CD) acted as a fluorescent probe for Cr(VI) and provided Cr(VI) adsorption sites. With a maximum adsorption capacity of 217.8 mg/g, the CS/CNCD composite hydrogel exhibited efficient adsorption properties. Meanwhile, with a detection limit of 0.04 μg/L, this hydrogel was used for selective and quantitative detection of Cr(VI). The determination of Cr(VI) was based on the inner filter effect (IFE) and static quenching. This hydrogel retained its effective adsorption ability even after four repeated regenerations. Furthermore, the economic feasibility of the CS/CNCD composite hydrogel over activated carbon was confirmed using cost analysis. This study provided one new method for producing low-cost adsorbents with effective sorption and sensitive detection for Cr(VI).
Project description:The photocatalytic reduction of Cr(VI) is investigated over iron(III)-based metal-organic frameworks (MOFs) structured as MIL-88B. It is found that MIL-88B (Fe) MOFs, containing Fe3-μ3-oxo clusters, can be used as photocatalyst for the reduction of Cr(VI) under visible light irradiation, which is due to the direct excitation of Fe3-μ3-oxo clusters. The amine-functionalized MIL-88B (Fe) MOFs (denoted as NH2-MIL-88B (Fe)) shows much higher efficiency for the photocatalytic Cr(VI) reduction under visible-light irradiation compared with MIL-88B (Fe). It is revealed that in addition to the direct excitation of Fe3-μ3-oxo clusters, the amine functionality in NH2-MIL-88B (Fe) can also be excited and then transferred an electron to Fe3-μ3-oxo clusters, which is responsible for the enhanced photocatalytic activity for Cr(VI) reduction. The enhanced photocatalytic activity for Cr(VI) reduction is also achieved for other two amine-functionalized iron(III)-based MOFs (NH2-MIL-53 (Fe) and NH2-MIL-101 (Fe)).
Project description:Hydrolysed polyacrylamide (HPAM) is widely used in many industrial fields where its rheological properties play a leading role. Recent discovery of the reduction of HPAM's viscosity by adding carbon quantum dots (CQDs), however, is controversial to the established theories. By using all atom molecular dynamics simulation with an OPLS-AA force field, this study aims to provide detailed molecular insight into such an uncommon phenomenon. The dynamic structures of the HPAM chain in the presence or absence of CQDs were clearly captured from the molecular aspect. The results reveal that the adsorption of CQD reduces the gyration radius of the HPAM chain, and it is the corresponding hydration effect that leads to the reduction of the viscosity. The amide rather than the carboxylate group along the HPAM chain is dominant in terms of the interaction with the CQDs, and the driven atoms depend on the surface where the polymer is adsorbed.