Hierarchical Ti-MOF Microflowers for Synchronous Removal and Fluorescent Detection of Aluminum Ions.

Bifunctional luminescence metal-organic frameworks with unique nanostructures have drawn ongoing attention for simultaneous determination and elimination of metal ions in the aqueous environment, but still remain a great challenge. In this work, three-dimensional hierarchical titanium metal-organic framework (Ti-MOF) microflowers were developed by a secondary hydrothermal method for not only highly sensitive and selective detection of Al(III), but also simultaneously efficient decontamination. The resulting Ti-MOF microflowers with a diameter of 5-6 µm consisted of nanorods with a diameter of ∼200 nm and a length of 1-2 µm, which provide abundant, surface active sites for determination and elimination of Al(III) ions. Because of their substantial specific surface area and superior fluorescence characteristics, Ti-MOF microflowers are used as fluorescence probes for quantitative determination of Al(III) in the aqueous environment. Importantly, the specific FL enhancement by Al(III) via a chelation-enhanced fluorescence mechanism can be utilized for selective and quantitative determination of Al(III). The Al(III) detection has a linear range of 0.4-15 µM and a detection limit as low as 75 nM. By introducing ascorbic acid, interference of Fe(III) can be avoided to achieve selective detection of Al(III) under various co-existing cations. It is noteworthy that the Ti-MOF microflowers exhibit excellent adsorption capacity for Al(III) with a high adsorption capacity of 25.85 mg g-1. The rapid adsorption rate is consistent with a pseudo-second order kinetic model. Ti-MOF is a promising contender as an adsorbent and a fluorescent chemical sensor for simultaneous determination and elimination of Al(III) due to its exceptional water stability, high porosity, and intense luminescence.

High Electrochemical Sensitivity of TiO2- x Nanosheets and an Electron-Induced Mutual Interference Effect toward Heavy Metal Ions Demonstrated Using X-ray Absorption Fine Structure Spectra.

Mutual interference is a severe issue that occurs during the electrochemical detection of heavy metal ions. This limitation presents a notable drawback for its high sensitivity to specific targets. Here, we present a high electrochemical sensitivity of ∼237.1 µA cm-2 µM-1 toward copper(II) [Cu(II)] based on oxygen-deficient titanium dioxide (TiO2- x) nanosheets. We fully demonstrated an atomic-level relationship between electrochemical behaviors and the key factors, including the high-energy (001) facet percentage, oxygen vacancy concentration, surface -OH content, and charge carrier density, is fully demonstrated. These four factors were quantified using Raman, electron spin resonance, X-ray photoelectron spectroscopy spectra, and Mott-Schottky plots. In the mutual interference investigation, we selected cadmium(II) [Cd(II)] as the target ion because of the significant difference in its stripping potential (∼700 mV). The results show that the Cd(II) can enhance the sensitivity of TiO2- x nanosheets toward Cu(II), exhibiting an electron-induced mutual interference effect, as demonstrated by X-ray absorption fine structure spectra.

Selective Determination of Cr(VI) by Glutaraldehyde Cross-Linked Chitosan Polymer Fluorophores.

Selective determination of aquatic chromium is critically important because of the dramatic differences in health and environment impacts by trivalent and hexavalent forms of chromium; however, it is challenging. In this work, for the first time, a nonconjugated polymer fluorophore (GCPF) was synthesized by cross-linking chitosan with glutaraldehyde via Schiff base reactions and systematically investigated for selective determination of Cr(VI). The results revealed that the synthesized GCPF exhibited excellent photostability and water solubility. More importantly, GCPF possessed dramatically enhanced fluorescence intensity originated from the n-π* transitions of the Schiff base subfluorophore groups (e.g., C═N) that can be selectively and sensitively quenched by Cr(VI) through oxidative damages to C═N group. An effective EDTA masking agent approach was employed to minimize ionic interferences. In the presence of high concentration of interference ions including Cr(III), the quenching GCPF fluorescence is capable of selectively determining Cr(VI) within a concentration range up to 50 µM and a detection limit of 0.22 µM. The analytical performance of GCPF was also confirmed by analyzing real surface water and industrial samples.

Surface-Electronic-State-Modulated, Single-Crystalline (001) TiO2 Nanosheets for Sensitive Electrochemical Sensing of Heavy-Metal Ions.

Intrinsically low conductivity and poor reactivity restrict many semiconductors from electrochemical detection. Usually, metal- and carbon-based modifications of semiconductors are necessary, making them complex, expensive, and unstable. Here, for the first time, we present a surface-electronic-state-modulation-based concept applied to semiconductors. This concept enables pure semiconductors to be directly available for ultrasensitive electrochemical detection of heavy-metal ions without any modifications. As an example, a defective single-crystalline (001) TiO2 nanosheet exhibits high electrochemical performance toward Hg(II), including a sensitivity of 270.83 µA µM-1 cm-2 and a detection limit of 0.017 µM, which is lower than the safety standard (0.03 µM) of drinking water established by the World Health Organization (WHO). It has been confirmed that the surface oxygen vacancy adsorbs an O2 molecule while the Ti3+ donates an electron, forming the O2•- species that facilitate adsorption of Hg(II) and serve as active sites for electron transfer. These findings not only extend the electrochemical sensing applications of pure semiconductors but also stimulate new opportunities for investigating atom-level electrochemical behaviors of semiconductors by surface electronic-state modulation.

A nanoparticulate liquid binding phase based DGT device for aquatic arsenic measurement.

A nanomaterials-based DGT device constructed with commercial dialysis membrane as diffusive layer and nanoparticulate Fe3O4 aqueous suspension as binding phase is developed and validated for in situ aquatic arsenic measurement. The Fe3O4NPs binding phase is capable of quantitatively accumulated both As(III) and As(V) species. As(III) and As(V) species coexist in the vast majority of environmental water samples. The large difference in diffusion coefficients of As(III) (DAs(III)=3.05×10(-7)cm(2)s(-1)) and As(V) (DAs(V)=1.63×10(-7)cm(2)s(-1)) makes the accurate DGT determination of total arsenic concentration of samples containing both species difficult. An effective diffusion coefficient (DAs¯=DAs(III)[1/(1+x)]+DAs(V)[x/(1+x)],where,x=As(V)/As(III)) approach is therefore proposed and validated for accurate DGT determination of total arsenic when As(III) and As(V) coexist. The experimental results demonstrate that for samples having As(V)/As(III) ratios between 0.1 and 0.9, the DGT determined total arsenic concentrations using DAs¯are within ±93-99% of that determined by ICP-MS. The general principle demonstrated in this work opens up a new avenue of utilizing functional nanomaterials as DGT binding phase, paving a way for developing new generation nanomaterials-based DGT devices that can be readily produced in massive numbers at low costs, facilitating the widespread use of DGT for large-scale environmental assessment and other applications.