Revealing the solid-solution interface interference behaviors between Cu2+ and As(III) via partial peak area analysis of simulations and experiments.

The mutual interference in the sensing detection of heavy metal ions (HMIs) is considerably serious and complex. Besides, the co-existed ions may change the stripping peak intensity, shape and position of the target ion, which partly makes peak current analysis inaccurate. Herein, a promising approach of partial peak area analysis was proposed firstly to research the mutual interference. The interference between two species on their electrodeposition processes was investigated by simulating different kinetics parameters, including surface coverage, electro-adsorption, -desorption rate constant, etc. It was proved that the partial peak area is sensitive and regular to these interference kinetics parameters, which is favorable for distinctly identifying different interferences. Moreover, the applicability of the partial peak area analysis was verified on the experiments of Cu2+, As(III) interference at four sensing interfaces: glassy carbon electrode, gold electrode, Co3O4, and Fe2O3 nanoparticles modified electrodes. The interference behaviors between Cu2+ and As(III) relying on solid-solution interfaces were revealed and confirmed by physicochemical characterizations and kinetics simulations. This work proposes a new descriptor (partial peak area) to recognize the interference mechanism and provides a meaningful guidance for accurate detection of HMIs in actual water environment.

Practical Strategy for Arsenic(III) Electroanalysis without Modifier in Natural Water: Triggered by Iron Group Ions in Solution.

Significant progress has been made in nanomaterial-modified electrodes for highly efficient electroanalysis of arsenic(III) (As(III)). However, the modifiers prepared using some physical methods may easily fall off, and active sites are not uniform, causing the potential instability of the modified electrode. This work first reports a promising practical strategy without any modifiers via utilizing only soluble Fe3+ as a trigger to detect trace-level As(III) in natural water. This method reaches an actual detection limit of 1 ppb on bare glassy carbon electrodes and a sensitivity of 0.296 µA ppb-1 with excellent stability. Kinetic simulations and experimental evidence confirm the codeposition mechanism that Fe3+ is preferentially deposited as Fe0, which are active sites to adsorb As(III) and H+ on the electrode surface. This facilitates the formation of AsH3, which could further react with Fe2+ to produce more As0 and Fe0. Meanwhile, the produced Fe0 can also accelerate the efficient enrichment of As0. Remarkably, the proposed sensing mechanism is a general rule for the electroanalysis of As(III) that is triggered by iron group ions (Fe2+, Fe3+, Co2+, and Ni2+). The interference analysis of coexisting ions (Cu2+, Zn2+, Al3+, Hg2+, Cd2+, Pb2+, SO42-, NO3-, Cl-, and F-) indicates that only Cu2+, Pb2+, and F- showed inhibitory effects on As(III) due to the competition of active sites. Surprisingly, adding iron power effectively eliminates the interference of Cu2+ in natural water, achieving a higher sensitivity for 1-15 ppb As(III) (0.487 µA ppb-1). This study provides effective solutions to overcome the potential instability of modified electrodes and offers a practical sensing platform for analyzing other heavy-metal anions.

Highly Sensitive and Stable Determination of As(III) under Near-Neutral Conditions: Benefit from the Synergetic Catalysis of Pt Single Atoms and Active S Atoms over Pt1/MoS2.

Designing new catalysts with high activity and stability is crucial for the effective analysis of environmental pollutants under mild conditions. Here, we developed a superior catalyst of Pt single atoms anchored on MoS2 (Pt1/MoS2) to catalyze the determination of As(III). A detection sensitivity of 3.31 µA ppb-1 was obtained in acetate buffer solution at pH 6.0, which is the highest compared with those obtained by other Pt-based nanomaterials currently reported. Pt1/MoS2 exhibited excellent electrochemical stability during the detection process of As(III), even in the coexistence of Cu(II), Pb(II), and Hg(II). X-ray absorption fine structure spectroscopy and theoretical calculations revealed that Pt single atoms were stably fixed by four S atoms and activated the adjacent S atoms. Then, Pt and S atoms synergistically interacted with O and As atoms, respectively, and transferred some electrons to H3AsO3, which change the rate-determining step of H3AsO3 reduction and reduce reaction energy barriers, thereby promoting rapid and efficient accumulation for As(0). Compared with Pt nanoparticles, the weaker interaction between arsenic species and Pt1/MoS2 enabled the effortless regeneration and cyclic utilization of active centers, which is more favorable for the oxidation of As(0). This work provides inspiration for developing highly efficient sensing platforms from the perspective of atomic-level catalysis and affords references to explore the detection mechanism of such contaminants.

Au25 Nanoclusters Exhibit Superhigh Catalytic Activity in Electrochemical Detection of As(III).

An atomic-level Au nanocluster, as an excellent photocatalyst, is generally not considered as an efficient electrocatalyst due to its poor stability. Herein, a method is proposed to stabilize abundant Au25 on Fe2O3 nanoplates (Au25/OV-Fe2O3) successfully with oxygen vacancies (OV) created. Au25/OV-Fe2O3 shows superhigh catalysis in the electrochemical reduction toward As(III). The record-breaking sensitivity (161.42 µA ppb-1) is two orders of magnitude higher than currently reported, where an ultratrace limit of detection (9 ppt) is obtained, suggesting promising applications in the analysis of organic and bioactive substances. The stability of Au25 is attributed to the Au-Fe bond formed after loading Au25 nanoclusters on Fe2O3 nanoplates through "electron compensation" and bond length (Au-S) shortening. Moreover, the ligand S atoms in Au25 nanoclusters significantly contribute to the reduction of As(III). The fantastic stability and superior catalytic ability of Au25/OV-Fe2O3 provide guidelines to stabilize Au nanoclusters on metal oxides, indicating their potential electroanalytical applications.

Boosting sensitive and selective detection toward Pb(II) via activation effect of Co and orbital coupling between Pb and O over Co@Co3O4 nanocatalyst.

Fruitful achievements on electrochemical detection toward Pb(II) have been achieved, and their good performance is generally attributed to the adsorption property of nanomaterials. However, the design of sensing interfaces from the electronic structure and electron transfer process is limited. Here, Co@Co3O4 acquired an ultra-high detection sensitivity of 103.11 µA µM-1 toward Pb(II), outperforming the results previously reported. The interfacial oxygen atoms build an electron bridge for Co activating Co3O4. Particularly, new energy levels of oxygen atoms were generated and matched with that of Pb(II). The strong orbital coupling effect between O and Pb makes the Co@Co3O4 sensitive and selective toward Pb(II). Compared with Co metal and Co3O4, Pb(II) got more electrons from Co@Co3O4, and longer Pb-O bonds were formed, allowing more Pb(II) to be catalyzed and reduced. Also, the superior stability and reproducibility of electrochemical detection make electrodes practicably. This work reveals that metals can stimulate intrinsically catalytic activity of their metal oxides, with the generation of orbit energy levels that match to a specific analyte. It provides a promising strategy for constructing sensitive and selective sensing interfaces toward ultra-low concentration analyte in body fluid and other complex samples.

Close band center and rapid adsorption kinetics facilitate selective electrochemical sensing of heavy metal ions.

Combining density functional theory calculation with experiments and kinetics simulation, a multiscale framework describing the influence of reactant-substrate interaction on electrochemical performance was proposed. It was found that the close band center and the rapid adsorption kinetics facilitated the highly selective response of Ni(111) toward Cu(ii), providing a useful tactic to investigate the mechanism of electro-selectivity. This work not only verified that the interaction strength in the ex situ conditions, and kinetics rate could be applied to evaluate the electrochemical selectivity, but also contributed to the options and forecasting of selective electrode materials for heavy metal ions.

Zero-valent iron nanomaterial Fe0@Fe2MnO4 for ultrasensitive electroanalysis of As(iii): Fe0 influenced surficial redox potential.

A novel zero-valent iron nanomaterial (Fe0@Fe2MnO4) was synthesized and achieved an ultrasensitive electrochemical detection of As(iii). It was found that the enhanced sensitivity is attributed to the surficial catalytic redox couple Fe(ii)/Fe(iii) induced by Fe0 of Fe0@Fe2MnO4. Besides, the catalytic kinetics was modelled and simulated, and the strong influence of the oxidation potential of the catalytic redox species on sensitivity was revealed. By tailoring the surficial atomic and electronic structures of the material, the redox potential can be altered, which can be used for controlling the electro-sensitivity and selectivity in electroanalysis.

Nanometal Oxides with Special Surface Physicochemical Properties to Promote Electrochemical Detection of Heavy Metal Ions.

Heavy metal ions (HMIs) are one of the major environmental pollution problems currently faced. To monitor and control HMIs, rapid and reliable detection is required. Electrochemical analysis is one of the promising methods for on-site detection and monitoring due to high sensitivity, short response time, etc. Recently, nanometal oxides with special surface physicochemical properties have been widely used as electrode modifiers to enhance sensitivity and selectivity for HMIs detection. In this work, recent advances in the electrochemical detection of HMIs using nanometal oxides, which are attributed to specific crystal facets and phases, surficial defects and vacancies, and oxidation state cycle, are comprehensively summarized and discussed in aspects of synthesis, characterization, electroanalysis application, and mechanism. Moreover, the challenges and opportunities for the development and application of nanometal oxides with functional surface physicochemical properties in electrochemical determination of HMIs are presented.

Ultra-Sensitive and Selective Detection of Arsenic(III) via Electroanalysis over Cobalt Single-Atom Catalysts.

Achieving highly sensitive and selective detection of trace-level As(III) and clarifying the underlying mechanism is still a intractable problem. The electroanalysis of As(III) relies on the electrocatalytic ability of the sensing interface. Herein, we first adopt single-atom catalysts as the electrocatalyst in As(III) detection. Cobalt single-atoms anchored on nitrogen-doped carbon material (Co SAC) were found to have an extraordinary sensitivity of 11.44 µA ppb-1 with excellent stability and repeatability, which so far is the highest among non-noble metal nanomaterials. Co SAC also exhibited a superior selectivity toward As(III) compared with some bivalent heavy metal ions (HMIs). Combining X-ray absorption spectroscopy (XAFS), density functional theory (DFT) calculation, and reaction kinetics simulation, we demonstrated that Co single atoms stabilized in N2C2 support serve as active sites to catalyze H3AsO3 reduction via the formation of Co-O hybridization bond, leading to a lower energy barrier, promoting the breakage of As-O bonds. Importantly, the first electron transfer is the rate-limiting step of arsenic reduction and is found to be more favorable on Co-SAC both thermodynamically and kinetically. This work not only expands the potential applicaiton of single-atom catalysts in the detection and treatment of As(III), but also provides atomic-level catalytic insights into HMIs sensing interfaces.

Identifying Phase-Dependent Electrochemical Stripping Performance of FeOOH Nanorod: Evidence from Kinetic Simulation and Analyte-Material Interactions.

Metal hydroxide nanomaterials are widely applied in the energy and environment fields. The electrochemical performance of such materials is strongly dependent on their crystal phases. However, as there are always multiple factors relating to the phase-dependent electrochemistry, it is still difficult to identify the determining one. The well-defined crystal phases of α- and ß-FeOOH nanorods are characterized through the transmission electron microscopy by a series of rotation toward one rod, where the cross-section shape and the growth direction along the [001] crystalline are first verified for 1D FeOOH nanostructures. The electrosensitivity of the two materials toward Pb(II) is tested, where α-FeOOH performs an outstanding sensitivity whilst it is only modest for ß-FeOOH. Experiments via Fourier transform infrared spectroscopy, X-ray absorption fine structure (XAFS), etc., show that α-FeOOH presents a larger Pb(II) adsorption capacity due to more surficial hydroxyl groups and weaker PbO bond strength. The reaction kinetics are simulated and the adsorption capacity is found to be the determining factor for the distinct Pb(II) sensitivities. Combining experiment with simulation, this work reveals the physical insights of the phase-dependent electrochemistry for FeOOH and provides guidelines for the functional application of metal hydroxide nanomaterials.

Changing the Blood Test: Accurate Determination of Mercury(II) in One Microliter of Blood Using Oriented ZnO Nanobelt Array Film Solution-Gated Transistor Chips.

The measurement of ultralow concentrations of heavy metal ions (HMIs) in blood is challenging. A new strategy for the determination of mercury ions (Hg2+ ) based on an oriented ZnO nanobelt (ZnO-NB) film solution-gated field-effect transistor (FET) chip is adopted. The FET chips are fabricated with ZnO-NB film channels with different orientations utilizing the Langmuir-Blodgett (L-B) assembly technique. The combined simulation and I-V behavior results show that the nanodevice with ZnO-NBs parallel to the channel has exceptional performance. The sensing capability of the oriented ZnO-NB film FET chips corresponds to an ultralow minimum detectable level (MDL) of 100 × 10-12 m in deionized water due to the change in the electrical double layer (EDL) arising from the synergism of the field-induced effect and the specific binding of Hg2+ to the thiol groups (-SH) on the film surface. Moreover, the prepared FET chips present excellent selectivity toward Hg2+ , excellent repeatability, and a rapid response time (less than 1 s) for various Hg2+ concentrations. The sensing performance corresponds to a low MDL of 10 × 10-9 m in real samples of a drop of blood.

Metal Replacement Causing Interference in Stripping Analysis of Multiple Heavy Metal Analytes: Kinetic Study on Cd(II) and Cu(II) Electroanalysis via Experiment and Simulation.

Although it has been recognized that the interference between heavy metal ions (HMIs) becomes a severe problem for the simultaneous electroanalysis of multiple HMIs, the factor leading to the interference is still difficult to identify, due to the limited understanding of the electroanalytic kinetics. In this work, a kinetic model is built for the electroanalysis of HMIs, and the electroanalytic results are simulated for Cd(II), Cu(II), and their mixture as examples for the interference investigation. The mutual interference between Cd and Cu is observed on the glassy carbon electrode. By applying the kinetic model, the replacement of deposited Cd by Cu(II) at the codeposition stage is regarded as the main reason for the interference, and the corresponding suggestion for selecting suitable electrode materials to avoid such interference is also provided.