Unveiling the Solvent Effect in Plasmon Enhanced Electrochemistry via the Nanoparticle-Impact Technique.

Plasmon-enhanced electrochemistry (PEEC) has been observed to facilitate energy conversion systems by converting light energy to chemical energy. However, comprehensively understanding the PEEC mechanism remains challenging due to the predominant use of ensemble-based methodologies on macroscopic electrodes, which fails to measure electron-transfer kinetics due to constraints from mass transport and the averaging effect. In this study, we have employed nanoparticle impact electrochemistry (NIE), a newly developed electroanalytical technique capable of measuring electrochemical dynamics at a single-nanoparticle level under optimal mass transport conditions, along with microscopic electron-transfer theory for data interpretation. By investigating the plasmon enhanced hydrogen evolution reaction (HER) at individual silver nanoparticles (AgNPs), we have clearly revealed the previously unknown influence of solvent effects within the PEEC mechanism. This finding suggests an additional approach to optimize plasmon-assisted electrocatalysis and electrosynthesis systems.

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.

From Ensemble Electrochemistry to Nano-Impact Electrochemistry: Altered Reaction Selectivity.

Selective electrochemical production of valued chemicals is of significant importance but remains a great challenge in chemistry. Conventional approaches for enhancing reaction selectivity focus on the improvement of the catalysts themselves. In this work, we systematically studied the reaction kinetics and mass transport behavior of LaNiO3 nanocubes (LaNiO3 NCs) catalyzed hydrogen peroxide reduction reaction (HPRR) at ensemble and single nanoparticle levels using nano-impact electrochemistry (NIE). We find that the selectivity of HPRR was altered at individual random-walk nanoparticles as compared to their ensemble counterpart without changing the reaction kinetics, due to the significantly enhanced mass transport at single nanoparticles. This discovery offers the scope of new catalytic approaches for engineering electrochemical reactions in general.

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.