Operando Spectroscopy Observation of Mo Clusters-Ti3 C2 TX Catalyst/Support Interface's Dynamic Evolution in Hydrogen Evolution Reaction.

The interaction between catalyst and support plays an important role in electrocatalytic hydrogen evolution (HER), which may explain the improvement in performance by phase transition or structural remodeling. However, the intrinsic behavior of these catalysts (dynamic evolution of the interface under bias, structural/morphological transformation, stability) has not been clearly monitored, while the operando technology does well in capturing the dynamic changes in the reaction process in real time to determine the actual active site. In this paper, nitrogen-doped molybdenum atom-clusters on Ti3 C2 TX (MoACs /N-Ti3 C2 TX ) is used as a model catalyst to reveal the dynamic evolution of MoAcs on Ti3 C2 TX during the HER process. Operando X-ray absorption structure (XAS) theoretical calculation and in situ Raman spectroscopy showed that the Mo cluster structure evolves to a 6-coordinated monatomic Mo structure under working conditions, exposing more active sites and thus improving the catalytic performance. It shows excellent HER performance comparable to that of commercial Pt/C, including an overpotential of 60 mV at 10 mA cm-2 , a small Tafel slope (56 mV dec-1 ), and high activity and durability. This study provides a unique perspective for investigating the evolution of species, interfacial migration mechanisms, and sources of activity-enhancing compounds in the process of electroreduction.

Fabrication of a Flexible Gold Nanorod Polymer Metafilm via a Phase Transfer Method as a SERS Substrate for Detecting Food Contaminants.

Surface enhanced Raman scattering (SERS) has been widely used in detection of food safety due to the nondestructive examination property. Here, we reported a flexible SERS film based on a polymer-immobilized gold nanorod polymer metafilm. Polystyrene-polyisoprene-polystyrene (SIS), a transparent and flexible, along with having excellent elasticity, polymer, was chosen as the main support of gold nanorods. A simple phase transfer progress was adopted to mix the gold nanorods with the polymer, which can further be used in most water-insoluble polymers. The SERS film performed satisfactorily while being tested in a series of standard Raman probes, like crystal violet (CV) and malachite green (MG). Moreover, the excellent reproducibility and elastic properties make the film a promising substrate in practical detection. Hence, the MG detection on the fish surface and trace thiram detection on orange pericarp were inspected with detection results of 1 × 10-10 and 1 × 10-6 M, which were below the demand of the National standard of China, exactly matching the realistic application requirements.

Rapid fabrication of flexible and transparent gold nanorods/poly (methyl methacrylate) membrane substrate for SERS nanosensor application.

Flexible substrates have been proposed for daily-life applications in SERS detection due to the prominent sample collection properties such as they can be wrapped around non-planar object surface. Combining the noble metals with polymers, flexible SERS substrates could be fabricated with advantages of light weight, transparency and high SERS sensitivity. Herein, we prepare a gold nanorods (AuNRs)/poly(methyl methacrylate) (PMMA) film as flexible SERS substrate by self-assembling a uniformly AuNRs array layer on PMMA template. This AuNRs/PMMA film performs excellently on thiram trace detection with the lowest detection concentration of 0.5 ppb. The fabricated substrates were applied for practical detection with cucumber by directly covering the AuNRs/PMMA flexible film on the target surface. Furthermore, the high SERS sensitivity as well as great reproducibility present a wide range of prospections for the further application of non-plane surface.