Application of a 2D Molybdenum Telluride in SERS Detection of Biorelevant Molecules

Two-dimensional (2D) transition-metal dichalcogenides have become promising candidates for surface-enhanced Raman spectroscopy (SERS), but currently very few examples of detection of relevant molecules are available. Herein, we show the detection of the lipophilic disease marker beta-sitosterol on few-layered MoTe2 films. The chemical vapor deposition (CVD)-grown films are capable of nanomolar detection, exceeding the performance of alternative noble-metal surfaces. We confirm that the enhancement occurs through the chemical enhancement (CE) mechanism via formation of a surface-analyte complex, which leads to an enhancement factor of approximate to 10(4), as confirmed by Fourier transform infrared (FTIR), UV-vis, and cyclic voltammetry (CV) analyses and density functional theory (DFT) calculations. Low values of signal deviation over a seven-layered MoTe2 film confirms the homogeneity and reproducibility of the results in comparison to noble-metal substrate analogues. Furthermore, beta-sitosterol detection within cell culture media, a minimal loss of signal over 50 days, and the opportunity for sensor regeneration suggest that MoTe2 can become a promising new SERS platform for biosensing.Peer reviewe

Revealing the activity of Co3Mo3N and Co3Mo3N0.5 as electrocatalysts for the hydrogen evolution reaction

The hydrogen evolution reaction (HER) from water is governed by electrocatalysts used. Multiple factors such as crystal structure, composition and morphology dictate the final catalytic performance. However, as multicomponent materials are developed to replace noble metals in the HER, it has become increasingly difficult to identify intrinsically active materials. Hence, there is an imperative for phase-pure catalysts to be synthetized and tested without obscuring contributions from impurities or substrates. Herein, we demonstrate that phase-pure, unsupported Co3Mo3N achieves a competitively low overpotential (OVP) of 108 ± 8 mV at 10 mA cm‒2 in 0.5 M H2SO4. Density functional theory (DFT) reveals weakly binding metal sites as the catalytic centres for the HER in the nitride. Remarkably, the N-deficient Co3Mo3N0.5 shows similar electrochemical properties but has limited chemical stability under cathodic bias. Thus, even though nitrogen sites play only a minor role in catalytic performance, their occupancy is crucial for the stability of nitride catalysts in the corrosive electrolyte. The composite of Co3Mo3N on Ni-foam sustains 10 ± 0.7 mA cm‒2 at applied potential of just 20 mV over extended time, highlighting the utility of nitrides for future design of stable and active HER catalytic systems

Elucidating catalytic sites governing the performance toward the hydrogen evolution reaction in ternary nitride electrocatalysts

Proton exchange membrane electrolyzers are considered the most advanced devices for producing green hydrogen by water electrolysis. Their development requires catalytic materials that are stable under acidic conditions and drive the hydrogen evolution reaction (HER) forward efficiently which makes research into the identification of the catalytic sites important. We report that free-standing Co2Mo3N and Ni2Mo3N achieve overpotentials of 149 ± 8 and 158 ± 10 mV (in 0.5 M H2SO4) at a benchmark current density of 10 mA cm–2. Both nitrides remained stable and consistently deliver current densities >500 mA cm–2 at a potential as low as 308 ± 22 mV when they were immobilized on nickel foam. Replacing Ni for Fe in Ni2Mo3N leads to FexNi2–xMo3N (0.5 ≤ x ≤ 1.25) that show a decrease in catalytic activity as the value of x increases which confirms that Ni (rather than Mo and N) sites are catalytically active. The X-ray photoelectron spectroscopy data additionally suggests that preserving the low oxidation states of transition metals in the nitrides is important for achieving good catalytic performance toward the HER in acidic electrolytes

Can Plasmon Change Reaction Path? : Decomposition of Unsymmetrical Iodonium Salts as an Organic Probe

Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion of light to chemical energy at room temperature. However, the mechanistic insights of interaction between plasmon energy and organic molecules is still under debate. Herein, we proposed a comprehensive study of the plasmon-assisted reaction mechanism using unsymmetric iodonium salts (ISs) as an organic probe. The experimental and theoretical analysis allow us to exclude the possible thermal effect or hot electron transfer. We found that plasmon interaction with unsymmetrical ISs led to the intramolecular excitation of electron followed by the regioselective cleavage of C–I bond with the formation of electron-rich radical species, which cannot be explained by the hot electron excitation or thermal effects. The high regioselectivity is explained by the direct excitation of electron to LUMO with the formation of a dissociative excited state according to quantum-chemical modeling, which provides novel opportunities for the fine control of reactivity using plasmon energy.Peer reviewe

Zwitterionic iodonium species afford halogen bond-based porous organic frameworks

Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified in two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The channels are filled with disordered water molecules which can be reversibly removed on heating. Consistent with the remarkable strength and directionality of the halogen bonds (XBs) driving the crystal packing formation, the porous structure is stable and fully preserved on almost quantitative removal and readsorption of water. The porous systems described here are the first reported cases of one-component 3D organic frameworks whose assembly is driven by XB only (XOFs). These systems are a proof of concept for the ability of zwitterionic aryliodonium tectons in affording robust one-component 3D XOFs. The high directionality and strength of the XBs formed by these zwitterions and the geometrical constraints resulting from the tendency of their hypervalent iodine atoms to act as bidentate XB donors might be key factors in determining this ability

IS AZO-COUPLING OF P-NITROTHIOPHENOL A GOOD REACTION FOR THE EVALUATION OF PLASMON CATALYSIS MECHANISM?

The excitation of plasmon resonance on noble metals nanostructures delvers practical outcome in sensorics, photocatalysis. In plasmon-induced transformationsm, plasmon exciation allows to overcome the limitations of classical catalysis, such as high temperatures, pressures, and the use of complex catalytic systems. A model reaction for studying the mechanistic aspects of the plasmon-induced catalysis is the azo coupling of nitro- or -aminothiophenols. However, the nature of bonding between thiols and plasmonic metals is considered as chemisorption, which may be reversibile – one thiophenols can be replaced by other molecules

LASER-ASSISTED ABLATION OF UIO-66 METAL-ORGANIC FRAMEWORK ON THE PET SURFACE FOR NOVEL ELECTRODE MATERIALS

Currently, one of the main trends in the chemistry of MOFs is their use as a raw material for the production of carbon-based nanomaterials, which have a high potential for further use as electrocatalysts. However, despite the steady progress in the development of technologies, carbonization is a complex and energy-intensive process that requires optimization and search for new solution

Preparation of Selective and Reproducible SERS Sensors of Hg²⁺ Ions via a Sunlight-Induced Thiol–Yne Reaction on Gold Gratings

In this contribution, we propose a novel functional surface-enhanced Raman spectroscopy (SERS) platform for the detection of one of the most hazardous heavy metal ions, Hg2+. The design of the proposed sensor is based on the combination of surface plasmon-polariton (SPP) supporting gold grating with the high homogeneity of the response and enhancement and mercaptosuccinic acid (MSA) based specific recognition layer. For the first time, diazonium grafted 4-ethynylphenyl groups have undergone the sunlight-induced thiol−yne reaction with MSA in the presence of Eosine Y. The developed SERS platform provides an extremely sensitive, selective, and convenient analytical procedure to detect mercury ions with limit of detection (LOD) as low as 10−10 M (0.027 µg/L) with excellent selectivity over other metals. The developed SERS sensor is compatible with a portable SERS spectrophotometer and does not require the expensive equipment for statistical methods of analysis

Surface Plasmon-Polariton: A Novel Way To Initiate Azide–Alkyne Cycloaddition

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