Search for: All records

Abstract Transition metal dichalcogenides (TMDs) are known for their layered structure and tunable functional properties. However, a unified understanding on other transition metal chalcogenides (i.e. M 2 X) is still lacking. Here, the relatively new class of copper-based chalcogenides Cu 2 X (X = Te, Se, S) is thoroughly reported. Cu 2 X are synthesized by an unusual vapor–liquid assisted growth on a Al 2 O 3 /Cu/W stack. Liquid copper plays a significant role in synthesizing these layered systems, and sapphire assists with lateral growth and exfoliation. Similar to traditional TMDs, thickness dependent phonon signatures are observed, and high-resolution atomic images reveal the single phase Cu 2 Te that prefers to grow in lattice-matched layers. Charge transport measurements indicate a metallic nature at room temperature with a transition to a semiconducting nature at low temperatures accompanied by a phase transition, in agreement with band structure calculations. These findings establish a fundamental understanding and thrust Cu 2 Te as a flexible candidate for wide applications from photovoltaics and sensors to nanoelectronics. 

Abstract Chemical vapor deposition growth of metal carbides is of great interest as this method provides large area growth of MXenes. This growth is mainly done using a melted diffusion based process; however, different morphologies in growth process is not well understood. In this work, we report deterministic synthesis of layered (non-uniform c -axis growth) and planar (uniform c -axis growth) of molybdenum carbide (Mo 2 C) using a diffusion-mediated growth. Mo-diffusion limited growth mechanism is proposed where the competition between Mo and C adatoms determines the morphology of grown crystals. Difference in thickness of catalyst at the edge and center lead to enhanced Mo diffusion which plays a vital role in determining the structure of Mo 2 C. The layered structures exhibit an expansion in the lattice confirmed by the presence of strain. Density functional theory shows consistent presence of strain which is dependent upon Mo diffusion during growth. This work demonstrates the importance of precise control of diffusion through the catalyst in determining the structure of Mo 2 C and contributes to broader understanding of metal diffusion in growth of MXenes. 

Abstract In this work, an organic‐inorganic hybrid crystal, violet‐crystal (VC), was used to etch the nickel foam (NF) to fabricate a self‐standing electrode for the water oxidation reaction. The efficacy of VC‐assisted etching manifests the promising electrochemical performance towards the oxygen evolution reaction (OER), requiring only ~356 and ~376 mV overpotentials to reach 50 and 100 mA cm⁻², respectively. The OER activity improvement is attributed to the collectively exhaustive effects arising from the incorporation of various elements in the NF, and the enhancement of active site density. Furthermore, the self‐standing electrode is robust, exhibiting a stable OER activity after 4,000 cyclic voltammetry cycles, and ~50 h. The anodic transfer coefficients (α_a) show that the first electron transfer step is the rate‐determining step on the surface of NF‐VCs‐1.0 (NF etched by 1 g of VCs) electrode, while the chemical step involving dissociation following the first electron transfer step is identified as the rate‐limiting step in other electrodes. The lowest Tafel slope value observed in the NF‐VCs‐1.0 electrode indicates the high surface coverage of oxygen intermediates and more favorable OER reaction kinetics, as confirmed by high interfacial chemical capacitance and low charge transport/interfacial resistance. This work demonstrates the importance of VCs‐assisted etching of NF to activate the OER, and the ability to predict reaction kinetics and rate‐limiting step based onα_avalues, which will open new avenues to identify advanced electrocatalysts for the water oxidation reaction.