Solid-state synthesis of few-layer cobalt-doped MoS2 with CoMoS phase on nitrogen-doped graphene driven by microwave irradiation for hydrogen electrocatalysis

The high catalytic activity of cobalt-doped MoS2 (Co–MoS2) observed in several chemical reactions such as hydrogen evolution and hydrodesulfurization, among others, is mainly attributed to the formation of the CoMoS phase, in which Co occupies the edge-sites of MoS2. Unfortunately, its production represents a challenge due to limited cobalt incorporation and considerable segregation into sulfides and sulfates. We, therefore, developed a fast and efficient solid-state microwave irradiation synthesis process suitable for producing thin Co–MoS2 flakes (∼3–8 layers) attached on nitrogen-doped reduced graphene oxide. The CoMoS phase is predominant in samples with up to 15 at% of cobalt, and only a slight segregation into cobalt sulfides/sulfates is noticed at larger Co content. The Co–MoS2 flakes exhibit a large number of defects resulting in wavy sheets with significant variations in interlayer distance. The catalytic performance was investigated by evaluating the activity towards the hydrogen evolution reaction (HER), and a gradual improvement with increased amount of Co was observed, reaching a maximum at 15 at% with an overpotential of 197 mV at −10 mA cm−2, and a Tafel slope of 61 mV dec−1. The Co doping had little effect on the HER mechanism, but a reduced onset potential and charge transfer resistance contributed to the improved activity. Our results demonstrate the feasibility of using a rapid microwave irradiation process to produce highly doped Co–MoS2 with predominant CoMoS phase, excellent HER activity, and operational stability

Thermal stability of spherical nanoporous aggregates and formation of hollow structures by sintering—a phase-field study

Nanoporous structures are widely used for many applications and hence it is important to investigate their thermal stability. We study the stability of spherical nanoporous aggregates using phase-field simulations that explore systematically the effect of grain boundary diffusion, surface diffusion, and grain boundary mobility on the pathways for microstructural evolution. Our simulations for different combinations of surface and GB diffusivity and GB mobility show four distinct microstructural pathways en route to 100% density: multiple closed pores, hollow shells, hollow shells with a core, and multiple interconnected pores. The microstructures from our simulations are consistent with experimental observations in several different systems. Our results have important implications for rational synthesis of hollow nanostructures or aggregates with open pores, and for controlling the stability of nanoporous aggregates that are widely used for many applications

β-Mo2C Nanoparticles Produced by Carburization of Molybdenum Oxides with Carbon Black under Microwave Irradiation for Electrocatalytic Hydrogen Evolution Reaction

The synthesis of electrochemically active β-Mo2C nanoparticles for hydrogen production was achieved by a fast and energy-efficient microwave-assisted carburization process from molybdenum oxides and carbon black. With the use of microwave-based production methods, we aim to reduce the long-time high-temperature treatments and the use of hazardous gases often seen in traditional molybdenum carbide synthesis processes. In our process, carbon black not only serves as a carbon source but also as a susceptor (microwave absorber) and conductive substrate. The irradiation power, reaction time, and Mo:C ratio were optimized to achieve the highest electrocatalytic performance toward hydrogen production in an acidic electrolyte. A complete transformation of MoO3 to β-Mo2C nanoparticles and an additional graphitization of the carbon black matrix were achieved at 1000 W, 600 s, and Mo:C ratio above 1:7.5. Under these conditions, the optimized composite exhibited an excellent HER performance (η10 = 156 mV, Tafel slope of 53 mV·dec-1) and large turnover frequency per active site (3.09 H2·s-1 at an overpotential of 200 mV), making it among the most efficient non-noble-metal catalysts. The excellent activity was achieved thanks to the abundance of β-Mo2C nanoparticles, the intimate nanoparticle-substrate interface, and enhanced electron transport toward the carbon black matrix. We also investigated the flexibility of the synthesis method by adding additional Fe or V as secondary transition metals, as well as the effect of the substrate

Enhanced gas sensing performance of graphene/ZnS-CdS hetero-nanowires gas sensor synthesized by Langmuir-Blodgett self-assembly method

Graphene is a promising material in the field of solid-state gas sensors due to the unique two-dimensional structure. Here, we have shown by fabricating graphene/ZnS-CdS hetero-nanowire structure, the gas sensor sensitivity has a two-fold increase to 20% under 15 ppm gaseous concentration compared to a 10% response in pristine graphene. Spectroscopy and microscopy analysis indicate that the semi-conducting ZnS-CdS hetero-nanowires are 2 nm wide and densely packed on top of graphene. By combining UV illumination, the device approaches a fast response/recovery and high gas sensitivity, thus has a potential to be used in a detection of wide range of gases.

Controlled synthesis of tellurium nanowires by physical vapor deposition

One-dimensional tellurium nanostructures can exhibit distinct electronic properties from those seen in bulk Te. The electronic properties of nanostructured Te are highly dependent on their morphology, and thus controlled synthesis processes are required. Here, highly crystalline tellurium nanowires were produced via physical vapour deposition. We used growth temperature, heating rate, flow of the carrier gas, and growth time to control the degree of supersaturation in the region where Te nanostructures are grown. The latter leads to a control in the nucleation and morphology of Te nanostructures. We observed that Te nanowires grow via the vapour–solid mechanism where a Te particle acts as a seed. Transmission electron microscopy (TEM) and electron diffraction studies revealed that Te nanowires have a trigonal crystal structure and grow along the (0001) direction. Their diameter can be tuned from 26 to 200 nm with lengths from 8.5 to 22 μm, where the highest aspect ratio of 327 was obtained for wires measuring 26 nm in diameter and 8.5 μm in length. We investigated the use of bismuth as an additive to reduce the formation of tellurium oxides, and we discuss the effect of other growth parameters.Originally included in thesis in manuscript form. </p

New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate is <i>lower</i> than that of the surrounding medium. The catalytic activity of the Pt/CeO₂ and Pt/TiO₂ hybrids synthesized by this method for H₂ combustion reaction shows that complete conversion is achieved at temperatures as low as 100 °C with Pt–CeO₂ catalyst and at 50 °C with Pt–TiO₂ catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method

A Convenient Route for Au@Ti–SiO₂ Nanocatalyst Synthesis and Its Application for Room Temperature CO Oxidation

Small gold nanoparticles of size less than 5 nm encapsulated inside titanium modified silica shell have been reported. Here, a modified sol–gel method, which is a one-step process, produces Au@Ti–SiO₂ nanocatalyst with a good control of titanium loading. With a titanium loading of 0.9 and 2.2 wt % in silica, unprecedented low temperature activity (full conversion) is observed for this catalyst for CO oxidation reaction compared to Au@SiO₂ catalyst. A combination of optimum sized gold nanoparticles with a large amount of oxygen vacancies created due to Ti incorporation in silica matrix is considered to be the reason for this enhanced catalytic activity. The size of gold nanoparticles is maintained even after high temperature pretreatments, which show the benefit of encapsulation. The effect of the various pretreatments on the catalytic activity has also been reported