Enhancing Nitrogen Reduction Reaction through Formation of 2D/2D Hybrid Heterostructures of MoS2@rGO.

Given the challenging task of constructing an efficient nitrogen reduction reaction (NRR) electrocatalyst with enhanced ambient condition performance, properties such as high specific surface area, fast electron transfer, and design of the catalyst surface constitute a group of key factors to be taken into consideration to guarantee outstanding catalytic performance and durability. Thereof, this work investigates the contribution of the 2D/2D heterojunction interface between MoS2 and reduced graphene oxide (rGO) on the electrocatalytic synthesis of NH3 in an alkaline media. The results revealed remarkable NRR performance on the MoS2@rGO 2D/2D hybrid electrocatalyst, characterized by a high NRR sensitivity (faradaic efficiency) of 34.7% with an NH3 yield rate of 3.98 ± 0.19 mg h-1 cm-2 at an overpotential of -0.3 V vs RHE in 0.1 M KOH solution. The hybrid electrocatalysts also exhibited selectivity for NH3 synthesis against the production of the hydrazine (N2H4) byproduct, hindrance of the competitive hydrogen evolution reaction (HER), and good durability over an operation period of 8 h. In hindsight, the study presented a low-cost and highly efficient catalyst design for achieving enhanced ammonia synthesis in alkaline media via the formation of defect-rich ultrathin MoS2@rGO nanostructures, consisting predominantly of an HER-hindering hexagonal 2H-MoS2 phase.

Catalyst Design: Counter Anion Effect on Ni Nanocatalysts Anchored on Hollow Carbon Spheres.

Herein, the influence of the counter anion on the structural properties of hollow carbon spheres (HCS) support was investigated by varying the nickel metal precursor salts applied. TEM and SEM micrographs revealed the dimensional dependence of the HCS shell on the Ni precursor salt, as evidenced by thick (~42 nm) and thin (~23 nm) shells for the acetate and chloride-based salts, respectively. Importantly, the effect of the precursor salt on the textural properties of the HCS nanosupports (~565 m2/gNi(acet)) and ~607 m2/gNiCl), influenced the growth of the Ni nanoparticles, viz for the acetate-(ca 6.4 nm)- and chloride (ca 12 nm)-based salts, respectively. Further, XRD and PDF analysis showed the dependence of the reduction mechanism relating to nickel and the interaction of the nickel-carbon support on the type of counter anion used. Despite the well-known significance of the counter anion on the size and crystallinity of Ni nanoparticles, little is known about the influence of such counter anions on the physicochemical properties of the carbon support. Through this study, we highlight the importance of the choice of the Ni-salt on the size of Ni in Ni-carbon-based nanocatalysts.

From 0D to 2D: N-doped carbon nanosheets for detection of alcohol-based chemical vapours.

The application of N-doped carbon nanosheets, with and without embedded carbon dots, as active materials for the room temperature chemoresistive detection of methanol and/or ethanol is presented. The new carbons were made by converting 0D N-doped carbon dots (NCDs) to 2D nitrogen-doped carbon nanosheets by heat treatment (200-700 °C). The nanosheets exhibited a lateral size of ∼3 µm and a thickness of ∼12 nm at the highest annealing temperature. Both Raman and TEM analyses showed morphological transitions of the dots to the sheets, whilst XPS analysis revealed transformation of the N-bonding states with increasing temperature. PDF analysis confirmed the presence of defective carbon sheets. Room temperature screening of the chemical vapours of two alcohols (methanol and ethanol), revealed that the structure and the type of N-configuration influenced the detection of the chemical vapours. For instance, the lateral size of the nanosheets and the high charge density N-configurations promoted detection of both methanol and ethanol vapours at good sensitivity (-16.8 × 10-5 ppm-1 EtOH and 1.2 × 10-5 ppm-1 MeOH) and low LoD (∼44 ppmEtOH and ∼30.3 ppmMeOH) values. The study showed that the composite nature as well as the large basal area of the carbon nanosheets enabled generation of adequate defective sites that facilitated easy adsorption of the VOC analyte molecules, thereby eliminating the need to use conducting polymers or the formation of porous molecular frameworks for the alcohol detection.