This report focuses on a novel strategy for the preparation of transition metal–MoS2 hybrid nanoclusters based on a one-step, dual-target magnetron sputtering, and gas condensation process demonstrated for Ni-MoS2. Aberration-corrected STEM images coupled with EDX analysis confirms the presence of Ni and MoS2 in the hybrid nanoclusters (average diameter = 5.0 nm, Mo:S ratio = 1:1.8 ± 0.1). The Ni-MoS2 nanoclusters display a 100 mV shift in the hydrogen evolution reaction (HER) onset potential and an almost 3-fold increase in exchange current density compared with the undoped MoS2 nanoclusters, the latter effect in agreement with reported DFT calculations. This activity is only reached after air exposure of the Ni-MoS2 hybrid nanoclusters, suggested by XPS measurements to originate from a Ni dopant atoms oxidation state conversion from metallic to 2+ characteristic of the NiO species active to the HER. Anodic stripping voltammetry (ASV) experiments on the Ni-MoS2 hybrid nanoclusters confirm the presence of Ni-doped edge sites and reveal distinctive electrochemical features associated with both doped Mo-edge and doped S-edge sites which correlate with both their thermodynamic stability and relative abundance.
Materials show various responses to incident light, owing to their unique dielectric functions. A well‐known example is the distinct colors displayed by metals, providing probably the simplest method to identify gold, silver, and bronze since ancient times. With the advancement of nanotechnology, optical structures with feature sizes smaller than the optical wavelength have been routinely achieved. In this regime, the optical response is also determined by the geometry of the nanostructures, inspiring flourishing progress in plasmonics, photonic crystals, and metamaterials. Nevertheless, the nature of the materials still plays a decisive role in light–matter interactions, and this material‐dependent optical response is widely accepted as a norm in nanophotonics. Here, a counterintuitive system—plasmonic nanostructures composed of different materials but exhibiting almost identical reflection—is proposed and realized. The geometric disorder embedded in the system overwhelms the contribution of the material properties to the electrodynamics. Both numerical simulations and experimental results provide concrete evidence of the insensitivity of the optical response to different plasmonic materials. The same optical response is preserved with various materials, providing great flexibility of freedom in material selection. As a result, the proposed configuration may shed light on novel applications ranging from Raman spectroscopy, photocatalysis, to nonlinear optics.
Platinum is the most active anode and cathode catalyst in next-generation fuel cells using methanol as liquid source of hydrogen. Its catalytic activity can be significantly improved by alloying with 3d metals, although a precise tuning of its surface architecture is still required. Herein, we report the design of a highly active low temperature (below 0 • C) methanol dehydrogenation anode catalyst with reduced CO poisoning, based on ultra-low amount of precisely-defined PtxNi1-x (x = 0 to 1) bimetallic clusters (BCs) deposited on inert flat oxides by Cluster Beam Deposition (CBD). These BCs feature clear composition-dependent atomic arrangements and electronic structures stemming from their nucleation mechanism that are responsible for a volcano-type activity trend peaking at the Pt0.7Ni0.3 composition. Our calculations reveal that at this composition a cluster skin of Pt atoms with d-band centres downshifted by subsurface Ni atoms weakens the CO interaction that in turn triggers a significant increase in the methanol dehydrogenation activity.
1D carbon structures are attractive due to their mechanical, chemical and electrochemical properties. Further enhancements to these structures can be made by creating structural hierarchy, producing composites with catalytically active metal nanoparticle domains -however the synthesis of these materials can be costly and complicated. Here, through the combination of inexpensive acetylacetonate salts of Ni, Co and Fe with a solution of polyacrylonitrile (PAN) which was electrospun and subsequently heat treated, self-assembling carbon-metal fabrics (CMFs) containing unique 1D hierarchical structures can be created readily. Microscopic and spectroscopic measurements show that the CMFs form through the decomposition and exsolution of metal nanoparticle domains which then catalyse the formation of carbon nanotubes through the decomposition by-products of the PAN. These weakly bound nanoparticles form structures similar to trichomes found in plants, with a combination of base-growth, tip-growth and peapod-like structures, where the metal domain exhibits a core(graphitic)-shell(disorder) 2 carbon coating where the thickness is in-line with the metal-carbon binding energy. The applicability of these carbon-metal fabrics (CMFs) was demonstrated as a cathode in an allsolid-state zinc-air battery which exhibited superior performance to pure electrospun carbon fibres, in addition to enhanced mechanical flexibility due to the enhanced surface area of the hairy fibres and their metallic nanoparticle domains which acted as bifunctional catalysts to oxygen reduction and evolution. This work therefore unlocks a potentially new category of composite metal-carbon fibre based structures for energy storage applications and beyond, which can be created in a low cost manner.
For every three people on the planet, there are approximately two Tonnes (Te) of plastic waste. We show that carbon recovery from polystyrene (PS) plastic is enhanced by the coaddition of solvents to grow carbon nanotubes (CNTs) by liquid injection chemical vapour deposition. Polystyrene was loaded up to 4 wt% in toluene and heated to 780 °C in the presence of a ferrocene catalyst and a hydrogen/argon carrier gas at a 1:19 ratio. High resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and Raman spectroscopy were used to identify multiwalled carbon nanotubes (MWCNTs). The PS addition in the range from 0 to 4 wt% showed improved quality and CNT homogeneity; Raman “Graphitic/Defective” (G/D) values increased from 1.9 to 2.3; mean CNT diameters increased from 43.0 to 49.2 nm; and maximum CNT yield increased from 11.37% to 14.31%. Since both the CNT diameters and the percentage yield increased following the addition of polystyrene, we conclude that carbon from PS contributes to the carbon within the MWCNTs. The electrical contact resistance of acid-washed Bucky papers produced from each loading ranged from 2.2 to 4.4 Ohm, with no direct correlation to PS loading. Due to this narrow range, materials with different loadings were mixed to create the six wires of an Ethernet cable and tested using iPerf3; the cable achieved up- and down- link speeds of ~99.5 Mbps, i.e., comparable to Cu wire with the same dimensions (~99.5 Mbps). The lifecycle assessment (LCA) of CNT wire production was compared to copper wire production for a use case in a Boeing 747-400 over the lifespan of the aircraft. Due to their lightweight nature, the CNT wires decreased the CO2 footprint by 21 kTonnes (kTe) over the aircraft’s lifespan.
Au nanoparticles represent the most remarkable example of a size effect in heterogeneous catalysis.However, a major issue hindering the use of Au nanoparticles in technological applications is their rapid sintering. We explore the potential of stabilizing Au nanoclusters on SiO 2 by alloying them with a reactive metal, Ti. Mass-selected Au/Ti clusters (400 000 amu) and Au 2057 clusters (405 229 amu) were produced with a magnetron sputtering, gas condensation cluster beam source in conjunction with a lateral timeof-flight mass filter, deposited onto a silica support and characterised by XPS and LEIS. The sintering dynamics of mass-selected Au and Au/Ti alloy nanoclusters were investigated in real space and real time with atomic resolution aberration-corrected HAADF-STEM imaging, supported by model DFT calculations. A strong anchoring effect was revealed in the case of the Au/Ti clusters, because of a much increased local interaction with the support (by a factor 5 in the simulations), which strongly inhibits sintering, especially when the clusters are more than ∼0.60 nm apart. Heating the clusters at 100°C for 1 h in a mixture of O 2 and CO, to simulate CO oxidation conditions, led to some segregation in the Au/Ti clusters, but in line with the model computational investigation, Au atoms were still present on the surface. Thus size-selected, deposited nanoalloy Au/Ti clusters appear to be promising candidates for sustainable gold-based nanocatalysis.
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