Dynamic sampling of liquid metal structures for theoretical studies on catalysis.

Liquid metals have recently emerged as promising catalysts that can outcompete their solid counterparts for many reactions. Although theoretical modelling is extensively used to improve solid-state catalysts, there is currently no way to capture the interactions of adsorbates with a dynamic liquid metal. We propose a new approach based on ab initio molecular dynamics sampling of an adsorbate on a liquid catalyst. Using this approach, we describe time-resolved structures for formate adsorbed on liquid Ga-In, and for all intermediates in the methanol oxidation pathway on Ga-Pt. This yields a range of accessible adsorption energies that take into account the at-temperature motion of the liquid metal. We find that a previously proposed pathway for methanol oxidation on Ga-Pt results in unstable intermediates on a dynamic liquid surface, and propose that H desorption must occur during the path. The results showcase a more accurate way to treat liquid metal catalysts in this emerging field.

Structural and electronic changes in Ga-In and Ga-Sn alloys on melting.

The melting behaviour of surface slabs of Ga-In and Ga-Sn is studied using periodic density functional theory and ab initio molecular dynamics. Analysis of the structure and electronics of the solid and liquid phases gives insight into the properties of these alloys, and why they may act as promising CO2 reduction catalysts. We report melting points for slabs of hexa-layer Ga-In (386 K) and Ga-Sn (349 K) that are substantially lower than the pure hexa-layer Ga system (433 K), and attribute the difference to the degree to which the dopant (In or Sn) disrupts the layered Ga network. In molecular dynamics trajectories of the liquid structures, we find that dopant tends to migrate from the centre of the slab towards the surface and accumulate there. Bader charge calculations reveal that the surface dopant atoms have increased positive charge, and density of states analyses suggest the liquid alloys maintain metallic electronic behaviour. Thus, surface In and Sn may provide good binding sites for intermediates in CO2 reduction. This work contributes to our understanding of the properties of liquid metal systems, and provides a foundation for modelling catalysis on these materials.

Enhancing the hydrogen evolution activity of MoS2 basal planes and edges using tunable carbon-based supports.

The hydrogen adsorption free energy (ΔGHads) on the basal plane and edges of MoS2 is studied using periodic density functional theory, with the catalyst supported by a range of two-dimensional carbon-based materials. Understanding how ΔGHads can be tuned with support gives insight into MoS2 as a catalyst for the hydrogen evolution reaction. The supports studied here include graphene oxide materials, heteroatom doped (S, B, and N) graphene, and some insulator materials (hexagonal boron nitride and graphitic carbon nitride). For the basal plane of MoS2, a wide range of values for ΔGHads are observed (between 1.4 and 2.2 eV) depending on the support material used. It is found that ΔGHads relates directly to the energy of occupied p-orbital states in the MoS2 catalyst, which is modified by the support material. On the Mo-edge of MoS2, different supports induce smaller variations in ΔGHads, with values ranging between -0.27 and 0.09 eV. However, a graphene support doped with graphitic N atoms produces a ΔGHads value of exactly 0 eV, which is thermodynamically ideal for hydrogen evolution. Furthermore, ΔGHads is found to relate closely and linearly to the amount of charge transfer between MoS2 and support when they adhere together. The support-induced tuning of ΔGHads on MoS2 observed here provides a useful tool for improving current MoS2 catalysts, and the discovery of variables which mediate changes in ΔGHads contributes to the rational design of new hydrogen evolution catalysts.

Size-dependent trends in the hydrogen evolution activity and electronic structure of MoS2 nanotubes.

The thermodynamics of hydrogen evolution on MoS2 nanotubes is studied for the first time using periodic density functional theory calculations to obtain hydrogen adsorption free energies (ΔG Hads ) on pristine nanotubes and those with S-vacancy defects. Armchair and zigzag MoS2 nanotubes of different diameters, ranging from 12 to 22 Å, are examined. The H adsorption energy is observed to become more favourable (lower ΔG Hads ) as nanotube diameter decreases, with ΔG Hads values ranging from 1.82 to 1.39 eV on the pristine nanotubes, and from 0.03 to -0.30 eV at the nanotube S-vacancy defect sites. An ideal thermoneutral ΔG Hads value of nearly 0 eV is observed at the S-vacancy site on nanotubes around 20 to 22 Å in diameter. For the pristine nanotubes, density of states calculations reveal that electron transfer from S to Mo occurs during H adsorption, and the energy gap between these two states yields a highly reliable linear correlation with ΔG Hads , where a smaller gap leads to a more favourable hydrogen adsorption. For the S-vacancy defect site the H adsorption resembles that on a pure metallic surface, meaning that a traditional d-band centre model can be applied to explain the trends in ΔG Hads . A linear relation between the position of the Mo d-states and ΔG Hads is found, with d-states closer to the Fermi level leading to strong hydrogen adsorption. Overall this work highlights the relevance of MoS2 nanotubes as promising hydrogen evolution catalysts and explains trends in their activity using the energies of the electronic states involved in binding hydrogen.