Nanocrystal Assemblies: Current Advances and Open Problems.

We explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

Tuning the electronic structure of gold cluster-assembled materials by altering organophosphine ligands.

Superatomic clusters can be assembled to build bulk matter, where the individual characteristics are preserved. The main benefit of these materials over conventional bulk species is the capability to tailor their features by altering the physicochemical identities of individual clusters. Electronic properties of metal clusters can be modified by a protective shell of ligands that attach to the surface and make the whole nanoparticle soluble in organic or aqueous solvents. In the present work, we demonstrate that properly chosen ligands provide not only steric protection from aggregation but also tune the redox activity of metal clusters. We investigate the role of the ligands in electronic structure tunability and ligand-field splitting. Our first-principles calculations agree with the experiments, showing that phosphine-protected gold materials are small gap semiconductors. The obtained bandgaps strongly depend on the ligand used. Hence, using phosphine and organophosphine ligands should be feasible and promising while designing the novel superatom-based materials since the desired range of the bandgap might be achieved (by the proper choice of the ligand).

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.

Dynamic Activation of Ga Sites by Pt Dopant in Low-Temperature Liquid-Metal Catalysts.

Liquid GaPt catalysts with Pt concentrations as low as 1×10-4  atomic % have recently been identified as highly active for the oxidation of methanol and pyrogallol under mild reaction conditions. However, almost nothing is known about how liquid state catalysts support these significant improvements in activity. Here, ab initio molecular dynamics simulations are employed to examine GaPt catalysts in isolation and interacting with adsorbates. We find that persistent geometric features can exist in the liquid state, given the correct environment. We postulate that the Pt dopant may not be limited to direct involvement in catalysis of reactions, but rather that its presence can also enable Ga atoms to become catalytically active.

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.

Liquid metal synthesis solvents for metallic crystals.

In nature, snowflake ice crystals arrange themselves into diverse symmetrical six-sided structures. We show an analogy of this when zinc (Zn) dissolves and crystallizes in liquid gallium (Ga). The low-melting-temperature Ga is used as a "metallic solvent" to synthesize a range of flake-like Zn crystals. We extract these metallic crystals from the liquid metal solvent by reducing its surface tension using a combination of electrocapillary modulation and vacuum filtration. The liquid metal-grown crystals feature high morphological diversity and persistent symmetry. The concept is expanded to other single and binary metal solutes and Ga-based solvents, with the growth mechanisms elucidated through ab initio simulation of interfacial stability. This strategy offers general routes for creating highly crystalline, shape-controlled metallic or multimetallic fine structures from liquid metal solvents.

Concentration dependent alloying behaviour of liquid GaAu.

Liquid GaAu systems provide the possibility of developing dynamic and self-healing materials for a variety of applications, including catalysis. GaAu systems provide both dynamic capability by being liquid at just above room temperature, as a result of the Ga, and likely catalytic activity, resulting from the Au. While the formation of a Ga2Au intermetallic is known, the behaviours that result from lower Au concentrations within a liquid Ga solvent are hitherto unknown. Here, ab initio molecular dynamics are used to understand how different low concentrations of Au operate within a liquid Ga solvent. We determine that Au concentrations of between 15% Au wt and 25% Au wt will give rise to the highest abundance of stabilised single Au atoms.

Molecular crystals vs. superatomic lattice: a case study with superalkali-superhalogen compounds.

Using a first-principles approach, we study the assembly of atomically-precise cluster solids with atomic precision. The aims are to create binary assemblies of clusters through charge transfer between neutral molecular clusters, and employing intercluster electrostatic attraction as a driving force for co-assembly. We combined pairs of complementary clusters in which one cluster is electron-donating (superalkali) and the other is electron-accepting (superhalogen). From the analysis of the binding energy between superatomic counterparts, charge transfer, and the relative size of the clusters, we analyze the resulting structures as either molecular crystals or superatomic lattices. We demonstrate that the substitution of a single atom can result in minor changes to the crystal structure of the binary solids or entirely new packing structures. The [N4Mg6Li]+[AlCl4]-, [N4Mg6Na]+[AlCl4]-, [N4Mg6K]+[AlCl4]-, [N4Mg6Li]+[AlF4]-, [N4Mg6Na]+[AlF4]-, and [N4Mg6K]+[AlF4]- compounds all form the same close-packed superatomic lattice structure through halogen bonding, with subtle differences in the orientation of the superatoms. These salts may also form molecular crystals where clusters are held to one another by electrostatic interactions. Our results emphasize how the structure of superatomic solids can be tuned upon single atom substitution.

Catalytic Potential of Post-Transition Metal Doped Graphene-Based Single-Atom Catalysts for the CO2 Electroreduction Reaction.

Catalysts are required to ensure electrochemical reduction of CO2 to fuels proceeds at industrially acceptable rates and yields. As such, highly active and selective catalysts must be developed. Herein, a density functional theory study of p-block element and noble metal doped graphene-based single-atom catalysts in two defect sites for the electrochemical reduction of CO2 to CO and HCOOH is systematically undertaken. It is found that on all of the systems considered, the thermodynamic product is HCOOH. Pb/C3 , Pb/N4 and Sn/C3 are identified as having the lowest overpotential for HCOOH production while Al/C3 , Al/N4 , Au/C3 and Ga/C3 are identified as having the potential to form higher order products due to the strength of binding of adsorbed HCOOH.

Clustering of metal dopants in defect sites of graphene-based materials.

Single-atom catalysts are promising candidates for many industrial reactions. However, making true single-atom catalysts is an experimental dilemma, due to the difficulty of keeping dopant single atoms stable at temperature and under pressure. This difficulty can lead to clustering of the metal dopant atoms in defect sites. However, the electronic and geometric structure of sub-nanoscale clusters in single-atom defects has not yet been explored. Furthermore, recent studies have proven sub-nanoscale clusters of dopants in single-atom defect sites can be equally good or better catalysts than their single-atom counterparts. Here, a comprehensive DFT study is undertaken to determine the geometric and electronic structure effects that influence clustering of noble and p-block dopants in C3- and N4-defect sites in graphene-based systems. We find that the defect site is the primary driver in determining clustering dynamics in these systems.

Bimetallic superalkali substitution in the CsPbBr3 perovskite: Pseudocubic phases and tunable bandgap.

Perovskites attract attention as efficient light absorbers for solar cells due to their high-power conversion efficiency (up to 24%). The high photoelectric conversion efficiency is greatly affected by a suitable band structure. Cation substitution can be an effective approach to tune the electronic band structure of lead halide perovskites. In this work, superalkali cations were introduced to replace the Cs+ cation in the CsPbBr3 material. The bimetallic superalkalis (LiMg, NaMg, LiCa, and NaCa) were inserted since they are structurally simple systems and have a strong tendency to lose one electron to achieve a closed-shell cation. The cation substitution in the lead halide perovskite leads to changes in the shape of both valence and conduction bands compared to CsPbBr3. Introducing superalkali cations produces extra electronic states close to the Fermi level, which arise from the formation of alkali earth metal states at the top of the valence band. Our first-principles computations reveal that bimetallic superalkali substitution decreases the bandgap of the perovskite. The bandgaps of MgLi-PbBr3 (1.35 eV) and MgNa-PbBr3 (1.06 eV) are lower than the bandgap of CsPbBr3 (2.48 eV) and within the optimal bandgap (i.e., 1.1-1.4 eV) for single-junction solar cells. Thus, the MgLi-PbBr3 and MgNa-PbBr3 inorganic perovskites are promising candidates for high-efficiency solar cells.

Emergent electronic properties in Co-deposited superatomic clusters.

We report an intercluster compound based on co-deposition of the Au cluster [Au9(PPh3)8](NO3)3 and the fulleride KC60(THF). Electronic properties characteristic for a charge interaction between superatoms emerge within the solid state material [Au9(PPh3)8](NO3)3-x(C60)x, as confirmed by UV-VIS and Raman spectroscopy and I-V measurements. These emergent properties are related to the superatomic electronic states of the initial clusters. The material is characterized by Fourier-transform infrared spectroscopy, x-ray diffraction, Raman spectroscopy, and electrical measurements. Structural optimization and ab initio band structure calculations are performed with density functional theory to interpret the nature of the electronic states in the material; Bader charge calculations assign effective oxidation states in support of the superatomic model of cluster interactions.

Structural, Thermal, and Electronic Properties of Two-Dimensional Gallium Oxide (ß-Ga2 O3 ) from First-Principles Design.

Two-dimensional (2D) materials with exotic electronic, optical and mechanical properties have attracted tremendous attention in the last two decades, due to their potential applications in electronics, energy storage and conversion technologies. However, only a few dozen 2D materials have been successfully synthesized or exfoliated. Motivated by the recent discovery of 2D gallenene, we have explored new 2D allotropes of ß-Ga2 O3 , an emerging wide-band gap transparent conductive oxide (TCO) with a wide range of semiconducting applications. All the possible 2D allotropes of ß-Ga2 O3 with high energetic stability have been predicted using particle swarm optimization, combined with density functional theory calculations. The structural and dynamical stability of the predicted 2D allotropes has been analyzed. Although ß-Ga2 O3 is not a van der Waals material, results predict that one or two allotropes of ß-Ga2 O3 are stable. In addition, the accurate band structures of these 2D semiconducting oxides have been calculated using both the GGA and LDA-1/2 approach. Remarkably, monolayer Ga2 O3 (100) has a larger indirect band gap of 4 eV, demonstrating a new avenue for the discovery of 2D ß-Ga2 O3 based nano-devices with enhanced electronic properties.

A mechanistic understanding of surface Bi enrichment in dilute GaBi systems.

Experiment has shown that dilute GaBi systems produce a range of self-organised nanostructured patterns at the surface [Tang et al., Nat. Nanotechnol., 2021, 16, 431-439]. Using extensive ab initio molecular dynamics simulations, we elucidate the mechanisms underlying the formation of the Bi surface islands in Bi-doped Ga liquid metals. Here, we show that in order for internal Bi atoms to diffuse to the surface a lateral extension of the Ga surface network is required. Furthermore, the absence of surface Bi patterning perturbs the Ga surface network providing a preferred path for an internal Bi to diffuse. By understanding how and why Bi nucleates at a surface, we increase the ability to control, manipulate and design such systems for use in future electronic devices.

Unique surface patterns emerging during solidification of liquid metal alloys.

It is well-understood that during the liquid-to-solid phase transition of alloys, elements segregate in the bulk phase with the formation of microstructures. In contrast, we show here that in a Bi-Ga alloy system, highly ordered nanopatterns emerge preferentially at the alloy surfaces during solidification. We observed a variety of transition, hybrid and crystal-defect-like patterns, in addition to lamellar and rod-like structures. Combining experiments and molecular dynamics simulations, we investigated the influence of the superficial Bi and Ga2O3 layers during surface solidification and elucidated the pattern-formation mechanisms, which involve surface-catalysed heterogeneous nucleation. We further demonstrated the dynamic nature and robustness of the phenomenon under different solidification conditions and for various alloy systems. The surface patterns we observed enable high-spatial-resolution nanoscale-infrared and surface-enhanced Raman mapping, which reveal promising potential for surface- and nanoscale-based applications.

Modulating the thermal and structural stability of gallenene via variation of atomistic thickness.

Using ab initio molecular dynamics, we show that a recently discovered form of 2D Ga-gallenene-exhibits highly variable thickness dependent properties. Here, 2D Ga of four, five and six atomic layers thick are found to be thermally stable to 457 K, 350 K and 433 K, respectively; all well above that of bulk Ga. Analysis of the liquid structure of 2D Ga shows a thickness dependent ordering both parallel and perpendicular to the Ga/vacuum interface. Furthermore, ground state optimisations of 2D Ga to 12 atomic layers thick shows a return to a bulk-like bonding structure at 10 atoms thick, therefore we anticipate that up to this thickness 2D Ga structures will each exhibit novel properties as discrete 2D materials. Gallenene has exciting potential applications in plasmonics, sensors and electrical contacts however, for the potential of 2D Ga to be fully realised an in depth understanding of its thickness dependent properties is required.

Two-dimensional aluminium, gallium, and indium metallic crystals by first-principles design.

Rapidly emerging two-dimensional (2D) atomic layer crystals exhibit diverse, tunable electronic properties. They appear to be more flexible than 3D crystals with greater versatility and improved functionality in a wide range of potential applications. Among these 2D materials, metallic crystals are relatively unexplored although two allotropes of gallenene (2D gallium) have been synthesized on a range of substrates. Based on these experimental findings, we investigate systematically the group 13 metals using first-principles density functional theory calculations and an unbiased structural search. In this study, the electronic structure, bonding characteristics, and phonon properties of predicted 2D allotropes of group 13 metals are calculated, including the expected effects of strain induced by substrates on the dynamical stability. Theoretical results predict that most group 13 elements have one or more stable 2D allotropes with the preferred allotrope depending on the cell shape relaxation and strain, indicating that the substrate will determine the overall allotrope preferred. This demonstrates a new avenue for the discovery of thermodynamically stable 2D metallic layers, with properties potentially suitable for electronic and optoelectronic applications.

N4Mg6M (M = Li, Na, K) superalkalis for CO2 activation.

Superatoms have exciting properties, including diverse functionalization, redox activity, and magnetic ordering, so the resulting cluster-assembled solids hold the promise of high tunability, atomic precision, and robust architectures. By utilizing adamantane-like clusters as building blocks, a new class of superatoms N4Mg6M (M = Li, Na, K) is proposed here. The studied superalkalis feature low adiabatic ionization energies, an antibonding character in the interactions between magnesium and nitrogen atoms, and highly delocalized highest occupied molecular orbital (HOMO). Consequently, the N4Mg6M superalkalis might easily lose their HOMO electrons when interacting with superhalogen electrophiles to form stable superatom [superalkali]+[superhalogen]- compounds. Moreover, the studied superalkalis interact strongly with carbon dioxide, and the resulting N4Mg6M/CO2 systems represent two strongly interacting ionic fragments (i.e., N4Mg6M+ and CO2 -). In turn, the electron affinity of the N2 molecule (of -1.8 eV) is substantially lower than that observed for carbon dioxide (EA = -0.6 eV) and consequently, the N2 was found to form the weakly bound [N4Mg6M][N2] complex rather than the desired ionic [N4Mg6M]+[N2]- product. Thus, the N4Mg6M superalkalis have high selectivity over N2 when it comes to CO2 reduction and also are themselves stable. We believe that the results described within this paper will be useful for understanding CO2 activation, which is the first step for producing fuels from CO2. Moreover, we demonstrate that designing novel superatomic systems and exploring their physicochemical features might be used to create desirable functional materials.

Modified Lennard-Jones potentials for nanoscale atoms.

A classical 6-12 Lennard-Jones (LJ) equation has been widely used to model materials and is the potential of choice in studies when the focus is on fundamental issues. Here we report a systematic study comparing the pair interaction potentials within solid-state materials (i.e., [Co6 Se8 (PEt3 )6 ][C60 ]2 , [Cr6 Te8 (PEt3 )6 ][C60 ]2 , [Ni9 Te6 (PEt3 )8 ][C60 ]) using density functional theory (DFT) calculations and LJ parametrization. Both classical (6-12 LJ) and modified LJ (mLJ) models were developed. In the mLJ approach, the exponents 6 and 12 are replaced by different integer number n and 2n, respectively, and an additional parameter (α) is introduced to describe intermolecular distance shift arising within the geometric centers' approach (instead of the shortest interatomic distance between particles). A general LJ approach reexamination reveals that in the case of nanoatoms, the attractive term decays with distance as the inverse fourth power, and the dominating at short distances repulsive term decays as the inverse eighth power. The modification of the LJ equation is even more prominent for interaction profiles, where intermolecular distance corresponds to separation between geometric centers of particles. In this approach, the attractive term decays with distance as the inverse 12th power, while the repulsive term decays rapidly (as the inverse 24th power). Thus, the mLJ models (e.g., 4-8 LJ) rather than the 6-12 classical ones seem to be a better choice for the description of binary interactions of nanoatoms. The developed mLJ models and electronic structure characteristics give an insight into the explanation of the unique physicochemical properties of superatomic-based solid-state materials.

Ultra stable superatomic structure of doubly magic Ga13 and Ga13Li electrolyte.

We report the extreme thermal stability of the superatomic electronic structure for 13-atom gallium clusters and the Ga13Li electrolyte. Using previously-validated first-principles simulations, [K. G. Steenbergen and N. Gaston, Phys. Rev. B: Condens. Matter Mater. Phys., 2013, 88, 161402-161405] we show that the superatomic shell progression of doubly-magic Ga13- remains stable up to 1000 K, making this cluster an ideal candidate for high-temperature applications requiring an exceptionally stable electronic structure. Using the neutral and cationic clusters for comparison, we quantify the extent to which cluster stability (geometric and electronic) is modified through addition or subtraction of a single electron. Finally, combining 13-atom gallium with lithium, we illustrate that superatomic closed-shell Ga13Li exhibits the same exceptionally high thermal stability as naked Ga13-. For technological use as a superatomic electrolyte, we demonstrate that Ga13Li has a low affinity to water as well as a low Li+ binding energy.