Toward the Effective Exploitation of Topological Phases of Matter in Catalysis: Chemical Reactions at the Surfaces of NbAs and TaAs Weyl Semimetals

By means of density functional theory and experiments, surface chemical reactivity of single crystals of NbAs and TaAs Weyl semimetals is studied. Weyl semimetals exhibit outstanding reactivity toward simple molecules (oxygen, carbon monoxide, and water), with several active sites available for surface chemical reactions (adsorption, decomposition, formation of reaction products, recombination of decomposition fragments). When different chemical species are adsorbed on Weyl semimetals, strong lateral interactions between coadsorbed species occur, evidenced by CO‐promoted water decomposition at room temperature. The resulting ? OH groups react with CO to form HCOO, which is an intermediate species in water–gas shift reaction. These findings unambiguously demonstrate that Weyl semimetals could be effectively used in catalysis, whereas their employment in nanoelectronics or plasmonics is complicated by the poor ambient stability, due to the rapid surface oxidation, inevitably occurring unless protective capping layers are used.     

Revisiting the Chemical Stability of Germanium Selenide (GeSe) and the Origin of its Photocatalytic Efficiency

Recently, germanium selenide (GeSe) has emerged as a promising van der Waals semiconductor for photovoltaics, solar light harvesting, and water photoelectrolysis cells. Contrary to previous reports claiming perfect ambient stability based on experiments with techniques without surface sensitivity, here, by means of surface-science investigations and density functional theory, it is demonstrated that actually both: i) the surface of bulk crystals; and ii) atomically thin flakes of GeSe are prone to oxidation, with the formation of self-assembled germanium-oxide skin with sub-nanometric thickness. Surface oxidation leads to the decrease of the bandgap of stoichiometric GeSe and GeSe_1−x, while bandgap energy increases upon surface oxidation of Ge_1−xSe. Remarkably, the formation of a surface oxide skin on GeSe crystals plays a key role in the physicochemical mechanisms ruling photoelectrocatalysis: the underlying van der Waals semiconductor provides electron–hole pairs, while the germanium-oxide skin formed upon oxidation affords the active sites for catalytic reactions. The self-assembled germanium-oxide/germanium-selenide heterostructure with different bandgaps enables the activation of photocatalytic processes by absorption of light of different wavelengths, with inherently superior activity. Finally, it is discovered that, depending on the specific solvent-GeSe interaction, the liquid phase exfoliation of bulk crystals can induce the formation of Se nanowires.     

Surface Instability and Chemical Reactivity of ZrSiS and ZrSiSe Nodal‐Line Semimetals

Materials exhibiting nodal‐line fermions promise superb impact on technology for the prospect of dissipationless spintronic devices. Among nodal‐line semimetals, the ZrSiX (X = S, Se, Te) class is the most suitable candidate for such applications. However, the surface chemical reactivity of ZrSiS and ZrSiSe has not been explored yet. Here, by combining different surface‐science tools and density functional theory, it is demonstrated that the formation of ZrSiS and ZrSiSe surfaces by cleavage is accompanied by the washing up of the exotic topological bands, giving rise to the nodal line. Moreover, while the ZrSiS has a termination layer with both Zr and S atoms, in the ZrSiSe surface, reconstruction occurs with the appearance of Si surface atoms, which is particularly prone to oxidation. It is demonstrated that the chemical activity of ZrSiX compounds is mostly determined by the interaction of the Si layer with the ZrX sublayer. A suitable encapsulation for ZrSiX should not only preserve their surfaces from interaction with oxidative species, but also provide a saturation of dangling bonds with minimal distortion of the surface.     

Surface Reconstruction,Oxidation Mechanism,and Stability of Cd3As2

Cadmium arsenide (Cd₃As₂) has recently attracted considerable interest for the presence of 3D massless Dirac fermions with ultrahigh mobility and magnetoresistance. However, its surface properties are currently largely unexplored both theoretically and experimentally, due to the very large unit cell and the challenging growth of single‐crystal samples, respectively. Here, by combining ab initio calculations with surface‐science spectroscopic experiments, the presence of a surface reconstruction is unveiled in centimeter‐scale (112)‐oriented Cd₃As₂ single‐crystal foils produced by the self‐selecting vapor growth. Outermost Cd atoms descend into the As‐sublayer with a subsequent self‐passivation of the dangling bonds with As atoms, forming the triangle lattice previously imaged by scanning tunneling microscopy. Moreover, the oxidation mechanism of this reconstructed surface, dominated by the formation of As? O? Cd bonds, is revealed. Interestingly, it is found that the band structure of the reconstructed surface of Cd₃As₂ is quite robust against surface oxidation. Both computational and experimental findings point to a successful exploitation in technology of Cd₃As₂ single crystals.     

CsPbBr3:Na with an Adjustable Bandgap,Improved Luminescence Stability,and its Application in WLEDs with Excellent Color Quality and Vision Performance

It is still a great challenge to obtain multicolor tunable luminescence and improve the stability of luminescence through reasonable design of materials in the field of white light-emitting diodes (WLEDs). In particular, it is more important to improve the luminescence intensity and stability of blue-emitting materials. Here, the properties of CsPbBr₃, CsPbBr₃:Na_, and NaPbBr₃ are investigated theoretically by using density functional theory (DFT). Based on the DFT theoretical calculation results, it is assumed that unexpected performance may be achieved by replacing Cs in CsPbBr₃ with Na or passivating the surface of CsPbBr₃ with Na. As expected, the tunable luminescence from blue to green is successfully achieved from CsPbBr₃:Na, and the stability is improved. After experimental optimization, the obtained CsPbBr₃:Na (CPBN-4) with high luminescence stability is used as blue-emitting materials to construct the WLED devices with excellent color quality (CRI 92) and correlated color temperature of 9582 K.