Highly effective electrocatalysts promoting CO 2 reduction reaction (CO 2 RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metalorganic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN 4) and zinc-bis (dihydroxy) complex (ZnO 4) as linkage (PcCu-O 8-Zn). The PcCu-O 8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s −1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H 2 /CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO 4 complexes act as CO 2 RR catalytic sites while CuN 4 centers promote the protonation of adsorbed CO 2 during CO 2 RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO 2 RR toward syngas synthesis.

Quantum conductance calculations on the mechanically deformed monolayers of MoS 2 and WS 2 were performed using the non-equlibrium Green's functions method combined with the Landauer-Büttiker approach for ballistic transport together with the density-functional based tight binding (DFTB) method. Tensile strain and compression causes significant changes in the electronic structure of TMD single layers and eventually the transition semiconductor-metal occurs for elongations as large as 11% for the 2D-isotropic deformations in the hexagonal structure. This transition enhances the electron transport in otherwise semiconducting materials.

Using a set of first-principles calculations, we studied the electronic structures of two-dimensional transition metal carbides and nitrides, so called MXenes, functionalized with F, O, and OH. Our projected band structures and electron localization function analyses reveal the existence of nearly free electron (NFE) states in variety of MXenes. The NFE states are spatially located just outside the atomic structure of MXenes and are extended parallel to the surfaces. Moreover, we found that the OH-terminated MXenes offer the NFE states energetically close to the Fermi level. In particular, the NFE states in some of the OHterminated MXenes, such as Ti2C(OH)2, Zr2C(OH)2, Zr2N(OH)2, Hf2C(OH)2, Hf2N(OH)2, Nb2C(OH)2, and Ta2C(OH)2, are partially occupied. This is in remarkable contrast to graphene, graphane, and MoS2, in which their NFE states are located far above the Fermi level and thus they are unoccupied. As a prototype of such systems, we investigated the electron transport properties of Hf2C(OH)2 and found that the NFE states in Hf2C(OH)2 provide almost perfect transmission channels without nuclear scattering for electron transport. Our results indicate that these systems might find applications in nanoelectronic devices. Our findings provide new insights into the unique electronic band structures of MXenes.Introduction:

The transition-metal dichalcogenides (TMD) MoS2 and WS2 show remarkable electromechanical properties. Strain modifies the direct band gap into an indirect one, and substantial strain even induces an semiconductor-metal transition. Providing strain through mechanical contacts is difficult for TMD monolayers, but state-of-the-art for TMD nanotubes. We show using density-functional theory that similar electromechanical properties as in monolayer and bulk TMDs are found for large diameter TMD single- (SWNT) and multi-walled nanotubes (MWNTs). The semiconductor-metal transition occurs at elongations of 16%. We show that Raman signals of the in-plane and out-of-plane lattice vibrations depend significantly and linearly on the strain, showing that Raman spectroscopy is an excellent tool to determine the strain of the individual nanotubes and hence monitor the progress of nanoelectromechanical experiments in situ. TMD MWNTs show twice the electric conductance compared to SWNTs, and each wall of the MWNTs contributes to the conductance proportional to its diameter.

Two-dimensional (2D) transition metal dichalcogenides (TMDs), like MoS2, have unique electronic and optical properties, which can further be tuned using ion bombardment and post-synthesis ion-beam mediated methods combined with exposure of the irradiated sample to precursor gases. The optimization of these techniques requires a complete understanding of the response of 2D TMDs to ion irradiation, which is affected by the reduced dimensionality of the system. By combining analytical potential molecular dynamics with first-principles calculations, we study the production of defects in free-standing MoS2 sheets under noble gas ion irradiation for a wide range of ion energies when nuclear stopping dominates, and assess the probabilities for different defects to appear. We show that depending on the incident angle, ion type and energy, sulfur atoms can be sputtered away predominantly from the top or bottom layers, creating unique opportunities for engineering mixed MoSX compounds where X are chemical elements from group V or VII. We study the electronic structure of such systems, demonstrate that they can be metals, and finally discuss how metal/semiconductor/metal junctions, which exhibit negative differential resistance, can be designed using focused ion beams combined with the exposure of the system to fluorine.