A number of important reactions such as the oxygen evolution reaction (OER) are catalyzed by transition metal oxides (TMOs), the surface reactivity of which is rather elusive. Therefore, rationally tailoring adsorption energy of intermediates on TMOs to achieve desirable catalytic performance still remains a great challenge. Here we show the identification of a general and tunable surface structure, coordinatively unsaturated metal cation (MCUS), as a good surface reactivity descriptor for TMOs in OER. Surface reactivity of a given TMO increases monotonically with the density of MCUS, and thus the increase in MCUS improves the catalytic activity for weak-binding TMOs but impairs that for strong-binding ones. The electronic origin of the surface reactivity can be well explained by a new model proposed in this work, wherein the energy of the highest-occupied d-states relative to the Fermi level determines the intermediates' bonding strength by affecting the filling of the antibonding states. Our model for the first time well describes the reactivity trends among TMOs, and would initiate viable design principles for, but not limited to, OER catalysts.

Twinned growth behaviour in the rapidly emerging area of two-dimensional nanomaterials still remains unexplored although it could be exploited to fabricate heterostructure and superlattice materials. Here we demonstrate how one can utilize the twinned growth relationship between two two-dimensional materials to construct vertically stacked heterostructures. As a demonstration, we achieve 100% overlap of the two transition metal dichalcogenide layers constituting a ReS2/WS2 vertical heterostructure. Moreover, the crystal size of the stacked structure is an order of magnitude larger than previous reports. Such twinned transition metal dichalcogenides vertical heterostructures exhibit great potential for use in optical, electronic and catalytic applications. The simplicity of the twinned growth can be utilized to expand the fabrication of other heterostructures or two-dimensional material superlattice and this strategy can be considered as an enabling technology for research in the emerging field of two-dimensional van der Waals heterostructures.

The quality of graphene grown via chemical vapor deposition still has very great disparity with its theoretical property due to the inevitable formation of grain boundaries. The design of single-crystal substrate with an anisotropic twofold symmetry for the unidirectional alignment of graphene seeds would be a promising way for eliminating the grain boundaries at the wafer scale. However, such a delicate process will be easily terminated by the obstruction of defects or impurities. Here we investigated the isotropic growth behavior of graphene single crystals via melting the growth substrate to obtain an amorphous isotropic surface, which will not offer any specific grain orientation induction or preponderant growth rate toward a certain direction in the graphene growth process. The as-obtained graphene grains are isotropically round with mixed edges that exhibit high activity. The orientation of adjacent grains can be easily self-adjusted to smoothly match each other over a liquid catalyst with facile atom delocalization due to the low rotation steric hindrance of the isotropic grains, thus achieving the smoothing stitching of the adjacent graphene. Therefore, the adverse effects of grain boundaries will be eliminated and the excellent transport performance of graphene will be more guaranteed. What is more, such an isotropic growth mode can be extended to other types of layered nanomaterials such as hexagonal boron nitride and transition metal chalcogenides for obtaining large-size intrinsic film with low defect.

This work aims to reveal the origin of the large onset overpotential and sluggish kinetics of the oxygen reduction reaction (ORR) on Pt, a standing problem that hinders the progress of fuel cell technology. By investigating various possible reaction steps and pathways through detailed DFT calculations on Pt(111) surface covered by rationalized phase structures of oxygenated adsorbates, we show that the ORR overpotential and Tafel kinetics originate from the potential-dependent formation of a site-blocking spectator phase, √3 × √3-structured oxygen adatoms (O*), which coexists with a relatively weak blocking phase, (√3 × √3)­R30°-patterned adsorption network of hydroxyl group (OH*) and water molecule (H2O*) at ORR relevant potentials. The OH*/H2O* phase provides sites for ORR to proceed through a dissociative pathway consisting of four proton/electron transfer (PET) steps. The first step, PET-coupled O2 adsorption, is identified as the activity-determining step. Different from the usual beliefs, we found the O2 and O* do not directly accept proton during the reduction steps; rather, OH* and H2O* act as PET mediators to facilitate the O2 adsorption and dissociation and the O* reduction. These findings unveil the distinctly multiple roles of various oxygenated adsorbates as intermediates, spectators, and PET mediators in ORR. The implications of these findings on designing Pt-based catalysts are discussed. It is concluded that the binding strength of O* impacts the ORR activity of Pt-based surface predominantly by modulating the number of the available active sites, rather than the activation barriers for the rate-determining step.

The self-assembly of two-dimensional (2D) nanomaterials, an emerging research area, still remains largely unexplored. The strong interlayer attraction between 2D nanosheets leads to face-to-face stacking rather than edge-to-edge coupling. We demonstrate, for the first time, how one can induce and control an edge-to-edge self-assembly process for 2D nanomaterials. The extremely weak van der Waals coupling and strong anisotropy of ReS2 allow us to realize an oriented self-assembly (OSA) process. The aspect ratio of the resulting ReS2 nanoscrolls can be well controlled. In addition, we perform simulations to further explain and confirm the OSA process, demonstrating its great potential to be expanded as a general edge-to-edge self-assembly process suitable for other 2D nanomaterials.