Nanostructured transition metal dichalcogenides (TMDs) are proven to be efficient and robust earth-abundant electrocatalysts to potentially replace precious platinum-based catalysts for the hydrogen evolution reaction (HER). However, the catalytic efficiency of reported TMD catalysts is still limited by their low-density active sites, low conductivity, and/or uncleaned surface. Herein, a general and facile method is reported for high-yield, large-scale production of water-dispersed, ultrasmall-sized, high-percentage 1T-phase, single-layer TMD nanodots with high-density active edge sites and clean surface, including MoS , WS , MoSe , Mo W S , and MoSSe, which exhibit much enhanced electrochemical HER performances as compared to their corresponding nanosheets. Impressively, the obtained MoSSe nanodots achieve a low overpotential of -140 mV at current density of 10 mA cm , a Tafel slope of 40 mV dec , and excellent long-term durability. The experimental and theoretical results suggest that the excellent catalytic activity of MoSSe nanodots is attributed to the high-density active edge sites, high-percentage metallic 1T phase, alloying effect and basal-plane Se-vacancy. This work provides a universal and effective way toward the synthesis of TMD nanostructures with abundant active sites for electrocatalysis, which can also be used for other applications such as batteries, sensors, and bioimaging.
The crystal phase-based heterostructures of noble metal nanomaterials are of great research interest for various applications, such as plasmonics and catalysis. However, the synthesis of unusual crystal phases of noble metals still remains a great challenge, making the construction of heterophase noble metal nanostructures difficult. Here, we report a one-pot wetchemical synthesis of well-defined heterophase fcc-2H-fcc gold nanorods (fcc: face-centred cubic; 2H: hexagonal close-packed with stacking sequence of "AB") at mild conditions. Single particle-level experiments and theoretical investigations reveal that the heterophase gold nanorods demonstrate a distinct optical property compared to that of the conventional fcc gold nanorods. Moreover, the heterophase gold nanorods possess superior electrocatalytic activity for the carbon dioxide reduction reaction over their fcc counterparts under ambient conditions. First-principles calculations suggest that the boosted catalytic performance stems from the energetically favourable adsorption of reaction intermediates, endowed by the unique heterophase characteristic of gold nanorods.
Phase engineering is arising as an attractive strategy to tune the properties and functionalities of nanomaterials. In particular, amorphous/crystalline heterophase nanostructures have exhibited some intriguing properties. Herein, the one-pot wet-chemical synthesis of two types of amorphous/crystalline heterophase PdCu nanosheets is reported, in which one is amorphous phase-dominant and the other one is crystalline phase-dominant. Then the aging process of the synthesized PdCu nanosheets is studied, during which their crystallinity increases, accompanied by changes in some physicochemical properties. As a proof-of-concept application, their aging effect on catalytic hydrogenation of 4-nitrostyrene is investigated. As a result, the amorphous phase-dominant nanosheets initially show excellent chemoselectivity. After aging for 14 days, their catalytic activity is higher than that of crystalline phase-dominant nanosheets. This work demonstrates the intriguing properties of heterophase nanostructures, providing a new platform for future studies on the regulation of functionalities and applications of nanomaterials by phase engineering.
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