ABSTRACT
MoS2 is a promising semiconducting material that has been widely studied for applications in catalysis and energy storage. The covalent chemical functionalization of MoS2 can be used to tune the optoelectronic and chemical properties of MoS2 for different applications. However, 2H-MoS2 is typically chemically inert and difficult to functionalize directly and thus requires pretreatments such as a phase transition to 1T-MoS2 or argon plasma bombardment to introduce reactive defects. Apart from being inefficient and inconvenient, these methods can cause degradation of the desirable properties and introduce unwanted defects. Here, we demonstrate that 2H-MoS2 can be simultaneously electrochemically exfoliated and chemically functionalized in a facile and scalable procedure to fabricate functionalized thin (â¼4 nm) MoS2 layers. The aryl diazonium salts used for functionalization have not only been successfully covalently grafted onto the 2H-MoS2, as verified by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, but also aid the exfoliation process by increasing the interlayer spacing and preventing restacking. Electrochemical energy storage is one application area to which this material is particularly suited, and characterization of supercapacitor electrodes using this exfoliated and functionalized material revealed that the specific capacitance was increased by â¼25% when functionalized. The methodology demonstrated for the simultaneous production and functionalization of two-dimensional (2D) materials is significant, as it allows for control over the flake morphology with increased repeatability. This electrochemical functionalization technique could also be extended to other types of transition-metal dichalcogenides (TMDs), which are also typically chemically inert with different functional species to adjust to specific applications.
ABSTRACT
The development of well-defined nanomaterials as non-noble metal electrocatalysts has broad application prospect for hydrogen generation technology. Recently, multi-metal electrocatalysts for hydrogen evolution reaction (HER) have attracted extensive attention due to their high catalytic performance arising from the synergistic effect of multi-metal interaction. However, most multi-metal catalysts suffer from the limited synergistic effect because of poor interfacial compatibility between different components. Here, a novel multi-metal catalyst (Ni/MoO2@CoFeOx) nanosheet with a crystalline/amorphous structure is demonstrated, which shows high HER activity. Ni/MoO2@CoFeOx exhibits an ultra-low overpotential of 18, 39, and 93 mV at 10 mA cm-2 in alkaline water, alkaline seawater and natural seawater, respectively, which outperformances most of the state-of-the-art non-noble metal compounds. In addition, the catalyst shows exceptional stability under 500 mA cm-2 in alkaline solution. In-situ Raman and other advanced structural characterization confirms the excellent catalytic activity is mainly contributed by: (1) the strong synergistic effect of multi-metal components provides multiple active sites in the catalytic process; (2) the crystalline/amorphous interface in Ni/MoO2@CoFeOx boosts the catalytically active sites and structure stability; (3) the crystalline phase enhances the intrinsic conductivity greatly; and (4) the amorphous phase provides abundant unsaturated sites for improved intrinsic catalytic activity. This work provides a feasible way to design electrocatalyst with high activity and stability for practical applications.
ABSTRACT
Atomically dispersed metal-nitrogen-carbon catalysts (M-N-C) have been widely used in the field of energy conversion, which has already attracted a huge amount of attention. Due to their unsaturated d-band electronic structure of the center atoms, M-N-C catalysts can be applied in different electrocatalytic reactions by adjusting their own microscopic electronic structures to achieve the optimization of the structure-activity relationship. Consequently, it is of great significance for the revelation of electrocatalytic mechanism and structure-activity relationship of M-N-C catalysts. Thus, this review first introduces the relative research methods, including in situ/operando characterization techniques and theoretical calculation methods. Furthermore, clarifying the electrocatalytic mechanism and structure-activity relationship of M-N-C catalysts in different electrochemical energy conversion reactions is focused. Moreover, the future research directions are pointed out based on the discussion. This review will provide good guidance to systematically study the catalytic mechanism of single-atom catalysts and reasonably design the single-atom catalysts.
ABSTRACT
Transitional metal carbides and nitrides (MXenes) have promise for incorporation into multifunctional composites due to their high electrical conductivity and excellent mechanical and tribological properties. It is unclear, however, to what extent MXenes are also able to improve the mechanical properties of the composites and, if so, what would be the optimal flake size and morphology. Herein, Ti3C2Tx MXene is demonstrated to be indeed a good candidate for mechanical reinforcement in polymer matrices. In the present work, the strain-induced Raman band shifts of mono-/few-/multilayer MXenes flakes have been used to study the mechanical properties of MXene and the interlayer/interfacial stress transfer on a polymer substrate. The mechanical performance of MXene was found to be less dependent upon flake thickness compared to that of graphene. This enables Ti3C2Tx MXene to offer an efficient mechanical reinforcement to a polymer matrix with a flake length of >10 µm and a thickness of 10s of nanometers. Therefore, the degree of exfoliation of MXenes is not as demanding as other two-dimensional (2D) materials for the purpose of mechanical enhancement in polymers. In addition, the active surface chemistry of MXene facilitates possible functionalization to enable a stronger interface with polymers for applications, such as strain engineering and mechanical enhancement, and in materials including membranes, coatings, and textiles.
