Vivek B. Shenoy

Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution

Efficient evolution of hydrogen through electrocatalysis at low overpotentials holds tremendous promise for clean energy. Hydrogen evolution can be easily achieved by electrolysis at large potentials that can be lowered with expensive platinum-based catalysts. Replacement of Pt with inexpensive, earth-abundant electrocatalysts would be significantly beneficial for clean and efficient hydrogen evolution. To this end, promising results have been reported using 2H (trigonal prismatic) XS₂ (where X  =  Mo or W) nanoparticles with a high concentration of metallic edges. The key challenges for XS₂ are increasing the number and catalytic activity of active sites. Here we report monolayered nanosheets of chemically exfoliated WS₂ as efficient catalysts for hydrogen evolution with very low overpotentials. Analyses indicate that the enhanced electrocatalytic activity of WS₂ is associated with the high concentration of the strained metallic 1T (octahedral) phase in the as-exfoliated nanosheets. Our results suggest that chemically exfoliated WS₂ nanosheets are interesting catalysts for hydrogen evolution.

Structural evolution during the reduction of chemically derived graphene oxide

The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed.

Conducting MoS2 Nanosheets as Catalysts for Hydrogen Evolution Reaction

We report chemically exfoliated MoS2 nanosheets with a very high concentration of metallic 1T phase using a solvent free intercalation method. After removing the excess of negative charges from the surface of the nanosheets, highly conducting 1T phase MoS2 nanosheets exhibit excellent catalytic activity toward the evolution of hydrogen with a notably low Tafel slope of 40 mV/dec. By partially oxidizing MoS2, we found that the activity of 2H MoS2 is significantly reduced after oxidation, consistent with edge oxidation. On the other hand, 1T MoS2 remains unaffected after oxidation, suggesting that edges of the nanosheets are not the main active sites. The importance of electrical conductivity of the two phases on the hydrogen evolution reaction activity has been further confirmed by using carbon nanotubes to increase the conductivity of 2H MoS2.

An adaptive finite element approach to atomic-scale mechanics—the quasicontinuum method

Mixed atomistic and continuum methods offer the possibility of carrying out simulations of material properties at both larger length scales and longer times than direct atomistic calculations. The quasicontinuum method links atomistic and continuum models through the device of the finite element method which permits a reduction of the full set of atomistic degrees of freedom. The present paper gives a full description of the quasicontinuum method, with special reference to the ways in which the method may be used to model crystals with more than a single grain. The formulation is validated in terms of a series of calculations on grain boundary structure and energetics. The method is then illustrated in terms of the motion of a stepped twin boundary where a critical stress for the boundary motion is calculated and nanoindentation into a solid containing a subsurface grain boundary to study the interaction of dislocations with grain boundaries.

Anomalous Strength Characteristics of Tilt Grain Boundaries in Graphene

Perfect Imperfections Graphene is composed of six-atom rings, but will include a number of five- and seven-atom rings as defects. Using simulations, Grantab et al. (p. 946) show that more defects do not necessarily lead to greater deterioration of mechanical properties. Mismatches caused by differences in the orientation of neighboring crystals are divided into low- and high-angle grain boundaries, and typically it is the lower-angle boundaries that are stronger. In graphene, by contrast, the larger-angle boundaries, which consist of higher-defect densities, are better able to accommodate the strain and prevent failure that originates in the breakup of the seven-member graphene rings. This suggests ways for synthesizing imperfect graphene sheets that will have mechanical properties that are close to those of perfect graphene. Simulations indicate that high-angle boundaries can better accommodate strain and prevent failure in graphene. Graphene in its pristine form is one of the strongest materials tested, but defects influence its strength. Using atomistic calculations, we find that, counter to standard reasoning, graphene sheets with large-angle tilt boundaries that have a high density of defects are as strong as the pristine material and, unexpectedly, are much stronger than those with low-angle boundaries having fewer defects. We show that this trend is not explained by continuum fracture models but can be understood by considering the critical bonds in the strained seven-membered carbon rings that lead to failure; the large-angle boundaries are stronger because they are able to better accommodate these strained rings. Our results provide guidelines for designing growth methods to obtain sheets with strengths close to that of pristine graphene.

Hydrogen Bond Networks in Graphene Oxide Composite Paper: Structure and Mechanical Properties

A multilayered composite structure formed by a random stacking of graphene oxide (GO) platelets is an attractive candidate for novel applications in nanoelectromechanical systems and paper-like composites. We employ molecular dynamics simulations with reactive force fields to elucidate the structural and mechanical properties of GO paper-like materials. We find that the large-scale properties of these composites are controlled by hydrogen bond networks that involve functional groups on individual GO platelets and water molecules within the interlayer cavities. Water content controls both the extent and collective strength of these interlayer hydrogen bond networks, thereby affecting the interlayer spacing and elastic moduli of the composite. Additionally, the chemical composition of the individual GO platelets also plays a critical role in establishing the mechanical properties of the composite--a higher density of functional groups leads to increased hydrogen bonding and a corresponding increase in stiffness. Our studies suggest the possibility of tuning the properties of GO composites by altering the density of functional groups on individual platelets, the water content, and possibly the functional groups participating in hydrogen bonding with interlayer water molecules.

Tuning the Electronic Properties of Semiconducting Transition Metal Dichalcogenides by Applying Mechanical Strains

Semiconducting transition metal dichalcogenides (TMDs) are emerging as the potential alternatives to graphene. As in the case of graphene, the monolayer of TMDs can easily be exfoliated using mechanical or chemical methods, and their properties can also be tuned. At the same time, semiconducting TMDs (MX(2); M = Mo, W and X = S, Se, Te) possess an advantage over graphene in that they exhibit a band gap whose magnitude is appropriate for applications in the opto-electronic devices. Using ab initio simulations, we demonstrate that this band gap can be widely tuned by applying mechanical strains. While the electronic properties of graphene remain almost unaffected by tensile strains, we find TMDs to be sensitive to both tensile and shear strains. Moreover, compared to that of graphene, a much smaller amount of strain is required to vary the band gap of TMDs. Our results suggest that mechanical strains reduce the band gap of semiconducting TMDs causing an direct-to-indirect band gap and a semiconductor-to-metal transition. These transitions, however, significantly depend on the type of applied strain and the type of chalcogenide atoms. The diffuse nature of heavier chalcogenides require relatively more tensile and less shear strain (when the monolayer is expanded in y-direction and compressed in x-direction) to attain a direct-to-indirect band gap transition. In addition, our results demonstrate that the homogeneous biaxial tensile strain of around 10% leads to semiconductor-to-metal transition in all semiconducting TMDs, while through pure shear strain this transition can only be achieved by expanding and compressing the monolayer of MTe(2) in the y- and x-directions, respectively. Our results highlight the importance of tensile and pure shear strains in tuning the electronic properties of TMDs by illustrating a substantial impact of the strain on going from MS(2) to MSe(2) to MTe(2).

Ti3C2 MXene as a High Capacity Electrode Material for Metal (Li, Na, K, Ca) Ion Batteries

Two-dimensional (2-D) materials are capable of handling high rates of charge in batteries since metal ions do not need to diffuse in a 3-D lattice structure. However, graphene, which is the most well-studied 2-D material, is known to have no Li capacity. Here, adsorption of Li, as well as Na, K, and Ca, on Ti3C2, one representative MXene, is predicted by first-principles density functional calculations. In our study, we observed that these alkali atoms exhibit different adsorption energies depending on the coverage. The adsorption energies of Na, K, and Ca decrease as coverage increases, while Li shows little sensitivity to variance in coverage. This observed relationship between adsorption energies and coverage of alkali ions on Ti3C2 can be explained by their effective ionic radii. A larger effective ionic radius increases interaction between alkali atoms, thus lower coverage is obtained. Our calculated capacities for Li, Na, K, and Ca on Ti3C2 are 447.8, 351.8, 191.8, and 319.8 mAh/g, respectively. Compared to materials currently used in high-rate Li and Na ion battery anodes, MXene shows promise in increasing overall battery performance.

Quasicontinuum Models of Interfacial Structure and Deformation

Microscopic models of the interaction between grain boundaries (GBs) and both dislocations and cracks are of importance in understanding the role of microstructure in altering the mechanical properties of a material. A recently developed mixed atomistic and continuum method is reformulated to allow for the examination of the interactions between GBs, dislocations, and cracks. These calculations elucidate plausible microscopic mechanisms for these defect interactions and allow for the quantitative evaluation of critical parameters such as the force needed to induce GB migration.

Growth of Semiconducting Graphene on Palladium

We report in situ scanning tunneling microscopy studies of graphene growth on Pd(111) during ethylene deposition at temperatures between 723 and 1023 K. We observe the formation of monolayer graphene islands, 200-2000 A in size, bounded by Pd surface steps. Surprisingly, the topographic image contrast from graphene islands reverses with tunneling bias, suggesting a semiconducting behavior. Scanning tunneling spectroscopy measurements confirm that the graphene islands are semiconducting, with a band gap of 0.3 +/- 0.1 eV. On the basis of density functional theory calculations, we suggest that the opening of a band gap is due to the strong interaction between graphene and the Pd substrate. Our findings point to the possibility of preparing semiconducting graphene layers for future carbon-based nanoelectronic devices via direct deposition onto strongly interacting substrates.