Bifunctional 2D superlattice electrocatalysts of alternating layered double hydroxide (LDH)−transition metal dichalcogenide (TMD) heterolayers were synthesized by interstratification of the exfoliated nanosheets. Density functional theory calculations predict an increased interfacial charge transfer between interstratified LDH and TMD nanosheets, which would lead to enhanced electrocatalytic activity. The electrostatically driven self-assembly of oppositely charged 2D building blocks, i.e., exfoliated Ni−Al-LDH/Ni−Fe-LDH and MoS 2 nanosheets, yields mesoporous heterolayered Ni−Al-LDH−MoS 2 /Ni−Fe-LDH−MoS 2 superlattices. The synthesized superlattices show improved electrocatalytic activity with enhanced durability for oxygen and hydrogen evolution reactions and water splitting. The interstratification improves the chemical stability of LDH in acidic media, thus expanding its possible applications. The high electrocatalytic activity of the superlattices may be attributed to an enhanced affinity for OH − /H + , improved electrical conduction and charge transfer, and the increase of active sites. This study indicates that the formation of superlattices via self-assembly of 2D nanosheets provides useful methodology to explore high-performance electrocatalysts with improved stability.

Despite the high energy densities, lithium–sulfur (Li–S) batteries suffer from insufficient cycle life originating from the shuttling process involving lithium polysulfides (LiPSs). Various approaches have been introduced to resolve the shuttling problem, but they are not usually effective for electrodes with high sulfur contents. Here, we report an exfoliated 2D lepidocrocite titanium oxide nanosheet as a component for sulfur cathodes to suppress polysulfide dissolution markedly. In particular, the Lewis acidity originating from undercoordinated Ti species as well as the large surface area associated with the 2D structure endow 2D lepidocrocite titanium oxide with an efficient interaction with LiPSs. As a result, even with a sulfur content of 80 wt %, the Li–S cell exhibits 1023.5 mAh g–1 at 50 mA g–1 and a capacity retention of 82.3% after 300 cycles measured at 1000 mA g–1. The considerably improved cycling performance provides useful insight for designing sulfur cathodes, that is, the incorporation of acidic 2D metal oxide nanosheets.

Holey 2D nanosheets of low‐valent Mn2O3 can be synthesized by thermally induced phase transition of exfoliated layered MnO2 nanosheets. The heat treatment of layered MnO2 nanosheets at elevated temperatures leads not only to transitions to low‐valent manganese oxides but also to the creation of surface hole in the 2D nanosheet crystallites. Despite distinct phase transitions, highly anisotropic 2D morphology of the precursor MnO2 material remains intact upon the heat treatment whereas the diameter of surface hole becomes larger with increasing heating temperature. The obtained holey 2D Mn2O3 nanosheets show promising electrocatalyst performances for oxygen evolution reaction, which are much superior to that of nonporous Mn2O3 crystal. Among the present materials, the holey Mn2O3 nanosheet calcined at 500 °C displays the best electrocatalyst functionality with markedly decreased overpotential, indicating the importance of heating condition in optimizing the electrocatalytic activity. Of prime importance is that this material shows much better catalytic activity for Li–O2 batteries than does nonporous Mn2O3, underscoring the critical role of porous 2D morphology in this functionality. This study clearly demonstrates the unique advantage of holey 2D nanosheet morphology in exploring economically feasible transition metal oxide‐based electrocatalysts and electrodes for Li–O2 batteries.

The crystal phase of nanostructured metal oxide can be effectively controlled by the hybridization of gallium oxide with reduced graphene oxide (rGO) at variable concentrations. The change of the ratio of Ga2O3/rGO is quite effective in tailoring the crystal structure and morphology of nanostructured gallium oxide hybridized with rGO. This is the first example of the phase control of metal oxide through a change of the content of rGO hybridized. The calculations based on density functional theory (DFT) clearly demonstrate that the different surface formation energy and Ga local symmetry of Ga2O3 phases are responsible for the phase transition induced by the change of rGO content. The resulting Ga2O3-rGO nanocomposites show promising electrode performance for lithium ion batteries. The intermediate Li-Ga alloy phases formed during the electrochemical cycling are identified with the DFT calculations. Among the present Ga2O3-rGO nanocomposites, the material with mixed α-Ga2O3/β-Ga2O3/γ-Ga2O3 phase can deliver the largest discharge capacity with the best cyclability and rate characteristics, highlighting the importance of the control of Ga2O3/rGO ratio in optimizing the electrode activity of the composite materials. The present study underscores the usefulness of the phase-control of nanostructured metal oxides achieved by the change of rGO content in exploring novel functional nanocomposite materials.

No abstract

The best electrode performance of metal oxide-graphene nanocomposite material for lithium secondary batteries can be achieved by using the colloidal mixture of layered CoO 2 and graphene nanosheets as a precursor. The intervention of layered CoO 2 nanosheets in-between graphene nanosheets is fairly effective in optimizing the pore and composite structures of the Co 3 O 4 -graphene nanocomposite and also in enhancing its electrochemical activity via the depression of interaction between graphene nanosheets. The resulting CoO 2 nanosheet-incorporated nanocomposites show much greater discharge capacity of ~1750 mAhg −1 with better cyclability and rate characteristics than does CoO 2 -free Co 3 O 4 -graphene nanocomposite (~1100 mAhg −1 ). The huge discharge capacity of the present nanocomposite is the largest one among the reported data of cobalt oxide-graphene nanocomposite. Such a remarkable enhancement of electrode performance upon the addition of inorganic nanosheet is also observed for Mn 3 O 4 -graphene nanocomposite. The improvement of electrode performance upon the incorporation of inorganic nanosheet is attributable to an improved Li + ion diffusion, an enhanced mixing between metal oxide and graphene, and the prevention of electrode agglomeration. The present experimental findings underscore an efficient and universal role of the colloidal mixture of graphene and redoxable metal oxide nanosheets as a precursor for improving the electrode functionality of graphene-based nanocomposites.Graphene-based nanocomposite is one of the most currently investigated materials in the fields of chemistry, physics, materials science, and nanotechnology because of its intriguing physicochemical properties and promising functionalities [1][2][3][4] . This family of materials boasts excellent functionalities for many energy-related applications such as secondary batteries, supercapacitors, photocatalysts, photovoltaics, and fuel cells [4][5][6][7][8][9][10][11][12] . One of the most promising applications of the graphene-based nanocomposites is an electrode for secondary batteries. An increasing demand for the large-scale application of secondary batteries evokes intense research efforts for the exploration of novel graphene-based electrode materials showing excellent rate characteristics and high electrochemical stability 11 . The hybridization of electrode materials with highly conductive graphene nanosheets leads to a significant improvement of electrode performance at high current density via the increase of electrical conductivity 12 . Additionally the porous stacking structure of the graphene-based nanocomposite can relieve the drastic volume change and

Composition-tailored Mn1-x Rux O2 2 D nanosheets and their reassembled nanocomposites with mesoporous stacking structure are synthesized by a soft-chemical exfoliation reaction and the subsequent reassembling of the exfoliated nanosheets with Li(+) cations, respectively. The tailoring of the chemical compositions of the exfoliated Mn1-x Rux O2 2 D nanosheets and their lithiated nanocomposites can be achieved by adopting the Ru-substituted layered manganese oxides as host materials for exfoliation reaction. Upon the exfoliation-reassembling process, the substituted ruthenium ions remain stabilized in the layered Mn1-x Rux O2 lattice with mixed Ru(3+) /Ru(4+) oxidation state. The reassembled Li-Mn1-x Rux O2 nanocomposites show promising pseudocapacitance performance with large specific capacitances of approximately 330 F g(-1) for the second cycle and approximately 360 F g(-1) for the 500th cycle and excellent cyclability, which are superior to those of the unsubstituted Li-MnO2 homologue and many other MnO2 -based materials. Electrochemical impedance spectroscopy analysis provides strong evidence for the enhancement of the electrical conductivity of 2 D nanostructured manganese oxide upon Ru substitution, which is mainly responsible for the excellent electrode performance of Li-Mn1-x Rux O2 nanocomposites. The results underscore the powerful role of the composition-controllable metal oxide 2 D nanosheets as building blocks for exploring efficient electrode materials.

Remarkable improvement in electrode performance of Mn3O4-graphene nanocomposites for lithium ion batteries can be obtained by incorporation of a small amount of exfoliated layered MnO2 or RuO2 nanosheets. The metal oxide nanosheet-incorporated Mn3O4-reduced graphene oxide (rGO) nanocomposites are synthesized via growth of Mn3O4 nanocrystals in the mesoporous networks of rGO and MnO2/RuO2 2D nanosheets. Incorporation of metal oxide nanosheets is highly effective in optimizing porous composite structure and charge transport properties, resulting in a remarkable increase of discharge capacity of Mn3O4-rGO nanocomposite with significant improvement of cyclability and rate performance. The observed enormous discharge capacity of synthesized Mn3O4-rGO-MnO2 nanocomposite (∼1600 mA·h·g(-1) for the 100th cycle) is the highest value among reported data for Mn3O4-rGO nanocomposite. Despite much lower electrical conductivity of MnO2 than RuO2, the MnO2-incorporated nanocomposite at optimal composition (2.5 wt %) shows even larger discharge capacities with comparable rate characteristics compared with the RuO2-incorporated homologue. This finding underscores that the electrode performance of the resulting nanosheet-incorporated nanocomposite is strongly dependent on its pore and composite structures rather than on the intrinsic electrical conductivity of the additive nanosheet. The present study clearly demonstrates that, regardless of electrical conductivity, incorporation of metal oxide 2D nanosheet is an effective way to efficiently optimize the electrode functionality of graphene-based nanocomposites.