B. C. Pan

Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution.

Molybdenum disulfide (MoS2) has emerged as a promising electrocatalyst for catalyzing protons to hydrogen via the so-called hydrogen evolution reaction (HER). In order to enhance the HER activity, tremendous effort has been made to engineer MoS2 catalysts with either more active sites or higher conductivity. However, at present, synergistically structural and electronic modulations for HER still remain challenging. In this work, we demonstrate the successfully synergistic regulations of both structural and electronic benefits by controllable disorder engineering and simultaneous oxygen incorporation in MoS2 catalysts, leading to the dramatically enhanced HER activity. The disordered structure can offer abundant unsaturated sulfur atoms as active sites for HER, while the oxygen incorporation can effectively regulate the electronic structure and further improve the intrinsic conductivity. By means of controllable disorder engineering and oxygen incorporation, an optimized catalyst with a moderate degree of disorder was developed, exhibiting superior activity for electrocatalytic hydrogen evolution. In general, the optimized catalyst exhibits onset overpotential as low as 120 mV, accompanied by extremely large cathodic current density and excellent stability. This work will pave a new pathway for improving the electrocatalytic activity by synergistically structural and electronic modulations.

Structures of medium-sized silicon clusters

Silicon is the most important semiconducting material in the microelectronics industry. If current miniaturization trends continue, minimum device features will soon approach the size of atomic clusters. In this size regime, the structure and properties of materials often differ dramatically from those of the bulk. An enormous effort has been devoted to determining the structures of free silicon clusters. Although progress has been made for Sin with n < 8, theoretical predictions for larger clusters are contradictory and none enjoy any compelling experimental support. Here we report geometries calculated for medium-sized silicon clusters using an unbiased global search with a genetic algorithm. Ion mobilities determined for these geometries by trajectory calculations are in excellent agreement with the values that we measure experimentally. The cluster geometries that we obtain do not correspond to fragments of the bulk. For n = 12–18 they are built on a structural motif consisting of a stack of Si9 tricapped trigonal prisms. For n ⩾ 19, our calculations predict that near-spherical cage structures become the most stable. The transition to these more spherical geometries occurs in the measured mobilities for slightly larger clusters than in the calculations, possibly because of entropic effects.

Oxygen Vacancies Confined in Ultrathin Indium Oxide Porous Sheets for Promoted Visible-Light Water Splitting

Finding an ideal model for disclosing the role of oxygen vacancies in photocatalysis remains a huge challenge. Herein, O-vacancies confined in atomically thin sheets is proposed as an excellent platform to study the O-vacancy-photocatalysis relationship. As an example, O-vacancy-rich/-poor 5-atom-thick In2O3 porous sheets are first synthesized via a mesoscopic-assembly fast-heating strategy, taking advantage of an artificial hexagonal mesostructured In-oleate complex. Theoretical/experimental results reveal that the O-vacancies endow 5-atom-thick In2O3 sheets with a new donor level and increased states of density, hence narrowing the band gap from the UV to visible regime and improving the carrier separation efficiency. As expected, the O-vacancy-rich ultrathin In2O3 porous sheets-based photoelectrode exhibits a visible-light photocurrent of 1.73 mA/cm(2), over 2.5 and 15 times larger than that of the O-vacancy-poor ultrathin In2O3 porous sheets- and bulk In2O3-based photoelectrodes.

Ultrathin Spinel‐Structured Nanosheets Rich in Oxygen Deficiencies for Enhanced Electrocatalytic Water Oxidation

Electrochemical water splitting is a clean technology for H2 fuels, but greatly hindered by the slow kinetics of the oxygen evolution reaction (OER). Herein, a series of spinel-structured nanosheets with oxygen deficiencies and ultrathin thicknesses were designed to increase the reactivity and the number of active sites of the catalysts, which were then taken as an excellent platform for promoting the water oxidation process. Theoretical investigations showed that the oxygen vacancies confined in the ultrathin nanosheet could lower the adsorption energy of H2O, leading to increased OER efficiency. As expected, the NiCo2O4 ultrathin nanosheets rich in oxygen vacancies exhibited a large current density of 285 mA cm(-2) at 0.8 V and a small overpotential of 0.32 V, both of which are superior to the corresponding values of bulk samples or samples with few oxygen deficiencies and even higher than those of most reported non-precious-metal catalysts. This work should provide a new pathway for the design of advanced OER catalysts.

Atomically-thin molybdenum nitride nanosheets with exposed active surface sites for efficient hydrogen evolution

Exploring efficient electrocatalysts for hydrogen production is one of the most promising pathways to face the energy crisis in the new century. Herein, we highlight metallic molybdenum nitride (MoN) nanosheets with atomic thickness as highly efficient platinum-free electrocatalysts for the hydrogen evolution reaction (HER). Theoretical calculations demonstrate that the atomically-thin MoN nanosheets show metallic behavior, which can effectively facilitate electron transport during the catalytic process. Structural analyses reveal that the surfaces of the atomically-thin MoN nanosheets are wholly comprised of apical Mo atoms, thus providing an ideal material prototype to reveal the role of Mo atoms during HER catalysis. Through detailed investigations of the HER activity, the active surface sites of the atomically-thin MoN nanosheets are identified, of which the surface Mo atoms can act as the active sites for transforming protons into hydrogen. This novel mechanism will not only broaden our vision on understanding the HER mechanism for other Mo-based electrocatalysts, but also benefit the exploration and optimization of advanced catalysts for future energy production.

High-performance flexible electrochromic device based on facile semiconductor-to-metal transition realized by WO3·2H2O ultrathin nanosheets

Ultrathin nanosheets are considered as one kind of the most promising candidates for the fabrication of flexible electrochromic devices (ECDs) due to their permeable channels, high specific surface areas, and good contact with the substrate. Herein, we first report the synthesis of large-area nanosheets of tungsten oxide dihydrate (WO3·2H2O) with a thickness of only about 1.4 nm, showing much higher Li+ diffusion coefficients than those of the bulk counterpart. The WO3·2H2O ultrathin nanosheets are successfully assembled into the electrode of flexible electrochromic device, which exhibits wide optical modulation, fast color-switching speed, high coloration efficiency, good cyclic stability and excellent flexibility. Moreover, the electrochromic mechanism of WO3·2H2O is further investigated by first-principle density functional theory (DFT) calculations, in which the relationship between structural features of ultrathin nanosheets and coloration/bleaching response speed is revealed.

Ionization of medium-sized silicon clusters and the geometries of the cations

We have performed a systematic ground state geometry search for the singly charged Sin cations in the medium-size range (n⩽20) using density functional theory in the local density approximation (LDA) and generalized gradient approximation (GGA). The structures resulting for n⩽18 generally follow the prolate “stacked Si9 tricapped trigonal prism” pattern recently established for the lowest energy geometries of neutral silicon clusters in this size range. However, the global minima of Sin and Sin+ for n=6, 8, 11, 12, and 13 differ significantly in their details. For Si19 and Si20 neutrals and cations, GGA renders the prolate stacks practically isoenergetic with the near-spherical structures that are global minima in LDA. The mobilities in He gas evaluated for all lowest energy Sin+ geometries using the trajectory method agree with the experiment, except for n=18 where the second lowest isomer fits the measurements. The effect of gradient corrections for either the neutral or cationic clusters is subtle, but...

Heterogeneous spin states in ultrathin nanosheets induce subtle lattice distortion to trigger efficient hydrogen evolution

The exploration of efficient nonprecious metal eletrocatalysis of the hydrogen evolution reaction (HER) is an extraordinary challenge for future applications in sustainable energy conversion. The family of first-row-transition-metal dichalcogenides has received a small amount of research, including the active site and dynamics, relative to their extraordinary potential. In response, we developed a strategy to achieve synergistically active sites and dynamic regulation in first-row-transition-metal dichalcogenides by the heterogeneous spin states incorporated in this work. Specifically, taking the metallic Mn-doped pyrite CoSe2 as a self-adaptived, subtle atomic arrangement distortion to provide additional active edge sites for HER will occur in the CoSe2 atomic layers with Mn incorporated into the primitive lattice, which is visually verified by HRTEM. Synergistically, the density functional theory simulation results reveal that the Mn incorporation lowers the kinetic energy barrier by promoting H-H bond formation on two adjacently adsorbed H atoms, benefiting H2 gas evolution. As a result, the Mn-doped CoSe2 ultrathin nanosheets possess useful HER properties with a low overpotential of 174 mV, an unexpectedly small Tafel slope of 36 mV/dec, and a larger exchange current density of 68.3 μA cm(-2). Moreover, the original concept of coordinated regulation presented in this work can broaden horizons and provide new dimensions in the design of newly highly efficient catalysts for hydrogen evolution.

Half-metallic ferromagnetism in synthetic Co9Se8 nanosheets with atomic thickness.

Controlling the synthesis of atomic-thick nanosheets of nonlayered materials is extremely challenging because of the lack of an intrinsic driving force for anisotropic growth of two-dimensional (2D) structures. In that case, control of the anisotropy such as oriented attachment of small building blocks during the reaction process will be an effective way to achieve 2D nanosheets. Those atomic-thick nanosheets possess novel electronic structures and physical properties compared with the corresponding bulk samples. Here we report Co(9)Se(8) single-crystalline nanosheets with atomic thickness and unique lamellar stacking formed by 2D oriented attachment. The atomic-thick Co(9)Se(8) nanosheets were found to exhibit intrinsic half-metallic ferromagnetism, as supported by both our experimental measurements and theoretical calculations. This work will not only open a new door in the search for new half-metallic ferromagnetic systems but also pave a practical way to design ultrathin, transparent, and flexible paperlike spintronic devices.

Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction

Ultrathin metal layers can be highly active carbon dioxide electroreduction catalysts, but may also be prone to oxidation. Here we construct a model of graphene confined ultrathin layers of highly reactive metals, taking the synthetic highly reactive tin quantum sheets confined in graphene as an example. The higher electrochemical active area ensures 9 times larger carbon dioxide adsorption capacity relative to bulk tin, while the highly-conductive graphene favours rate-determining electron transfer from carbon dioxide to its radical anion. The lowered tin–tin coordination numbers, revealed by X-ray absorption fine structure spectroscopy, enable tin quantum sheets confined in graphene to efficiently stabilize the carbon dioxide radical anion, verified by 0.13 volts lowered potential of hydroxyl ion adsorption compared with bulk tin. Hence, the tin quantum sheets confined in graphene show enhanced electrocatalytic activity and stability. This work may provide a promising lead for designing efficient and robust catalysts for electrolytic fuel synthesis.