Gradient tungsten-doped Bi3TiNbO9 ferroelectric photocatalysts with additional built-in electric field for efficient overall water splitting.

Bi3TiNbO9, a layered ferroelectric photocatalyst, exhibits great potential for overall water splitting through efficient intralayer separation of photogenerated carriers motivated by a depolarization field along the in-plane a-axis. However, the poor interlayer transport of carriers along the out-of-plane c-axis, caused by the significant potential barrier between layers, leads to a high probability of carrier recombination and consequently results in low photocatalytic activity. Here, we have developed an efficient photocatalyst consisting of Bi3TiNbO9 nanosheets with a gradient tungsten (W) doping along the c-axis. This results in the generation of an additional electric field along the c-axis and simultaneously enhances the magnitude of depolarization field within the layers along the a-axis due to strengthened structural distortion. The combination of the built-in field along the c-axis and polarization along the a-axis can effectively facilitate the anisotropic migration of photogenerated electrons and holes to the basal {001} surface and lateral {110} surface of the nanosheets, respectively, enabling desirable spatial separation of carriers. Hence, the W-doped Bi3TiNbO9 ferroelectric photocatalyst with Rh/Cr2O3 cocatalyst achieves an efficient and durable overall water splitting feature, thereby providing an effective pathway for designing excellent layered ferroelectric photocatalysts.

Constructing Anatase-Brookite TiO2 Phase Junction by Thermal Topotactic Transition to Promote Charge Separation for Superior Photocatalytic H2 Generation.

Phase junctions of photocatalysts can promote the separation of photogenerated charge carriers for efficient utilization of the carriers. Construction of phase junctions and establishing their structure-performance relationship are still required. Herein, polycrystalline TiO2 decahedral plates with different phases were synthesized by thermal treatment-induced topotactic transition of titanium oxalate crystals. The phase of TiO2 evolved from pure anatase to anatase-brookite, anatase-brookite-rutile, and then to anatase-rutile, while the morphology of the decahedral plates was well maintained. The biphase anatase-brookite was found to be most efficient in photocatalytic hydrogen generation. Specifically, the hydrogen generation rate of the biphase anatase-brookite TiO2 was nearly 2.4 times greater than that of the biphase anatase-rutile TiO2. The spatially resolved surface photovoltage measurements indicate the more efficient separation of photogenerated charge carriers and thus greater photocatalytic activity of the former. This work provides a strategy for developing efficient phase-junction photocatalysts.

Catalytically Active Site Identification of Molybdenum Disulfide as Gas Cathode in a Nonaqueous Li-CO2 Battery.

Li-CO2 batteries have recently attracted attention as promising candidates for next-generation energy storage devices due to their extremely high theoretical energy density. The real application of Li-CO2 cells involves addressing several drawbacks, including high charging potential, poor coulombic efficiency, and low rechargeability. Molybdenum disulfide supported on carbon nanotubes (MoS2/CNT) with various ratios functioned as a cathode catalyst for Li-CO2 batteries. The optimal MoS2/CNT composite achieved a maximum discharge capacity of 8551 mAh g-1 with a coulombic efficiency of 96.7%. This hybrid also obtained an initial charging plateau of 3.87 V at a current density of 100 mA g-1 with a cutoff capacity of 500 mAh g-1. It provided ideal electrochemical stability of 142 cycles at the current densities of 100 mA g-1, which was comparable with that of some precious metal catalysts. This optimized MoS2/CNT was also cycled at 200 and 400 mA g-1 for 112 and 55 times, respectively. Density functional theory calculations demonstrated that the sulfided Mo-edge (s-Mo-edge) on MoS2 materials showed appropriate adsorption strengths of Li, CO2, and Li2CO3. Moreover, joint results of Raman profiles and extended X-ray absorption fine structure spectra elucidated that the catalytic efficiencies of MoS2/CNT hybrids were proportional to the quantities of exposed s-Mo-edge active sites.

Amorphous Phosphorus-Doped Cobalt Sulfide Modified on Silicon Pyramids for Efficient Solar Water Reduction.

Cobalt sulfide (CoS x) functioned as a co-catalyst to accelerate the kinetics of photogenerated electrons on Si photocathode, leading to the enhancement of solar hydrogen evolution efficiency. By doping phosphorus heteroatoms, CoS x materials showed an improved catalytic activity because of superior surface area and quantity of active sites. Furthermore, increased vacancies in unoccupied electronic states were observed, as more phosphorus atoms doped into CoS x co-catalysts. Although these vacant sites improved the capability to accept photoinduced electrons from Si photoabsorber, chemisorption energy of atomic hydrogen on catalysts was the dominant factor affecting in photoelectrochemical performance. We suggested that P-doped CoS x with appropriate doping quantities showed thermoneutral hydrogen adsorption. Excess phosphorus dopants in CoS x contributed to excessively strong adsorption with H atoms, causing the poor consecutive desorption ability of photocatalytic reaction. The optimal P-doped CoS x-decorated Si photocathode showed a photocurrent of -20.6 mA cm-2 at 0 V. Moreover, a TiO2 thin film was deposited on the Si photocathode as a passivation layer for improving the durability. The current density of 10 nm TiO2-modified photocathode remained at approximately -13.3 mA cm-2 after 1 h of chronoamperometry.

An Unusual Strong Visible-Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen-Occupied Oxygen Vacancies.

Increasing visible light absorption of classic wide-bandgap photocatalysts like TiO2 has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible-light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail-like absorption band in hydrogen-free oxygen-deficient TiO2 , an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO2 by intentionally introducing atomic hydrogen-mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo-electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide-bandgap semiconductors to fully capture solar light.

Inversion domain boundaries in MoSe2 layers.

Structural defects, including point defects, dislocation and planar defects, significantly affect the physical and chemical properties of low-dimensional materials, such as layered compounds. In particular, inversion domain boundary is an intrinsic defect surrounded by a 60° grain boundary, which significantly influences electronic transport properties. We study atomic structures of the inversion domain grain boundaries (IDBs) in layered transition metal dichalcogenides (MoSe2 and MoS2) obtained by an exfoliation method, based on the aberration-corrected scanning transmission electron microscopy observation and density functional theory (DFT) calculation. The atomic-scale observation shows that the grain boundaries consist of two different types of 4-fold ring point shared and 8-fold ring edge shared chains. The results of DFT calculations indicate that the inversion domain grain boundary behaves as a metallic one-dimensional chain embedded in the semiconducting MoSe2 matrix with the occurrence of a new state within the band gap.

Ultrafast Growth of High-Quality Monolayer WSe2 on Au.

The ultrafast growth of high-quality uniform monolayer WSe2 is reported with a growth rate of ≈26 µm s-1 by chemical vapor deposition on reusable Au substrate, which is ≈2-3 orders of magnitude faster than those of most 2D transition metal dichalcogenides grown on nonmetal substrates. Such ultrafast growth allows for the fabrication of millimeter-size single-crystal WSe2 domains in ≈30 s and large-area continuous films in ≈60 s. Importantly, the ultrafast grown WSe2 shows excellent crystal quality and extraordinary electrical performance comparable to those of the mechanically exfoliated samples, with a high mobility up to ≈143 cm2 V-1 s-1 and ON/OFF ratio up to 9 × 106 at room temperature. Density functional theory calculations reveal that the ultrafast growth of WSe2 is due to the small energy barriers and exothermic characteristic for the diffusion and attachment of W and Se on the edges of WSe2 on Au substrate.

Selective Breaking of Hydrogen Bonds of Layered Carbon Nitride for Visible Light Photocatalysis.

Selective breaking of the hydrogen bonds of graphitic carbon nitride can introduce favorable features, including increased band tails close to the band edges and the creation of abundant pores. These features can simultaneously improve the three basic processes of photocatalysis. As a consequence, the photocatalytic hydrogen-generation activity of carbon nitride under visible light is drastically increased by tens of times.

Metal/Oxide Interface Nanostructures Generated by Surface Segregation for Electrocatalysis.

Strong metal/oxide interactions have been acknowledged to play prominent roles in chemical catalysis in the gas phase, but remain as an unexplored area in electrocatalysis in the liquid phase. Utilization of metal/oxide interface structures could generate high performance electrocatalysts for clean energy storage and conversion. However, building highly dispersed nanoscale metal/oxide interfaces on conductive scaffolds remains a significant challenge. Here, we report a novel strategy to create metal/oxide interface nanostructures by growing mixed metal oxide nanoparticles on carbon nanotubes (CNTs) and then selectively promoting migration of one of the metal ions to the surface of the oxide nanoparticles and simultaneous reduction to metal. Employing this strategy, we have synthesized Ni/CeO2 nanointerfaces coupled with CNTs. The Ni/CeO2 interface promotes hydrogen evolution catalysis by facilitating water dissociation and modifying the hydrogen binding energy. The Ni/CeO2-CNT hybrid material exhibits superior activity for hydrogen evolution as a result of synergistic effects including strong metal/oxide interactions, inorganic/carbon coupling, and particle size control.

Large-area synthesis of high-quality and uniform monolayer WS2 on reusable Au foils.

Large-area monolayer WS2 is a desirable material for applications in next-generation electronics and optoelectronics. However, the chemical vapour deposition (CVD) with rigid and inert substrates for large-area sample growth suffers from a non-uniform number of layers, small domain size and many defects, and is not compatible with the fabrication process of flexible devices. Here we report the self-limited catalytic surface growth of uniform monolayer WS2 single crystals of millimetre size and large-area films by ambient-pressure CVD on Au. The weak interaction between the WS2 and Au enables the intact transfer of the monolayers to arbitrary substrates using the electrochemical bubbling method without sacrificing Au. The WS2 shows high crystal quality and optical and electrical properties comparable or superior to mechanically exfoliated samples. We also demonstrate the roll-to-roll/bubbling production of large-area flexible films of uniform monolayer, double-layer WS2 and WS2/graphene heterostructures, and batch fabrication of large-area flexible monolayer WS2 film transistor arrays.

An Amorphous Carbon Nitride Photocatalyst with Greatly Extended Visible-Light-Responsive Range for Photocatalytic Hydrogen Generation.

Amorphous carbon nitride (ACN) with a bandgap of 1.90 eV shows an order of magnitude higher photocatalytic activity in hydrogen evolution under visible light than partially crystalline graphitic carbon nitride with a bandgap of 2.82 eV. ACN is photocatalytically active under visible light at a wavelength beyond 600 nm.

Greatly Enhanced Electronic Conduction and Lithium Storage of Faceted TiO2 Crystals Supported on Metallic Substrates by Tuning Crystallographic Orientation of TiO2.

Electronic conduction along the [001] direction of a faceted anatase TiO2 particle in contact with two tungsten probes is found to be an order of magnitude higher than that along the [010] direction due to a smaller potential barrier of the TiO2 (001)-tungsten interface for electron transport than the TiO2 (010)-tungsten interface. This finding could guide the design of TiO2 -based electrodes.

Increasing the visible light absorption of graphitic carbon nitride (melon) photocatalysts by homogeneous self-modification with nitrogen vacancies.

A novel reduced melon photocatalyst with a bandgap of 2.03 eV developed here has a widened visible light absorption range and suppressed radiative recombination of photo-excited charge carriers due to the homogeneous self-modification with nitrogen vacancies. As a consequence, the reduced melon shows a much superior photocatalytic activity compared to the pristine melon in generating •OH radicals and degrading the organic pollutant Rhodamine B.

Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition.

The controlled growth of large-area, high-quality, single-crystal graphene is highly desired for applications in electronics and optoelectronics; however, the production of this material remains challenging because the atomistic mechanism that governs graphene growth is not well understood. The edges of graphene, which are the sites at which carbon accumulates in the two-dimensional honeycomb lattice, influence many properties, including the electronic properties and chemical reactivity of graphene, and they are expected to significantly influence its growth. We demonstrate the growth of single-crystal graphene domains with controlled edges that range from zigzag to armchair orientations via growth-etching-regrowth in a chemical vapor deposition process. We have observed that both the growth and the etching rates of a single-crystal graphene domain increase linearly with the slanted angle of its edges from 0° to ∼19° and that the rates for an armchair edge are faster than those for a zigzag edge. Such edge-structure-dependent growth/etching kinetics of graphene can be well explained at the atomic level based on the concentrations of the kinks on various edges and allow the evolution and control of the edge and morphology in single-crystal graphene following the classical kinetic Wulff construction theory. Using these findings, we propose several strategies for the fabrication of wafer-sized, high-quality, single-crystal graphene.

High-quality, highly concentrated semiconducting single-wall carbon nanotubes for use in field effect transistors and biosensors.

We developed a simple and scalable selective synthesis method of high-quality, highly concentrated semiconducting single-wall carbon nanotubes (s-SWCNTs) by in situ hydrogen etching. Samples containing ~93% s-SWCNTs were obtained in bulk. These s-SWCNTs with good structural integrity showed a high oxidation resistance temperature of ~800 °C. Thin-film transistors based on the s-SWCNTs demonstrated a high carrier mobility of 21.1 cm(2) V(-1) s(-1) at an on/off ratio of 1.1 × 10(4) and a high on/off ratio of 4.0 × 10(5) with a carrier mobility of 7.0 cm(2) V(-1) s(-1). A biosensor fabricated using the s-SWCNTs had a very low dopamine detection limit of 10(-18) mol/L at room temperature.

Fibrous hybrid of graphene and sulfur nanocrystals for high-performance lithium-sulfur batteries.

Graphene-sulfur (G-S) hybrid materials with sulfur nanocrystals anchored on interconnected fibrous graphene are obtained by a facile one-pot strategy using a sulfur/carbon disulfide/alcohol mixed solution. The reduction of graphene oxide and the formation/binding of sulfur nanocrystals were integrated. The G-S hybrids exhibit a highly porous network structure constructed by fibrous graphene, many electrically conducting pathways, and easily tunable sulfur content, which can be cut and pressed into pellets to be directly used as lithium-sulfur battery cathodes without using a metal current-collector, binder, and conductive additive. The porous network and sulfur nanocrystals enable rapid ion transport and short Li(+) diffusion distance, the interconnected fibrous graphene provides highly conductive electron transport pathways, and the oxygen-containing (mainly hydroxyl/epoxide) groups show strong binding with polysulfides, preventing their dissolution into the electrolyte based on first-principles calculations. As a result, the G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles. These results demonstrate the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.

Crystallinity-dependent substitutional nitrogen doping in ZnO and its improved visible light photocatalytic activity.

Increasing visible light absorption of wide-bandgap photocatalysts (for example, ZnO and TiO2) plays a pivotal role in improving their photocatalytic activity. In this work, we show that substitutional nitrogen doping can be realized in semi-crystalline zinc oxide (ZnO) nanoparticles but fails for highly crystalline ZnO by heating the ZnO at a temperature of 400°C in gaseous ammonia atmosphere. The results suggest that substitutional nitrogen for lattice oxygen is strongly dependent on the crystallinity of ZnO. The nitrogen doped ZnO obtained shows an improved visible light photocatalytic activity in the degradation of organic dyes due to its increased visible light absorption. The origin of the increased visible light absorption is theoretically attributed to the formed N 2p localized states in the bandgap.

Heteroepitaxial growth of single-walled carbon nanotubes from boron nitride.

The growth of single-walled carbon nanotubes (SWCNTs) with predefined structure is of great importance for both fundamental research and their practical applications. Traditionally, SWCNTs are grown from a metal catalyst with a vapor-liquid-solid mechanism, where the catalyst is in liquid state with fluctuating structures, and it is intrinsically unfavorable for the structure control of SWCNTs. Here we report the heteroepitaxial growth of SWCNTs from a platelet boron nitride nanofiber (BNNF), which is composed of stacked (002) planes and is stable at high temperatures. SWCNTs are found to grow epitaxially from the open (002) edges of the BNNFs, and the diameters of the SWCNTs are multiples of the BN (002) interplanar distance. In situ transmission electron microscopy observations coupled with first principles calculations reveal that the growth of SWCNTs from the BNNFs follows a vapor-solid-solid mechanism. Our work opens opportunities for the control over the structure of SWCNTs by hetero-crystallographic epitaxy.