Highly Efficient and Selective Visible-Light Driven Photoreduction of CO2 to CO by Metal-Organic Frameworks-Derived NiCoO Porous Microrods.

Photocatalytic CO2 reduction by solar energy into carbonaceous feedstock chemicals is recognized as one of the effective ways to mitigate both the energy crisis and greenhouse effect, which fundamentally relies on the development of advanced photocatalysts. Here, the exploration of porous microrod photocatalysts based on novel NiCoO solid solutions derived from bimetallic metal-organic frameworks (MOFs) is reported. They exhibit overall enhanced photocatalytic performance with both high activity and remarkable selectivity for reducing CO2 into CO under visible-light irradiation, which are superior to most related photocatalysts reported. Accordingly, the Ni0.2 -Co0.8 -O microrod (MR-N0.2 C0.8 O) photocatalyst delivers high efficiency for photocatalytic CO2 reduction into CO at a rate up to ≈277 µmol g-1 h-1 , which is ≈35 times to that of its NiO counterpart. Furthermore, they display a high selectivity of ≈85.12%, which is not only better than that of synthesized Co3 O4 (61.25%) but also superior to that of reported Co3 O4 -based photocatalysts. It is confirmed that the Co and Ni species are responsible for CO2 CO conversion activity and selectivity, respectively. In addition, it is verified, by adjusting the Ni contents, that the band structure of NiCoO microrods can be tailored with favorable reduction band potentials, which thus enhance the selectivity toward CO2 photoreduction.

MOFs-Derived Fusiform In2 O3 Mesoporous Nanorods Anchored with Ultrafine CdZnS Nanoparticles for Boosting Visible-Light Photocatalytic Hydrogen Evolution.

The development of efficient visible-light-driven photocatalysts is one of the critically important issues for solar hydrogen production. Herein, high-efficiency visible-light-driven In2 O3 /CdZnS hybrid photocatalysts are explored by a facile oil-bath method, in which ultrafine CdZnS nanoparticles are anchored on NH2 -MIL-68-derived fusiform In2 O3 mesoporous nanorods. It is disclosed that the as-prepared In2 O3 /CdZnS hybrid photocatalysts exhibit enhanced visible-light harvesting, improves charges transfer and separation as well as abundant active sites. Correspondingly, their visible-light-driven H2 production rate is significantly enhanced for more than 185 times to that of pristine In2 O3 nanorods, and superior to most of In2 O3 -based photocatalysts ever reported, representing their promising applications in advanced photocatalysts.

Production of Hydrogen Peroxide by Photocatalytic Processes.

Hydrogen peroxide (H2 O2 ) has received increasing attention because it is not only a mild and environmentally friendly oxidant for organic synthesis and environmental remediation but also a promising new liquid fuel. The production of H2 O2 by photocatalysis is a sustainable process, since it uses water and oxygen as the source materials and solar light as the energy. Encouraging processes have been developed in the last decade for the photocatalytic production of H2 O2 . In this Review we summarize research progress in the development of processes for the photocatalytic production of H2 O2 . After a brief introduction emphasizing the superiorities of the photocatalytic generation of H2 O2 , the basic principles of establishing an efficient photocatalytic system for generating H2 O2 are discussed, highlighting the advanced photocatalysts used. This Review is concluded by a brief summary and outlook for future advances in this emerging research field.

Shape-Enhanced Photocatalytic Activities of Thoroughly Mesoporous ZnO Nanofibers.

1D mesoporous materials have attracted extensive interest recently, owning to their fascinating properties and versatile applications. However, it remains as a grand challenge to develop a simple and efficient technique to produce oxide nanofibers with mesoporous architectures, controlled morphologies, large surface areas, and optimal performances. In this work, a facile foaming-assisted electrospinning strategy with foaming agent of tea saponin is used to produce thoroughly mesoporous ZnO nanofibers with high purity and controlled morphology. Interestingly, mesoporous fibers with elliptical cross-section exhibit the significantly enhanced photocatalytic activity for hydrogen production, as compared to the counterparts with circular and rectangular cross-sections, and they also perform better than the commercial ZnO nanopowders. The unexpected shape dependence of photocatalytic activities is attributed to the different stacking modes of the mesoporous fibers, and a geometrical model is developed to account for the shape dependence. This work represents an important step toward producing thoroughly mesoporous ZnO nanofibers with tailored morphologies, and the discovery that fibers with elliptical cross-section render the best performance provides a valuable guideline for improving the photocatalytic performance of such mesoporous nanomaterials.

General strategy for fabricating thoroughly mesoporous nanofibers.

Recently, preparation of mesoporous fibers has attracted extensive attentions because of their unique and broad applications in photocatalysis, optoelectronics, and biomaterials. However, it remains a great challenge to fabricate thoroughly mesoporous nanofibers with high purity and uniformity. Here, we report a general, simple and cost-effective strategy, namely, foaming-assisted electrospinning, for producing mesoporous nanofibers with high purity and enhanced specific surface areas. As a proof of concept, the as-fabricated mesoporous TiO2 fibers exhibit much higher photocatalytic activity and stability than both the conventional solid counterparts and the commercially available P25. The abundant vapors released from the introduced foaming agents are responsible for the creation of pores with uniform spatial distribution in the spun precursor fibers. The present work represents a critically important step in advancing the electrospinning technique for generating mesoporous fibers in a facile and universal manner.

Boosted photocatalytic hydrogen production over two-dimensional/two-dimensional Ta3N5/ReS2 van der Waals heterojunctions.

Currently, two-dimensional/two-dimensional (2D/2D) van der Waals heterojunctions, as novel and excellent candidates for photocatalysts, have attracted significant attention because of their fundamentally improved interfacial charge separation/transfer and massive reactive centers. Herein, novel 2D/2D Ta3N5-nanosheet/ReS2-nanosheet van der Waals heterojunction photocatalysts are rationally designed through a method combining template-assisted and solution-adsorption processes. The resultant heterojunctions exhibit enhanced interfacial charge transfer, boosted light absorption and significantly increased reaction sites for hydrogen evolution. Correspondingly, they deliver a high photocatalytic hydrogen production activity of 615 µmol g-1 h-1, which is ∼3 and ∼12 times greater than that of bare Ta3N5 nanosheets and ReS2 nanosheets, respectively, and superior to those in the most recent reports about photocatalytic water splitting on Ta3N5 material, implying their potential applications as advanced catalysts for hydrogen evolution.

Advanced Supercapacitors Based on Porous Hollow Carbon Nanofiber Electrodes with High Specific Capacitance and Large Energy Density.

Hollow carbon nanofibers with hierarchical porous shells were prepared by NaOH activation of the electrospinning SiCNO fibers, followed by carbonization treatment. By adjusting the carbonization temperature, porous hollow carbon nanofibers with different Brunauer-Emmett-Teller (BET) specific surface areas and total pore volumes are obtained, both of which are explored as electrode materials for supercapacitors. It was found that the obtained products (HCF800) possess the highest BET specific surface area of 2628.10 m2/g and the largest pore volume of 2.32 cm3/g when the carbonized temperature was designed at 800 °C, thus displaying the best supercapacitor performance. The electrochemical results in a three-electrode system show that HCF800 exhibits a high specific capacitance of 330.11 F/g as the discharge current density is 1 A/g and still maintains 65.3% of its original specific capacitance when the current density reaches 20 A/g. Moreover, in a two-electrode system, HCF800 also exhibits an excellent specific capacity of 259.86 F/g at a current density of 1 A/g, marvelous cyclic stability with the specific capacitance retention of 95.3% even after 10,000 cycles, and a large energy density of 12.99 W h/kg at 1.0 A/g. Significantly, the supercapacitor performance of these porous hollow carbon nanofibers is also superior to that of many previously reported carbon materials, which proved them to be worthy candidates for high-performance electrode materials.

Hydrogenated TiO2 Nanorod Arrays Decorated with Carbon Quantum Dots toward Efficient Photoelectrochemical Water Splitting.

Limited light harvesting and charge collection are recognized as grand challenges for the exploration of highly efficient TiO2 photoanodes. To overcome these intrinsic shortcomings, we reported the designed photoanode based on TiO2 nanoarrays with both hydrogenation treatment and surface decoration of carbon quantum dots (CQDs) toward efficient photoelectrochemical water splitting. The results revealed that hydrogenation treatment could cause the formation of oxygen vacancies to suppress the recombination of photoinduced carriers. Meanwhile, the decorated CQDs could not only play as the electron reservoirs to trap photoinduced electrons but also remarkably enhance the solar light harvesting due to their upconversion effect. The as-fabricated photoanodes exhibited a large photocurrent density of ∼3.0 mA/cm2 at 1.23 V versus reversible hydrogen electrode under simulated sunlight, which was the highest one among hydrogenated TiO2 photoanodes ever reported and was ∼6 times that of pristine analogues.

WO3/BiVO4 Type-II Heterojunction Arrays Decorated with Oxygen-Deficient ZnO Passivation Layer: A Highly Efficient and Stable Photoanode.

In the present work, we report a ternary WO3/BiVO4/ZnO photoanode with boosted PEC efficiency and stability toward highly efficient water splitting. The type-II WO3/BiVO4 heterojunction arrays are firstly prepared by hydrothermal growth of WO3 nanoplate arrays onto the substrates of fluorine-doped tin oxide (FTO)-coated glass, followed by spin-coating of BiVO4 layers onto the WO3 nanoplate surfaces. After that, thin ZnO layers are further introduced onto the WO3/BiVO4 heterojunction arrays via atomic layer deposition (ALD), leading to the construction of ternary WO3/BiVO4/ZnO photoanodes. It is verified that the ZnO thin layer in the WO3/BiVO4/ZnO photoanode contains abundant oxygen vacancies, which could act as an effective passivation layer to enhance the charge separation and surface water oxidation kinetics of photogenerated carriers. The as-prepared WO3/BiVO4/ZnO photoanode produces a photocurrent of 2.96 mA cm-2 under simulated sunlight with an incident photon-to-current conversion efficiency (IPCE) of ∼72.8% at 380 nm at a potential of 1.23 V versus RHE without cocatalysts, both of which are comparable to the state-of-the-art WO3/BiVO4 counterparts. Moreover, the photocurrent of the WO3/BiVO4/ZnO photoanode shows only 9% decay after 6 h, suggesting its high photoelectrochemical (PEC) stability.

Elimination of S Vacancy as the Cause for the n-Type Behavior of MoS2 from the First-Principles Perspective.

Molybdenum disulfide (2H-MoS2) based low-dimensional nanostructure materials have great potential for applications in electronic and optoelectronic devices. However, some of the properties such as the origin of the native n-type electrical conductivity (EC) observed in these materials still remain elusive. Here, the defect properties in the 2H-MoS2 bulk system are systematically investigated by first-principles calculation to address these issues. We find that the S vacancy VS with low formation energy cannot be the origin of n-type EC owing to its deep defect levels within the valence band region. All other donor defects such as antisite MoS or Mo interstitial MoI also have deep levels that can trap electrons leading to depressed EC. SMo and SI could be the origin of the p-type EC in 2H-MoS2, but the concentrations are expected to be rather low due to their high formation energies and can only be enhanced under S-rich/Mo-poor conditions. These results provide the underlying insights on the defect properties 2H-MoS2 and explain well the experimental observations.

Mesporous 3C-SiC Hollow Fibers.

In the present work, for the first time, we reported the exploration of mesoporous 3C-SiC hollow fibers via single-spinneret electrospinning of polyureasilazane (PSN) and polyvinylpyrrolidone (PVP) solution followed by high-temperature pyrolysis treatment. The resultant products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM) and N2 adsorption. The as-prepared hollow fibers with totally mesoporous walls were uniformly sized in diameter and high purity in morphology. They were composed of single-crystalline 3C-SiC nanoparticles with a surface area of 21.75 m2/g and average pore diameter of ~34 nm. The PSN concentration played a determined role on the formation of hollow fibers rather than the conventional solid counterparts, enabling their growth in a tunable manner. A possible mechanism was proposed for the formation of mesoporous SiC hollow fiber.

A transparent CdS@TiO2 nanotextile photoanode with boosted photoelectrocatalytic efficiency and stability.

In the present work, we report the exploration of a transparent CdS@TiO2 nanotextile photoanode with boosted photoelectrocatalytic (PEC) efficiency and stability, by the controllable coating of an amorphous TiO2 ultrathin layer via the atomic layer deposition (ALD) technique. The optimal CdS@TiO2 nanotextile photoanode with a 3.5 nm TiO2 ultrathin layer exhibits a photocurrent density of 1.8 mA cm-2 at 0 V vs. RHE, which is 11 times higher than that of the pristine CdS counterpart. The photocatalytic H2 evolution rate of CdS@TiO2 ranges up to 47.5 mmol g-1 h-1, which is superior to those reported for one-dimensional CdS-based counterparts. Moreover, the photocurrent of CdS@TiO2 nanotextile photoanodes shows only 9% decay after 9 h, suggesting its profoundly enhanced PEC stability, in comparison with that of pristine CdS photoanodes (almost down to zero after 3 hours). It is verified that the introduced TiO2 nanoshells could limit the charge recombination, facilitate the charge separation, reduce the charge transfer resistance, and enhance the wettability of the electrodes, resulting in their significantly enhanced PEC performance.

Tailored Fabrication of Thoroughly Mesoporous BiVO4 Nanofibers and Their Visible-Light Photocatalytic Activities.

Bismuth vanadate (BiVO4) is considered as a potentially attractive candidate for the O2 evolution and photodegradation of organic pollutants. In an effort to develop visible-light-driven photocatalysts with high activities, the thoroughly mesoporous BiVO4 nanofibers were fabricated via a foaming-assisted electrospinning strategy. It was found that the introduced foaming agent of diisopropyl azodiformate within the solutions plays a crucial role on the formation of thoroughly mesoporous BiVO4 nanofibers, making their growth tunable. The obtained mesoporous BiVO4 nanofibers possess well-defined one-dimensional mesoporous architectures with high purity in their morphology and a surface area of 22.5 m(2)/g, which is ∼4 times that of conventional solid counterparts (5.8 m(2)/g). Accordingly, they exhibit much higher efficient photocatalytic activities toward the degradation of rhodamine B under visible-light irradiation, which is 3 times that of conventional solid counterparts, suggesting their promising application as novel and efficient photocatalysts for water purification.

Highly Efficient Photocatalytic Hydrogen Evolution in Ternary Hybrid TiO2/CuO/Cu Thoroughly Mesoporous Nanofibers.

Development of novel hybrid photocatalysts with high efficiency and durability for photocatalytic hydrogen generation is highly desired but still remains a grand challenge currently. In the present work, we reported the exploration of ternary hybrid TiO2/CuO/Cu thoroughly mesoporous nanofibers via a foaming-assisted electrospinning technique. It is found that by adjusting the Cu contents in the solutions, the unitary (TiO2), binary (TiO2/CuO, TiO2/Cu), and ternary (TiO2/CuO/Cu) mesoporous products can be obtained, enabling the growth of TiO2/CuO/Cu ternary hybrids in a tailored manner. The photocatalytic behavior of the as-synthesized products as well as P25 was evaluated in terms of their hydrogen evolution efficiency for the photodecomposition water under Xe lamp irradiation. The results showed that the ternary TiO2/CuO/Cu thoroughly mesoporous nanofibers exhibit a robust stability and the most efficient photocatalytic H2 evolution with the highest release rate of ∼851.3 µmol g(-1) h(-1), which was profoundly enhanced for more than 3.5 times with respect to those of the pristine TiO2 counterparts and commercial P25, suggesting their promising applications in clean energy production.

Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls.

Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 µmol g(-1)·h(-1) and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts.

Tailored Electrospinning of WO3 Nanobelts as Efficient Ultraviolet Photodetectors with Photo-Dark Current Ratios up to 1000.

In this work, polycrystalline WO3 nanobelts were fabricated via an electrospinning process combined with subsequent air calcination. The resultant products were characterized by X-ray diffraction, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy in regard to the structures. It has been found that the applied voltage during the electrospinning process played the determined role in the formation of the WO3 nanobelts, allowing the controlled growth of the nanobelts. The ultraviolet (UV) photodetector assembled by an individual WO3 nanobelt exhibits a high sensitivity and a precise selectivity to the different wavelength lights, with a very low dark current and typical photo-dark current ratio up to 1000, which was the highest for any WO3 photodectectors ever reported. This work could not only push forward the facile preparation of WO3 nanobelts but also represent, for the first time, the possibility that the polycrystalline WO3 nanobelts could be a promising building block for the highly efficient UV photodetectors.