Approaching the Volcano Top: Iridium/Silicon Nanocomposites as Efficient Electrocatalysts for the Hydrogen Evolution Reaction.

Electrolysis of water to generate hydrogen is an important issue for the industrial production of green and sustainable energy. The best electrocatalyst currently available for the hydrogen evolution reaction (HER) is platinum. We herein show that iridium can be manipulated to achieve a record high HER activity surpassing platinum in every aspect: a lower overpotential at any given current density, a higher current density, and mass activity for all bias potentials applied and a catalyst cost reduction of 50% for the same hydrogen generation rate. The superior HER activity was achieved by a binary Ir/Si nanowire catalyst design in which (as density functional theory calculations show) two distinct strategies act in synergy: (i) decreasing the size of the iridium nanoparticles to ∼2.2 nm and (ii) dividing the H2-generation process to three steps occurring on two different catalysts: H adsorption on iridium, H diffusion to silicon, and H2 desorption from silicon.

Publisher Correction: A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

The original HTML version of this Article omitted to list Yeshayahu Lifshitz as a corresponding author and incorrectly listed Shuit-Tong Lee as a corresponding author.Correspondingly, the original PDF version of this Article incorrectly stated that "Correspondence and requests for materials should be addressed to X.J. (email: xin.jiang@uni-siegen.de), or to Y.L. (email: yangl@suda.edu.cn), or to S.-T.L. (email: shayli@technion.ac.il), or to Z.K. (email: zhkang@suda.edu.cn)", instead of the correct "Correspondence and requests for materials should be addressed to X.J. (email: xin.jiang@uni-siegen.de), or to Y. Liu (email: yangl@suda.edu.cn), or to Y. Lifshitz (email: shayli@technion.ac.il), or to Z.K. (email: zhkang@suda.edu.cn)".This has now been corrected in the PDF and HTML versions of the Article.

Local-Curvature-Controlled Non-Epitaxial Growth of Hierarchical Nanostructures.

Site-selective growth on non-spherical seeds provides an indispensable route to hierarchical complex nanostructures that are interesting for diverse applications. However, this has only been achieved through epitaxial growth, which is restricted to crystalline materials with similar crystal structures and physicochemical properties. A non-epitaxial growth strategy is reported for hierarchical nanostructures, where site-selective growth is controlled by the curvature of non-spherical seeds. This strategy is effective for site-selective growth of silica nanorods from non-spherical seeds of different shapes and materials, such as α-Fe2 O3 , NaYF4 , and ZnO. This growth strategy is not limited by the stringent requirements of epitaxy and is thus a versatile general method suitable for the preparation of hierarchical nanostructures with controlled morphologies and compositions to open up a verity of applications in self-assembly, nanorobotics, catalysis, electronics, and biotechnology.

Impacts of Carbon Dots on Rice Plants: Boosting the Growth and Improving the Disease Resistance.

A series of ∼5 nm sized carbon dots (CDs) with different oxygen contents were fabricated and employed as a model material with which to explore the impacts of carbon nanoparticles on rice-plant growth. We show that CDs can penetrate into all parts of rice plants, including the cell nuclei. Systematic investigations provide insight into the different processes by which seed germination, root elongation, seedling length, enzyme (RuBisCO) activity, and carbohydrate generation are increased. CDs are capable of entering the cell, reaching the nucleus, loosening the DNA structure, and increasing the thionin (Os06g32600) gene expression, which finally enhanced the rice-plant disease-resistance ability. CDs can be degraded by plant to form plant-hormone analogues and CO2, and then the hormone analogues promote the rice-plant growth, while the CO2 is converted into carbohydrates through the Calvin cycle of photosynthesis. The outcome of these processes is a 14.8% enhancement of the total rice yield and an increase of the rice-plant resistance to diseases.

A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

Syngas, a CO and H2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO2 and H+/H2O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C3N4 composite (a CO2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co3O4, MoS2, Au and Pt serve as the HER component. The Co3O4-CDots-C3N4 electrocatalyst is found to be the most efficient among the combinations studied. The H2/CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H2. Insight into the mechanisms balancing between CO2 reduction and H2 evolution when applying the HER-CDots-C3N4 catalyst concept is provided.

Centimeter-Long Single-Crystalline Si Nanowires.

The elongation of free-standing one-dimensional (1D) functional nanostructures into lengths above the millimeter range has brought new practical applications as they combine the remarkable properties of nanostructured materials with macroscopic lengths. However, it remains a big challenge to prepare 1D silicon nanostructures, one of the most important 1D nanostructures, with lengths above the millimeter range. Here we report the unprecedented preparation of ultralong single-crystalline Si nanowires with length up to 2 cm, which can function as the smallest active material to facilitate the miniaturization of macroscopic devices. These ultralong Si nanowires with augmented flexibility are of emerging interest for flexible electronics. We also demonstrate the first single-nanowire-based wearable joint motion sensor with superior performance to reported systems, which just represents one example of novel devices that can be built from these nanowires. The preparation of ultralong Si nanowires will stimulate the fabrication and miniaturization of electric, optical, medical, and mechanical devices to impact the semiconductor industry and our daily life in the near future.

Hydroxyl-Group-Dominated Graphite Dots Reshape Laser Desorption/Ionization Mass Spectrometry for Small Biomolecular Analysis and Imaging.

Small molecules play critical roles in life science, yet their facile detection and imaging in physiological or pathological settings remain a challenge. Matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) is a powerful tool for molecular analysis. However, conventional organic matrices (CHCA, DHB, etc.) used in assisting analyte ionization suffer from intensive background noise in the mass region below m/z 700, which hinders MALDI MS applications for small-molecule detection. Here, we report that a hydroxyl-group-dominated graphite dot (GD) matrix overcomes limitations of conventional matrices and allows MALDI MS to be used in fast and high-throughput analysis of small biomolecules. GDs exhibit extremely low background noise and ultrahigh sensitivity (with limit of detection <1 fmol) in MALDI MS. This approach allows identification of complex oligosaccharides, detection of low-molecular-weight components in traditional Chinese herbs, and facile analysis of puerarin and its metabolites in serum without purification. Moreover, we show that the GDs provide an effective matrix for the direct imaging or spatiotemporal mapping of small molecules and their metabolites (m/z < 700) simultaneously at the suborgan tissue level. Density functional theory calculations further provide the mechanistic basis of GDs as an effective MALDI matrix in both the positive-ion and negative-ion modes. Collectively, our work uncovered a useful matrix which reshapes MALDI MS technology for a wide range of applications in biology and medicine.

Carbon Dots as Fillers Inducing Healing/Self-Healing and Anticorrosion Properties in Polymers.

Self-healing is the way by which nature repairs damage and prolongs the life of bio entities. A variety of practical applications require self-healing materials in general and self-healing polymers in particular. Different (complex) methods provide the rebonding of broken bonds, suppressing crack, or local damage propagation. Here, a simple, versatile, and cost-effective methodology is reported for initiating healing in bulk polymers and self-healing and anticorrosion properties in polymer coatings: introduction of carbon dots (CDs), 5 nm sized carbon nanocrystallites, into the polymer matrix forming a composite. The CDs are blended into polymethacrylate, polyurethane, and other common polymers. The healing/self-healing process is initiated by interfacial bonding (covalent, hydrogen, and van der Waals bonding) between the CDs and the polymer matrix and can be optimized by modifying the functional groups which terminate the CDs. The healing properties of the bulk polymer-CD composites are evaluated by comparing the tensile strength of pristine (bulk and coatings) composites to those of fractured composites that are healed and by following the self-healing of scratches intentionally introduced to polymer-CD composite coatings. The composite coatings not only possess self-healing properties but also have superior anticorrosion properties compared to those of the pure polymer coatings.

The Light-Induced Field-Effect Solar Cell Concept - Perovskite Nanoparticle Coating Introduces Polarization Enhancing Silicon Cell Efficiency.

Solar cell generates electrical energy from light one via pulling excited carrier away under built-in asymmetry. Doped semiconductor with antireflection layer is general strategy to achieve this including crystalline silicon (c-Si) solar cell. However, loss of extra energy beyond band gap and light reflection in particular wavelength range is known to hinder the efficiency of c-Si cell. Here, it is found that part of short wavelength sunlight can be converted into polarization electrical field, which strengthens asymmetry in organic-c-Si heterojunction solar cell through molecule alignment process. The light harvested by organometal trihalide perovskite nanoparticles (NPs) induces molecular alignment on a conducting polymer, which generates positive electrical surface field. Furthermore, a "field-effect solar cell" is successfully developed and implemented by combining perovskite NPs with organic/c-Si heterojunction associating with light-induced molecule alignment, which achieves an efficiency of 14.3%. In comparison, the device with the analogous structure without perovskite NPs only exhibits an efficiency of 12.7%. This finding provides a novel concept to design solar cell by sacrificing part of sunlight to provide "extra" asymmetrical field continuously as to drive photogenerated carrier toward respective contacts under direct sunlight. Moreover, it also points out a method to combine promising perovskite material with c-Si solar cell.

C3 N-A 2D Crystalline, Hole-Free, Tunable-Narrow-Bandgap Semiconductor with Ferromagnetic Properties.

Graphene has initiated intensive research efforts on 2D crystalline materials due to its extraordinary set of properties and the resulting host of possible applications. Here the authors report on the controllable large-scale synthesis of C3 N, a 2D crystalline, hole-free extension of graphene, its structural characterization, and some of its unique properties. C3 N is fabricated by polymerization of 2,3-diaminophenazine. It consists of a 2D honeycomb lattice with a homogeneous distribution of nitrogen atoms, where both N and C atoms show a D6h -symmetry. C3 N is a semiconductor with an indirect bandgap of 0.39 eV that can be tuned to cover the entire visible range by fabrication of quantum dots with different diameters. Back-gated field-effect transistors made of single-layer C3 N display an on-off current ratio reaching 5.5 × 1010 . Surprisingly, C3 N exhibits a ferromagnetic order at low temperatures (<96 K) when doped with hydrogen. This new member of the graphene family opens the door for both fundamental basic research and possible future applications.

A rhodium/silicon co-electrocatalyst design concept to surpass platinum hydrogen evolution activity at high overpotentials.

Currently, platinum-based electrocatalysts show the best performance for hydrogen evolution. All hydrogen evolution reaction catalysts should however obey Sabatier's principle, that is, the adsorption energy of hydrogen to the catalyst surface should be neither too high nor too low to balance between hydrogen adsorption and desorption. To overcome the limitation of this principle, here we choose a composite (rhodium/silicon nanowire) catalyst, in which hydrogen adsorption occurs on rhodium with a large adsorption energy while hydrogen evolution occurs on silicon with a small adsorption energy. We show that the composite is stable with better hydrogen evolution activity than rhodium nanoparticles and even exceeding those of commercial platinum/carbon at high overpotentials. The results reveal that silicon plays a key role in the electrocatalysis. This work may thus open the door for the design and fabrication of electrocatalysts for high-efficiency electric energy to hydrogen energy conversion.

Reversible and Precise Self-Assembly of Janus Metal-Organosilica Nanoparticles through a Linker-Free Approach.

Reversible self-assembly of nanoparticles into ordered structures is essential for both fundamental study and practical applications. Although extensive work has been conducted, the demand for simple, cheap, reversible, and versatile ordering methods is still a central issue in current nanoscience and nanotechnology. Here we report a reversible and precise self-assembly of nanoparticles through a linker-free and fast approach by manipulating the interparticle forces, e.g., van der Waals (VDW) force and electrostatic force. Because VDW force is nondirectional, an oriented interaction is achieved to induce the directional binding of nanoparticles utilizing the Janus nanostructure. An effective sol-gel approach has been developed to synthesize metal-organosilica Janus nanoparticles. Dimers and trimers can be obtained by tuning the steric hindrance. After assembly, "hot-spots" can be generated between adjacent nanoparticles, and dramatic enhancement has been observed in surface-enhanced Raman scattering. The present strategy overcomes several limitations of existing approaches and allows the controlled assembly of small particles into various structures.

Synthesis of aligned symmetrical multifaceted monolayer hexagonal boron nitride single crystals on resolidified copper.

Atomically smooth hexagonal boron nitride (h-BN) films are considered as a nearly ideal dielectric interface for two-dimensional (2D) heterostructure devices. Reported mono- to few-layer 2D h-BN films, however, are mostly small grain-sized, polycrystalline and randomly oriented. Here we report the growth of centimetre-sized atomically thin h-BN films composed of aligned domains on resolidified Cu. The films consist of monolayer single crystalline triangular and hexagonal domains with size of up to ∼10 µm. The domains converge to symmetrical multifaceted shapes such as "butterfly" and "6-apex-star" and exhibit ∼75% grain alignment for over millimetre distances as verified through transmission electron microscopy. Scanning electron microscopy images reveal that these domains are aligned for over centimetre distances. Defect lines are generated along the grain boundaries of mirroring h-BN domains due to the two different polarities (BN and NB) and edges with the same termination. The observed triangular domains with truncated edges and alternatively hexagonal domains are in accordance with Wulff shapes that have minimum edge energy. This work provides an extensive study on the aligned growth of h-BN single crystals over large distances and highlights the obstacles that are needed to be overcome for a 2D material with a binary configuration.

ZnO nanowires growth via reduction of ZnO powder by H2.

A unique approach of ZnO nanowire growth mediated via reduction of ZnO by H2 is presented. It is less complex and more controllable than the conventional carbothermal method (reduction of ZnO by C). The chemical vapor deposition system employed allows precise control of all deposition parameters: (1) source and substrate temperatures, (2) carrier gas compositions, flow and pressure of several gases, (3) growth along a large range of distances from the source. In situ residual gas analysis allows real-time feedback of the process reactions. Controlled, stabilized, homogenous growth (characterized by scanning electron microscopy and x-ray diffraction) over relatively large areas is demonstrated.

Water splitting. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway.

The use of solar energy to produce molecular hydrogen and oxygen (H2 and O2) from overall water splitting is a promising means of renewable energy storage. In the past 40 years, various inorganic and organic systems have been developed as photocatalysts for water splitting driven by visible light. These photocatalysts, however, still suffer from low quantum efficiency and/or poor stability. We report the design and fabrication of a metal-free carbon nanodot-carbon nitride (C3N4) nanocomposite and demonstrate its impressive performance for photocatalytic solar water splitting. We measured quantum efficiencies of 16% for wavelength λ = 420 ± 20 nanometers, 6.29% for λ = 580 ± 15 nanometers, and 4.42% for λ = 600 ± 10 nanometers, and determined an overall solar energy conversion efficiency of 2.0%. The catalyst comprises low-cost, Earth-abundant, environmentally friendly materials and shows excellent stability.

Smart liquid SERS substrates based on Fe3O4/Au nanoparticles with reversibly tunable enhancement factor for practical quantitative detection.

There is a strong correlation between the surface enhanced Raman scattering (SERS) enhancement factor (EF), the excitation wavelength, and the feature properties (composition, size, geometry, and analytes). The prediction of the EF of specific substrates, crucial to the quantitative SERS detection, is however still very difficult. The present work presents smart liquid SERS substrates consisting of suspensions of Fe3O4/Au nanoparticles, which provide high spot-to-spot uniformity, reproducibility and good reversibility. The EF of these substrates can be reversibly tuned by applying an external magnetic field. The EF magnetic tuning is within 2 orders of magnitude per substrate in the range of 10(4)-10(7). The ability to reversibly adjust the SERS EF enables to reduce EF variations caused by external effects such as substrate-to-substrate differences and long-term-storage degradation. This improves the quantitative detection of analytes and might be a significant step forward in employing SERS for practical applications.

Growth of SiO(x) nanowires by laser ablation.

Amorphous SiO(x) nanowires (NWs) were synthesized using laser ablation of silicon-containing targets. The influence of various parameters such as target composition, substrate type, substrate temperature and carrier gas on the growth process was studied. The NWs were characterized using high resolution scanning and transmission electron microscopes (HRSEM and HRTEM) with their attachments: electron dispersive spectroscopy (EDS) and energy electron loss spectroscopy (EELS). A metal catalyst was found essential for the NW growth. A growth temperature higher than 1000 °C was necessary for the NW formation using an Ar-based carrier gas at 500 Torr. The use of Ar-5%H(2) instead of pure Ar resulted in a higher yield and longer NWs. Application of a diffusion barrier on top of the Si substrate guaranteed the availability of metal catalyst droplets on the surface, essential for the NW growth. Ni was found to be a better catalyst than Au in terms of the NW yield and length. Two alternative sequences for the evolution of the amorphous SiO(x) NWs were considered: (a) the formation of Si NWs first and their complete oxidation afterwards, which seems to be doubtful, (b) the direct formation of SiO(x) NWs, which is more likely to occur. The direct formation mechanism was proposed to advance in three stages: preferential adsorption of SiO(x) clusters on the catalyst surface first, a successive surface diffusion to the catalyst droplet lower hemisphere, and finally the formation and growth of the NW between the catalyst and the substrate.