A three-dimensional copper metal—organic framework with the rare chabazite (CHA) topology namely FJI-Y11 has been constructed with flexibly carboxylic ligand 5,5′-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic acid (H4L). FJI-Y11 exhibits high water stability with the pH range from 2 to 12 at temperature as high as 373 K. Importantly, FJI-Y11 also shows high efficiency of hydrogen isotope separation using dynamic column breakthrough experiments under atmospheric pressure at 77 K. Attributed to its excellent structural stability, FJI-Y11 possesses good regenerated performance and maintains high separation efficiency after three cycles of breakthrough experiments.
All-inorganic cesium lead halide perovskite quantum dots (QDs) have been a promising candidate for optoelectronic devices in recent years, such as light-emitting diodes, photodetectors and solar cells, owing to their superb optoelectronic properties. Still, the stability issue of nanocrystals is a bottleneck for their practical application. Herein, we report a facile method for the synthesis of a series of phosphine ligand modified CsPbBr3 QDs with high PL intensity. By introducing organic phosphine ligands, the tolerance of CsPbBr3 QDs to ethanol, water and UV light was dramatically improved. Moreover, the phosphine ligand modified QD films deposited on the glass subtracts exhibit superior PL intensity and optical stability to those of pristine QD based films.
The development of high-efficiency peroxidase mimetics is highly desirable in view of high cost and low stability of natural enzymes. From the perspective of mimicking active site microenvironment at low cost, we herein report a novel histidine-functionalized graphene quantum dot (His-GQD)/hemin complex, which exhibits the highest catalytic rate for the peroxidase-based chromogenic reaction among the hemin-containing mimetics reported so far. Also, our peroxidase mimetic shows excellent tolerance to strongly acidic conditions and can function in a wide temperature range. Lineweaver-Burk plots and comprehensive electron paramagnetic resonance analysis reveal a ping-pong type catalytic mechanism for this mimetic. In addition, His-GQD/hemin demonstrates high efficiency and accuracy in detecting H2O2 and blood glucose. Our work provides an effective design of artificial enzymes for practical applications.
A diverse range of remarkable boron nitride (BN) nanostructures subsuming nano-horns, nano-rods, nano-platelets, and clusters of hollow nanospheres (nano-onions, arguably of greatest applied and fundamental interest) have been produced exclusively from crystalline BN precursor powder via lamp ablation. The procedure is safe, devoid of toxic reagents, simple, rapid and scalable—generating some genres of nanoparticles that had previously proved elusive. Product structure and composition were unambiguously assessed by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy.
In this work, homogeneous Ni0.33Co0.67Se hollow nanoprisms were synthesized successfully in virtue of Kirkendall effect. It is the first time for bimetallic Ni-Co compounds Ni0.33Co0.67Se to be used in lithium-ion batteries (LIBs). Impressively, the Ni0.33Co0.67Se hollow nanoprisms show superior specific capacity (1,575 mAh/g at the current density of 100 mA/g) and outstanding rate performance (850 mAh/g at 2,000 mA/g) as anode material for LIBs. This work proves the potential of bimetallic chalcogenide compounds as high performance anode materials for LIBs.
Here, the structural transformations of H4ETTC induced by coronene (COR) and selective adsorption behaviors of COR in different templates were investigated by scanning tunnelling microscope (STM). It was discovered that the assembled architecture of H4ETTC at the HOPG/ heptanoic acid interface depended on the concentration of COR, and the clusters of COR were obtained in the kagomé nanoporous network of H4ETTC molecules at a high concentration of COR solution. In addition, COR clusters can also be formed in the hexagonal porous structure of hexaphenylbenzene (HPB) molecules modified by alkyl chains at the HOPG/heptanoic acid interface. When both H4ETTC and HPB assembly structures, based on hydrogen bonding and van der Waals force respectively, were selected as the host templates, COR showed selectivity for HPB template to form HPB/COR hexagonal host–guest architecture. Density functional theory (DFT) calculations were also performed to disclose the mechanisms involved.
Oligo(p-phenyleneethynylene)s (OPEs) end-capped with (alkynyl)bis(diphosphine)ruthenium and thiol/thiolate groups stabilize ca. 2 nm diameter gold nanoparticles (AuNPs). The morphology, elemental composition and stability of the resultant organometallic OPE/AuNP hybrid materials have been defined using a combination of molecular- and nano-material chacterization techniques. The hybrids display long-term stability in solution (more than a month), good solubility in organic solvents, reversible ruthenium-centered oxidation, and transparency beyond 800 nm, and possess very strong nonlinear absorption activity at the first biological window, and unprecedented two-photon absorption activity in the second biological window (σ2 up to 38,000 GM at 1,050 nm).
Realizing the reduction of N2 to NH3 at low temperature and pressure is always the unremitting pursuit of scientists and then electrochemical nitrogen reduction reaction offers an intriguing alternative. Here, we develop a feasible way, gamma irradiation, for constructing defective structure on the surface of WO3 nanosheets, which is clearly observed at the atomic scale by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The abundant oxygen vacancies ensure WO3 nanosheets with a Faradaic efficiency of 23% at −0.3 V vs. RHE. Moreover, we start from the regulation of the surface state to suppress proton availability towards hydrogen evolution reaction (HER) on the active site and thus boost the selectivity of nitrogen reduction.
Small-sized bimetallic nanoparticles that possess numerous accessible metal sites and optimal geometric/electronic structures show great promise for advanced synergetic catalysis but remain synthetic challenge so far. Here, an universial synthetic method is developed for building a library of bimetallic nanoparticles on mesoporous sulfur-doped carbon supports, consisting of 24 combinations of 3 noble metals (that is, Pt, Rh, Ir) and 7 other metals, with average particle sizes ranging from 0.7 to 1.4 nm. The synthetic strategy is based on the strong metal-support interaction arising from the metal-sulfur bonding, which suppresses the metal aggregation during the H2-reduction at 700 °C and ensure the formation of small-sized and alloyed bimetallic nanoparticles. The enhanced catalytic properties of the ultrasmall bimetallic nanoparticles are demonstrated in the dehydrogenation of propane at high temperature and oxidative dehydrogenations of N-heterocycles.
Colloidal nanoparticles with anisotropic architectures have attracted a variety of interest and attention due to different physical and chemical properties compared with the isotropic counterparts, making them promising candidates in many fundamental studies and practical applications. Particularly, carbon and silica-based anisotropic nanoparticles can be one stand out by combing both intrinsic merits of carbons and silica, such as structural stability, biocompatibility, large surface area, and ease of functionalization with the anisotropic structural complexity. In this review, we aim to provide an updated summary of the research related to the anisotropic carbon and silica-based nanostructures, covering both their synthesis and applications.
Anisotropic two-dimensional (2D) materials exhibit lattice-orientation dependent optical and electrical properties. Carriers doping of such materials has been used to modulate their energy band structures for opto-electronic applications. Herein, we show that by stacking monolayer rhenium disulfide (ReS2) on a flat gold film, the electrons doping in ReS2 can affect the in-plane anisotropic Raman enhancement of molecules adsorbed on ReS2. The change of enhancement factor and the degree of anisotropy in enhancement with layer number are sensitively dependent on the doping level of ReS2 by gold, which is further confirmed by Kelvin probe force microscopy (KPFM) measurements. These findings could open an avenue for probing anisotropic electronic interactions between molecules and 2D materials with low symmetry using Raman enhancement effect.
Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm2 in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr2O3. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.
Two-dimensional (2D) nanomaterials have attracted a great deal of attention since the discovery of graphene in 2004, due to their intriguing physicochemical properties and wide-ranging applications in catalysis, energy-related devices, electronics and optoelectronics. To maximize the potential of 2D nanomaterials for their technological applications, controlled assembly of 2D nanobulding blocks into integrated systems is critically needed. This mini review summarizes the reported strategies of 2D materials-based assembly into integrated functional nanostructures, from in-situ assembly method to post-synthesis assembly. The applications of 2D assembled integrated structures are also covered, especially in the areas of energy, electronics and sensing, and we conclude with discussion on the remaining challenges and potential directions in this emerging field.
Electrochemical water splitting (EWS) is a highly clean and efficient method for high-purity hydrogen production. Unfortunately, EWS suffers from the sluggish and complex oxygen evolution reaction (OER) kinetics at anode. At present, the efficient, stable, and low-cost non-precious metal based OER electrocatalyst is still a great and long-term challenge for the future industrial application of EWS technology. Herein, we develop a simple and fast approach for gram-scale synthesis of flower-like cobalt-based layered double hydroxides nanosheet aggregates by ultrasonic synthesis, which show outstanding electrocatalytic performance for the oxygen evolution reaction in alkaline media, such as preeminent stability, small overpotential of 300 mV at 10 mA·cm−2 and small Tafel slope of 110 mV·dec−1.
As a promising graphene analogue, two-dimensional (2D) polymer nanosheets with unique 2D features, diversified topological structures and as well as tunable electronic properties, have received extensive attention in recent years. Here in this review, we summarized the recent research progress in the preparation methods of 2D polymer nanosheets, mainly including interfacial polymerization and solution polymerization. We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications, such as batteries, supercapacitors, electrocatalysis and photocatalysis. Finally, on the basis of their current development, we put forward the existing challenges and some personal perspectives.