Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

High-entropy alloys (HEAs), which are defined as near-equimolar alloys of five or more elements, are attracting ever increasing attention because of the unique properties in a variety of applicatio...

High-Entropy Alloys as a Platform for Catalysis: Progress, Challenges, and Opportunities

Gold nanorods (NRs), pseudo-one-dimensional rod-shaped nanoparticles (NPs), have become one of the burgeoning materials in the recent years due to their anisotropic shape and adjustable plasmonic properties. With the continuous improvement in synthetic methods, a variety of materials have been attached around Au NRs to achieve unexpected or improved plasmonic properties and explore state-of-the-art technologies. In this review, we comprehensively summarize the latest progress on Au NRs, the most versatile anisotropic plasmonic NPs. We present a representative overview of the advances in the synthetic strategies and outline an extensive catalogue of Au-NR-based heterostructures with tailored architectures and special functionalities. The bottom-up assembly of Au NRs into preprogrammed metastructures is then discussed, as well as the design principles. We also provide a systematic elucidation of the different plasmonic properties associated with the Au-NR-based structures, followed by a discussion of the promising applications of Au NRs in various fields. We finally discuss the future research directions and challenges of Au NRs.

Gold Nanorods: The Most Versatile Plasmonic Nanoparticles

Seawater electrolysis represents a potential solution to grid-scale production of carbon-neutral hydrogen energy without reliance on freshwater. However, it is challenged by high energy costs and detrimental chlorine chemistry in complex chemical environments. Here we demonstrate chlorine-free hydrogen production by hybrid seawater splitting coupling hydrazine degradation. It yields hydrogen at a rate of 9.2 mol h–1 gcat–1 on NiCo/MXene-based electrodes with a low electricity expense of 2.75 kWh per m3 H2 at 500 mA cm–2 and 48% lower energy equivalent input relative to commercial alkaline water electrolysis. Chlorine electrochemistry is avoided by low cell voltages without anode protection regardless Cl– crossover. This electrolyzer meanwhile enables fast hydrazine degradation to ~3 ppb residual. Self-powered hybrid seawater electrolysis is realized by integrating low-voltage direct hydrazine fuel cells or solar cells. These findings enable further opportunities for efficient conversion of ocean resources to hydrogen fuel while removing harmful pollutants. Seawater electrolysis is promising for grid-scale H2 production without freshwater reliance, but high energy costs and detrimental Cl chemistry reduce its practical potential. Here, authors developed an energy-saving hybrid seawater electrolyzer for chlorine-free H2 production and N2H4 degradation.

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Energy-saving hydrogen production by chlorine-free hybrid seawater splitting coupling hydrazine degradation.

Self-assembly of colloidal nanoparticles (NPs) into superstructures offers a flexible and promising pathway to manipulate the nanometer-sized particles and thus make full use of their unique properties. This bottom-up strategy builds a bridge between the NP regime and a new class of transformative materials across multiple length scales for technological applications. In this field, anisotropic NPs with size- and shape-dependent physical properties as self-assembly building blocks have long fascinated scientists. Self-assembly of anisotropic NPs not only opens up exciting opportunities to engineer a variety of intriguing and complex superlattice architectures, but also provides access to discover emergent collective properties that stem from their ordered arrangement. Thus, this has stimulated enormous research interests in both fundamental science and technological applications. This present review comprehensively summarizes the latest advances in this area, and highlights their rich packing behaviors from the viewpoint of NP shape. We provide the basics of the experimental techniques to produce NP superstructures and structural characterization tools, and detail the delicate assembled structures. Then the current understanding of the assembly dynamics is discussed with the assistance of in situ studies, followed by emergent collective properties from these NP assemblies. Finally, we end this article with the remaining challenges and outlook, hoping to encourage further research in this field.

Self-assembly of anisotropic nanoparticles into functional superstructures

Redesigning heterogeneous catalysts so that they can simultaneously integrate the efficiency and durability under reaction environments with respect to gas fuel production, such as hydrogen (H2), o...

General Strategy to Optimize Gas Evolution Reaction via Assembled Striped-Pattern Superlattices.

Although the strength of Raman signals can be increased by many orders of magnitude on noble metal nanoparticles, this enhancement is confined to an extremely short distance from the Raman-active surface. The key to the development of Raman spectroscopy for applications in diagnosis and detection of cancer and inflammatory diseases, and in pharmacology, relies on the capability of detecting analytes that are noninteractive with Raman-active surfaces. Here, a new Raman enhancement system is constructed, superficial-layer-enhanced Raman scattering (SLERS), by covering elongated tetrahexahedral gold nanoparticle arrays with a superficial perovskite (CH3 NH3 PbBr3 ) film. Plasmonic decay is depressed along the vertical direction away from the noble metal surface and the penetration depth is increased in the perovskite media. The vertical penetration of SLERS is verified by the spatial distribution of the analytes via Raman imaging in layer-scanning mode.

Superficial‐Layer‐Enhanced Raman Scattering (SLERS) for Depth Detection of Noncontact Molecules

A simple method was adopted in which ultrathin cerium oxide nanoplates (<1.4 nm) were synthesized to increase the surface atomic content, allowing transformation from a face-centered cubic (fcc) phase to a body-centered tetragonal (bct) phase. Three types of cerium oxide nanoparticles of different thicknesses (1.2 nm ultrathin nanoplates, 2.2 nm nanoplates, and 5.4 nm nanocubes) were examined using transmission electron microscopy and X-ray diffraction. The metastable bct phase was observed only in ultrathin nanoplates. Thermodynamic energy analysis confirmed that the surface energy of the ultrathin nanoplates is the cause of the remarkable stabilization of the metastable bct phase. The mechanism of surface energy regulation can be expanded to other metallic oxides, thus providing a new means for manipulating and stabilizing novel materials under ambient conditions that otherwise would not be recovered.

A Metastable Crystalline Phase in Two-Dimensional Metallic Oxide Nanoplates

The engineering of metal-organic frameworks (MOFs) into membranes and films is being investigated, to transform laboratory-synthesized MOFs into industrially viable products for a range of attractive applications. However, rational design and construction of highly permeable MOF thin films, without trade-offs in terms of structural mechanical stability, remains a significant challenge. Herein, a simple, general strategy is reported to prepare thin MOF nanosheet (NS)-assembled frame film via heteroepitaxial growth from metal hydroxide film. As the thin MOF NS-assembled film significantly enhances the permeability of mass though the film, the resultant gold nanoparticle (Au NP)@MOF film exhibits much higher catalytic efficiency than the Au NP@MOF bulk film. Meanwhile, the unique framework of the MOF NS-assembled film resists torsion and collapse, so the composite catalyst exhibits long-term stability.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201903180

A Metal–Organic Framework Nanosheet‐Assembled Frame Film with High Permeability and Stability

Molecules in confined spaces exhibit unusual behaviors that are not typically observed in bulk systems. Such behavior can provide alternative strategies for exploring new reaction pathways. Cleavage of the C=N bond of Nile red (NR) in solution is an irreversible reaction. Here, we used spatial confinement within a cationic micelle-confined system to convert this reaction to a reversible process. The fluorescence of NR shifted between red and green for nine cycles. The new chemical pathway based on spatial confinement can be attributed to two factors: increasing the local concentration of reactants and reducing the reaction energy barrier. This effect is supported by both experimental evidence and theoretical calculations. The cross-linked silica shell comprising the confinement chamber stabilizes the enclosed molecules. This reduces fluorophore leakage and maintains fluorescence intensity in most environments, including in solution, on paper, and in hydrogel films, and expands practical applications in encrypted information and multi-informational displays.

Keyan Liu

Papers

General Strategy to Optimize Gas Evolution Reaction via Assembled Striped-Pattern Superlattices.

Superficial‐Layer‐Enhanced Raman Scattering (SLERS) for Depth Detection of Noncontact Molecules

A Metastable Crystalline Phase in Two-Dimensional Metallic Oxide Nanoplates

A Metal–Organic Framework Nanosheet‐Assembled Frame Film with High Permeability and Stability

Spatial Confinement Tunes Cleavage and Re-Formation of C=N Bonds in Fluorescent Molecules.