Oriented Linear Self-Assembly of Colloidal Nanocrystals through Regioselective Formation of Hydrogen-Bonded Supramolecular Bridges.

The linear assembly of nanocrystals (NCs) with orientational order presents a significant challenge in the field of colloidal assembly. This study presents an efficient strategy for assembling oleic acid (OAH)-capped, faceted rare earth NCs─such as nanorods, nanoplates, and nanodumbbells─into flexible chain-like superstructures. Remarkably, these NC chains exhibit a high degree of particle orientation even with an interparticle distance reaching up to 15 nm. Central to this oriented assembly method is the facet-selective adsorption of low-molecular-weight polyethylene glycol (PEG), such as PEG-400 (Mn = 400), onto specific facets of NCs. This regioselectivity is achieved by exploiting the lower binding affinity of OAH ligands on the (100) facets of rare earth NCs, enabling facet-specific ligand displacement and subsequent PEG attachment. By adjusting the solvent polarity, the linear assembly of NCs is induced by the solvophobic effect, which simultaneously promotes the formation of hydrogen-bonded PEG supramolecular bridges. These supramolecular bridges effectively connect NCs and exhibit sufficient robustness to maintain the structural integrity of the chains, despite the large interparticle spacing. Notably, even when coassembling different types of NCs, the resulting multicomponent chains still feature highly selective facet-to-facet connections. This work not only introduces a versatile method for fabricating well-aligned linear superstructures but also provides valuable insights into the fundamental principles governing the facet-selective assembly of NCs in solution.

Densely Branched Carbon Nanotubes for Boosting the Electrochemical Performance of Li-S Batteries.

To address the inherent limitations of conventional carbon nanotubes (CNTs), such as their tendency to agglomerate and scarcity of catalytic sites, the development of branched carbon nanotubes (BCNTs) with a unique hierarchical structure has emerged as a promising solution. Herein, gram scale quantities of densely branched and structurally consistent Ni-Fe decorated branched CNTs (Ni-Fe@BCNT) have been prepared. This uniform and densely branched architecture ensures excellent dispersibility and superior electrical conductivity. Additionally, each branched tip is equipped with Ni-Fe particles, thereby providing numerous catalytic sites which endow them with exceptional catalytic activity for the conversion of polysulfides. The polypropylene (PP) separator modified with Ni-Fe@BCNT interlayer is fabricated as a multifunctional barrier for Li-S batteries. The experimental results demonstrate that Ni-Fe@BCNT interlayer can effectively suppress the shuttle effect of polysulfides and enhance their redox kinetics. The outstanding catalytic ability of Ni-Fe@BCNT interlayer enables batteries with high specific capacities, outstanding rate performance, and remarkable cycling stability. This approach proposed in this work paves a new path for synthesizing BCNTs and shows great potential for scaling up the production of BCNTs to address more demanding applications.

Encasing Few-Layer MoS2 within 2D Ordered Cubic Graphitic Cages to Smooth Trapping-Conversion of Lithium Polysulfides for Dendrite-Free Lithium-Sulfur Batteries.

The industrialization of lithium-sulfur (Li-S) batteries faces challenges due to the shuttling effect of lithium polysulfides (LiPSs) and the growth of lithium dendrites. To address these issues, a simple and scalable method is proposed to synthesize 2D membranes comprising a single layer of cubic graphitic cages encased with few-layer, curved MoS2. The distinctive 2D architecture is achieved by confining the epitaxial growth of MoS2 within the open cages of a 2D-ordered mesoporous graphitic framework (MGF), resulting in MoS2@MGF heterostructures with abundant sulfur vacancies. The experimental and theoretical studies establish that these MoS2@MGF membranes can act as a multifunctional interlayer in Li-S batteries to boost their comprehensive performance. The inclusion of the MoS2@MGF interlayer facilitates the trapping and conversion kinetics of LiPSs, preventing their shuttling effect, while simultaneously promoting uniform lithium deposition to inhibit dendrite growth. As a result, Li-S batteries with the MoS2@MGF interlayer exhibit high electrochemical performance even under high sulfur loading and lean electrolyte conditions. This work highlights the potential of designing advanced MoS2-encased heterostructures as interlayers, offering a viable solution to the current limitations plaguing Li-S batteries.

Shape-Mediated Oriented Assembly of Concave Nanoparticles under Cylindrical Confinement.

This contribution describes the self-assembly of colloidal nanodumbbells (NDs) with tunable shapes within cylindrical channels. We present that the intrinsic concave geometry of NDs endows them with peculiar packing and interlocking behaviors, which, in conjunction with the adjustable confinement constraint, leads to a variety of superstructures such as tilted-ladder chains and crossed-chain superlattices. A mechanistic investigation, corroborated by geometric calculations, reveals that the phase behavior of NDs under strong confinement can be rationalized by the entropy-driven maximization of the packing efficiency. Based on the experimental results, an empirical phase diagram is generated, which could provide general guidance in the design of intended superstructures from NDs. This study provides essential insight into how the interplay between the particle shape and confinement conditions can be exploited to direct the orientationally ordered assembly of concave nanoparticles into unusual superlattices.

Amphiphilic Self-Assembly of Nanocrystals at Emulsion Interface Renders Fast and Scalable Quasi-Nanosheet Formation.

Scalable assembly of nanocrystals (NCs) into two-dimensional (2D) nanosheets has aroused great interest, yet it remains under-explored. This is because current 2D assembly methods rely mainly on the use of solid- or liquid-air interfaces, which are inherently difficult for upscaling and thus lack practicability. Here, with a microemulsion-based amphiphilic assembly technique, we achieve a fast and scalable preparation of free-standing nanosheets comprising few-layer, tightly packed NCs, namely, quasi-nanosheets (quasi-NSs). Acetic acid, acting as both solvent and surface-treatment agent, is used to render the initially hydrophobic NCs amphiphilic, while simultaneously inducing the interfacial instability right after the assembly of NCs at the emulsion interface to afford quasi-NSs. This amphiphilic assembly method is applicable to a variety of NCs, and multicomponent quasi-NSs are also attainable upon coassembly of different types of NCs. In addition, the structural advantages of quasi-NSs in catalysis are showcased by using NiFe2O4 quasi-NSs as electrocatalysts for the oxygen evolution reaction. This work opens a new route for the scalable construction of 2D NC sheets with designated components and functions.

Native Ligand Carbonization Renders Common Platinum Nanoparticles Highly Durable for Electrocatalytic Oxygen Reduction: Annealing Temperature Matters.

Current protocols for synthesizing monodisperse platinum (Pt) nanoparticles typically involve the use of hydrocarbon molecules as surface-capping ligands. Using Pt nanoparticles as catalysts for the oxygen reduction reaction (ORR), however, these ligands must be removed to expose surface sites. Here, highly durable ORR catalysts are realized without ligand removal; instead, the native ligands are converted into ultrathin, conformal graphitic shells by simple thermal annealing. Strikingly, the annealing temperature is a critical factor dictating the ORR performance of Pt catalysts. Pt nanoparticles treated at 500 °C show a very poor ORR activity, whereas those annealed at 700 °C become highly active along with exceptional stability. In-depth characterization reveals that thermal treatment from 500 to 700 °C gradually opens up the porosity in carbon shells through graphitization. Importantly, such graphitic-shell-coated Pt catalysts exhibit a superior ORR stability, largely retaining the activity after 20 000 cycles in a membrane electrode assembly. Moreover, this ligand carbonization strategy can be extended to modify commercial Pt/C catalysts with substantially enhanced stability. This work demonstrates the feasibility of boosting the ORR performance of common Pt nanoparticles by harnessing the native surface ligands, offering a robust approach of designing highly durable catalysts for proton-exchange-membrane fuel cells.

A universal, green, and self-reliant electrolytic approach to high-entropy layered (oxy)hydroxide nanosheets for efficient electrocatalytic water oxidation.

The development and exploration of high-entropy materials with tunable chemical compositions and unique structural characteristics, although challenging, have attracted increasingly greater attention over the past few years. Here, we report a universal and green method to prepare high-entropy layered (oxy)hydroxide (HE-LH) nanosheets under ambient conditions. This method is based on a self-reliant electrochemical process, utilizing only low-cost metal foils and electrolytes as reactant, with no need of involving extra alkali salts and/or organic reagents. Importantly, the composition of HE-LH nanosheets is widely tunable by simply adjusting the combination of metal foils. As a representative example, quinary layered (oxy)hydroxide (CoFeNiCrV-LH) nanosheets are rationally designed, which exhibit superior electrocatalytic activity and long-term durability towards the electrocatalytic oxygen evolution reaction, outperforming both CoFe layered double hydroxides and most previously reported transition-metal-based electrocatalysts. Comprehensive characterization and analysis reveal that the high-entropy effects play a significant role in forming the defect-rich, low-crystalline microstructures, along with large specific surface areas and optimized electronic configurations, thus enabling the boosted electrocatalytic performance. This electrochemical synthetic approach is generally applicable to the scalable synthesis of diverse HE-LH materials towards versatile promising applications.

2D FeP Nanoframe Superlattices via Space-Confined Topochemical Transformation.

Self-assembled nanocrystal superlattices represent an emergent class of designer materials with potentially programmable functionalities. The ability to construct hierarchically structured nanocrystal superlattices with tailored geometry and porosity is critical for extending their applications. Here, 2D superlattices comprising monolayer FeP nanoframes are synthesized through a space-confined topochemical transformation approach induced by the Kirkendall effect, using carbon-coated Fe3 O4 nanocube superlattices as a precursor. The particle shape and the close-packed nature of Fe3 O4 nanocubes as well as the interconnected carbon layer network contribute to the topochemical transformation process. The resulting 2D FeP nanoframe superlattices possess several unique and advantageous structural features that are unavailable in conventional 3D nanocrystal superlattices, which make them particularly attractive for catalytic applications. As a proof of concept, such 2D FeP nanoframe superlattices are harnessed as highly efficient and durable electrocatalysts for the hydrogen evolution reaction, the performance of which is superior to that of most FeP-based catalysts reported previously. This topochemical transformation approach is scalable and general, representing a new route of designing hierarchical superlattices with highly open features that cannot be accessible by traditional self-assembly methods.

Direct Probing of the Oxygen Evolution Reaction at Single NiFe2O4 Nanocrystal Superparticles with Tunable Structures.

Due to the precisely controllable size, shape, and composition, self-assembled nanocrystal superlattices exhibit unique collective properties and find wide applications in catalysis and energy conversion. Identifying their intrinsic electrocatalytic activity is challenging, as their averaged properties on ensembles can hardly be dissected from binders or additives. We here report the direct measurement of the oxygen evolution reaction at single superparticles self-assembled from ∼8 nm NiFe2O4 and/or ∼4 nm Au nanocrystals using scanning electrochemical cell microscopy. Combined with coordinated scanning electron microscopy, it is found that the turnover frequency (TOF) estimated from single NiFe2O4 superparticles at 1.92 V vs RHE ranges from 0.2 to 11 s-1 and is sensitive to size only when it is smaller than ∼800 nm in diameter. After the incorporation of Au nanocrystals, the TOF increases by ∼6-fold and levels off with further increasing Au content. Our study demonstrates the first direct single entity electrochemical study on individual nanocrystal superlattices with tunable structures and unravels the intrinsic structure-activity relationship that is not accessible by other methods.

Self-assembled mesostructured Co0.5Fe2.5O4 nanoparticle superstructures for highly efficient oxygen evolution.

Self-assembly of colloidal nanoparticles (NPs) into well-defined superstructures has been recognized as one of the most promising ways to fabricate rationally-designed functional materials for a variety of applications. Introducing hierarchical mesoporosity into NP superstructures will facilitate mass transport while simultaneously enhancing the accessibility of constituent NPs, which is of critical importance for widening their applications in catalysis and energy-related fields. Herein, we develop a colloidal co-assembly strategy to construct mesostructured, carbon-coated Co0.5Fe2.5O4 NP superstructures (M-C@CFOSs), which show great promise as highly efficient electrocatalysts for the oxygen evolution reaction (OER). Specifically, organically-stabilized SiO2 NPs are employed as both building blocks and sacrificial template, which co-assemble with Co0.5Fe2.5O4 NPs to afford binary NP superstructures through a solvent drying process. M-C@CFOSs are obtainable after in situ ligand carbonization followed by the selective removal of SiO2 NPs. The hierarchical mesoporous structure of M-C@CFOSs, combined with the conformal graphitic carbon coating derived from the native organic ligands, significantly improves their electrocatalytic performance as OER electrocatalysts when compared with nonporous Co0.5Fe2.5O4 NP superstructures. This work establishes a new and facile approach for designing NP superstructures with hierarchical mesoporosity, which may find wide applications in energy storage and conversion.

Uniformly coating ZnAl layered double oxide nanosheets with ultra-thin carbon by ligand and phase transformation for enhanced adsorption of anionic pollutants.

The increasing severity of water pollution has strongly urged to develop green and efficient adsorbents for waste-water treatment. In this work, ZnAl layered double oxide nanosheets uniformly coated with ultra-thin amorphous carbon shells (ZnAl-LDO@C) were fabricated by modifying ZnAl layered double hydroxides (LDHs) with molecular ligands followed by calcination. Compared with their counterparts derived from the pristine ZnAl-LDH, ZnAl-LDO@C nanosheets exhibit higher specific surface area with abundant and highly accessible active sites. The adsorption performance of the ZnAl-LDO@C nanosheets for methyl orange (MO) and hexavalent chromium [Cr(VI)] ions was investigated in detail. It is found that the channel-like hydrophilic carbon shells facilitate the diffusion of water molecules and ions, leading to the fast adsorption rate. In addition, the rich oxygen-containing functional groups in the amorphous carbon shells can efficiently improve the adsorption capacity through multiple interactions. As a result, ZnAl-LDO@C nanosheets exhibit superior adsorption performance for MO and Cr(VI), outperforming most LDH- or LDO-based adsorbents reported previously. Meanwhile, a new oriented overlapping intercalation mechanism for MO adsorption was proposed for the first time to clarify how MO molecules arrange at the interlayer space.