Electrolyte-Induced Morphology Evolution to Boost Potassium Storage Performance of Perylene-3,4,9,10-tetracarboxylic Dianhydride.

Organic materials have attracted extensive attention for potassium-ion batteries due to their flexible structure designability and environmental friendliness. However, organic materials generally suffer from unavoidable dissolution in aprotic electrolytes, causing an unsatisfactory electrochemical performance. Herein, we designed a weakly solvating electrolyte to boost the potassium storage performance of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). The electrolyte induces an in situ morphology evolution and achieves a nanowire structure. The weakly dissolving capability of ethylene glycol diethyl ether-based electrolyte and unique nanowire structure effectively avoid the dissolution of PTCDA. As a result, PTCDA shows excellent cycling stability (a capacity retention of 89.1% after 2000 cycles) and good rate performance (70.3 mAh g-1 at 50C). In addition, experimental detail discloses that the sulfonyl group plays a key role in inducing morphology evolution during the charge/discharge process. This work opens up new opportunities in electrolyte design for organic electrodes and illuminates further developments of potassium-ion batteries.

In Situ Visual Observation of Surface Energy-Controlled Heterogeneous Nucleation of Metal Nanocrystals.

Electrochemical growth of metal nanocrystals is pivotal for material synthesis, processing, and resource recovery. Understanding the heterogeneous interface between electrolyte and electrode is crucial for nanocrystal nucleation, but the influence of this interaction is still poorly understood. This study employs advanced in situ measurements to investigate the heterogeneous nucleation of metals on solid surfaces. By observing the copper nanocrystal electrodeposition, an interphase interaction-induced nucleation mechanism highly dependent on substrate surface energy is uncovered. It shows that a high-energy (HE) electrode tended to form a polycrystalline structure, while a low-energy (LE) electrode induced a monocrystalline structure. Raman and electrochemical characterizations confirmed that HE interface enhances the interphase interaction, reducing the nucleation barrier for the sturdy nanostructures. This leads to a 30.92-52.21% reduction in the crystal layer thickness and a 19.18-31.78% increase in the charge transfer capability, promoting the formation of a uniform and compact film. The structural compactness of the early nucleated crystals enhances the deposit stability for long-duration electrodeposition. This research not only inspires comprehension of physicochemical processes correlated with heterogeneous nucleation, but also paves a new avenue for high-quality synthesis and efficient recovery of metallic nanomaterials.

MnFe Prussian Blue Analogue Open Cages for Sodium-Ion Batteries: Simultaneous Evolution of Structure, Morphology, and Energy Storage Properties.

Prussian blue analogues (PBAs) exhibiting hollow morphologies have garnered considerable attention owing to their remarkable electrochemical properties. In this study, a one-pot strategy is proposed for the synthesis of MnFe PBA open cages. The materials are subsequently employed as cathode electrode in sodium-ion batteries (SIBs). The simultaneous evolution of structure, morphology, and performance during the synthesis process is investigated. The findings reveal substantial structural modifications as the reaction time is prolonged. The manganese content in the samples diminishes considerably, while the potassium content experiences an increase. This compositional variation is accompanied by a significant change in the spin state of the transition metal ions. These structural transformations trigger the occurrence of the Kirkendall effect and Oswald ripening, culminating in a profound alteration of the morphology of MnFe PBA. Moreover, the shifts in spin states give rise to distinct changes in their charge-discharge profiles and redox potentials. Furthermore, an exploration of the formation conditions of the samples and their variations before and after cycling is conducted. This study offers valuable insights into the intricate relationship between the structure, morphology, and electrochemical performance of MnFe PBA, paving the way for further optimizations in this promising class of materials for energy storage applications.

Liquid Crystalline Nanoparticles via Polymerization-Induced Self-Assembly: Morphology Evolution and Function Regulation.

Liquid crystalline nanoparticles (LC NPs) are a kind of polymer NPs with LC mesogens, which can form special anisotropic morphologies due to the influence of LC ordering. Owing to the stimuli-responsiveness of the LC blocks, LC NPs show abundant morphology evolution behaviors in response to external regulation. LC NPs have great application potential in nano-devices, drug delivery, special fibers and other fields. Polymerization-induced self-assembly (PISA) method can synthesize LC NPs at high solid content, reducing the harsh demand for reaction solvent of the LC polymers, being a better choice for large-scale production. In this review, we introduced recent research progress of PISA-LC NPs by dividing them into several parts according to the LC mesogen, and discussed the improvement of experimental conditions and the potential application of these polymers.

Homogenizing Zn Deposition in Hierarchical Nanoporous Cu for a High-Current, High Areal-Capacity Zn Flow Battery.

A Zn anode can offset the low energy density of a flow battery for a balanced approach toward electricity storage. Yet, when targeting inexpensive, long-duration storage, the battery demands a thick Zn deposit in a porous framework, whose heterogeneity triggers frequent dendrite formation and jeopardizes the stability of the battery. Here, Cu foam is transferred into a hierarchical nanoporous electrode to homogenize the deposition. It begins with alloying the foam with Zn to form Cu5 Zn8 , whose depth is controlled to retain the large pores for a hydraulic permeability ≈10-11  m2 . Dealloying follows to create nanoscale pores and abundant fine pits below 10 nm, where Zn can nucleate preferentially due to the Gibbs-Thomson effect, as supported by a density functional theory simulation. Morphological evolution monitored by in situ microscopy confirms uniform Zn deposition. The electrode delivers 200 h of stable cycles in a Zn-I2 flow battery at 60 mAh cm-2 and 60 mA cm-2 , performance that meets practical demands.

The Importance of Nonequilibrium to Equilibrium Transition Pathways for the Efficiency and Stability of Organic Solar Cells.

Controlled morphology of solution-processed thin films have realized impressive achievements for non-fullerene acceptor (NFA)-based organic solar cells (OSCs). Given the large set of donor-acceptor pairs, employing various processing conditions to realize optimal morphology for high efficiency and stable OSCs is a strenuous task. Therefore, comprehensive correlations between processing conditions and morphology evolution pathways have to be developed for efficient performance and stability of devices. Within the framework of the blend system, crystallization transitions of NFA molecules are tracked utilizing the first heating scan of differential scanning calorimeter (DSC) measurement correlating with respective morphology evolution of blend films. Real-time dynamics measurements and morphology characterizations are combined to provide optimal morphology transition pathways as NFA molecules are shown to be released from the mixed-phase to form balanced ordered packing with variant processing conditions. Polymer:NFA films are fabricated using blade coating incorporating solvent additive or thermal annealing as processing conditions as a correlation is formulated between performance and stability of solar cells with morphology transition pathways. This work demonstrates the significance of processing condition-controlled transition pathways for the realization of optimal morphology leading to superior OSC devices.

MXene-Supported, Atomic-Layered Iridium Catalysts Created by Nanoparticle Re-Dispersion for Efficient Alkaline Hydrogen Evolution.

Tailoring the structure of metal components and interaction with their anchored substrates is essential for improving the catalytic performance of supported metal catalysts; the ideal catalytic configuration, especially down to the range of atomic layers, clusters, and even single atoms, remains a subject under intensive study. Here, an Ir-on-MXene (Mo2 TiC2 Tx ) catalyst with controlled morphology changing from nanoparticles down to flattened atomic layers, and finally ultrathin layers and single atoms dispersed on MXene nanosheets at elevated temperature, is presented. The intermediate structure, consisting of mostly Ir atomic layers, shows the highest activity toward the hydrogen evolution reaction (HER) under industry-compatible alkaline conditions. In addition, the better HER activity of Ir atomic layers than that of single atoms suggests that the former serves as the main active sites. Detailed mechanism analysis reveals that the nanoparticle re-dispersion process and Ir atomic layers with a moderate interaction to the substrate associate with unconventional electron transfer from MXene to Ir, leading to suitable H* adsorption. The results indicate that the structural design is important for the development of highly efficient catalysts.

Morphology-engineered carbon quantum dots embedded on octahedral CdIn2S4 for enhanced photocatalytic activity towards pollutant degradation and hydrogen evolution.

In recent years, carbon quantum dots (CQDs) and CdIn2S4 have considered as the representatives of the most potential photocatalysts applied in the field of photocatalysis for efficiently solving energy shortage and environmental pollution. In this work, a novel CQDs hybridized CdIn2S4 (CQDs/CIS) heterostructure with 2D nanosheet/3D nanooctahedra morphology was successfully fabricated by a simple in-situ solvothermal method. Most interestingly, the morphology of hybrid gradually evolved from 3D octahedron to 2D nanosheet with the increase of CQDs. This unique 2D/3D structure and synergistic effect between CQDs and CdIn2S4 increased the multi-dimensional active reaction sites and enhanced the quantum yield and the separation efficiency of photogenerated electron pairs. Therefore, CQDs/CIS hybrids showed excellent photocatalytic activities of H2 generation, RhB and TCH degradation. Especially, CQDs/CIS-3 heterostructure presented the highest photocatalytic efficiency and its hydrogen generation activity (956.79 µmol g-1 h-1) was 7.57-fold improvement by contrast with pure CdIn2S4 (126.35 µmol g-1 h-1). Moreover, RhB and TCH degradation rate constants of CQDs/CIS-3 were about 8.14 and 2.32 times higher than those of CdIn2S4, respectively. Furthermore, the effect of CQDs on the evolution of heterostructure morphology and photocatalytic mechanism were also proposed. This research work would offer useful enlightenment for elucidating the affect of CQDs on the morphology evolution and construction of CQDs-based hybrid with excellent performances for H2 production and pollutant removal.

A Symmetry-Based Kinematic Theory for Nanocrystal Morphology Design.

The growth of crystalline nanoparticles (NPs) generally involves three processes: nucleation, growth, and shape evolution. Among them, the shape evolution is less understood, despite the importance of morphology for NP properties. Here, we propose a symmetry-based kinematic theory (SBKT) based on classical growth theories to illustrate the process. Based on the crystal lattice, nucleus (or seed) symmetry, and the preferential growth directions under the experimental conditions, the SBKT can illustrate the growth trajectories. The theory accommodates the conventional criteria of the major existing theories for crystal growth and provides tools to better understand the symmetry-breaking process during the growth of anisotropic structures. Furthermore, complex dendritic growth is theoretically and experimentally demonstrated. Thus, it provides a framework to explain the shape evolution, and extends the morphogenesis prediction to cases, which cannot be treated by other theories.

Enhanced tensile and electrochemical performance of MXene/CNT hierarchical film.

Nowadays, it is highly desirable to achieve high strength, flexibility and electrochemical performance for supercapacitor electrodes simultaneously. Herein, few-layer MXene flakes are assembled into free-standing films by facile vacuum-filtration method, in which hydrophilic-functionalized carbon nanotubes (CNTs) are further incorporated. The morphology of MXene/CNT composite films evolves from compact to 'CNT in MXene' to laminar to 'MXene in CNT' and finally to separate structures when increasing the CNT weight percentage. Among them, the laminar structure in which thin MXene and CNT layers are stacked alternately is demonstrated to be the best. The laminar MXene/CNT film possesses much higher strength, elongation and specific capacitance than MXene film due to the engineered porosity, good interaction between MXene flakes and CNTs, and proper CNTs' distribution. As a result, high specific capacitance of 423.4 F g-1at 1 A g-1and capacitance retention of nearly 60% at 10 A g-1are accomplished. Moreover, the composite film is flexible and withstands bending up to 180°, indicating that the proposed laminar MXene/CNT composite film is a superb candidate for flexible supercapacitors.

Morphology evolution and enhanced broadband photoresponse behavior of two-dimensional Bi2Te3nanosheets.

Bismuth telluride (Bi2Te3), as an emerging two-dimensional (2D) material, has attracted extensive attention from scientific researchers due to its excellent optoelectronic, thermoelectric properties and topological structure. However, the application research of Bi2Te3mainly focuses on thermoelectric devices, while the research on optoelectronic devices is scarce. In this work, the morphology evolution and growth mechanism of 2D Bi2Te3nanosheets with a thickness of 12 ± 3 nm were systematically studied by solvothermal method. Then, the Bi2Te3nanosheets were annealed at 350 °C for 1 h and applied to self-powered photoelectrochemical-type broadband photodetectors. Compared with the as-synthesized Bi2Te3photodetector, the photocurrent of the photodetector based on the annealed Bi2Te3is significantly enhanced, especially enhanced by 18.3 times under near-infrared light illumination. Furthermore, the performance of annealed Bi2Te3photodetector was systematically studied. The research results show that the photodetector not only has a broadband response from ultraviolet to near-infrared (365-850 nm) under zero bias voltage, but also obtains the highest responsivity of 6.6 mA W-1under green light with an incident power of 10 mW cm-2. The corresponding rise time and decay time are 17 ms and 20 ms, respectively. These findings indicate that annealed Bi2Te3nanosheets have great potential to be used as self-powered high-speed broadband photodetectors with high responsivity.

Constructing Cylindrical Nanostructures Via Directional Morphology Evolution Induced by Seeded Polymerization.

Herein, spindle-shaped block copolymer (BCP) nanoparticles are used in seeded polymerization of methyl methacrylate as a novel approach to generating cylindrical nanostructures. The chain-extension of BCP seeds by an amorphous coil-type polymer within the seed core composed of semifluorinated liquid-crystalline blocks triggers the deforming, stretching, and directional growth of the seeds along the long axis, eventually leads to nanorods.

Construction of Highly Ordered Glyco-Inside Nano-Assemblies through RAFT Dispersion Polymerization of Galactose-Decorated Monomer.

Glyco-assemblies derived from amphiphilic sugar-decorated block copolymers (ASBCs) have emerged prominently due to their wide application, for example, in biomedicine and as drug carriers. However, to efficiently construct these glyco-assemblies is still a challenge. Herein, we report an efficient technology for the synthesis of glyco-inside nano-assemblies by utilizing RAFT polymerization of a galactose-decorated methacrylate for polymerization-induced self-assembly (PISA). Using this approach, a series of highly ordered glyco-inside nano-assemblies containing intermediate morphologies were fabricated by adjusting the length of the hydrophobic glycoblock and the polymerization solids content. A specific morphology of complex vesicles was captured during the PISA process and the formation mechanism is explained by the morphology of its precursor and intermediate. Thus, this method establishes a powerful route to fabricate glyco-assemblies with tunable morphologies and variable sizes, which is significant to enable the large-scale fabrication and wide application of glyco-assemblies.

Morphology Evolution of a High-Efficiency PSC by Modulating the Vapor Process.

The morphological quality of the photoactive layer is the key component affecting the performance metrics of a photovoltaic device. Therefore, fine adjustment of the crystallization dynamics is urgently required. By manipulating the amount of dimethyl sulfoxide (DMSO) remaining in the spin-coated perovskite films during the annealing treatment, an obvious morphological evolution arises. The crystallization kinetics is significantly altered due to the formation of intermediate phases and the variation of DMSO vapor pressure via producing the semienclosed space with a covering. On the one hand, the obviously formed intermediate phase MA2 Pb3 I8 (DMSO)2 retards the crystallization process. On the other hand, the DMSO vapor in the semienclosed space intrigues the recrystallization process and results in Ostwald ripening to produce large-aspect-ratio grains with fewer defect states, decreased carrier doping, and longer carrier lifetimes. Thus, nonradiative processes are greatly suppressed. Besides, combined with X-ray photoelectron spectroscopy measurement and the surface energy of MAI- and PbI-terminated surface model calculated by density functional theory, the defect states are identified and the causes of Pb0 defect states are explained. Using this strategy, a high power conversion efficiency of 20.09% is achieved based on MAPbI3 photovoltaic solar cell, and the long-term ambient shelf and thermal stability are obviously improved.

Overcoming Kinetic Trapping for Morphology Evolution during Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly (PISA) is a powerful technique to synthesize assemblies with various morphologies. However, PISA mediated by long, stabilizing chains usually produces kinetically trapped spheres; thus, the morphology evolution remains a challenge. Here, a convenient and general strategy for facilitating the morphological evolution by the copolymerization of solvophilic monomers is reported. With the incorporation of only 7% (molar ratio) solvophilic 3-(triethoxysilyl)propyl methacrylate (TESPMA) into poly(N,N-dimethylaminoethyl methacrylate)-b-poly(benzyl methacrylate) (PDMA-b-PBzMA) spheres, PDMA-b-P(BzMA-co-TESPMA) assemblies evolve from spheres to worms, octopi-like and jellyfish-like structures, vesicles, and large compound vesicles. This non-specific effect is further confirmed by the copolymerization of BzMA with other solvophilic monomers, including N,N-dimethylaminoethyl methacrylate (DMA), N,N-diethylaminoethyl methacrylate (DEA), and 2-hydroxypropyl methacrylate (HPMA). This work provides a convenient approach to promote morphology evolution and develops the formulations design of PISA.

Comparative evaluation of maximum parsimony and Bayesian phylogenetic reconstruction using empirical morphological data.

The use of discrete morphological data in Bayesian phylogenetics has increased significantly over the last years with the proposal of total evidence analysis and the treatment of fossils as terminal taxa in Bayesian molecular dating. Both approaches rely on the assumption that probabilistic Markov models reasonably accommodate all the complexity of morphological evolution of discrete traits. The performance of such morphological models used in Bayesian phylogenetics has been thoroughly investigated, but conclusions so far were based mostly on simulated data. In this study, we have surveyed MorphoBank and obtained a large number of morphological matrices to evaluate Bayesian phylogenetic inference (BI) under Lewis' Mk model in comparison with the maximum parsimony (MP) algorithm. We found that trees estimated by both methods frequently differed and that BI generated a larger amount of polytomic tree topologies. The number of trees contained in the 95% Bayesian credibility interval was significantly greater than the number of equally parsimonious trees. We also investigated which factors mostly influenced the topological difference between maximum parsimony and Bayesian tree topologies and found that the number of terminals in morphological matrices was the variable with the highest association with the topological distance between trees inferred by BI and MP. Surprisingly, we show that differences between both approaches were not influenced by increasing sample size. Our results, which were based on a large set of empirical matrices, corroborate recent findings that BI is less precise than MP.

Water-Writing Pattern on PEDOT:PSS Inverse Opal Films through the Synergistic Effect of Morphology/Conformation Transition.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has received tremendous attention in the energy field owing to its high conductivity, ease of processing, biocompatibility, and low cost-effectiveness. Combining PEDOT:PSS and photonic crystals (PCs) is expected to promote the development of high-performance optoelectronic devices. The conductivity of PEDOT:PSS at present can only be measured through specific equipment, and the visualization of optoelectronic integration still remains a challenge. In this study, various patterned PEDOT:PSS inverse opal (PEDOT:PSS-IO) films are constructed by associating the conductivity of PEDOT:PSS with the structural color of PCs based on the synergistic effect of morphology/conformation transition, which achieves the visualization of optoelectronic integration. Morphology transition of the PEDOT:PSS-IO film alters from the interconnected to gradual closure pore structure, accompanied by an unusual blueshift of the stopband, which can be attributed to the collapse/reconstruction of the frame of the PEDOT:PSS-IO film. Conformation transition of PEDOT chains converts from the benzene to quinone structure, accompanying an enhancement of conductivity, which resulted from PSS removal and secondary doping. Under the induction of a polar solvent, the PEDOT:PSS-IO film brings the changes in optical/electrical dual-signals based on the synergistic effect of morphology/conformation transition. This phenomenon can be developed for the creation of a conductive PC pattern by using a polar solvent (water) as an ink, which is beneficial for the visualization of optoelectronic integration. This work provides essential significance for the fabrication of functional optoelectronic devices.

Composition-driven morphological evolution of BaTiO3 nanowires for efficient piezocatalytic hydrogen production.

Hydrogen production from water by piezocatalysis is very attractive owing to its high energy efficiency and novelty. BaTiO3, a highly piezoelectric material, is particularly suitable for this application due to its high piezoelectric potential, non-toxic nature, and physicochemical stability. Owing to the critical role of morphology on properties, one-dimensional (1D) materials are expected to exhibit superior water-splitting performance and thus there is a need to optimise the processing conditions to develop outstanding piezocatalysts. In the present work, piezoelectric BaTiO3 nanowires (NWs) were hydrothermally synthesised with precursor Ba:Ti molar ratios of 1:1, 2:1, and 4:1. The morphology, defect chemistry, and hydrogen evolution reaction (HER) efficiency of the as-synthesised BaTiO3 NWs were systematically investigated. The results showed that the morphological features, aspect ratio, structural stability and defect contents of the 1D morphologies collectively have a significant impact on the HER efficiency. The morphological evolution mechanism of the 1D structures were described in terms of ion exchange and dissolution-growth processes of template-grown BaTiO3 NWs for different Ba:Ti molar ratios. Notably, the BaTiO3 NWs synthesised with Ba:Ti molar ratio of 2:1 displayed high crystallinity, good defect concentrations, and good structural integrity under ultrasonication, resulting in an outstanding HER efficiency of 149.24 µmol h-1g-1 which is the highest obtained for nanowire morphologies. These results highlight the importance of synthesis conditions for BaTiO3 NWs for generating excellent piezocatalytic water splitting performance. Additionally, post-ultrasonication tested BaTiO3 NWs demonstrated unexpected photocatalytic activity, with the BTO-1 sample (1:1 Ba:Ti) exhibiting 56% photodegradation of RhB in 2 h of UV irradiation.

In-situ activator-induced evolution of morphology on carbon materials for supercapacitors.

Carbonaceous materials with diverse morphologies have shown unique and excellent performance in many fields, such as catalysis, adsorption, separation and energy storage. However, regulating the structural changes of these morphologies accurately using simple approaches is a difficult process. In this study, porous carbon materials with a morphology that changed from carbon spindles to fold-carbon spheres and then to regular carbon spheres were prepared assisted by in-situ activator of KNO3 in co-assembly of resorcinol/phenol resin and 1-alkyl-3-methylimidazolium bromide. The activation of KNO3 greatly improves the hydrophily, pore volume and surface area of the inert carbon skeleton, and increases heteroatom defects for the carbon framework. As electrode materials of supercapacitors, the influence of different structures on energy storage performance was studied. The obtained fold-carbon spheres showed a higher capacitance (405 F g-1) than flake, spindle and spherical porous carbon, which is due to convenient electrolyte transmission and completely available active sites.

Growth, structure, and morphology of van der Waals epitaxy Cr1+δTe2 films.

The preparation of two-dimensional magnetic materials is a key process to their applications and the study of their structure and morphology plays an important role in the growth of high-quality thin films. Here, the growth, structure, and morphology of Cr1+δTe2 films grown by molecular beam epitaxy on mica with variations of Te/Cr flux ratio, growth temperature, and film thickness have been systematically investigated by scanning tunneling microscopy, reflection high-energy electron diffraction, scanning electron microscope, and X-ray photoelectron spectroscopy. We find that a structural change from multiple phases to a single phase occurs with the increase in growth temperature, irrespective of the Cr/Te flux ratios, which is attributed to the desorption difference of Te atoms at different temperatures, and that the surface morphology of the films grown at relatively high growth temperatures (≥ 300 °C) exhibits a quasi-hexagonal mesh-like structure, which consists of nano-islands with bending surface induced by the screw dislocations, as well as that the films would undergo a growth-mode change from 2D at the initial stage in a small film thickness (2 nm) to 3D at the later stage in thick thicknesses (12 nm and 24 nm). This work provides a general model for the study of pseudo-layered materials grown on flexible layered substrates.