Unique Growth Mechanism Research Articles

Dynamic modelling and predictive position/force control of a plant-inspired growing robot.

This paper presents the development and control of a dynamic model for a plant-inspired growing robot, termed the "vine-robot," using the Euler-Lagrangian method. The unique growth mechanism of the vine-robot enables it to navigate complex environments by extending its body. We derive the dynamic equations of motion and employ model predictive control (MPC) to regulate the task space position, orientation, and interaction forces. Simulation experiments are conducted to evaluate the performance of the proposed model and control strategy. The results demonstrate that the model effectively achieves sub-millimeter precision in the position control in both static and time varying refrence trajectroies, and sub micronewton in force control.

Simple Fabrication and Unique Fiber Growth Mechanism of Copper(I) 4-Toluenethiolate-Based Fibrous Coordination Polymer.

Coordination polymers (CPs) exhibit various distinctive properties owing to the metals incorporated in their main chains. These properties make CPs appealing for applications in optoelectronic devices and sensors and as precursors for inorganic materials with controlled morphologies. However, only a few CPs form fibrous structures, and the fabrication methods require complicated procedures, thus, limiting their range of applications. In this study, we report the easily feasible fabrication of fibrous CP, specifically, copper(I) 4-toluenethiolate (CuSArMe), and investigate its unique fiber growth mechanism. The reaction of CuI and 4-toluenethiol in acetonitrile in the presence of triethylamine quickly produced aggregated CuSArMe particles. With continuous stirring at ambient temperature (∼20 °C), wavy fibers grew from the surface of the aggregates, eventually forming an entangled fibrous structure. Structural evaluations of CuSArMe using powder X-ray diffraction analyses revealed that the regularity of the crystal phase increased as the morphology changed from aggregated particles to fibrous structures, suggesting that the transformation was a crystallization-driven process. Additionally, the conversion of fibrous CuSArMe to Cu2S, a known semiconductor, was demonstrated while maintaining the fiber-like structure and providing the desired materials.

Ultrahigh Potassium Storage Capacity of Ca2Si Monolayer with Orderly Multilayered Growth Mechanism.

As the rising renewable energy demands and lithium scarcity, developing high-capacity anode materials to improve the energy density of potassium-based batteries (PBBs) is increasingly crucial. In this work, a unique orderly multilayered growth (OMLG) mechanism on a 2D-Ca2Si monolayer is theoretically demonstrated for potassium storage by first-principles calculations. The global-energy-minimum Ca2Si monolayer is a semiconductor with isotropic mechanical properties and remarkable electrochemical properties, such as a low potassium ion migration energy barrier of 0.07eV and a low open circuit voltage ranging from 0.224 to 0.003V. Most notably, 2D-Ca2Si demonstrates an ultrahigh theoretical specific capacity of 5459mAhg-1 and a total specific capacity of 610mAhg-1, reaching up to 89% of the capacity of a potassium metal anode. Remarkably, the OMLG mechanism facilitates stable, dendrite-free deposition of hcp-K metal layers on the 2D-Ca2Si surface, where the ultrahigh and gradually converging lattice match as the layers increase is the key to achieving theoretically near-infinite growth. The study theoretically demonstrates the Ca2Si monolayer a highly promising anode material, and offers a novel potassium storage strategy for designing 2D anode materials with high specific capacity, rapid potassium-ion migration, and good safety.

Nonclassical Growth Mechanism of Double-Walled Metal-Oxide Nanotubes Implying Transient Single-Walled Structures.

The formation of imogolite nanotubes is reported to be a kinetic process involving intermediate roof-tile nanostructures. Here, the structural evolution occurring during the synthesis of aluminogermanate double-walled imogolite nanotubes is in situ monitored, thanks to an instrumented autoclave allowing the control of the temperature, the continuous measurement of pH and pressure, and the regular sampling of gas and solution. Chemical analyses confirm the completion of the precursor's conversion with the release of CO2, ethanol, and dioxane as main side products. The combination of microscopic observations, infrared, and absorption spectroscopies with small and wide-angle X-ray scattering experiments unravel a unique growth mechanism implying transient single-walled nanotubes instead of the self-assembly of stacked proto-imogolite tiles. The growth formation of these transient nanotubes is followed at the molecular level by Quick-X-ray absoprtion specotrscopy experiments. Multivariate data analysis evidences that the near neighboring atomic environment of Ge evolves from monotonous to a more complex one as the reaction progresses. The following transformation into a double-walled nanotube takes place at a nearly constant mean radius, as demonstrated by the simulation of X-ray scattering diagrams. Overall, transient nanotubes appear to serve for the anchoring of a new wall, corresponding to a mechanism radically different from that proposed in the literature.

Surfactant-Free Ultrasonication-Assisted Synthesis of 2d Tellurium Based on Metastable 1T'-MoTe2.

Elemental 2D materials (E2DMs) have been attracting considerable attention owing to their chemical simplicity and excellent/exotic properties. However, the lack of robust chemical synthetic methods seriously limits their potential. Here, a surfactant-free liquid-phase synthesis of high-quality 2D tellurium is reported based on ultrasonication-assisted exfoliation of metastable 1T'-MoTe2. The as-grown 2D tellurium nanosheets exhibit excellent single crystallinity, ideal 2D morphology, surfactant-free surface, and negligible 1D by-products. Furthermore, a unique growth mechanism based on the atomic escape of Te atoms from metastable transition metal dichalcogenides and guided 2D growth in the liquid phase is proposed and verified. 2D tellurium-based field-effect transistors show ultrahigh hole mobility exceeding 1000 cm2V-1s-1 at room temperature attributing to the high crystallinity and surfactant-free surface, and exceptional chemical and operational stability using both solid-state dielectric and liquid-state electrical double layer. The facile ultrasonication-assisted synthesis of high-quality 2D tellurium paves the way for further exploration of E2DMs and expands the scope of liquid-phase exfoliation (LPE) methodology toward the controlled wet-chemical synthesis of functional nanomaterials.

Ln2Te6O15 (Ln = La, Gd, and Eu) "Anti-Glass" Phase-Assisted Lanthanum-Tellurite Transparent Glass-Ceramics: Eu3+ Emission and Local Site Symmetry Analysis.

The presence of lanthanide-tellurite "anti-glass" nanocrystalline phases not only affects the transparency in glass-ceramics (GCs) but also influences the emission of a dopant ion. Therefore, a methodical understanding of the crystal growth mechanism and local site symmetry of doped luminescent ions when embedded into the precipitated "anti-glass" phase is crucial, which unfolds the practical applications of GCs. Here, we examined the Ln2Te6O15 "anti-glass" nanocrystalline phase growth mechanism and local site symmetry of Eu3+ ions in transparent GCs produced from 80TeO2-10TiO2-(5 - x)La2O3-5Gd2O3-xEu2O3 glasses, where x = 0, 1, 2. A crystallization kinetics study identifies a unique crystal growth mechanism via a constrained nucleation rate. The extent of "anti-glass" phase precipitation and its growth in GCs with respect to heat-treatment duration is demonstrated using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) analysis. Qualitative analysis of XRD confirms the precipitation of both La2Te6O15 and Gd2Te6O15 nanocrystalline phases. Rietveld refinement of powder X-ray diffraction patterns reveals that Eu3+ ions occupy "Gd" sites in Gd2Te6O15 over "La" sites in La2Te6O15. Raman spectroscopy reveals the conversion of TeO3 units to TeO4 units with Eu2O3 addition. This confirms the polymerizing role of Eu2O3 and consequently high crystallization tenacity with increasing Eu2O3 concentration. The measured Eu3+ ion photoluminescence spectra revealed its local site symmetry. Moreover, the present GCs showed adequate thermal cycling stability (∼50% at 423 K) with the highest activation energy of around 0.3 eV and further suggested that the present transparent GCs would be a potential candidate for the fabrication of red-light-emitting diodes (LEDs) or red component phosphor in W-LEDs.

Robust Pt/TiO2/Ni(OH)2 nanosheet arrays enable outstanding performance for high current density alkaline water electrolysis

Herein, we developed a novel and simple strategy to construct Pt-decorated TiO2/β-Ni(OH)2 nanosheet arrays that steadily deliver large current densities in alkaline electrolyte. It is of great interest to find that the versatile role of few-layered Ti3C2 endows the unique growth mechanism of Pt/TiO2/β-Ni(OH)2. It is worth noting that the interconnected array electrode exhibits noticeable hydrogen evolution reaction (HER) performance, achieving ultralow overpotentials of 107, 145 and 184 mV at high current densities of 500, 1000 and 1500 mA cm−2, respectively, which outperforms most reported HER electrocatalysts. It requires only 1.95 V to drive 1000 mA cm−2 towards full water electrolysis along with considerable stability. It is demonstrated for the first time that the synergistic effect of Pt and TiO2/Ni(OH)2 the enhanced HER performance. This work reports a robust nanoarray support for Pt electrocatalyst to break through its intrinsic barrier in alkaline HER and under large current density.

Dual Mechanism of Natural Polyphenols on crystal whiskers formation on calcium oxalate monohydrate crystal surface

Designing (macro)molecules controlling crystallization is an essential approach to regulate structure and properties of crystalline materials and circumvent detrimental mineralization in nature, biological, and synthetic systems. Here we discovered four novel, natural polyphenols, including gallic acid, ellagic acid, punicalagin, and tannic acid, as a new class of inhibitors for nucleation and crystal growth of calcium oxalate (CaOx), a primary constitution of kidney stones. Study of time-resolved growth reveals that polyphenols regulate the kinetics of crystal-liquid interface acting as a dual role of growth promoter and inhibitor which displays a new record of growth promotion up to 75% or complete suppression, dependent upon the modifier concentration. Time-elapsed in situ atomic force microscopy measurements unveil these modifiers regulate the growth mode from spiral-mediated to generation of two-dimensional (2D) islands and layer spreading mechanism, leading to formation of step bunches growing out of (010) surface and forming macroscopically crystal whiskers. The governing regime between growth promotion and inhibition is determined by inhibitors concentration but can be influenced by crystallization driving force. Such unique growth mechanism of crystal whiskers may also provide potential implications for understanding and synthesizing branched and hierarchical structures of biomimetic materials.

Cubic-like In2O3/α-Fe2O3 heterostructures assembled with 2D porous nanoplates for superior triethylamine gas-sensing behavior

Cubic-like In2O3/α-Fe2O3 heterostructures assembled with 2D porous nanoplates have been prepared by solvothermal method and subsequent calcination process. The introduction of Fe3+ component plays an important role for the morphological evolution of In2O3-based samples with unique crystal nucleation and growth mechanism. Compared with flower-like In2O3 self-assemblies composed of tower-like structural units, In2O3/α-Fe2O3 composites can display superior trimethylamine (TEA) gas-sensing behavior. For example, the optimal working temperature is reduced from 250 to 170 °C, and the response value of In/Fe-2 materials is 375.43, which is about 6.23 times than that of In2O3 sensors. The enhanced gas-sensing properties are mainly attributed to large specific surface area (234.4 m2/g), the effective In2O3-α-Fe2O3 heterojunctions, unique surface/interface effects, and tunable electron transmission mechanism.

Porous Membranes with Special Wettabilities: Designed Fabrication and Emerging Application

Porous materials have become a burgeoning research interest in materials science because of their intrinsic porous characteristics, versatile chemical compositions, and abundant functionalities. Re...

Response characteristics of inflow-stimulated Kelvin-Helmholtz vortex in compressible shear layer

By numerically solving the Navier-Stokes equations, the response characteristics of inflow-stimulated Kelvin-Helmholtz vortex in compressible shear layer arestudied. The mixing characteristics and the unique growth mechanism of the vortex structure are clearly revealed. By employing the index of vorticity thickness, the mixing properties are quantitatively analyzed. Based on the flow visualization results, the spatial size and the structure angle of the flow coherent structure are investigated by utilizing spatial correlation analysis. The evolution mechanism of the vortex structure in supersonic mixing layer induced by inlet forcing is revealed by analyzing the dynamical performances of the flow structure under different frequency disturbances. The numerical results show that with low forcing frequency at <i>f</i> = 5 kHz, the mixing efficiency is remarkably increased in the near-field of the flow. Whereas, in the far-field downstream the flow, the size of the structure reaches saturation state and the vortex passage frequency is locked, which causes the vorticity thickness to stabilize from 12mm to 14mm. Meanwhile, in a free mixing layer, the pairing and merging process occur in the flow field to promote the growth of the vortex structure, while in mixing layer with inlet forcing, the growth mechanism is that the vortex core engulfs a string of vortices induced by Kelvin-Helmholtz instability. The process of engulfment contributes much to the growth of the vortex structure. The analysis of spatial correlation distribution shows that in the area where engulfment occurs, the contour line shows the property of long and narrow ellipse instead of full ellipse and the structure in the area possesses the characteristics of intense rotation and inclination. Besides, with high inlet forcing frequency at <i>f</i> = 20 kHz, the size of the vortices becomes full in the near-field, and the vorticity thickness stabilizes between 3mm and 4 mm downstream the flow field. Meanwhile, the size of the vortex in controlled supersonic mixing layer is dominated by the imposed high-frequency forcing. An equation describing the quantitative relationship between the vortex characteristics and the imposed forcing frequency is derived, that is, the size of the uniform distribution vortex is approximately equal to the ratio of the value of convective velocity to inlet forcing frequency.

Organic salt mediated growth of phase pure and stable all-inorganic CsPbX3 (X = I, Br) perovskites for efficient photovoltaics

All-inorganic CsPbX3 (X = I, Br) perovskites without organic component are promising for long-term stability but face main challenges of facile fabrication and phase stability. Here we discover a general organic methylamine acetate salt mediated growth method to deposit high quality phase pure and stable CsPbX3 (X = I, Br) perovskite films via a novel precursor consisting of stoichiometric cesium acetate (CsAc), methylamine halide (MAX) and lead halide (PbX2). Interestingly, these organic salts of CsAc and MAX could efficiently promote the crystallization process especially lower the crystallization temperature, but do not introduce the incorporation of organic MA cation into all-inorganic CsPbX3 perovskites. These phase pure and stable CsPbX3 perovskites with tunable band gaps can be fabricated into high efficiency photovoltaics. Our organic salt mediated growth of all-inorganic perovskite not only reveals the all-inorganic CsPbX3 perovskite’s unique crystal growth mechanism but also demonstrates their promising application for photovoltaics.

Low-Temperature Wafer-Scale Deposition of Continuous 2D SnS2 Films.

Semiconducting 2D materials, such as SnS2 , hold immense potential for many applications ranging from electronics to catalysis. However, deposition of few-layer SnS2 films has remained a great challenge. Herein, continuous wafer-scale 2D SnS2 films with accurately controlled thickness (2 to 10 monolayers) are realized by combining a new atomic layer deposition process with low-temperature (250 °C) postdeposition annealing. Uniform coating of large-area and 3D substrates is demonstrated owing to the unique self-limiting growth mechanism of atomic layer deposition. Detailed characterization confirms the 1T-type crystal structure and composition, smoothness, and continuity of the SnS2 films. A two-stage deposition process is also introduced to improve the texture of the films. Successful deposition of continuous, high-quality SnS2 films at low temperatures constitutes a crucial step toward various applications of 2D semiconductors.

Correlating surface growth of nanoporous gold with electrodeposition parameters to optimize amperometric sensing of nitrite

Nanoporous gold (NPG) films were electrodeposited on a gold substrate and the generated platform was used for amperometric determination of nitrite. The electrochemical characterization of different NPG surfaces showed that the electrocatalytic activity concerning the nitrite anodic oxidation is strongly modulated by changes in the electrodeposition parameters. Microstructural analysis using scanning electron microscopy, profilometry and X-ray diffraction revealed changes in the deposited layers, following a unique growth mechanism strongly dependent on applied potential and electrodeposition time. Accordingly, more negative potentials resulted in changes in morphology from highly branched standing flakes to flat dense surfaces, whereas higher electrodeposition times led to the evolution of nanodendrites. NPG electrodes prepared by electrodeposition at −4 V for 100 s were selected as the best platform for nitrite determinations at 0.77 V. Evaluation of sensing characteristics demonstrated the sensor exhibits a very fast response time (<4 s), a detection limit of 10 nM and two linear ranges (1–110 μM and 110–2000 μM) with sensitivity values found to be 0.02 μA μM−1 cm−2 and 0.012 μA μM−1 cm−2, respectively. Other analytical properties such as reproducibility, selectivity and long term stability were also investigated and the results showed the fabricated sensor has favorable features for detection of nitrite in real samples, as demonstrated in experiments involving successful nitrite determinations in meat and lake water samples.

Large-Grain Tin-Rich Perovskite Films for Efficient Solar Cells via Metal Alloying Technique.

Fast research progress on lead halide perovskite solar cells has been achieved in the past a few years. However, the presence of lead (Pb) in perovskite composition as a toxic element still remains a major issue for large-scale deployment. In this work, a novel and facile technique is presented to fabricate tin (Sn)-rich perovskite film using metal precursors and an alloying technique. Herein, the perovskite films are formed as a result of the reaction between Sn/Pb binary alloy metal precursors and methylammonium iodide (MAI) vapor in a chemical vapor deposition process carried out at 185 °C. It is found that in this approach the Pb/Sn precursors are first converted to (Pb/Sn)I2 and further reaction with MAI vapor leads to the formation of perovskite films. By using Pb-Sn eutectic alloy, perovskite films with large grain sizes up to 5 µm can be grown directly from liquid phase metal. Consequently, using an alloying technique and this unique growth mechanism, a less-toxic and efficient perovskite solar cell with a power conversion efficiency (PCE) of 14.04% is demonstrated, while pure Sn and Pb perovskite solar cells prepared in this manner yield PCEs of 4.62% and 14.21%, respectively. It is found that this alloying technique can open up a new direction to further explore different alloy systems (binary or ternary alloys) with even lower melting point.

Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin.

Expanded porphyrins are large-cavity macrocycles with enormous potential in coordination chemistry, anion sensing, photodynamic therapy, and optoelectronics. In the last two decades, the surface science community has assessed the physicochemical properties of tetrapyrrolic-like macrocycles. However, to date, the sublimation, self-assembly and atomistic insights of expanded porphyrins on surfaces have remained elusive. Here, we show the self-assembly on Au(111) of an expanded aza-porphyrin, namely, an "expanded hemiporphyrazine", through a unique growth mechanism based on long-range orientational self-assembly. Furthermore, a spatially controlled "writing" protocol on such self-assembled architecture is presented based on the STM tip-induced deprotonation of the inner protons of individual macrocycles. Finally, the capability of these surface-confined macrocycles to host lanthanide elements is assessed, introducing a novel off-centered coordination motif. The presented findings represent a milestone in the fields of porphyrinoid chemistry and surface science, revealing a great potential for novel surface patterning, opening new avenues for molecular level information storage, and boosting the emerging field of surface-confined coordination chemistry involving f-block elements.

Evolution mechanism of vortices in a supersonic mixing layer controlled by the pulsed forcing

Pulsed actuation is one of the most fundamental control types to study regularity of flow structures in supersonic mixing layers, which helps to predict the aero-optical effects caused by the supersonic mixing layer where the different-sized vortices dominate the flow field. However, the knowledge about the evolution mechanism of vortices in the supersonic mixing layer which is controlled by the pulsed forcing is limited. Based on the large eddy simulation (LES), the visualized flow field of a supersonic mixing layer controlled by the pulsed forcing is presented and the unique growth mechanism of the vortices in such a case is revealed clearly. The method of position extraction of the vortex core in the supersonic mixing layer, which is a quantitative technique to obtain the instantaneous location of a vortex in flow field, is employed to calculate the dynamic characteristics (e.g., instantaneous convective speed and size) of the vortices quantitatively. The pulsed forcings of different frequencies are imposed on the same supersonic mixing layer respectively, and the instantaneous convective speed and size of the vortices for each pulse frequency considered in this study are then computed. By comparing the dynamic characteristics of the vortices between cases, the evolution mechanism of the vortices in the supersonic mixing layer controlled by the pulsed forcing is revealed.as follows. 1) Growth of the vortices in the supersonic mixing layer controlled by the pulsed forcing no longer depends on the pairing nor merging between adjacent vortices, which is just the growth mechanism of vortices in a free supersonic mixing layer. Actually, the size of a vortex in the controlled supersonic mixing layer is dominated by the imposed pulse frequency, so the size of each vortex in such a flow field is approximately identical. 2) The number of vortices in the controlled supersonic mixing layer is proportional to the pulse frequency, whereas the size of vortex is inversely proportional to the pulse frequency. That is, the higher the pulse frequency, the bigger the number of vortices in the controlled flow field is and the smaller the size of every vortex. 3) The average convective speed of vortices in the controlled supersonic mixing layer gradually decreases with pulse frequency increasing because the pulsed forcing essentially drags on the movement of vortices in flow field. Finally, an equation which describes the quantitative relationship between the dynamic characteristics of a vortex and the pulsed forcing frequency is derived, that is, the product of the average convective speed of vortices in the controlled supersonic mixing layer and the imposed pulse period is approximately equal to the mean diameter of vortices in the flow field.

Characterization and adsorption properties of the electrolytic carbon derived from CO2 conversion in molten salts

The amorphous carbon derived from a “molten salt CO2 capture and electrochemical transformation” process, was characterized and studied for the adsorption of aqueous solutes. XRF and TG measurements showed that the electrolytic carbon (E-carbon) had a higher purity than the commonly available biochars and activated carbons due to its unique growth mechanism in molten salts. The analysis on morphology, diameter distribution and porosity indicated that the E-carbon, with an inhomogeneous porous structure, exhibited an average particle size of 9.8 μm in aqueous solution, and a BET surface area of 614 m2 g−1. The major surface oxygen-containing functional group for E-carbon was carboxyl group, which was primarily due to the cathodic deoxygenation of carbonate ions and the surface modifying effect of melt. The spontaneous Cu(II) adsorption by E-carbon followed the pseudo-second-order kinetic model and the Langmuir isotherm. Through the surface complexation and surface-precipitation processes, the E-carbon exhibited a maximum adsorptive capacity of 29.9 mg g−1 for Cu (II) adsorption. It also showed a good performance on methylene blue adsorption due to its favorable adsorption-related features, such as high purity, porosity and having a large number of surface functional groups. The E-carbon is envisaged to be used as an adsorptive material for decontamination.

Dry-growth of silver single-crystal nanowires from porous Ag structure

A fabrication method of single crystal Ag nanowires in large scale is introduced without any chemical synthesis in wet processes, which usually generates fivefold twinned nanowires of fcc metals. Dense single-crystal nanowires grow on a mechanically polished surface of micro-porous Ag structure, which is created from Ag micro-particles. The diameter and the length of the nanowires can be controlled simply by changing the temperature and the time of the heating during the nanowire growth in air. Unique growth mechanism is described in detail, based on stress-induced migration accelerated by the micro-porous structure where the origin of Ag nanowires growth is incubated. Transmission electron microscopy analysis on the single crystal nanowires is also presented. This simple method offered an alternative preparation for metallic nanowires, especially with the single crystal structure in numerous applications.

Growth mechanism for alternating supply epitaxy: the unique pathway to achieve uniform silicon carbide films on multiple large-diameter silicon substrates

The unique growth mechanism of alternating supply epitaxy enables uniform 3C-SiC to be deposited on multiple large-diameter Si wafers.