Active Nucleation Sites Research Articles

Design and Synthesis of Sb-Doped CuS@C Hollow Nanocubes as Efficient Anode Materials for Sodium-Ion Battery.

Copper sulfide has received widespread attention for application as anode materials in sodium-ion batteries due to their potent capabilitiess and eco-friendly properties. However, it is a challenge to achieve a high rate capability and long cycle stability owing to the heterogeneous transfer of sodium ions during charge-discharge, the interior poor electron conductivity and repeated volumetric expansion of copper sulfide. In this study, Sb-doped copper sulfide hollow nanocubes coated with carbon shells (Sb-CuS@C) was designed and constructed as anode nanomaterials in sodium-ion batteries. Thanks to the intrinsic good electron conductivity and chemical stability of carbon shells, Sb-CuS@C possesses a higher overall electron transfer as anode material, avoids agglomeration and structural destruction during the cycling. As a result, the synthesized Sb-CuS@C achieved an excellent reversible capacity of 595 mA h g-1 after 100 cycles at 0.5 A g-1 and a good rate capability of 340 mA h g-1 at a higher 10 A g-1. DFT calculations clarify that the uniformly doped Sb would act as active sodiophilic nucleation sites to help adsorbing sodium-ion during discharging and leading uniform sodium deposition. This work provides a new insight into the structural and componential modification for common transition-metal sulfides towards application as anode materials in sodium-ion battery.

Roller-like Spore Carbon Sphere-Orientated Graphene Fibers Prepared via Rheological Engineering for Lithium Sulfur Batteries.

Flexible batteries with large energy densities, lightweight nature, and high mechanical strength are considered as an eager goal for portable electronics. Herein, we first propose free-standing graphene fiber electrodes containing roller-like orientated spore carbon spheres via rheological engineering. With the help of the orientated microfluidic cospinning technology and the plasma reduction method, spore carbon spheres are self-assembled and orientedly dispersed into numerous graphene flakes, forming graphene fiber electrodes enriched with internal rolling woven structures, which cannot only enhance the electrical contact between active materials but also effectively improve the mechanical strength and structure stability of graphene fiber electrodes. When the designed graphene fibers are combined with the active sulfur cathode and lithium metal anode, the assembled flexible lithium sulfur batteries possess superior electrochemical performance with high capacity (>1000 mA h g-1) and excellent cycling life as well as good mechanical properties. According to density functional theory and COMSOL simulations, the roller-like spore carbon sphere-orientated graphene fiber hosts provide reinforced trapping-catalytic-conversion behavior to soluble polysulfides and nucleation active sites to lithium metal, thus synergistically suppressing the shuttle effect of polysulfides at the cathode side and lithium dendrite growth at the anode side, thereby boosting the whole electrochemical properties of lithium sulfur batteries.

Performance of surface structures in enhancing heat transfer rates of miniaturized pulsating heat pipe

Enhancement of the thermal performance by modifying the evaporator surface of a miniaturized pulsating heat pipe (PHP) is the primary target of the present work. Four PHPs having different evaporator surface types i.e., smooth, dimple cavity array, tunnel cavity, and rectangular cavity array were investigated numerically to compare the gas-liquid interfacial behavior and evaluate the role of bubble nucleation, slug-plug movement, and drop-film condensation on the thermal performance. Detailed modeling of evaporating and condensing interfaces shows that activation of nucleation sites at all defined discrete structures and undisturbed liquid flow path at the evaporator promote heat transfer rate. Through thermo fluidic analysis around different surface structures, evaporation dynamics is analyzed to understand the suitability of a structure type for enhancement of heat transfer. Associated slug-plug motion through the adiabatic zone and processes at the condenser have been also discussed to propose the characteristics of an ideal enhanced PHP. The capacity to transfer heat has been also characterized using thermal resistance for different structured PHPs which may be a guiding factor for the design of heat sinks for thermal applications.

The novel Auricularia-like MoS2 as binder-free electrodes for enhanced capacitive deionization

Molybdenum disulfide (MoS2) has been proven to be an effective and promising electrode material for capacitive deionization (CDI) due to its unique architectures and excellent electrochemical activity. However, MoS2-based electrodes still suffer from the high contact electrical resistance between MoS2 and the current collectors because of the necessity of adding binder during their fabrication. In this work, a flexible MoS2-based electrode with no binders was successfully fabricated. It was found that the frameworks of stainless-steel mesh with surface treatment could serve as an ideal substrate to provide plenty of active nucleation sites for the growth of MoS2. Consequently, a novel morphology of MoS2 with Auricularia-like architectures was produced. Based on electrochemical impedance spectroscopy (EIS), the charge transfer resistance was reduced to nearly zero after the treatment, highly increasing the transportation of charges inside the electrodes compared to the common MoS2-based electrodes. As a result, the binder-free MoS2-based electrodes demonstrated a superior desalination performance of 28.76 mg g-1 (1.2 V) for NaCl solution, which was superior to that of common MoS2-based and many other advanced materials-based electrodes. The novel MoS2-based electrode not only facilitates the utilization of MoS2 in CDI but also paves the way for its application in other electrochemical domains.

Flow boiling heat transfer enhancement of R134a in additively manufactured minichannels with microengineered surfaces

Additive manufacturing (AM) of metal components has opened new frontiers in heat transfer applications owing to its wide design freedom, which enables previously unexplored geometries with enhanced thermal performance to be developed. Open minichannels, on the other hand, consist of an extra manifold situated above the common flow channels, have been demonstrated to effectively reduce pressure drop and two-phase flow instability by mitigating backflow and maldistribution. In this paper, we synergized open minichannel design methodology with an ultrascalable surface microstructuring method for AM AlSi10Mg to improve flow boiling heat transfer performance of R134a. Experiments were conducted at the refrigerant mass flow rates (ṁ) of 0.005 kg/s to 0.01 kg/s (corresponding to mass fluxes of 73 to 146 kg/m2⋅s), and effective heat fluxes (qeff) of 1.8 kW/m2 to 141 kW/m2, by supplying 2 ℃ subcooled liquid to the minichannel inlet at saturation pressure (Psat) of 7.27 bar. The effects of heat flux, nucleation site density, mass flow rate and location of nucleation sites on the harmonic-average heat transfer coefficient (have) and pressure drop (ΔP) along the flow direction are investigated and compared against a conventionally manufactured (Al6061) counterpart. Our results show that the proposed etching process significantly improves the cooling performance of AM microstrucured minichannels, resulting in 210% higher have than Al6061 with negligible pressure drop penalty. The flow visualization results reveal a sequential order of nucleation site activation with increasing heat flux for microstructured open minichannels, which starts from the top of fins, followed by the corners and other three surfaces within the channels. This also results in the non-negligible effects of mass flow rate on cooling performance for microstructured minichannels, with approximately 10%–66% higher have at the lowest mass flow rate. Besides, the pressure drop penalty resulting from plain AM rough surface is also reduced by up to 13% through the proposed microstructuring process. In all, this work not only successfully identifies the dominant mechanisms in AM microstructured open minichannels, but it also provides useful minichannel design guidelines for high-performance two-phase cooling devices by AM.

Bi-Directional Modification to Quench Detrimental Redox Reactions and Minimize Interfacial Energy Offset for NiOX/Perovskite-Based Solar Cells.

The quality of the buried heterojunction of nickel oxide (NiOX)/perovskite is crucial for efficient charge carrier extraction and minimizing interfacial non-radiative recombination in inverted perovskite solar cells (PSCs). However, NiOX has limitations as a hole transport layer (HTL) due to energy level mismatch, low conduction, and undesirable redox reactions with the perovskite layer, which impede power conversion efficiency (PCE) and long-term stability. In this study, para-amino 2,3,5,6-tetrafluorobenzoic acid (PATFBA) is proposed as a bifacial defect passivator to tailor the NiOX/perovskite interface. The acid group and adjacent fluorine atoms of PATFBA effectively passivate NiOX surface defects, thereby improving its Ni3+/Ni2+ ratio, hole extraction capability, and energy band alignment with perovskite, while also providing active sites for homogenous nucleation. Meanwhile, the amine and adjacent fluorine atomsstabilize the buried perovskite interface by passivating interfacial defects, resulting in higher crystalline perovskite films with supressed non-radaitive recombination. Furthermore, the PATFBA buffer layer prevents redox reactions between Ni3+ and perovskite.These synergistic bi-directional interactions lead to optimized inverted PSCs with a PCE of 20.51% compared to 16.89% for pristine devices and the unencapsulated PATFBA-modified devices exhibit outstanding thermal and long-term stability. This work provides a new engineering approach to buried interfaces through the synergy of functional groups.

Spontaneous grain refinement effect of rare earth zinc alloy anodes enables stable zinc batteries.

Irreversible interfacial reactions at the anodes pose a significant challenge to the long-term stability and lifespan of zinc (Zn) metal batteries, impeding their practical application as energy storage devices. The plating and stripping behavior of Zn ions on polycrystalline surfaces is inherently influenced by the microscopic structure of Zn anodes, a comprehensive understanding of which is crucial but often overlooked. Herein, commercial Zn foils were remodeled through the incorporation of cerium (Ce) elements via the 'pinning effect' during the electrodeposition process. By leveraging the electron-donating effect of Ce atoms segregated at grain boundaries (GBs), the electronic configuration of Zn is restructured to increase active sites for Zn nucleation. This facilitates continuous nucleation throughout the growth stage, leading to a high-rate instantaneous-progressive composite nucleation model that achieves a spatially uniform distribution of Zn nuclei and induces spontaneous grain refinement. Moreover, the incorporation of Ce elements elevates the site energy of GBs, mitigating detrimental parasitic reactions by enhancing the GB stability. Consequently, the remodeled ZnCe electrode exhibits highly reversible Zn plating/stripping with an accumulated capacity of up to 4.0Ah cm-2 in a Zn symmetric cell over 4000h without short-circuit behavior. Notably, a ∼0.4Ah Zn||NH4V4O10 pouch cell runs over 110 cycles with 83% capacity retention with the high-areal-loading cathode (≈20mg cm-2). This refining-grains strategy offers new insights into designing dendrite-free metal anodes in rechargeable batteries.

Research on boiling heat transfer of aqueous extracts vacuum drying based on fractal theory

Traditional Chinese Medicine (TCM) aqueous extracts are highly viscous pseudoplastic porous media that boiling during vacuum drying, and the drying mechanism significantly differs from that of conventional solid materials. To reveal the heat transfer mechanism, a simulation model of aqueous extracts nucleate boiling was built based on fractal theory, and the effects of superheat, material temperature, viscosity and contact angle on fractal characteristics and heat transfer were studied. Results demonstrate that within a superheat range from 11 °C and 74 °C, the fractal dimension of active nucleation sites on the drying wall ranges between 1.75 and 1.86. The nuclear boiling heat flux increases with the increase in superheat, material temperature, specific heat capacity, thermal conductivity, and contact angle; or with the decrease in viscosity. The research can offer theoretical guidance for the development of drying processes and the optimization of technology in high viscosity pseudoplastic porous media.

Nucleation, growth and bubble detachment in liquid-vapor phase change on structured surfaces

Comprehensive grasp of heat and mass transfer, particularly in applications involving liquid-vapor phase change, hinges on management of nucleation, growth, and detachment of vapor bubbles. Various parameters influence the dynamics of phase-change heat and mass transfer and thus dictate the interactions between the surface, the liquid, and the vapor, profoundly impacting the underlying processes. To tailor these phenomena and harness them for technical applications involving high heat flux densities and intense mass transfer, such as boiling and electrolysis, surface functionalization is under intense development. By designing structured surfaces and creating preferential nucleation sites that promote heterogeneous nucleation, it is possible to exert control over the location and density of active nucleation sites on the surface. This, in turn, enables the regulation of bubble growth and detachment from the surface. With the aim of identifying optimal surface treatments for functionalizing surfaces and enhancing their performance in phase-change applications, we evaluated the nucleation, growth and detachment of a single bubble in a liquid-vapor phase change on untextured and laser-textured surfaces during water electrolysis. Platinum was chosen as the preferential material due to its favourable electrochemical properties for the hydrogen evolution reaction in acidic media. Electrolysis was performed at various voltages and the bubble dynamics were evaluated through high-speed imaging to investigate the intricacies of bubble growth and their mutual interactions. At 3.5 V using the laser textured surface, hydrogen bubbles detaching from the electrode surface had on average 40% smaller diameter, while the frequency of their detachment was 2,5-times higher compared to the untextured surface. This opens the possibility for further research that could lead to improving the efficiency of electrolysis.

Study of nucleate boiling growth regime on thin surfaces.

In a context of energy transition, heat exchanges are a key for energy sobriety. Among those exchanges, nucleate boiling is the preferred heat transfer method for high heat flux. Vaporisation plays an important role in the nuclear industry, but also in thermal machines such as cooling systems in data centers. In spite of decades studying boiling thermodynamics, modelling heat transfers in the nucleate boiling is still a major difficulty because of its numerous parameters. In the 1960s, scientists developed promising models called heat flux partitioning models. These models have been improved over the years, but they need closure laws about bubbles dynamics and nucleation site density. For the purpose of improving those models, we took part in an international collaboration (ANR TraThI) to study interface heat transfer. Project focuses on boiling with a controlled nucleation site density with a strong emphasis on studying isolated bubbles in water pool boiling, and later addressing multiple bubble interactions in pool and flow boiling. This work focuses on the bubble growth regimes on thin metallic foil observed in a water pool boiling experiment, with a distinction between microlayer and contact line growth regime. Pulsed nanosecond laser was used to create active nucleation site, while high-speed infrared thermography and shadowgraphy were implemented to record transient wall temperatures and bubble dynamics, respectively. This work shows that our experimental configuration induced two different bubble growth regimes, depending on the imposed heat flux and the recent past at the nucleation site and its vicinity. Study provides a framework for further in-depth investigations with different experimental configurations.

Boiling heat flux partitioning model with bubble tracking method considering bubble merger and stochastic characteristics

This study presents the development and validation of a numerical tool of heat partitioning model for boiling heat transfer using a bubble tracking method. It was aimed to account for the effect of stochastic phenomena in the boiling process by simulating individual bubbles. Saturated pool boiling conditions on a horizontal plate heater were analyzed to demonstrate the effectiveness of the proposed model. The model was devised based on the observations from high-resolution pool boiling experiments, assuming a truncated sphere for bubble shape and using simplified microlayer size and thickness models. The developed heat partitioning model was verified by comparisons with the conventional heat partitioning model. Afterward, the validation of the model was conducted by comparing the result of the simulation with the experimental data of the saturated pool boiling. In this validation, measured values of nucleation site density, departure diameter, single-phase heat transfer coefficients, etc. were applied. Additionally, the effect of stochastic phenomena on boiling heat transfer was evaluated using the bubble tracking method, focusing on nucleation timing and nucleation site distribution. Stochastic nucleation was found to reduce the bubble merger probability compared to simultaneous nucleation, leading to increased microlayer evaporation. Stochastic site distribution, on the other hand, decreased active nucleation sites due to the site suppression effect, resulting in reduced microlayer evaporation compared to uniform site distribution.

Effect of Evaporation Temperature and Mg2+ Concentration on the Crystallization of Ammonium Sulfate

AbstractThis study investigates the influences of the evaporation temperature and Mg2+ concentration on the crystallization of an ammonium sulfate mother liquor. Specifically, their effects on the solubility, metastable zone width, crystallization amount, average particle size, and coefficient of variation of ammonium sulfate are examined through the laser and evaporation crystallization methods. Results show that solubility increases and the metastable zone width narrows with an increase in the evaporation temperature. At an evaporation temperature of 338.15 K, the controllability of the crystallization process improves and explosive nucleation does not easily occur. In this case, crystals with large average particle sizes, regular morphologies, and high crystallinity are obtained. With an increase in the Mg2+ concentration in the solvent, solubility decreases. The added Mg2+ covers the active nucleation sites, thus hindering the nucleation of ammonium sulfate and widening the metastable zone width. At a Mg2+ concentration of 0.9 g L−1 or higher, Mg2+ covers the active surfaces of the grains. This inhibits normal crystal growth and hinders the nucleation and growth of ammonium sulfate crystals, so the crystallization amount of ammonium sulfate significantly reduces.

Calcium crosslinked macroporous bacterial cellulose scaffolds with enhanced in situ mineralization and osteoinductivity for cranial bone regeneration

The inherent biological inertness and lack of three-dimensional (3D) macroporous structures greatly hinder the use of pristine bacterial cellulose (BC) as a tissue engineering scaffold for bone regeneration. To address this issue, we developed a simple and effective strategy to fabricate a BC-based scaffold with excellent bioactivity and macroporous structure by crosslinking short-cut BC nanofibers using Ca2+. The Ca2+ crosslinked macroporous BC scaffold (MPBC@Ca) presents better structural stability due to the enhanced cellulose hydration. Importantly, the Ca2+ on the surface of BC nanofibers can serve as an active nucleation site to accelerate the deposition of hydroxyapatite (HAp), which is beneficial for the construction of biomimetic bone tissue extracellular matrix (ECM) microenvironment. The HAp-deposited MPBC@Ca scaffolds (HAp-MPBC@Ca) with biomimetic ECM microenvironment have excellent cytocompatibility and enhanced osteogenic differentiation of stem cells in vitro. Furthermore, the results of in vivo tests revealed that the HAp-MPBC@Ca scaffold has favorable osteoinductivity and accelerates cranial bone tissue regeneration. This study proposes a novel strategy to improve the bioactivity of BC and presents the great potential of biomimetic ECM microenvironment BC-based scaffold for repairing large cranial bone defects.

Ultra-stable dendrite-free Na and Li metal anodes enabled by tin selenide host material

Lithium/sodium metal anodes are considered promising candidates to realize high-energy–density batteries because of their high theoretical specific capacity and low potential. However, their cycling stability are hindered by uncontrolled dendrites growth. Herein, SnSe nanoparticles are tightly anchored on the fiber of carbon cloth (CC) to construct SnSe@CC host material in order to control Li/Na nucleation behavior and restrain dendrites growth. It is demonstrated that the alloying product of Li15Sn4/Na15Sn4 with strong metal affinity can provide abundant active nucleation sites, and three-dimensional structure of CC host can significantly decrease the local electric current, thereby guiding homogeneous metal deposition without Li and Na dendrites. Meanwhile, the conversion product of Li2Se/Na2Se will uniformly cover on the surface of metal to serve as ultra-stable solid state interface film. As a result, high-capacity Li metal anode (20 mAh·cm−2) and Na metal anode (10 mAh·cm−2) can work steadily with ultra-long lifespans over 5000 and 6000 h with low overpotentials of 7 mV and 141 mV, respectively. Moreover, the assembled Li and Na metal full batteries exhibit superior electrochemical performances, confirming the practicability of metal anode confined in composite host. Such a strategy of conversion-alloying-type materials as hosts opens up a new path for dendrite-free metal anode electrode.

Substrate Screening for the Epitaxial Growth of a Single-Crystal Graphene Wafer.

Epitaxial growth of a two-dimensional (2D) single crystal necessitates the symmetry group of the substrate being a subgroup of that of the 2D material. As a consequence of the theory of 2D material epitaxy, high-index surfaces, which own very low symmetry, have been successfully used to grow various 2D single crystals, while the rule of selecting the best substrates for 2D single crystal growth is still absent. Here, extensive density functional theory calculations were conducted to investigate the growth of graphene on abundant high-index Cu substrates. Although step edges are commonly regarded as the most active sites for graphene nucleation, our study reveals that, in some cases, graphene nucleation on terraces is superior than that near a step edge. To achieve parallel alignments of graphene islands, it is essential to either suppress terrace nucleation or ensure consistent orientations templated by both the terrace and step edge. In agreement with most experimental observations, we show that Cu substrates for the growth of single-crystalline graphene include vicinal Cu(111) surfaces, vicinal Cu(110) surfaces with Miller indices of (nn1) (n > 3), and vicinal Cu(100) surfaces with Miller indices of (n11) (n > 3).

Wearable Plasmonic Sensors Engineered via Active-Site Maximization of TiVC MXene for Universal Physiological Monitoring at the Molecular Level.

Two-dimensional transition metal carbon/nitrides (MXenes) are promising candidates to revolutionize next-generation wearable sensors as high-performance surface-enhanced Raman scattering (SERS) substrates. However, low sensitivity of pure MXene nanosheets and weak binding force or uncontrolled in situ growth of plasmonic nanoparticles on hybrid MXene composites limit their progress toward universal and reliable sensors. Herein, we designed and manufactured a highly sensitive, structurally stable wearable SERS sensor by in situ fabrication of plasmonic nanostructures on the flexible TiVC membranes via the maximization of chemically reducing sites using alkaline treatment. DFT calculations and experimental characterization demonstrated that the hydroxyl functional groups on the surface of MXenes can facilitate the reduction of metal precursors and the nucleation of gold nanoparticles (AuNPs) and can be covalently attached to AuNPs. Thus, the fabricated flexible TiVC-OH-Au sensor satisfied the rigorous mechanical requirements for wearable sensors. In addition, combining the electromagnetic (EM) enhancement from dense AuNPs formed by the activation of nucleation sites and charge transfer (CT) between target molecule and substrate induced by the abundant DOS near the Fermi level of TiVC, the fabricated sensor exhibits ultrasensitivity, long-term stability, good signal repeatability, and excellent mechanical durability. Moreover, the proof-of-concept application of the wearable SERS sensor in sweat sensing was demonstrated to monitor the content of nicotine, methotrexate, nikethamide, and 6-acetylmorphine in sweat at the molecular level, which was an important step toward the universality and practicality of the wearable sensing technology.

Coordination Engineering of N, O Co‐Doped Cu Single Atom on Porous Carbon for High Performance Zinc Metal Anodes

AbstractTraditional challenges of poor cycling stability and low Coulombic efficiency in Zinc (Zn) metal anodes have limited their practical application. To overcome these issues, this work introduces a single metal‐atom design featuring atomically dispersed single copper (Cu) atoms on 3D nitrogen (N) and oxygen (O) co‐doped porous carbon (CuNOC) as a highly reversible Zn host. The CuNOC structure provides highly active sites for initial Zn nucleation and further promotes uniform Zn deposition. The 3D porous architecture further mitigates the volume changes during the cycle with homogeneous Zn2+ flux. Consequently, CuNOC demonstrates exceptional reversibility in Zn plating/stripping processes over 1000 cycles at 2 and 5 mA cm−2 with a fixed capacity of 1 mAh cm−2, while achieving stable operation and low voltage hysteresis over 700 h at 5 mA cm−2 and 5 mAh cm−2. Furthermore, density functional theory calculations show that co‐doping N and O on porous carbon with atomically dispersed single Cu atoms creates an efficient zincophilic site for stable Zn nucleation. A full cell with the CuNOC host anode and high loading V2O5 cathode exhibits outstanding rate‐capability up to 5 A g−1 and a stable cycle life over 400 cycles at 0.5 A g−1.

A mesoscopic numerical method for enhanced pool boiling heat transfer on conical surfaces under action of electric field

The saturated pool boiling heat transfer on a conical structure surface under the action of an electric field is numerically investigated by using the lattice Boltzmann (LB) model coupled with an electric field model. A comparison study of boiling heat transfer phenomenon smooth surface and conical surface without the action of an electric field is first conducted in order to quantitatively analyze the mechanism of the electric field effect on boiling heat transfer on the conical structure surface. It is discovered that the conical structure has more active nucleation sites during the nucleate boiling regime, improving the boiling heat transfer efficiency and enhancing the critical heat flux (CHF). However, in the transition boiling stage and film boiling stage, the conical structure increases the flow resistance of the fluid on the fin surface, hindering heat transfer between the vapor and liquid and producing lower heat transfer performance than smooth surface. Based on the aforementioned findings, the boiling heat transmission on the conical structure surface is enhanced by applying an electric field. Numerical results indicate that the effect of the electric field on the boiling heat transfer performance on the conical structure surface is related to the boiling regime. In the earlier stage of the nucleation boiling regime, when an electric field is present, the onset time of bubble nucleation is slightly delayed, bubble size decreases a little, and boiling is slightly suppressed. However, the combination effect of electric field and conical structure, especially the tip effect, prevents the spread and diffusion of dry areas on the heating surface, thereby enhancing boiling heat transfer in the fully developed nucleate boiling stage. The tip effect grows more evidently in the transition boiling regime and film boiling regime, and increasing electric field intensity causes boiling to continue in the nucleate boiling regime at a higher superheat level. As a result, boiling heat transfer performance is greatly improved, and CHF steadily rises.

Synthesis of high-quality nano-H-ZSM-5 single crystals zeolite from montmorillonite and MTO catalytic studies

Clay is a rich aluminosilicate resource with unique advantages as a raw material for zeolites production. However, synthesizing nanosized single-crystalline zeolites through a simple approach using clay remains a significant challenge. In this paper, acid-washed montmorillonite (MSR) was used to prepare nano-H-ZSM-5 single crystals with high crystallinity, uniform grain size and permeable straight pores under the induction of a small amount of organic template tetrapropylammonium hydroxide (TPAOH). Through temperature-staged treatment, the nucleation and growth process of zeolite were decoupled, ultimately achieving precise control over the size of the nano-single crystals. Mechanistic study showed that the low-temperature aging process produces smaller structural units which probably derived from the geopolymer topology of the clay, providing more active sites for zeolite nucleation, leading to the rapid crystallization during the high-temperature process. The porous structure promotes material diffusion, inhibits aromatic cycling and reduces carbon formation in the pores. The large specific surface area and nanoscale multilayer pore structure delay carbon accumulation and increase carbon holding capacity. These properties make nano-ZSM-5 single crystals an excellent choice for high olefin selectivity and long catalytic life in the methanol-to-olefin reaction. This synthetic route provides a general strategy for preparing nanosized zeolite single crystals from clay.

Alkalized MXene/carbon nanotube composite for stable Na metal anodes.

Ti3C2 MXenes are emerging 2D materials and have attracted increasing attention in sodium metal anode fabrication because of their high conductivity, multifunctional groups and excellent mechanical performances. However, the severe self-restacking of Ti3C2 MXenes is not conducive to dispersing Na+ and limits the function of regulating sodium deposition. Herein, an alkalized MXene/carbon nanotube (CNT) composite (named A-M-C) is introduced to regulate Na deposition behavior, which consists of Na3Ti5O12 microspheres, Ti3C2 MXene nanosheets and CNTs. Ti3C2 MXene nanosheets with large interlayer spaces and "sodiophilic" functional groups can provide abundant active sites for uniform nucleation and deposition of Na. Plenty of nanosheets are grown on the surface of the microsphere, thereby reducing the local current density, which can guide initial Na nucleation and promote Na dendrite-free growth. Furthermore, CNTs increase the electrical conductivity of the composite and achieve fast Na+ transport, improving the cycling stability of Na metal batteries. As a result, at a capacity of 1 mA h cm-2, the A-M-C electrode achieves a high average coulombic efficiency (CE) of 99.9% after 300 cycles at 2 mA cm-2. The symmetric cells of A-M-C/Na provide a long cycling life of more than 1400 h at 1 mA cm-2 with a minimal overpotential of 19 mV at an areal capacity of 1 mA h cm-2. The A-M-C/Na//NVP@C full cell presents a high coulombic efficiency of 98% with 100 mA g-1 in the first cycle. The strategy in this work provides new insights into fabricating novel MXene-based anode materials for dendrite-free sodium deposition.