Integration of photothermal water evaporation with photocatalytic microplastics upcycling via nanofluidic thermal management.

Photothermal heating and photocatalytic treatment are two solar-driven water processing approaches by harnessing NIR and UV-vis light, respectively, which can fully utilize solar energy if integrated. However, it remains a challenge to achieve high performance in both approaches when integrated in a material due to uncontrollable heat diffusion. Here, we report a demonstration of heat confinement on photothermal sites and fluid cooling on photocatalysis sites at the nanoscale, within a well-designed heat and fluid confinement nanofiber reactor. Photothermal and photocatalytic nanostructures were alternatively aligned in electrospun nanofibers for on-demand nanofluidic thermal management as well as easy folding into 3D structures with enhanced light utilization and mass transfer. Such a design showed simultaneously high photothermal evaporation rate (2.59 kg m-2 h-1, exceeding the limit rate) and efficient photocatalytic upcycling of microplastics pollutant into valued products. Enabled by controlled photothermal heating, the valued main product (i.e., methyl acetate) can be evaporated out with 100% selectivity by in situ separation.

In Situ Transmission Electron Microscopy Investigation on Oriented Attachment of Nanodiamonds.

Oriented attachment (OA) plays an important role in the assembly of nanoparticles and the regulation of their size and morphology, which is expected to be an effective means to modulate the properties of nanodiamonds (NDs). However, there remains a dearth of comprehensive investigation into the OA mechanism of NDs. Using in situ transmission electron microscopy, we conducted atomic-resolution investigation on the OA events of ND pairs under electron beam irradiation. The occurrence of an OA event is contingent upon the alignment between two ND surfaces, and the coalesced particles undergo recrystallization to form spherical shapes. Both experimental observations and molecular dynamics (MD) simulations reveal that ND pairs exhibit a preference for coalescing along the {111} surfaces. Additionally, MD simulations indicate that kinetic factors, such as contact surface area and contact angle, also influence the coalescence process.

Thermodynamically and Kinetically Stabilized Pt Clusters Against Sintering on CeO2 Nanofibers Through Enclosing CeO2 Nanocubes.

Sintering is a major concern for the deactivation of supported metals catalysts, which is driven by the force of decreasing the total surface energy of the entire catalytic system. In this work, a double-confinement strategy is demonstrated to stabilize 2.6 nm-Pt clusters against sintering on electrospun CeO2 nanofibers decorated by CeO2 nanocubes (m-CeO2 ). Thermodynamically, with the aid of CeO2 -nanocubes, the intrinsically irregular surface of polycrystalline CeO2 nanofibers becomes smooth, offering adjacent Pt clusters with decreased chemical potential differences on a relatively uniform surface. Kinetically, the Pt clusters are physically restricted on each facet of CeO2 nanocubes in a nanosized region. In situ high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observation reveals that the Pt clusters can be stabilized up to 800 °C even in a high density, which is far beyond their Tammann temperature, without observable size growth or migration. Such a sinter-resistant catalytic system is endowed with boosted catalytic activity toward both the hydrogenation of p-nitrophenol after being aged at 500 °C and the sinter-promoting exothermic oxidation reactions (e.g., soot oxidation) at high temperatures over 700 °C. This work offers new opportunities for exploring sinter-resistant nanocatalysts, starting from the rational design of whole catalytic system in terms of thermodynamic and kinetic aspects.

Heterostructured Interface Enables Uniform Zinc Deposition for High-Performance Zinc-Ion Batteries.

Zinc metal has considerable potential as a high-energy anode material for aqueous batteries due to its high theoretical capacity and environmental friendliness. However, dendrite growth and parasitic reactions at the electrode/electrolyte interface remain two serious problems for the Zn metal anode. Here, the heterostructured interface of ZnO rod array and CuZn5 layer is fabricated on the Zn substrate (ZnCu@Zn) to address these two issues. The zincophilic CuZn5 layer with abundant nucleation sites ensures the initial uniform Zn nucleation process during cycling. Meanwhile, the ZnO rod array grown on the surface of the CuZn5 layer can guide the subsequent homogeneous Zn deposition via spatial confinement and electrostatic attraction effects, leading to the dendrite-free Zn electrodeposition process. Consequently, the derived ZnCu@Zn anode exhibits an ultra-long lifespan of up to 2500 h with symmetric cells at the current density and capacity of 0.5 mA cm-2 /0.5 mA h cm-2 . Besides, a remarkable cyclability (75% retention for 2500 cycles at 2 A g-1 ) is achieved in the ZnCu@Zn||MnO2 full cell with a capacity of 139.7 mA h g-1 . This heterostructured interface with specific functional layers provides a feasible strategy for the design of high-performance metal anodes.

Facile Synthesis of Sponge-Like Porous Nano Carbon-Coated Silicon Anode with Tunable Pore Structure for High-Stability Lithium-Ion Batteries.

To address the challenge of the huge volume expansion of silicon anode, carbon-coated silicon has been developed as an effective design strategy due to the improved conductivity and stable electrochemical interface. However, although carbon-coated silicon anodes exhibit improved cycling stability, the complex synthesis methods and uncontrollable structure adjustment still make the carbon-coated silicon anodes hard to popularize in practical application. Herein, we propose a facile method to fabricate sponge-like porous nano carbon-coated silicon (sCCSi) with a tunable pore structure. Through the strategy of adding water into precursor solution combined with a slow heating rate of pre-oxidation, a sponge-like porous structure can be formed. Furthermore, the porous structure can be controlled through stirring temperature and oscillation methods. Owing to the inherent material properties and the sponge-like porous structure, sCCSi shows high conductivity, high specific surface area, and stable chemical bonding. As a result, the sCCSi with normal and excessive silicon-to-carbon ratios all exhibit excellent cycling stability, with 70.6% and 70.2% capacity retentions after 300 cycles at 500 mA g-1, respectively. Furthermore, the enhanced buffering effect on pressure between silicon nanoparticles and carbon material due to the sponge-like porous structure in sCCSi is further revealed through mechanical simulation. Considering the facile synthesis method, flexible regulation of porous structure, and high cycling stability, the design of the sCCSi paves a way for the synthesis of high-stability carbon-coated silicon anodes.

Spring-Like Pseudoelectroelasticity of Monocrystalline Cu2S Nanowire.

Prediction from the dual-phase nature of superionic conductors-both solid and liquid-like-is that mobile ions in the material may experience reversible extraction-reinsertion by an external electric field. However, this type of pseudoelectroelasticity has not been confirmed in situ, and no details on the microscopic mechanism are known. Here, we in situ monitor the pseudoelectroelasticity of monocrystalline Cu2S nanowires (NWs) using transmission electron microscopy (TEM). Specifically, we reveal the atomic scale details including phase transformation, migration and redox reactions of Cu+ ions, nucleation, growth, as well as spontaneous shrinking of Cu protrusion. Caterpillar-diffusion-dominated deformation is confirmed by the high-resolution transmission electron microscopy (HRTEM) observation and  ab initio calculation, which can be driven by either an external electric field or chemical potential difference. The observed spring-like behavior was creatively adopted for electric nanoactuators. Our findings are crucial to elucidate the mechanism of pseudoelectroelasticity and could potentially stimulate in-depth research into electrochemical and nanoelectromechanical systems.

Self-Assembled Framework Formed During Lithiation of SnS2 Nanoplates Revealed by in Situ Electron Microscopy.

Lithium-ion batteries (LIBs) commercially dominate portable energy storage and have been extended to hybrid/electric vehicles by utilizing electrode materials with enhanced energy density. However, the energy density and cycling life of LIBs must extend beyond the current reach of commercial electrodes to meet the performance requirements for transportation applications. Carbon-based anodes, serving as the main negative electrodes in LIBs, have an intrinsic capacity limitation due to the intercalation mechanism. Some nanostructured carbon materials offer very interesting reversible capacities and can be considered as future anode materials. However, their fabrication processes are often complicated and expensive. Theoretically, using a lithium metal anode is the best way of delivering high energy density due to its largest theoretical capacity of more than 3800 mAh g-1; however, lithium metal is highly reactive with liquid electrolytes. Alternative anodes are being explored, including other lithium-reactive metals, such as Si, Ge, Zn, V, and so forth. These metals react reversibly with a large amount of Li per formula unit to form lithium-metal alloys, rendering these materials promising candidates for next-generation LIBs with high energy density. Though, most of these pure metallic anodes experience large volume changes during lithiation and delithiation processes that often results in cracking of the anode material and a loss electrical contact between the particles. Nanosized metal sulfides were recently found to possess better cycling stability and larger reversible capacities over pure metals. Further improvements and developments of metal sulfide-based anodes rely on a fundamental understanding of their electrochemical cycling mechanisms. Not only must the specific electrochemical reactions be correctly identified, but also the microstructural evolution upon electrochemical cycling, which often dictates the cyclability and stability of nanomaterials in batteries, must be clearly understood. Probing these dynamic evolution processes, i.e. the lithiation reactions and morphology evolutions, are often challenging. It requires both high-resolution chemical analysis and microstructural identification. In situ transmission electron microscopy (TEM) coupled with electron energy loss spectroscopy (EELS) has recently been raised as one of the most powerful techniques for monitoring electrochemical processes in anode materials for LIBs. In this work, we focus on elucidating the origin of the structural stability of SnS2 during electrochemical cycling by revealing the microstructural evolution of SnS2 upon lithiation using in situ TEM. Crystalline SnS2 was observed to undergo a two-step reaction after the initial lithium intercalation: (1) irreversible formation of metallic tin and amorphous lithium sulfide and (2) reversible transformation of metallic tin to Li-Sn alloys, which is determined to be the rate-determining step. More interestingly, it was discovered that a self-assembled composite framework formed during the irreversible conversion reaction, which has not been previously reported. Crystalline Sn nanoparticles are well arranged within an amorphous Li2S "matrix" in this self-assembled framework. This nanoscale framework confines the locations of individual Sn nanoparticles and prevents particle agglomeration during the subsequent cycling processes, therefore providing desired structural tolerance and warranting a sufficientelectron pathway. Our results not only explain the outstanding cycling stability of SnS2 over metallic tin anodes, but also provide important mechanistic insights into the design of high-performance electrodes for next-generation LIBs through the integration of a unique nanoframework.

High-performance Cu nanoparticles/three-dimensional graphene/Ni foam hybrid for catalytic and sensing applications.

A novel hybrid of Cu nanoparticles/three-dimensional graphene/Ni foam (Cu NPs/3DGr/NiF) was prepared by chemical vapor deposition, followed by a galvanic displacement reaction in Ni- and Cu-ion-containing salt solution through a one-step reaction. The as-prepared Cu NPs/3DGr/NiF hybrid is uniform, stable, recyclable and exhibits an extraordinarily high catalytic efficiency for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with a reduction rate constant K = 0.056 15 s-1, required time ∼30 s and excellent sensing properties for the non-enzymatic amperometric hydrogen peroxide (H2O2) with a linear range ∼50 µM-9.65 mM, response time ∼3 s, detection limit ∼1 µM. The results indicate that the as-prepared Cu NPs/3DGr/NiF hybrid can be used to replace expensive noble metals in catalysis and sensing applications.

Electron Beam Etching of CaO Crystals Observed Atom by Atom.

With the rapid development of nanoscale structuring technology, the precision in the etching reaches the sub-10 nm scale today. However, with the ongoing development of nanofabrication the etching mechanisms with atomic precision still have to be understood in detail and improved. Here we observe, atom by atom, how preferential facets form in CaO crystals that are etched by an electron beam in an in situ high-resolution transmission electron microscope (HRTEM). An etching mechanism under electron beam irradiation is observed that is surprisingly similar to chemical etching and results in the formation of nanofacets. The observations also explain the dynamics of surface roughening. Our findings show how electron beam etching technology can be developed to ultimately realize tailoring of the facets of various crystalline materials with atomic precision.

New Nanoconfined Galvanic Replacement Synthesis of Hollow Sb@C Yolk-Shell Spheres Constituting a Stable Anode for High-Rate Li/Na-Ion Batteries.

In the current research project, we have prepared a novel Sb@C nanosphere anode with biomimetic yolk-shell structure for Li/Na-ion batteries via a nanoconfined galvanic replacement route. The yolk-shell microstructure consists of Sb hollow yolk completely protected by a well-conductive carbon thin shell. The substantial void space in the these hollow Sb@C yolk-shell particles allows for the full volume expansion of inner Sb while maintaining the framework of the Sb@C anode and developing a stable SEI film on the outside carbon shell. As for Li-ion battery anode, they displayed a large specific capacity (634 mAh g-1), high rate capability (specific capabilities of 622, 557, 496, 439, and 384 mAh g-1 at 100, 200, 500, 1000, and 2000 mA g-1, respectively) and stable cycling performance (a specific capacity of 405 mAh g-1 after long 300 cycles at 1000 mA g-1). As for Na-ion storage, these yolk-shell Sb@C particles also maintained a reversible capacity of approximate 280 mAh g-1 at 1000 mA g-1 after 200 cycles.

Worm-Shape Pt Nanocrystals Grown on Nitrogen-Doped Low-Defect Graphene Sheets: Highly Efficient Electrocatalysts for Methanol Oxidation Reaction.

Although direct methanol fuel cell offers high energy use efficiency and low pollution emission, the lack of suitable electrode materials poses a great challenge to its commercial application. Herein, a facile and scalable approach is developed to fabricate a hybrid electrocatalyst consisting of strongly coupled worm-shape Pt nanocrystals and nitrogen-doped low-defect graphene (N-LDG) sheets. Interestingly, it is found that the formation of Pt nanoworms (NWs) is induced by the N atoms in the high-quality carbon matrix, which also allows the integration of their respective structural advantages and leads to a strong synergetic coupling effect. As a result, the obtained Pt NW/N-LDG catalyst exhibits an extremely high mass activity of 1283.1 mA mg-1 toward methanol oxidation reaction, accompanied by reliable long-term stability and good antipoisoning ability, which are dramatically enhanced as compared with conventional Pt nanoparticle catalysts dispersed on undoped LDG, reduced graphene oxide, and commercial carbon black supports.

Interfacial Stability of Li Metal-Solid Electrolyte Elucidated via in Situ Electron Microscopy.

Despite their different chemistries, novel energy-storage systems, e.g., Li-air, Li-S, all-solid-state Li batteries, etc., face one critical challenge of forming a conductive and stable interface between Li metal and a solid electrolyte. An accurate understanding of the formation mechanism and the exact structure and chemistry of the rarely existing benign interfaces, such as the Li-cubic-Li7-3xAlxLa3Zr2O12 (c-LLZO) interface, is crucial for enabling the use of Li metal anodes. Due to spatial confinement and structural and chemical complications, current investigations are largely limited to theoretical calculations. Here, through an in situ formation of Li-c-LLZO interfaces inside an aberration-corrected scanning transmission electron microscope, we successfully reveal the interfacial chemical and structural progression. Upon contact with Li metal, the LLZO surface is reduced, which is accompanied by the simultaneous implantation of Li+, resulting in a tetragonal-like LLZO interphase that stabilizes at an extremely small thickness of around five unit cells. This interphase effectively prevented further interfacial reactions without compromising the ionic conductivity. Although the cubic-to-tetragonal transition is typically undesired during LLZO synthesis, the similar structural change was found to be the likely key to the observed benign interface. These insights provide a new perspective for designing Li-solid electrolyte interfaces that can enable the use of Li metal anodes in next-generation batteries.

Microelectromechanical system for in situ quantitative testing of tension-compression asymmetry in nanostructures.

Tension-compression asymmetry is a topic of current interest in nanostructures, especially in strain engineering. Herein, we report a novel on-chip microelectromechanical system (MEMS) that can realize in situ quantitative mechanical testing of nanostructures under tension-compression functions. The mechanical properties of three kinds of nanostructures fabricated by focused ion beam (FIB) techniques were systematically investigated with the presented on-chip testing system. The results declare that both Pt nanopillars and C nanowires exhibit plastic deformation behavior under tension testing, with average Young's moduli of 70.06 GPa and 58.32 GPa, respectively. However, the mechanical deformation mechanisms of the two nanostructures changed in compression tests. The Pt nanopillar exhibited in-plane buckling behavior, while the C nanowire displayed 3D twisting behavior with a maximum strain of 25.47%, which is far greater than the tensile strain. Moreover, asymmetric behavior was also observed in the C nanospring during five loading-unloading tension-compression deformation tests. This work provides a novel insight into the asymmetric mechanical properties of nanostructures, with potential applications in nanotechnology research.

In Situ Polymer-Solution-Processed Graphene-PDMS Nanocomposites for Application in Intracranial Pressure Sensors.

Polydimethylsiloxane (PDMS) has emerged as a promising candidate for the dielectric layer in implantable sensors due to its exceptional biocompatibility, stability, and flexibility. This study introduces an innovative approach to produce graphene-reinforced PDMS (Gr-PDMS), where graphite powders are exfoliated into mono- and few-layer graphene sheets within the polymer solution, concurrently forming cross-linkages with PDMS. This method yields a uniformly distributed graphene within the polymer matrix with improved interfaces between graphene and PDMS, significantly reducing the percolation threshold of graphene dispersed in PDMS from 10% to 5%. As-synthesized Gr-PDMS exhibits improved mechanical and electrical properties, tested for potential use in capacitive pressure sensors. The results demonstrate an impressive pressure sensitivity up to 0.0273 kpa-1, 45 times higher than that of pristine PDMS and 2.5 times higher than the reported literature value. The Gr-PDMS showcases excellent pressure sensing ability and stability, fulfilling the requirements for implantable intracranial pressure (ICP) sensors.

Room-Temperature Growth of Square-Millimeter Single-Crystalline Two-Dimensional Metal Halides on Silicon.

Silicon is the cornerstone of electronics and photonics. In this context, almost all integrated devices derived from two-dimensional (2D) materials stay rooted in silicon technology. However, as the growth substrate, silicon has long been thought to be a hindrance for growing 2D materials through bottom-up methods that require high growth temperatures, and thus, indirect routes are usually considered instead. Although promising growth of large-area 2D materials on silicon has been demonstrated, the direct growth of single-crystalline materials using low-thermal-budget synthesis methods remains challenging. Here, we report the room-temperature growth of millimeter-scale single-crystal 2D metal halides on silicon substrates with a hydroxyl-terminated surface. Theoretical calculations reveal that the activation energy for surface diffusion can be reduced by an order of magnitude by terminating the surface with hydroxyl groups, from which on-silicon growth is greatly facilitated at room temperature and enables a 4-order-of-magnitude increase in area. The high quality and uniformity of the resulting single crystals are further evidenced. The optoelectronic devices employing the as-grown materials show an ultralow dark current of 10-13 A and a high detectivity of 1013 Jones, thereby corroborating a weak-light detection ability. These results would point to a rich space of surface modulation that can be used to surmount current limitations and demonstrate a promising strategy for growing 2D materials directly on silicon at room temperature to produce large single crystals.

Research Progress on Metal-Organic Frameworks by Advanced Transmission Electron Microscopy.

Metal-organic frameworks (MOFs), composed of metal nodes and inorganic linkers, are promising for a wide range of applications due to their unique periodic frameworks. Understanding structure-activity relationships can facilitate the development of new MOFs. Transmission electron microscopy (TEM) is a powerful technique to characterize the microstructures of MOFs at the atomic scale. In addition, it is possible to directly visualize the microstructural evolution of MOFs in real time under working conditions via in situ TEM setups. Although MOFs are sensitive to high-energy electron beams, much progress has been made due to the development of advanced TEM. In this review, we first introduce the main damage mechanisms for MOFs under electron-beam irradiation and two strategies to minimize these damages: low-dose TEM and cryo-TEM. Then we discuss three typical techniques to analyze the microstructure of MOFs, including three-dimensional electron diffraction, imaging using direct-detection electron-counting cameras, and iDPC-STEM. Groundbreaking milestones and research advances of MOFs structures obtained with these techniques are highlighted. In situ TEM studies are reviewed to provide insights into the dynamics of MOFs induced by various stimuli. Additionally, perspectives are analyzed for promising TEM techniques in the research of MOFs' structures.

Simulating Synaptic Behaviors through Frequency Modulation in a Capacitor-Memristor Circuit.

Memristors, known for their adjustable and non-volatile resistance, offer a promising avenue for emulating synapses. However, achieving pulse frequency-dependent synaptic plasticity in memristors or memristive systems necessitates further exploration. In this study, we present a novel approach to modulate the conductance of a memristor in a capacitor-memristor circuit by finely tuning the frequency of input pulses. Our experimental results demonstrate that these phenomena align with the long-term depression (LTD) and long-term potentiation (LTP) observed in synapses, which are induced by the frequency of action potentials. Additionally, we successfully implement a Hebbian-like learning mechanism in a simple circuit that connects a pair of memristors to a capacitor, resulting in observed associative memory formation and forgetting processes. Our findings highlight the potential of capacitor-memristor circuits in faithfully replicating the frequency-dependent behavior of synapses, thereby offering a valuable contribution to the development of brain-inspired neural networks.

Flexible-in-rigid polycrystalline titanium nanofibers: a toughening strategy from a macro-scale to a molecular-scale.

TiO2 nanomaterials, especially one-dimensional TiO2 nanofibers fabricated by electrospinning, have received considerable attention in the past two decades, for a variety of basic applications. However, their safe use and easy recycling are still hampered by the inherently subpar mechanical performance. Here, we toughened polycrystalline TiO2 nanofibers by introducing Al3+-species at the very beginning of electrospinning. The resultant long-and-continuous TiO2 nanofibers achieved a Young's modulus of 653.8 MPa, which is ca. 25-fold higher than that of conventional TiO2 nanofibers. Within each nanofiber, amorphous Al2O3-based oxide effectively hindered the coalescence of TiO2 nanocrystals and potentially repaired the surface groves. The solid-state 17O-NMR spectra further revealed the toughening strategy on a molecular scale, where relatively flexible Ti-O-Al bonds replaced rigid O-Ti-O bonds at the interfaces of TiO2 and Al2O3. Moreover, the modified TiO2 nanofibers exhibited superb sinter-resistance, without cracking over 900 °C, which was dynamically monitored by TEM. Therefore, flexible-in-rigid TiO2 fibrous mats can be facilely folded into 3D sponges through origami art. As a potential showcase, the TiO2 sponges were demonstrated as a duarable and renewable filtrator with a high filtration efficiency of 99.97% toward PM2.5 and 99.99% toward PM10 after working for 300 min. This work provides a rational strategy to produce flexible oxide nanofibers and gives an in-depth understanding of the toughening mechanism from the macro-scale to the molecular-scale.

Hierarchical triphase diffusion photoelectrodes for photoelectrochemical gas/liquid flow conversion.

Photoelectrochemical device is a versatile platform for achieving various chemical transformations with solar energy. However, a grand challenge, originating from mass and electron transfer of triphase-reagents/products in gas phase, water/electrolyte/products in liquid phase and catalyst/photoelectrode in solid phase, largely limits its practical application. Here, we report the simulation-guided development of hierarchical triphase diffusion photoelectrodes, to improve mass transfer and ensure electron transfer for photoelectrochemical gas/liquid flow conversion. Semiconductor nanocrystals are controllably integrated within electrospun nanofiber-derived mat, overcoming inherent brittleness of semiconductors. The mechanically strong skeleton of free-standing mat, together with satisfactory photon absorption, electrical conductivity and hierarchical pores, enables the design of triphase diffusion photoelectrodes. Such a design allows photoelectrochemical gas/liquid conversion to be performed continuously in a flow cell. As a proof of concept, 16.6- and 4.0-fold enhancements are achieved for the production rate and product selectivity of methane conversion, respectively, with remarkable durability.