Free-standing Materials Research Articles

Attenuation of flexural phonons in free-standing crystalline two-dimensional materials

Attenuation of flexural phonons in free-standing crystalline two-dimensional materials

A System Built for Both Deterministic Transfer Processes and Contact Photolithography

A home‐built compact system that functions as both a transfer stage for deterministic transfer processes and a mask aligner for contact photolithography, is constructed. The precision translation sample stage and optical microscope are shared between the two modes. In the transfer mode, assisted by either an adhesive or a heating element, the setup has been used to deterministically transfer freestanding semiconductors, 2D materials, and van der Waals electrodes. When configured in photolithography mode, the proposed instrument has been employed to fabricate various microscale patterns and devices, with minimum feature sizes of 1–2 μm achieved. The prototype instrument provides a feasible solution for performing high‐quality deterministic transfer and photolithography processes on one single tool in‐house.

Encapsulation hierarchical bimetallic oxide with flexible electrospinning carbon nanofibers for efficient capacitive deionization

Water scarcity, an intensifying issue, has spurred extensive research into the development of sophisticated freestanding pseudocapacitive electrode materials. Characterized by their precise morphology, intricate mechanics, and superior desalination capabilities, these materials are revolutionizing water treatment technologies. However, their broad adoption is hampered by complex fabrication processes and the necessity for various unique components. Herein, the paper introduces a streamlined method combining electrospinning and carbonization to produce a freestanding nitrogen-doped carbon nanofiber encapsulating manganese cobalt oxide (MCO) nanoparticles for desalination purposes. The approach significantly enhances interfacial interactions, mitigates volume shifts during sodium ion adsorption and desorption, and strengthens interfacial stability. Benefiting from its structural and compositional merits, the optimal MCO-1.0 electrode showcases exceptional electrochemical attributes. It achieves an impressive desalination efficiency (34.68 mg g−1), swift capacitive deionization rate (0.58 mg g−1 min−1), and superior cyclic durability. The study enhances our understanding of freestanding carbon fibers encapsulated with metal oxide nanoparticles, a key step toward developing robust electrodes for industrial applications.

A rigid free-standing supercapacitor electrode material made from fat coal-based activated carbon foam

A free-standing electrode material is a competitive candidate for supercapacitor due to its excellent capacity and volumetric energy density. Currently, most of the studies are focused on the preparations and performances of flexible free-standing electrode materials, whereas few on the development of rigid free-standing electrode materials. Herein, a vitrinite concentrate of fat coal is used as a raw material and carbon black as an addition agent to prepare a carbon foam by way of high-pressure pyrolysis. The prepared carbon foam is activated by KOH solution to further achieve an activated carbon foam by which we have fabricated a rigid free-standing electrode material. The assembled symmetric device with the rigid free-standing electrode material demonstrates an extremely high areal specific capacitance of 2304.41 mF cm−2 at 4 mA cm−2, an outstanding cycling stability of 100 % after 40 000 cycles, and an excellent volume energy density of 10.23 mWh cm−3 at 31.78 mW cm−3. These fascinating electrochemical performances of the electrode material are attributed to unique 3D interconnected porous structure of the activated carbon foam. The micron-sized 3D interconnected pores facilitate the transport of electrolyte ions within the electrodes. Meanwhile, micropores on the 3D interconnected pore wall provide abundant active sites for electrolyte ions.

Electrospun Core–Shell Carbon Nanofibers as Free-Standing Anode Materials for Sodium-Ion Batteries

Electrospun Core–Shell Carbon Nanofibers as Free-Standing Anode Materials for Sodium-Ion Batteries

3D-Continuous Nanoporous Covalent Framework Membrane Nanoreactors with Quantitatively Loaded Ultrafine Pd Nanocatalysts.

The confinement effect of catalytic nanoreactors containing metal catalysts within nanometer-sized volumes has attracted significant attention for their potential to enhance reaction rate and selectivity. Nevertheless, unregulated catalyst loading, aggregation, leaching, and limited reusability remain obstacles to achieving an efficient nanoreactor. A robust and durable catalytic membrane nanoreactor prepared by incorporating palladium nanocatalysts within a 3D-continuous nanoporous covalent framework membrane is presented. The reduction of palladium precursor occurs on the pore surface within 3D nanochannels, producing ultrafine palladium nanoparticles (Pd NPs) with their number density adjustable by varying metal precursor concentrations. The precise catalyst loading enables controlling the catalytic activity of the reactor while preventing excess metal usage. The facile preparation of Pd NP-loaded free-standing membrane materials allows hydrodechlorination in both batch and continuous flow modes. In batch mode, the catalytic activity is proportional to the loaded Pd amount and membrane area, while the membrane retains its activity upon repeated use. In continuous mode, the conversion remains above 95% for over 100h, with the reactant solution passing through a single 50µm-thick Pd-loaded membrane. The efficient nanoporous film-type catalytic nanoreactor may find applications in catalytic reactions for small chemical devices as well as in conventional chemistry and processes.

Work-function-prompted interfacial charge kinetics in hierarchical heterojunction flexible electrode for efficient capacitive deionization

The growing challenge of water scarcity has spurred extensive research into the development of advanced freestanding pseudocapacitive electrode materials. These electrodes, characterized by their controlled morphology, mechanical complexity, and enhanced desalination capabilities, are advancing water treatment technologies. Additionally, electrodes with interfacially influenced heterostructures demonstrate substantial potential to enhance electrochemical kinetics. However, their widespread adoption is hindered by intricate synthesis procedures and the necessity for multiple discrete components. Herein, the report introduces a cohesive approach that utilizes electrospinning and carbonization to create a freestanding, hierarchically porous nitrogen-doped carbon nanofiber network encapsulating FeNi3 alloy (FeNi3@CNFs) for desalination applications. The method enhances the interfacial effect, mitigates volume changes during sodium ion adsorption and desorption, and improves interfacial stability. By capitalizing on structural and compositional advantages, the novel FeNi3@CNFs electrode delivers outstanding electrochemical properties, including a high desalination capacity (46.47 mg g−1 at 1.2 V), rapid desalination rate (0.77 mg g−1 min−1), and enhanced cyclic durability. Computational analysis via Density Functional Theory shows that the work function prompts a surface charge redistribution at the FeNi3@CNFs heterojunction, optimizing the surface electronic structure and reducing the energy barrier for adsorption. The modification significantly boosts the diffusion kinetics of sodium adsorption. The study delineates a comprehensive methodology for fabricating high-performance heterostructured electrode materials that are effective for capacitive deionization.

Free-standing ultra-thin carbon nanofiber films with controllable thickness for lithium ion batteries

Thin and porous anode materials enable short ion migration distances and high-rate performance. However, the current freestanding anode materials are too thick (typically around 100 μm) for high-rate lithium ion batteries (LIBs). Here, we have developed a facile and scalable process to synthesize ultra-thin (<400 nm) freestanding films. In comparison to other chemical and physical deposition methods that yield thin films (<500 nm), our freestanding films do not require the substrate material, achieving a 100 % loading of active material. Our ultra-thin carbon nanofiber films exhibit an exceptional specific capacity of 599 mAh/g even after 10,000 cycles at a current density of 10 A/g. Compared to thick carbon nanofiber films, the utilization of ultra-thin carbon nanofiber films as anode materials exhibits a remarkable enhancement of more than tenfold in cycling performance

Solvent-free conversion of CO2 in carbonates through a sustainable macroporous catalyst

The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO2 capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (1H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br−, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO2 capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.

An innovative approach to characterize the elastic moduli of 2D materials from the central strain of bulged membrane

Freestanding 2D materials are essentially under the adhesive boundary condition instead of the typically assumed clamped boundary condition, and the membrane deformation in pressure bulge testing is actually similar as that of the slack membrane. A new bulge testing model of freestanding 2D materials is proposed from the central strain of the bulged membrane under a given pressure, based upon which the elastic moduli of 2D materials can be properly characterized by an easy testing approach. In this approach, instead of using a complex pressure loading and measuring system, the 2D materials mounted on the substrate with circular holes are simply placed into the vacuum chamber, and the moduli of materials can be characterized from their central strain measured via Raman spectroscopy. In addition, finite element modeling (FEM) is employed to validate the effectiveness of the model proposed in the present work. The present approach can provide a useful guideline on effectively characterizing the elastic moduli of 2D materials via a very simple approach, based upon which the elastic moduli can be characterized via a new technique, like Raman spectroscopy.

Hierarchical modulation of extracellular electron transfer processes in microbial fuel cell anodes for enhanced power output through improved Geobacter adhesion

Although microbial fuel cell (MFC) technology is nearing practical realization, the challenge of attaining higher power output continues to impede its widespread implementation. In this study, we successfully developed free-standing three-dimensional high-performance anode materials for MFCs using a straightforward "one-step" process based on garlic. The resulting anode not only promotes the accumulation of biomass and the enrichment of exoelectrogen Geobacter but also facilitates interfacial extracellular electron transfer. This led to rapid start-up within just three days, a robust power density of 12.37 W/m3, and an impressive 24.04 % coulombic efficiency in mixed-culture MFC reactors. Our investigation into the underlying mechanisms of exocellular electron transfer revealed improvements in both direct electron transfer and mediated electron transfer processes. Notably, the fabrication of carbonized garlic MFC anodes proves to be technically competitive and economically relevant. It not only paves the way for the development of high-performance MFCs but also provides valuable insights for the rational design of materials related to microbial electrochemical technologies.

Charge exchange of slow highly charged ions from an electron beam ion trap with surfaces and 2D materials

Abstract Electron beam ion traps allow studies of slow highly charged ion transmission through freestanding 2D materials as an universal testbed for surface science under extreme conditions. Here we review recent studies on charge exchange of highly charged ions in 2D materials. Since the interaction time with these atomically thin materials is limited to only a few femtoseconds, an indirect timing information will be gained. We will therefore discuss the interaction separated in three participating time regimes: energy deposition (charge exchange), energy release (secondary particle emission), and energy retention (material modification).

Efficient and Homogenous Precipitation of Sulfur Within a 3D Electrospun Heterocatalytic Rutile/Anatase TiO2-x Framework in Lithium–Sulfur Batteries

AbstractLithium–sulfur (Li–S) batteries can potentially outperform state-of-the-art lithium-ion batteries, but their further development is hindered by challenges, such as poor electrical conductivity of sulfur and lithium sulfide, shuttle phenomena of lithium polysulfides, and uneven distribution of solid reaction products. Herein, free-standing carbon nanofibers embedded with oxygen-deficient titanium dioxide nanoparticles (TiO2-x/CNFs) has been fabricated by a facile electrospinning method, which can support active electrode materials without the need for conductive carbon and binders. By carefully controlling the calcination temperature, a mixed phase of rutile and anatase was achieved in the TiO2-x nanoparticles. The hybridization of anatase/rutile TiO2-x and the oxygen vacancy in TiO2-x play a crucial role in enhancing the conversion kinetics of lithium polysulfides (LiPSs), mitigating the shuttle effect of LiPSs, and enhancing the overall efficiency of the Li–S battery system. Additionally, the free-standing TiO2-x/CNFs facilitate uniform deposition of reaction products during cycling, as confirmed by synchrotron X-ray imaging. As a result of these advantageous features, the TiO2-x/CNFs-based cathode demonstrates an initial specific discharge capacity of 787.4 mAh g−1 at 0.5 C in the Li–S coin cells, and a final specific discharge capacity of 584.0 mAh g−1 after 300 cycles. Furthermore, soft-packaged Li–S pouch cells were constructed using the TiO2-x/CNFs-based cathode, exhibiting excellent mechanical properties at different bending states. This study presents an innovative approach to developing free-standing sulfur host materials that are well suited for flexible Li–S batteries as well as for various other energy applications. Graphical Abstract

Enhanced sensitivity and tunability of thermomechanical resonance near the buckling bifurcation

The high susceptibility of ultrathin two-dimensional (2D) material resonators to force and temperature makes them ideal systems for sensing applications and exploring thermomechanical coupling. Although the dynamics of these systems at high stress has been thoroughly investigated, their behavior near the buckling transition has received less attention. Here, we demonstrate that the force sensitivity and frequency tunability of 2D material resonators are significantly enhanced near the buckling bifurcation. This bifurcation is triggered by compressive displacement that we induce via thermal expansion of the devices, while measuring their dynamics via an optomechanical technique. We understand the frequency tuning of the devices through a mechanical buckling model, which allows to extract the central deflection and boundary compressive displacement of the membrane. Surprisingly, we obtain a remarkable enhancement of up to 14× the vibration amplitude attributed to a very low stiffness of the membrane at the buckling transition, as well as a high frequency tunability by temperature of more than 4.02 % K−1. The presented results provide insights into the effects of buckling on the dynamics of free-standing 2D materials and thereby open up opportunities for the realization of 2D resonant sensors with buckling-enhanced sensitivity.

Valorization of mixed plastics waste for the synthesis of flexible superhydrophobic films

Superhydrophobic surfaces are typically created by enhancing nanoscale roughness or incorporating anti-wetting additives like silanes, nanoparticles, or fluorinated compounds. Limited by the availability of nano-structured templates, simple fabrication, flexibility of the material, and cost-effectiveness, the quest to synthesize superhydrophobic films remains challenging. Herein, we report the valorizing of mixed plastic waste for the synthesis of flexible superhydrophobic films via open-loop recycling. We focused on improving the nanoscale surface roughness of the material by using a series of steps including selective dissolution, thermally induced phase separation, controlled spin-casting, and annealing. We synthesized a two-layered superhydrophobic film with high surface roughness and sufficient mechanical strength, making it suitable for use as a free-standing material. The contact and sliding angles were found to be 159° and 4°, respectively, with an RMS (root mean square) surface roughness of 228 nm. This approach is demonstrated with mixtures of high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP), which are among the most abundant components of post-consumer plastic waste. Life cycle assessments show that synthesized superhydrophobic films have lower carbon dioxide emissions and embodied energy than virgin PE and PP derived from petroleum. Our design strategy not only yields a superhydrophobic product but also provides an alternative to plastic waste recycling by bypassing cost-intensive sorting techniques.Graphical

Organic Faradaic Desalination Cell Based on Polyimide Symmetric Electrodes

Capacitive deionization (CDI) is an energy-efficient and environmentally friendly deionization technology. However, the maximum desalination capacity of conventional carbon-based CDI systems is in the range of 5–25 mg g-1, which compromises the use of this technology in practical applications [1]. Faradaic deionization (FDI) is a promising electrochemical technique, based on storing the ions within the particles/layers of the electrode materials either by intercalation and/or faradic reactions. By this mechanism, FDI has expanded the deionization values above 50 mg g-1. In the last ten years, research on FDI has primarily focused on battery electrode materials, especially in inorganic intercalation compounds, typically used for energy storage [2]. However, inorganic materials have several drawbacks, such as decomposition and dissolution issues, which affect long-term performance along with safety and sustainability aspects and consequently might limit their practical deployment.As an alternative, we introduce in this work for the first time an all-polymer deionization cell in combination with a rocking-chair desalination (RCD) mechanism with the aim of boosting the deionization performance [3]. A proof-of-concept next generation technology is accomplished by using a redox-active naphthalene-polyimide (poly[N,N′-(ethane-1,2-diyl)-1,4,5,8-naphthalenetetracarboxiimide], named as PNDIE), which is a well conductive and free-standing electrode material, as anode and cathode in a symmetric FDI system. Our approach relies on the synergistic combination of smart redox polymer selection i.e. PNDIE, and the advance configuration of this material into a buckypaper electrode architecture. A detailed electrochemical characterization under various operational conditions in three electrodes standard half-cell and in two electrode coin-cell configurations was performed. The results of those experiments provide critical information to build an all-polymer rocking chair system with practical PNDIE electrodes (92.2 mgPNDIE; 9.6 cm2). This novel FDI lab-cell demonstrated a remarkable desalination capacity (155.4 mg g-1 at 0.01 A g-1) together with a high salt-removal rate and productivity (3.42 mg g-1 min-1 at 0.01 A g-1 and 62 L h-1 m-2, respectively). In addition, long-term stability experiments provided salt adsorption capacity retention values over 95 % after 100 cycles (23 days). Compared to the state-of-the-art deionization technologies (CDI, Hybrid CDI and FDI) the reported technique exhibits superior electrochemical and deionization performance. These results support the idea of using organic materials as a viable alternative for robust and sustainable “water-energy” electrochemical applications.

Electrochemical-driven removal of organic dyes by using bimetallic MOFs /waste cellulose acetate derived carbon foam as a freestanding electrode material

Converting the solid waste into high-value products were significant to environmental protection and resources saving. Waste cigarette filters, were made of cellulose acetate, a common kind of solid waste in daily life. In this work, waste cigarette filters were used as cellulose precursors and decorated with bimetallic MOFs to fabricate a light-weight, monolithic and porous carbon foam. The specific surface area and pore size of as-prepared carbon foams can be regulated through changing the mass ratio of ZIF-8 to ZIF-67. Importantly, as-prepared samples exhibited good electrochemical performances when accessed a great balance between the surface area and conductivity. The sample of C/Zn/Co-0.5:0.5 exhibited an excellent electrosorption capacity for methylene blue, which was high up to 2847 mg g−1. Moreover, it had a superior stability, and the removal efficiency for methylene blue remained above 90 % after 5 cycles. Thus, this study successfully realized the conversion of waste cigarette filters into porous materials, which can be regarded as an effective and economic adsorbent used in wastewater treatment.

Freestanding, flexible and interfused V2O5 nanowire/rGO composite fiber nonwoven fabric for high-capacity binder-free aqueous zinc-ion batteries

Aqueous zinc-ion batteries (ZIBs) have emerged as a promising alternative to traditional lithium-ion batteries due to their high safety, environmental friendliness, and cost-effectiveness, as well as their high theoretical capacity. However, developing freestanding cathodes with excellent electrochemical performance, including high specific capacity and energy density, still faces significant challenges. Herein, we present a freestanding, flexible, and interfused V2O5 nanowire/reduced graphene oxide (rGO) composite fiber nonwoven fabric for the cathode of aqueous ZIBs via a novel wet-spinning and wet-fusing assembly strategy. The resulting V2O5 nanowire/rGO composite fiber nonwoven fabric can be directly utilized as the cathode for aqueous ZIBs, demonstrating outstanding electrochemical performance, including high specific capacity (402.5 mAh g−1 at 0.1 A g−1), energy density (286.3 Wh kg−1 at 71.4 W kg−1), excellent rate capability, and long cycling life (4000 cycles). This study provides new insights into the development of high-performance flexible freestanding electrode materials for ZIBs

Fabrication, microstructure and optical properties of 〈110〉 textured CVD polycrystalline diamond infrared materials

The fabrication of “bulk” diamond materials with high transmittance and enough thickness was essential for application as infrared windows. The present work reported the preparation, microstructure and optical properties of polycrystalline diamond materials by MPCVD method using ultralow nitrogen doping (0–80 ppm). The effects of nitrogen concentration and synthesis temperature on the crystalline quality, microstructure, and infrared transmittance were systematically studied by XRD/Raman, SEM/TEM, and UV–VIS/FTIR spectrophotometer, respectively. The results showed that nitrogen doping with appropriate concentration could promote the formation of texture with strong <110> plane orientation, and the growth rate was significantly enhanced without obvious reduction in the optical quality. The freestanding diamond materials fabricated at the nitrogen concentration (10–20 ppm) had high <110> texture degree, enough thickness (>0.7 mm), fast growth rates (~3–6 μm/h), and peak transmittance of ~70.1 % in the infrared band (3.0–15.0 μm). The nitrogen doped diamonds fabricated by this process had excellent performance which showing potential applications as infrared windows for ultrahigh-speed aircrafts.

Sustainably flexible and free-standing organic carbonyl potassium salt with continuous conductive network as high-performance anode in K-ion batteries

Developing suitable electrode materials with high flexibility, superior cyclic performance and low-cost have been the new topic and difficulty in the up-coming wearable flexible device. Herein, organic potassium terephthalate (K2TP) with MWCNTs and conductive polymer PEDOT:PSS co-coated K2TP/2MWCNTs/PP composite endowing continuous conductive network, was initially developed as a pliable and free-standing anode material for potassium ion batteries. By analyzing the internal microstructure, external topography and varies electrochemical characterization of the prepared samples, the incorporation of reasonable MWCNTs and PEDOT:PSS allows for the construction of a continuous conductive network with a large specific surface area, the creation of an effective electron transfer channel, an improvement in the kinetics of K+ diffusion and the maintenance of structural integrality. A preeminent specific capacity of 154.3 mAh g−1 can be maintained after 100 cycles at the current density of 50 mA g−1, prevailing over the majority of claimed anode materials employed in K-ion batteries. Furthermore, a high-performance all-organic full battery based on flexible anode and cathode material was successfully assembled delivering an extraordinary energy density of 320 Wh Kg−1. These results can put forward the practical application of organic electrode materials in systems for massive-scale energy storage.