3D Porous Nanostructures Research Articles

Solvothermally grown Ni4W6O21(OH)2·4H2O films with rice-like and 3D porous nanostructures and their electrochromic properties

Solvothermally grown Ni4W6O21(OH)2·4H2O films with rice-like and 3D porous nanostructures and their electrochromic properties

Enhanced photocatalytic degradation of Cr (VI) and organic pollutants using novel 3D/2D MoS2/SnS2 heterostructures for water remediation

In this study, 3D flower-like MoS2 nanostructures were synthesized using a hydrothermal technique to form heterostructures with 2D porous SnS2 nanosheets. The resulting 3D/2D MoS2/SnS2 heterostructures were evaluated for their photocatalytic abilities in removing Cr (VI), tetracycline (TC), and methylene blue (MB) under simulated solar irradiation. The results demonstrate that the MoS2/SnS2 heterostructures significantly outperformed pristine MoS2 and SnS2 in photocatalytic efficiency. Specifically, the MoS2/SnS2 photocatalysts achieved 99.9% degradation of Cr (VI) within 50 min, 96% degradation of TC in the same timeframe, and 99.9% elimination of MB in just 10 min. The reduction rate constant for Cr (VI) reduction by MoS2/SnS2 photocatalysts was 0.117 min−1, surpassing that of pure SnS2 (0.007 min−1) and MoS2 (0.0034 min−1) by 16 and 30 times, respectively. This outstanding performance is attributed to the heterojunction formation between SnS2 and MoS2, which suppresses the recombination of photogenerated charge carriers and provides abundant reactive sites due to their large specific surface area. The proposed photodegradation mechanism illustrates the facilitated migration of photogenerated charge carriers under light irradiation, enabled by the energy band alignment at the MoS2/SnS2 interface. These findings represent a significant advancement in the development of photocatalysts based on 3D flower-like MoS2 and porous SnS2 nanostructures, offering promise for applications in wastewater treatment and environmental remediation.

Conducting Polymer-Based Gel Materials: Synthesis, Morphology, Thermal Properties, and Applications in Supercapacitors.

Despite the numerous ongoing research studies in the area of conducting polymer-based electrode materials for supercapacitors, the implementation has been inadequate for commercialization. Further understanding is required for the design and synthesis of suitable materials like conducting polymer-based gels as electrode materials for supercapacitor applications. Among the polymers, conductive polymer gels (CPGs) have generated great curiosity for their use as supercapacitors, owing to their attractive qualities like integrated 3D porous nanostructures, softness features, very good conductivity, greater pseudo capacitance, and environmental friendliness. In this review, we describe the current progress on the synthesis of CPGs for supercapacitor applications along with their morphological behaviors and thermal properties. We clearly explain the synthesis approaches and related phenomena, including electrochemical approaches for supercapacitors, especially their potential applications as supercapacitors based on these materials. Focus is also given to the recent advances of CPG-based electrodes for supercapacitors, and the electrochemical performances of CP-based promising composites with CNT, graphene oxides, and metal oxides is discussed. This review may provide an extensive reference for forthcoming insights into CPG-based supercapacitors for large-scale applications.

Electrolyte solvents as architects: How solvents guide the spontaneous formation of 3D porous nanostructures in Alloy- and Conversion-type battery anodes

During battery cycling, fragmented anode materials following alloying, conversion, and conversion-alloying reactions spontaneously form three-dimensional (3D) porous nanostructures, influenced by the electrolyte solvent. While it is known that various solvents can enhance anode energy capacity, rate performance, and cycling stability by promoting this 3D structure, the specific solvent property responsible for this transformation was unclear. Our study investigates the role of 48 commercial solvents in Sn nanoparticle self-assembly, using both experimental and simulation methods. We discovered that solvent electrophilicity is crucial in initiating a solvation layer, guiding the development of the 3D nanostructure. This finding is significant in addressing anode fragmentation issues in alloying, conversion, and conversion-alloying processes. The resulting 3D nanostructures show enhanced mechanical and chemical resilience, offering a cost-effective and robust method to improve battery performance. Our research provides new insights into nanostructured anode design, paving the way for advanced battery technologies and enhancing our understanding of nanostructure formation in batteries.

Direct Laser Processing and Functionalizing PI/PDMS Composites for an On-Demand, Programmable, Recyclable Device Platform.

Skin-interfaced high-sensitive biosensing systems to detect electrophysiological and biochemical signals have shown great potential in personal health monitoring and disease management. However, the integration of 3D porous nanostructures for improved sensitivity and various functional composites for signal transduction/processing/transmission often relies on different materials and complex fabrication processes, leading to weak interfaces prone to failure upon fatigue or mechanical deformations. The integrated system also needs additional adhesive to strongly conform to the human skin, which can also cause irritation, alignment issues, and motion artifacts. This work introduces a skin-attachable, reprogrammable, multifunctional, adhesive device patch fabricated by simple and low-cost laser scribing of an adhesive composite with polyimide powders and amine-based ethoxylated polyethylenimine dispersed in the silicone elastomer. The obtained laser-induced graphene in the adhesive composite can be further selectively functionalized with conductive nanomaterials or enzymes for enhanced electrical conductivity or selective sensing of various sweat biomarkers. The possible combination of the sensors for real-time biofluid analysis and electrophysiological signal monitoring with RF energy harvesting and communication promises a standalone stretchable adhesive device platform based on the same material system and fabrication process.

Free‐Standing Bacterial Cellulose‐Templated Radiative Cooling Liquid Crystal Films with Self‐Adaptive Solar Transmittance Modulation

AbstractPassive radiative cooling materials can efficiently reflect solar radiation and spontaneously dissipate heat through the long‐wave infrared (LWIR) transmission window to the coldouter space. They are highly attractive for application in walls and roofs of sustainable energy‐efficient buildings, but it is a challenging task to develop switchable radiative coolers for transparent windows. Herein, free‐standing bacterial cellulose‐templated radiative cooling liquid crystal films with high LWIR emissivity and self‐adaptive solar transmittance are reported. Biosynthetic silanized bacterial cellulose with 3D interconnected porous nanostructure is harnessed as a robust template for confining novel liquid crystals with smectic A to chiral nematic phase transition, thereby endowing the film with high solar transmittance modulation ability. The resulting film is found to not only exhibit a remarkable LWIR emissivity, but also adaptively change its solar transmittance between a transparent state and an opaque state according to environmental temperature variation. Outdoor radiative cooling experiments are performed, and the energy‐saving performance is evaluated through a simulation of a 12‐story reference office building with the films applied as radiative cooling windows. This research can shine light on the development of advanced radiative cooling materials with switchable transmittance and their widespread applications in buildings, vehicles, and transparent photovoltaics.

Three-Dimensional Porous Indium Single-Atom Catalysts with Improved Accessibility for CO2 Reduction to Formate.

Single-atom catalysts (SACs) present substantial potential in electrocatalytic CO2 reduction reactions; however, inferior accessibility of single-atom sites to CO2 limits the overall CO2RR performances. Herein, we propose to improve the accessibility between In sites and CO2 through the construction of a three-dimensional (3D) porous indium single-atom catalyst (In1/NC-3D). The NaCl template-mediated synthesis strategy generates the unique 3D porous nanostructure of In1/NC-3D. Multiple characterizations validate that In1/NC-3D exhibits increased exposure of active sites and enhanced CO2 transport/adsorption capacity compared to the bulk In1/NC, thus improving accessibility of active sites to CO2. As a result, the In1/NC-3D presents superior CO2RR performance to the bulk In1/NC, with a partial current density of formate of 67.24 mA cm-2 at -1.41 V, relative to a reversible hydrogen electrode (vs RHE). The CO2RR performances with high formate selectivity at a large current density also outperform most reported In-based SACs. Importantly, the In1/NC-3D is demonstrated to maintain an FEformate of >82% at -66.83 mA·cm-2 over 21 h. This work highlights the design of a 3D porous single-atom catalyst for efficient CO2RR, promoting the development of advanced catalysts toward advanced energy conversion.

Simultaneous detection of SARS-CoV-2 S1 protein by using flexible electrochemical and Raman enhancing biochip

Flexible laser-scribed graphene (LSG) substrates with gold nanoislands have been developed as biochips for in situ electrochemical (EC) and surface-enhanced Raman scattering (SERS) biodetection (biomolecules and viral proteins). A flexible biochip was fabricated using CO2 laser engraving polyimide (PI) films to form a 3D porous graphene-like nanostructure. Gold nanoislands were deposited on the LSG substrates to enhance the intensity of the Raman signals. Moreover, the addition of auxiliary and reference electrodes induced a dual-function EC-SERS biochip with significantly enhanced detection sensitivity. The biochip could selectively and easily capture SARS-CoV-2 S1 protein through the SARS-CoV-2 S1 antibody immobilized on EC-SERS substrates using 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS). The grafted antibody specifically bound to SARS-CoV-2, resulting in a significant increase in the SERS signal of the target analyte. The limit of detection (LOD) of the SARS-CoV-2 S1 protein was 5 and 100 ng/mL by using EC and SERS detection, respectively. Although the LOD of the SARS-CoV-2 S1 protein detected using SERS is only 100 ng/mL, it can provide fingerprint information for identification. To improve the LOD, EC detection was integrated with SERS detection. The three-electrode detection chip enables the simultaneous detection of SERS and EC signals, which provides complementary information for target identification. The dual-functional detection technology demonstrated in this study has great potential for biomedical applications, such as the rapid and sensitive detection of SARS-CoV-2.

3D porous p-n α-Fe2O3/NiO heteronanostructure for ultrasensitive H2S gas sensor

The porous p-n heterojunction nanocomposite is an important sensing material to enhance gas sensing performance by creating a cooperative effect at the formed interface within p-n junctions. In this paper, the 3D porous p-n α-Fe2O3/NiO heterojunction nanocomposite was prepared by a simple hydrothermal method, which was built by connecting numerous α-Fe2O3/NiO composite nanorods, nanoparticles and nanosheets. The formation of p-n heterojunctions between two oxides and the 3D porous nanostructure made this material show excellent gas sensing performance for H2S gas. The response of 5α-Fe2O3/NiO heteronanostructure sensor reached 239 for 20 ppm H2S at the optimum operating temperature of 300 °C. Additionally, it presented quick response-recovery times (38/35 s), high selectivity, long-term stability and ultra-low detection limit of 0.038 ppb. As a result, our work offers a simple method for creating 3D porous p-n α-Fe2O3/NiO heteronanostructure as a potential sensing material for detecting hydrogen sulfide.

Ferrous/Ferric Ions Crosslinked Type II Collagen Multifunctional Hydrogel for Advanced Osteoarthritis Treatment.

Osteoarthritis (OA) is a highly prevalent and intricate degenerative joint disease affecting an estimated 500 million individuals worldwide. Collagen-based hydrogels have sparked immense interest in cartilage tissue engineering, but substantial challenges persist in developing biocompatible and robust crosslinking strategies, as well as improving their effectiveness against the multifaceted nature of OA. Herein, a novel discovery wherein the simple incorporation of ferrous/ferric ions enables efficient dynamic crosslinking of type II collagen, leading to the development of injectable, self-healing hydrogels with 3D interconnected porous nanostructures, is unveiled. The ferrous/ferric ions crosslinked type II collagen hydrogels demonstrate exceptional physical properties, such as significantly enhanced mechanical strength, minimal swelling ratios, and remarkable resistance to degradation, while also exhibiting extraordinary biocompatibility and bioactivity, effectively promoting cell proliferation, adhesion, and chondrogenic differentiation. Additionally, the hydrogels reveal potent anti-inflammatory effects by upregulating anti-inflammatory cytokines while downregulating pro-inflammatory cytokines. In a rat model of cartilage defects, these hydrogels exhibit impressive efficacy, substantially accelerating cartilage tissue regeneration through enhanced collagen deposition and increased proteoglycan secretion. The innovative discovery of the multifunctional role of ferrous/ferric ions in endowing type II collagen hydrogels with a myriad of beneficial properties presents exciting prospects for developing advanced biomaterials with potential applications in OA.

Self-Oxidation Resistance of the Curved Surface of Achromatic Copper.

Copper surfaces that exhibit a wide range of achromatic colors while still metallic have not been studied, despite advancements in antireflection coatings. A series of achromatic copper films grown with [111] preferred orientation by depositing three-dimensional (3D) porous nanostructures is introduced via coherent/incoherent atomic sputtering epitaxy. The porous copper nanostructures self-regulate the giant oxidation resistance by constructing a curved surface that generates a series of mono-atomic steps, followed by shrinkage of the lattice spacing of one or two surface layers. First-principles calculations confirm that these structural components cooperatively increase the energy barrier against oxygen penetration. The achromaticity of the single-crystalline porous copper films is systematically tuned by geometrical parameters such as pore size distribution and three-dimensional linkage. The optimized achromatic copper films with high oxidation resistance show an unusual switching effect between superhydrophilicity and superhydrophobicity. The tailored 3D porous nanostructures can be used for numerous applications, such as antireflection coatings, microfluidic devices, droplet tweezers, and reversible wettability switches. This article is protected by copyright. All rights reserved.

Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries.

This work investigates the root cause of failure with the ultimate anode, Li metal, when employing conventional/composite separators and/or porous anodes. Then a feasible route of utilizing Li metal is presented. Our operando and microscopy studies have unveiled that Li+ flux passing through the conventional separator is not uniform, resulting in preferential Li plating/stripping. Porous anodes alone are subject to clogging with moderate- or high-loading cathodes. Here we discovered it is necessary to seek synergy from our separator and anode pair to deliver delocalized Li+ to the anode and then uniformly plate Li metal over the large surface areas of the porous anode. Our polymer composite separator containing a solid-state electrolyte (SE) can provide numerous Li+ passages through the percolated SE and pore networks. Our finite element analysis and comparative tests disclosed the synergy between the homogeneous Li+ flux and current density reduction on the anode. Our composite separators have induced compact and uniform Li plating with robust inorganic-rich solid electrolyte interphase layers. The porous anode decreased the nucleation overpotential and interfacial contact impedance during Li plating. Full cell tests with LiFePO4 and Li[Ni0.8Mn0.1Co0.1]O2 (NMC811) exhibited remarkable cycling behaviors: ∼80% capacity retention at the 750th and 235th cycle, respectively. A high-loading NMC811 (4 mAh cm-2) full cell displayed maximum cell-level energy densities of 334 Wh kg-1 and 783 Wh L-1. This work proposes a solution for raising energy density by adopting Li metal, which could be a viable option considering only incremental advancement in conventional cathodes lately.

Electrochemically Dealloyed 3D Porous Copper Nanostructure as Anode Current Collector of Li-Metal Batteries.

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAhcm-2 and under a high current density of 10mAcm-2 . This electrochemical fabrication method is facile and scalable for mass production. Results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

Free-Standing Dendritic Nanostructured Co/CNT/Carbon Nanofiber Composites for Efficient Water Splitting in Alkaline Media

Exploring highly efficient three-dimensional (3D) nanoarchitectures for H2 and O2 evolution reaction (HER and OER) has received tremendous interest. Here, a binder-free free-standing cobalt/bamboo-shaped carbon nanotube/carbon nanofiber (Co/CNT/CNF) film was prepared based on electrospinning, followed by thermal treatment. The synergistic effect between Co cores, CNT shells (5 nm), and CNF skeletons endows the as-prepared Co/CNT/CNF with a 3D porous dendritic nanostructure. Therefore, the unique Co/CNT/CNF film demonstrates prominent HER (overpotential = 129 mV) and OER (overpotential = 162 mV) catalysis behavior at 10 mA cm–2. Meanwhile, the as-prepared Co/CNT/CNF film displays excellent overall water splitting activity as well as durability (at least 40 h both under 10 and 40 mA cm–2). Moreover, the facile electrospinning followed by the thermal treatment approach is economically practical for flexible film production, which has great potential for industrial application in water splitting technology.

Synthesis of 3D Porous Cu Nanostructures on Ag Thin Film Using Dynamic Hydrogen Bubble Template for Electrochemical Conversion of CO2 to Ethanol.

Cu-based nanomaterials have been widely considered to be promising electrocatalysts for the direct conversion of CO2 to high-value hydrocarbons. However, poor selectivity and slow kinetics have hindered the use of Cu-based catalysts for large-scale industrial applications. In this work, we report on a tunable Cu-based synthesis strategy using a dynamic hydrogen bubble template (DHBT) coupled with a sputtered Ag thin film for the electrochemical reduction of CO2 to ethanol. Remarkably, the introduction of Ag into the base of the three-dimensional (3D) Cu nanostructure induced changes in the CO2 reduction reaction (CO2RR) pathway, which resulted in the generation of ethanol with high Faradaic Efficiency (FE). This observation was further investigated through Tafel and electrochemical impedance spectroscopic analyses. The rational design of the electrocatalyst was shown to promote the spillover of formed CO intermediates from the Ag sites to the 3D porous Cu nanostructure for further reduction to C2 products. Finally, challenges toward the development of multi-metallic electrocatalysts for the direct catalysis of CO2 to hydrocarbons were elucidated, and future perspectives were highlighted.

Super‐Amphiphilic Na2Ti3O7 Nanofibrous Film Enabling Water–Oil Miscibility (Adv. Mater. Interfaces 32/2022)

Flexible Super-Amphiphilic Film In article number 2201445, Conghu Hu, Licheng Hua, Jianke Dua, and colleagues describe a flexible Na2Ti3O7 (NTO) film composed of numerous nanofibrous into 3D porous nanostructures with super-amphiphilic properties that enable water and oil miscibility. The film has a high absorption capacity for water and poly-alpha-olefin (PAO) up to 32–36 times its weight. The absorption capacity of the NTO film for water-PAO miscibility can keep at ≈ 22 g g−1 after 20 cyclic applications.

Electrochemically Dealloyed 3D Porous Copper Nanostructure As High-Performance Anode Current Collector of Li-Metal Batteries

Li metal anode is the ultimate choice for Li batteries owning to its highest theoretical capacity (3806 mAh/g) and lowest redox potential (-3.04 V vs. standard hydrogen electrode) among possible candidates.[1] However, despite the advantages of Li metal anodes, a number of remaining challenges must be addressed before its commercialization: undesired dendrite growth of Li, and irreversible parasitic reactions between Li and electrolyte, etc.Stabilization of Li metal is essential for commercial application of Li metal anodes. In the past few years, several strategies have been developed to suppress Li dendrite growth and stabilize SEI formation during Li plating/stripping processes. Among these strategies, 3D current collectors showed its high potential in Li anode stabilization due to its much larger surface area, which can provide much more Li nucleation sites, alleviate volumetric changes of Li anode, and decrease practical current density. Thus, compared to flat Cu foil used in commercial Li-ion batteries, 3D Cu current collectors can facilitate uniform Li deposition, mitigate Li dendrite growth, and enhance Li cycling stability.[2]Our previous work reported a 3D porous Cu current collector fabricated via a facile one-step electrodeposition method directly on commercial Cu foil. [3] The fabricated 3D porous Cu current collector showed stable long-term cycling with a high areal capacity of 6 mAh/cm2 and no Li dendrite growth was observed during cycling process. However, for the one-step electrodeposition method, the thickness of the porous Cu deposition layer is limited. Thus, preparation of 3D porous Cu layers with both high thickness and high porosity is necessary to further improve the areal capacity of this current collector. Recently, we developed a new two-step electrochemical process to fabricate thick and porous Cu layer: a thick Cu-Zn alloy was first electrodeposited on commercial Cu foil, and Zn was then removed electrochemically, leaving a thick and highly porous 3D Cu layer. Compared to our previous method, this 3D Cu layer has a high thickness of ~14 um and porosity of ~72%. This new 3D Cu current collector can achieve stable Li cycling up to 230 h at high areal capacity of ~10 mAh/cm2 at a high current density of 10 mA/cm2, demonstrated its high commercial application potential in Li-metal batteries. Tarascon, J.M. and M. Armand, Issues and challenges facing rechargeable lithium batteries. Nature, 2001. 414(6861): p. 359-367.Yang, C.P., et al., Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nature Communications, 2015. 6.Ma, X., Z. Liu, and H. Chen, Facile and scalable electrodeposition of copper current collectors for high-performance Li-metal batteries. Nano Energy, 2019. 59: p. 500-507.

Super‐Amphiphilic Na2Ti3O7 Nanofibrous Film Enabling Water–Oil Miscibility

AbstractDue to their extraordinary affinity for both water and oil, super‐amphiphilic materials have garnered considerable interest. A Na2Ti3O7 (NTO) film with super‐amphiphilic properties that enable water and oil miscibility is offered. Multiple nanofibrous 3D porous nanostructures compose the super‐amphiphilic NTO layer. Up to 32–36 times its weight, the film has a high absorption capacity for water and poly‐alpha‐olefin (PAO). The average miscibility ratio of water to oil in the film is ≈6:5. The discovery of NTO nanofibrous film's super‐amphiphilic behavior has significant implications for the development of superwetting materials and their potential applications in the oil emulsion purification and catalyst anchoring industries.

Three-dimensional porous PtCu as highly efficient electrocatalysts for methanol oxidation reaction

Exploring affordable, durable, and effective electrocatalysts for methanol oxidation reaction (MOR) is of great importance to the industrial application of direct methanol fuel cells. Herein, a three-dimensional (3D) porous PtCu catalyst is synthesized by a facile and effective galvanic replacement method, which exhibits high activity and durability for MOR. The modulated electronic and strain effects of the Pt atoms are verified by extensive characterizations, and the mass and specific activities of the prepared catalyst are roughly 3.8 and 9.9 times higher than those of the commercial Pt/C catalysts, respectively. The robust activity of the prepared catalyst is probably owing to the optimized affination between Pt and the adsorbed poisoning species (mainly CO) induced by the electronic and strain effects of the Pt, as well as the unique 3D porous nanostructure.

Atomically Dispersed Fe-N5 Sites Anchored on 3D N-Doped Porous Carbon for Efficient Selective Oxidation of Aromatic Alkanes at Room Temperature.

On account of the increasing demand for aromatic ketones and the challenging task of mass production in the chemical industry, efficient and sustainable catalysts are urgently needed to catalyze the conversion of aromatic alkyl compounds into high value-added products via the activation of C-H bonds. Herein, Fe single-site atoms anchored on a N-doped three-dimensional (3D) porous carbon nanostructure (Fe-MEG-800) synthesized through the self-assembly hydrothermal method are reported. Detailed characterization analyses, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM), are employed to prove the isolated single Fe atom dispersing on the carbon nanostructure, along with X-ray absorption spectroscopy (XAS) and Mössbauer spectroscopy analysis confirming the Fe-N5 coordination structure. Furthermore, the 3D cross-linked structure not only provides an abundant open-framework structure for the mass transfer during the reaction but also facilitates the exposure of more active sites and promotes the reaction procedure. The as-prepared catalyst possesses high catalytic activity toward the C-H bond at room temperature. In the model reaction of oxidizing ethylbenzene (EB) to high-value acetophenone (AcPO), the conversion and the selectivity of the reaction are both over 99%. In addition, the catalyst also presents favorable stability with retaining high performance even after eight cycles. The possible adsorption sites of the reactant and oxidant are explored through density functional theory (DFT) calculations. Based on the analysis of experimental and theoretical results, a possible mechanism for the oxidation of EB to AcPO involving •OH, O2•-, and 1O2 is also proposed.