3D Porous Network Research Articles

3D interconnected honeycomb-like ginkgo nut-derived porous carbon decorated with β-cyclodextrin for ultrasensitive detection of methyl parathion

A novel and economical approach was proposed for synthesizing the β-cyclodextrin (β-CD) embellished ginkgo nut-derived porous carbon (GNDPC) with three-dimensional (3D) interconnected honeycomb-like morphology, which was employed to decorate the glassy carbon electrode (GCE) for the construction of methyl parathion (MP) electrochemical sensor (GNDPC@β-CD/GCE) for the first time. GNDPC with higher surface area possessed good adsorptive capacity and superior conductive property because of 3D interconnected honeycomb-like porous carbon network. β-CD improved the dispersibility of GNDPC and enhanced the molecular recognition and accumulation capability of GNDPC towards MP. The synergetic cooperation of β-CD and GNDPC realized the ultrasensitive detection property of MP (Limit of detection: 4.52 nM; Concentration: 0.005–15 μM). The constructed GNDPC@ β-CD/GCE displayed good MP determination feasibility in apple and pear juices (Recovery rate: 95.8–100.1%; Relative standard deviation: 2.12–4.17). This work exhibits a novel approach for the sensitive determination of MP in foods.

Accelerating redox kinetics by ZIF-67 derived amorphous cobalt phosphide electrocatalyst for high-performance lithium-sulfur batteries

The feasibility of the commercialization of lithium-sulfur (Li-S) batteries is troubled by sluggish redox conversion kinetics and the shuttle effect of polysulfides. Herein, a zeolitic imidazolate framework derived amorphous CoP combined with carbon nanotubes conductive network composites (aCoP@CNTs) has been synthesized as an effective dual-electrocatalyst for accelerating the redox kinetics of polysulfides to prolong the lifespan of Li-S batteries. Compared with crystalline CoP, unsaturated Co atoms of aCoP@CNTs exhibit stronger chemical adsorption capacity for polysulfides and serve as catalytic centers to accelerate the conversion from soluble polysulfides to solid-state lithium sulfide. Meanwhile, the 3D porous conductive network not only facilitates ion/electron transportation but also forms a physical barrier to limit the migration of polysulfides. Benefiting from the above preponderances, the batteries with aCoP@CNTs modified interlayer exhibited excellent cycle stability (initial discharge capacity of 1227.9 mAh g-1 at 0.2 C), rate performance (795.9 mAh g-1 at 2.5 C), long-term cycle reliability (decay rate of 0.049% per cycle at 1 C over 1000 cycles), and superior high-loading performance (high initial discharge capacity of 886 mAh g-1 and 753.6 mAh g-1 at 1 C under high S loading of 3 mg cm-2 and 4 mg cm-2).

Fluorine and phosphorus atoms cooperated on an N-doped 3D porous carbon network for enhanced ORR performance toward the zinc–air batteries

A three-dimensional N-doped porous carbon nanosheet catalyst cooperated by fluorine and phosphorus atoms was prepared in this work, which showed high oxygen reduction performance in 0.1 M KOH and a power density of 138 mW cm−2 in zinc–air battery.

Construction of three-dimensional hierarchical porous nitrogen-doped reduced graphene oxide/hollow cobalt ferrite composite aerogels toward highly efficient electromagnetic wave absorption

• NRGO/hollow CoFe 2 O 4 composite aerogels were constructed by a facile two-step route. • The prepared composite aerogels showed a 3D hierarchical porous network structure. • EM absorbing capacity was regulated by the ferrite structure and addition amounts. • Strong absorption, wide bandwidth, thin thickness and low loading were achieved. • The potential EM dissipation mechanism of attained composite aerogels was proposed. The development of graphene-based composites with low density, robust absorption, wide bandwidth and thin thickness remained a great challenge in the field of electromagnetic (EM) absorption. In this work, nitrogen-doped reduced graphene oxide/hollow cobalt ferrite (NRGO/hollow CoFe 2 O 4 ) composite aerogels were constructed by a solvothermal and hydrothermal two-step route. Results demonstrated that the as-fabricated composite aerogels had the ultralow density and a unique three-dimensional (3D) network structure, and lots of hollow CoFe 2 O 4 microspheres were almost homogeneously distributed on the wrinkled surfaces of lamellar NRGO. Moreover, superior EM absorbing capacity could be achieved by modulating the ferrite structure, addition amounts of hollow CoFe 2 O 4 and thicknesses. It was noteworthy that the NRGO/hollow CoFe 2 O 4 composite aerogel with the addition amount of ferrite of 15.0 mg possessed the minimum reflection loss of -44.7 dB and maximum absorption bandwidth of 5.2 GHz (from 12.6 to 17.8 GHz) at a very thin thickness of 1.8 mm and filling ratio of 15.0 wt.%. Furthermore, the possible EM attenuation mechanism had been proposed. The results of this work would be helpful for developing RGO-based 3D composites as lightweight, thin and highly efficient EM wave absorbers.

Modular metallotecton for engineering permanently porous frameworks: supernumerary role of ancillary ion.

The formation of robust supramolecular frameworks built from hetero-polytopic metal complexes and interacting with different ancillary ions remains a long-standing and underexplored desire. Herein, the secondary sphere interaction chemistry of [Ru(5-oxido-6-hydroxy-1,10-phenanthroline)a(5,6-dihydroxy-1,10-phenanthroline)(3-a)]-(a-2) (1) (a = 1, 3) coordination ion is reported, where the π-conjugated phenanthroline ligands are functionalized with catecholate groups used as H-bond donors and ligands. The deprotonation of the catechols is found to control the overall charge stoichiometry in 1, acting as a metallotecton to interact with anions of different basicity (Cl- in 1.Cl and Br- in 1.Br) as well as with Li+ cations (in 1.Li+). These interactions lead to the formation of 2D porous honeycomb networks without any significant alteration in the molecular packing. This implies that the self-assembly process is controlled by complementary intermolecular non-covalent interactions making the choice of the ancillary ion insignificant. The robust porous structure of the frameworks is established by uptake of D2O and I2 molecules within the microporous channels. This work demonstrates that supramolecular frameworks appear as flexible candidates for applications in gas sorption, separation and chemical sensing.

Achieving desirable charge transport by porous frame engineering for superior 3D printed rechargeable Ni-Zn alkaline batteries.

Rechargeable 3D printed batteries with extraordinary electrochemical potential are typical contenders as one of the promising energy storage systems. Low-cost, high-safety, and excellent rechargeable aqueous alkaline batteries have drawn extensive interest. But their practical applications are severely hampered by poor charge carrier transfer and limited electrochemical activity at high loading. Herein, we report a unique structure-based engineering strategy in 3D porous frames using a feasible 3D printing technique and achieve 3D printed full battery devices with outstanding electrochemical performance. By offering a 3D porous network to provide prominently stereoscopic support and optimize the pore structure of electrodes, the overall charge carrier transport of engineered 3D printed Ni-Zn alkaline batteries (E3DP-NZABs) is greatly enhanced, which is directly demonstrated through a single-wired characterization platform. The obtained E3DP-NZABs deliver a high areal capacity of 0.34 mA h cm-2 at 1.2 mA cm-2, and an outstanding capacity retention of 96.2% after 1500 cycles is also exhibited with an optimal electrode design. Particularly, parameter changes such as a decrease in pore sizes and an increase in 3D network thickness are favorable to resultant electrochemical performance. This work may represent a vital step to promote the practical application progress of alkaline batteries.

Aramid-based aerogels for driving water evaporation through both photo-thermal and electro-thermal effects

In this work, a 3D porous network water evaporator of ANF/CNT/PPy aerogel was prepared by freeze-drying and in situ polymerization of PPy, with high evaporation rate based on the photo-electro-thermal effect.

Combined Thermosensitive Gel Co-Loaded with Dermaseptin-PP and PTX Liposomes for Effective Local Chemotherapy.

Chemotherapeutic drugs are often ineffective due to the delivery. Local chemotherapy, which has high drug concentration, low systemic toxicity, and long duration, has shown excellent potential. Cationic antimicrobial peptides have been proved to enhance the tumor cells' uptake of chemotherapeutic drugs through the membrane-breaking effect. In this study, we designed and developed a thermosensitive gel co-loaded with Dermaseptin-PP and paclitaxel liposomes to increase local chemotherapy. The paclitaxel liposomes were prepared. Then, it was co-loaded with Dermaseptin-PP in a poloxamer-based thermosensitive gel to obtain Dermaseptin-PP/paclitaxel liposomes gel. The thermosensitivity of gels was investigated by test tube inversion method. The rheology was tested by rheometer. The in vitro cytotoxicity and the permeation in tumor of gels were examined by H157 cells and the 3D cell model, respectively. The retention in tumor and antitumor activity of gels were evaluated by H157 tumor-bearing nude mice. The particle size of paclitaxel liposomes was 148.97 ± 0.21 nm. The encapsulation rate was 86.1%, and the drug loading capacity was 19.4%. The gels had slow-release and temperature-sensitive properties. The porous 3D network structure of the gels could ensure that the drug was fixed into the tumor. In vitro and in vivo distribution studies showed that Dermaseptin-PP promoted the permeation of the gels in H157 multicellular tumor spheres and achieved longer retention in tumor. In vitro and in vivo antitumor studies demonstrated that Dermaseptin-PP/paclitaxel liposomes gel significantly inhibited the growth of tumors for local chemotherapy with good biosafety. This study provided a promising nanomedicine platform for combining antimicrobial peptides and chemotherapeutic drugs for local chemotherapy.

Myocardial injection of thermosensitive HADOPA/Ca-FVI/Alg hydrogels improves cardiac repair after myocardial infarction

Myocardial infarction (MI) is a common heart emergency that potentially causes death. Injectable hydrogels with excellent malleability and filling properties are suitable for myocardial injection and can avoid the need for open surgery. In this study, dopamine grafted hyaluronic acid (HADOPA) was synthesized and combined with sodium alginate (Alg) and Ca2+-loaded liposomes (Ca-FVI) to prepare a series of injectable thermosensitive sodium hyaluronate/sodium alginate hydrogels (HADOPA/Ca-FVI/Alg). At 37 °C, the HADOPA/Ca-FVI/Alg solution rapidly changed from liquid to hydrogel because of the crosslinking between sodium alginate and the Ca2+ released from Ca-FVI at a phase transition time of 100–200 s. The HADOPA/Ca-FVI/Alg scaffolds exhibited a porous 3D network structure, controlled porosity, and connected pore properties. Increasing the proportion of HADOPA increases the elasticity and absorbance of hydrogels. Experimental assessment showed that the hydrogels have good biocompatibility and that Alg1-HADOPA is more conducive to the adhesion, proliferation, and spreading of mouse cardiac myocytes while maintaining the best cell state. These findings suggest that HADOPA/Ca-FVI/Alg hydrogels improve cell proliferation and tissue repair, and that they are a promising therapeutic option for cardiac repair after MI.

Progress in Research and Application of Graphene Aerogel-A Bibliometric Analysis.

In recent years, graphene aerogel (GA) has been widely used as a 3D porous stable network structure material. In order to identify the main research direction of GA, we use the bibliometric method to analyze its hot research fields and applications from the Web of Science database. First, we collected all relevant literature and analyzed its bibliometrics of publication year, country, institution, etc., where we found that China and Chinese Academy of Sciences are the most productive country and institute, respectively. Then, the three hot fields of fabrication, energy storage, and environmental protection are identified and thoroughly discussed. Graphene aerogel composite electrodes have achieved very efficient storage capacity and charge/discharge stability, especially in the field of electrochemical energy storage. Finally, the current challenges and the future development trends are presented in the conclusion. This paper provides a new perspective to explore and promote the related development of GA.

Three-dimensional MOF-derived host with surface-preferred and spatial-selective effect for dendrite-free lithium metal battery

The large-scale applications of lithium metal batteries (LMBs) are still impeded by the unsatisfactory electrochemical performance of Li metal anode associated with the infinite volumetric change and the uncontrollable Li dendrite growth. Herein, free-standing and robust nitrogen-doped 3D porous carbon nanofibers networks embedded with Zn-carbon hybrid nanocages are obtained as stable hosts for guiding uniform Li nucleation and accommodating volume expansion. Benefiting from the reduced local current density and abundant lithiophilic sites with low nucleation barriers, the as-prepared NCNFs-Zn-CCs electrode can achieve a low overpotential of 20 mV at 3 mA cm−2 and a stable Li plating/stripping process for 3200 h were achieved in symmetric cells. This work opens a new avenue to explore and broaden the applications of lithiophilic carbon materials in next-generation lithium metal batteries with excellent cycling stability and rate performance.

Porous network of ultrathin V6O13-polyoxometalates nanosheets grown on carbon cloth as anode materials for high-performance lithium-ion batteries

Polyoxometalates (POM) have a wide range of applications in electrochemistry, catalysis, and energy storage due to their variable structure and nature. Here, we designed a novel 3D porous network of ultrathin V6O13-POM nanosheets on carbon cloth (V6O13-POM//CC) for the first time by one-pot hydrothermal method with the help of phosphotungstic acid. Serving as inorganic ligands, the anions of phosphotungstic acid coordinate with V cations, facilitating the assembly of nanoclusters and guiding to control of the morphology of V6O13-POM composites, which increases the specific surface area and multiple active sites for the reaction of lithium ions batteries (LIBs). Furthermore, the synergistic effect of V6O13 and POM improves the stability of the structure and increases the capacity of the electrode in LIBs. V6O13-POM//CC as an anode material exhibited a high reversible capacity of 2.03 mAh cm-2 at a high current density of 2 mA cm-2 after 120 cycles. To illustrate the generality of the synthesis strategy, we also obtained MoO3-POM//CC via a similar method. By using V6O13-POM//CC and MoO3-POM//CC as the anode materials, LIBs exhibited high reversible areal specific capacity and excellent cycling stability which are expected to achieve commercial applications.

Micron SiOx encapsulated into amorphous B, N Co-doped carbon nanotube network for high-capacity and long-durable Li-ion half/full batteries

Micron silicon suboxide (m-SiOx) with low-cost and advantageous capacity has been proposed as a prospective candidate for lithium-ion battery anodes, yet huge volumetric fluctuation and poor inherent conductivity should be addressed urgently. Herein, encapsulation of m-SiOx particles into amorphous B, N co-doped carbon nanotube network (SSBCN) via metal cation-assisted carbonization is shown. Rational preparation process enables in-situ synthesis of 3D porous carbon nanotubes network around m-SiOx, guaranteeing slight volume variation during cycling, effective electrical contact, fast electron and Li-ion transfer and speedy electrolyte penetration. In-situ Raman spectra confirm the additional utilization rate of m-SiOx. Heteroatomic active sites (Sn, N, B) further enhance lithium storage capacity. As anodes in half batteries, the SSBCN exhibits ultrahigh reversible capacities of 2072.8 mAh/g at 0.1 A/g, excellent rate performance of 501.8 mAh/g at 10 A/g and prominent long-term cycle stability of 400 and 1000 cycles at 1 and 5 A/g, respectively. Moreover, SSBCN//LiFePO4 (LFP) full batteries also display remarkable cycle durability with a 92.72% capacity retention after 600 cycles at 1C. This work outperforms most of the recently reported SiOx-based anodes and renders a new opportunity of m-SiOx in high-performance LIBs.

In situ growth Zn2GeO4 nanorods network on 3D conductive foam as free standing electrode for sodium-ion batteries

• Zn 2 GeO 4 nanorods were anchored on nickel foam as a binder free anode for SIBs. • Zn 2 GeO 4 @NF anode shows 3D interlinked porous network structure. • The Zn 2 GeO 4 @NF showed excellent electrochemical sodium storage performances. Large-scale energy storage and scarcity of lithium bring exploration interest of high-performance anode materials for sodium-ion batteries (SIBs). Herein, Zn 2 GeO 4 nanorods was anchored directly on nickel foam to form a free standing, binder free anode for SIBs, though a facile hydrothermal method. Benefiting from composite effect of nanorod network structure, conductive network and mechanical stability, the Zn 2 GeO 4 @NF reaches an initial discharge capacity of 882.0 mAh g -1 and maintains a capacity of 435.6 mAh g -1 after 400 cycles at 0.1A g -1 . At a higher current density (2 A g -1 ) Zn 2 GeO 4 @NF also delivers a reversible discharge capacity of 239.7 mAh g -1 , which is higher than that for the Zn 2 GeO 4 particles.

Ultralight Hierarchically Structured RGO Composite Aerogels Embedded with MnO2/Ti3C2Tx for Efficient Microwave Absorption.

Although intensive efforts have been devoted to fabricating Ti3C2Tx MXene composites for microwave absorption, it remains a great challenge to achieve excellent MA performance at low loading and thin thickness. Herein, a three-dimensional (3D) lightweight hierarchically structured MnO2/Ti3C2Tx/RGO composite aerogel with abundant heterointerfaces was fabricated via a hydrothermal and chemical reduction self-assembly method. The RGO aerogel embedded with laminated MnO2/Ti3C2Tx provides a lot of heterogeneous interfaces, 3D porous interconnected conductive networks, and reasonable combination of various loss materials for rich interfacial polarization, conductivity loss, multiple reflections and scattering, and good impedance matching. Benefiting from the synergy of different loss mechanisms, the maximum reflection loss (RL) is up to -66.5 dB (>99.9999% energy absorption) at only 10 wt % loading and 2.0 mm thickness, and even at only 1.5 mm thickness, the maximum RL value remains at -36 dB (>99.9% energy absorption). The work provides a promising route to construct 3D hierarchically heterogeneous composite aerogels for efficient MA at thin thickness and low loading.

A new strategy to minimize humidity influences on acoustic wave ultraviolet sensors using ZnO nanowires wrapped with hydrophobic silica nanoparticles

Surface acoustic wave (SAW) technology has been widely developed for ultraviolet (UV) detection due to its advantages of miniaturization, portability, potential to be integrated with microelectronics, and passive/wireless capabilities. To enhance UV sensitivity, nanowires (NWs), such as ZnO, are often applied to enhance SAW-based UV detection due to their highly porous and interconnected 3D network structures and good UV sensitivity. However, ZnO NWs are normally hydrophilic, and thus, changes in environmental parameters such as humidity will significantly influence the detection precision and sensitivity of SAW-based UV sensors. To solve this issue, in this work, we proposed a new strategy using ZnO NWs wrapped with hydrophobic silica nanoparticles as the effective sensing layer. Analysis of the distribution and chemical bonds of these hydrophobic silica nanoparticles showed that numerous C-F bonds (which are hydrophobic) were found on the surface of the sensitive layer, which effectively blocked the adsorption of water molecules onto the ZnO NWs. This new sensing layer design minimizes the influence of humidity on the ZnO NW-based UV sensor within the relative humidity range of 10–70%. The sensor showed a UV sensitivity of 9.53 ppm (mW/cm2)−1, with high linearity (R2 value of 0.99904), small hysteresis (<1.65%) and good repeatability. This work solves the long-term dilemma of ZnO NW-based sensors, which are often sensitive to humidity changes.

High thermal conductive shape-stabilized phase change materials based on water-borne polyurethane/boron nitride aerogel

Phase change materials (PCMs) applied in energy storage and temperature control system are important for energy conservation and environmental protection. In this work, structure-adjustable water-borne polyurethane (WPU)/boron nitride (BN) aerogels were synthesized via directional freeze-drying method, and used as supporting scaffolds to confine paraffin wax (PW) and obtain composite phase change materials. The three-dimensional (3D) porous thermal conductivity network of BN was derived by the in-situ ice crystal mound in aerogel, which endows the PW/WPU/BN composite PCM-2.5 with high thermal conductivity (0.96 W m−1 K−1) and high energy storage density (140.04 J/g). Shape-stabilized PCMs with high thermal conductivity and excellent electrical insulation prepared by the simple method have great potential for the thermal management of electronic products.

Synthesis and formation mechanism of PANI nanotubes prepared via facile aqueous solution polymerization

Polyaniline nanotubes were fabricated using itaconic acid as dopant and soft template via facile aqueous solution polymerization. On basis of scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR), the influence of polymerization conditions such as oxidizer/aniline molar ratio and oxidizer concentration on the morphology and chemical structure of PANI was studied. Polyaniline nanotubes with 3D porous network structure were successfully prepared under the optimal conditions. The formation mechanism of PANI nanotubes was thoroughly analyzed by the measurements such as transmission electron microscopy (TEM), 1H nuclear magnetic resonance (NMR), the diffusion ordered spectroscopy (DOSY) and relaxation time (T1 H) measurements. Itaconic acid micelles were used as "soft template" to form self-assembled polyaniline nanostructures. Meanwhile, in the micelles composed of aniline and itaconic acid, the aniline cations initiated by oxidizer free radicals were polymerized into polyaniline with the structure of nanotubes. Furthermore, the formation of polyaniline nanotubes was guaranteed by the double electric layer structure.

Interface and Structure Engineering of Tin‐Based Chalcogenide Anodes for Durable and Fast‐Charging Sodium Ion Batteries

AbstractTransition metal dichalcogenides with high theoretical capacity usually suffer from poor intrinsic electronic conductivity and drastic volumetric change upon cycling, degrading their attractiveness for electrochemical high‐power and long‐term applications. Herein, a high‐efficiency and extensible synthetic strategy for in situ encapsulating nanostructured SnSe0.5S0.5 into N‐doped graphene (SnSe0.5S0.5 @ NG) by robust interfacial CSeSn bonds with formation of 3D porous network nanohybrids, is reported. Systematic electrochemical studies indicate that interface and structure engineering on SnSe0.5S0.5, including defects implantation, chemical bonding interaction, and nanospace confinement design, endow it with robust structural stability, ultrafast Na+ storage kinetics, and highly reversible redox reaction. In addition, the introduction of foreign Se ligand not only facilitates the transport of electrons/ions by enhancing the conductivity and decreasing the diffusion energy barrier but also generates more reactivity sites, as demonstrated by density functional theory calculations. By virtue of these superiorities, the SnSe0.5S0.5 @ NG exhibits superior sodium storage performance with high‐rate capability and long durability over 2000 cycles at 2 A g−1. Impressively, the full battery, when coupling SnSe0.5S0.5 @ NG anode with Na3V2(PO4)3/C cathode, can deliver high energy density of 213 Wh kg−1. This work provides an effective structural engineering strategy to design advanced electrode material with potential application for sodium‐ion batteries.

A graphene-based porous composite hydrogel for efficient heavy metal ions removal from wastewater

A graphene-enhanced supramolecular hydrogel containing poly(acrylic acid)(PAA) and poly(4-vinylpyridine) (P4VP) was fabricated for the wastewater remediation. In this work, P4VP brushes were grown from functionalized graphene oxide (GO) through surface-initiated atom transfer radical polymerization. Then, the P4VP-grafted GO (i.e., GO-g-P4VP) was integrated into PAA matrix to form GO-g-P4VP@PAA hydrogel as a highly efficient adsorbent for extraction of toxic metal ions from wastewater. Due to the introduction of GO-g-P4VP, the GO-g-P4VP@PAA composite hydrogel exhibited good compressive strength, and a special interconnected 3D porous network was formed in the hydrogel. The effect of pH, initial heavy metal ion concentration, contact time, and adsorbent dosage regarding the adsorption capacity and removal efficiency of Pb2+ and Cd2+ on the hydrogel was examined. Under appropriate conditions, the GO-g-P4VP@PAA hydrogel can achieve maximum adsorption capacities of 257.28 mg/g for Pb2+, 175.79 mg/g for Cd2+. The adsorption kinetics of Pb2+ and Cd2+ on the GO-g-P4VP@PAA hydrogel followed a pseudo-second order model and the adsorption isotherms were more consistent with the Langmuir isotherm model. In addition, the GO-g-P4VP@PAA hydrogel exhibited good reusability. After five cycles, the removal efficiency of both Pb2+ and Cd2+ still remained above 80 %. These results demonstrate the GO-g-P4VP@PAA hydrogel serves as a desirable adsorbent in removal of heavy metal cations from wastewater.