Titanium dioxide (TiO2) shows excellent pseudocapacitive properties. However, the low internal conductivity of TiO2 limits its use in supercapacitor applications. Therefore, an efficient surface engineering process was developed to enhance the overall pseudocapacitive performance of rutile TiO2 nanorods. Specifically, surface-engineered TiO2 nanorod arrays coordinated on carbon cloth were established through the Kapton tape-assisted hydrothermal route. X-ray diffraction analysis confirmed the formation of a tetragonal TiO2 rutile phase. Morphological analysis revealed the formation of uniform nanorods with an apparent high surface-to-volume aspect ratio. X-ray photoelectron spectroscopy analysis showed that the TiO2 synthesized in the presence of Kapton tape and annealed under air had high content of hydroxyl groups and Ti3+, which is favorable for supercapacitor performance. Surface treatment of the samples led to significantly enhanced conductivity and electrochemical behavior of TiO2. The surface-engineered TiO2 nanorod arrays show specific capacitance of about 57.62 mF/cm2 at 10 mV/s in 2 M KOH, with excellent rate capability of about 83% at 200 mV/s, and also exhibit long cycle life, retaining 91% of their original capacitance after 10,000 charge/discharge cycles, which is among the highest values reported for TiO2-based supercapacitors.
Advanced functional materials with fascinating properties and extended structural design have greatly broadened their applications. Metamaterials, exhibiting unprecedented physical properties (mechanical, electromagnetic, acoustic, etc.), are considered frontiers of physics, material science, and engineering. With the emerging 3D printing technology, the manufacturing of metamaterials becomes much more convenient. Graphene, due to its superior properties such as large surface area, superior electrical/thermal conductivity, and outstanding mechanical properties, shows promising applications to add multi-functionality into existing metamaterials for various applications. In this review, the aim is to outline the latest developments and applications of 3D printed graphene-based metamaterials. The structure design of different types of metamaterials and the fabrication strategies for 3D printed graphene-based materials are first reviewed. Then the representative explorations of 3D printed graphene-based metamaterials and multi-functionality that can be introduced with such a combination are further discussed. Subsequently, challenges and opportunities are provided, seeking to point out future directions of 3D printed graphene-based metamaterials.
Metal sulfides including MoS2 and Bi2S3 materials, have been considered as a strong candidate for supercapacitor applications. However, the short-term stability and low surface area have limited the establishment of such eco-friendly materials in energy storage. In this work, an effective strategy is designed to in-situ combine transition metal sulfides with nitrogen doped reduced graphene oxide hydrogels and improve the overall supercapattery properties. Precisely, MoS2-N-rGO and Bi2S3-N-rGO hydrogels have been developed via hydrothermal route. The morphological analysis manifests two-dimensional 2D/2D heterostructure for the MoS2-N-rGO and 1D/2D heterostructure for the Bi2S3-N-rGO. The cyclic voltammetry studies showed a battery-like electrochemical behavior for the synthesized hydrogels. The calculated capacitance for MoS2-N-rGO and Bi2S3-N-rGO are about 438 F/g and 342 F/g @ 1 A/g with 50% and 41% of their capacitance initial values @ 20 A/g, respectively. The cycling performance showed that MoS2-N-rGO and Bi2S3-N-rGO can maintain 90% and 98% of their original specific capacitance after 1000 cycles life. Furthermore, the supercapattery device was fabricated using MoS2-N-rGO as cathode and Bi2S3-N-rGO as anode. The hybrid device is capable of offering 33.4 Wh/kg energy density, at 0.85 kW/kg power density, with 44.7% retention at 20 A/g. Notably, the overall electrochemical behavior of Mo-Bi supercapattery device is remarkable among the pointed behaviors for other hybrid devices.
The present study was conducted on 9 non-medicated, clinically healthy, adult mongrel male dogs. The dogs had no orthopedic abnormalities. Dogs were subjected to mid-diaphyseal circular bone defect (0.8 cm in diameter) in the left radius bones under general anesthesia. Dogs were divided randomly to be allocated into two groups, each of 3 dogs. The treated group (group T, n = 3), in which bone defects were implanted with the titanium oxide/graphene oxide/chitosan nanocomposite. The control group (group C, n = 3), in which bone defects were allowed for spontaneous healing. Dogs were subjected to clinical and radiographical evaluation 30 days postoperatively. All surgical procedures were conducted under the effect of total intravenous anesthesia (TIVA). Digital cranio-palmar and lateral views were taken for the operated limbs. Cortical defects and depth of the bone defects were recorded using the RadiAnt DICOM viewer version 1.1.2022 software. There was a significant decrease (P < 0.05) in the cortical defect in the treated group compared with the control groups 30 days postoperatively. The treated group recorded a significant decrease (P < 0.05) in 30 days compared to the baseline value. The depth of the bone defects decreased significantly (P < 0.05) in the treated group compared with the untreated group 30 days post-induction of the bone defects. There was a significant decrease (P < 0.05) in the treated group on 30 days compared to the baseline value. The titanium oxide/graphene oxide/chitosan nanocomposite accelerates the healing of bone defects.
Benefiting from the high capacity of Zn metal anodes and intrinsic safety of aqueous electrolytes, rechargeable Zn ion batteries (ZIBs) show promising application in the post-lithium-ion period, exhibiting good safety, low cost, and high energy density. However, its commercialization still faces problems with low Coulombic efficiency and unsatisfied cycling performance due to the poor Zn/Zn2+ reversibility that occurred on the Zn anode. To improve the stability of the Zn anode, optimizing the Zn deposition behavior is an efficient way, which can enhance the subsequent striping efficiency and limit the dendrite growth. The Zn deposition is a controlled kinetics-diffusion joint process that is affected by various factors, such as the interaction between Zn2+ ions and Zn anodes, ion concentration gradient, and current distribution. In this review, from an electrochemical perspective, we first overview the factors affecting the Zn deposition behavior and summarize the modification principles. Subsequently, strategies proposed for interfacial modification and 3D structural design as well as the corresponding mechanisms are summarized. Finally, the existing challenges, perspectives on further development direction, and outlook for practical applications of ZIBs are proposed.
This study evaluated the application of chitosan/polyvinyl alcohol/graphene oxide/nano titanium oxide (CS/PVA/GO/nano TiO2) hydrogels for bone defect reconstruction in dogs. Dogs were subjected to mid-diaphyseal circular bone defects (0.8 cm2) in the radius bones. Bone defects were implanted with the hydrogel in the treated group (n = 9), while the control group were subjected to spontaneous healing (n = 9). Dogs were subjected to clinical, radiographic, and scanning electron microscopy (SEM) evaluations at 15-, 30-, and 45-days post-surgery. Dogs in the treated group recorded no lameness by the end of the third week post-surgery, while dogs in the untreated group still exhibited lameness of grade 1. There was a significant decrease (p < 0.05) in the cortical defect (mm) of the treated group (5.46 ± 0.17 and 1.45 ± 0.13) compared with the control group (7.57 ± 0.05 and 7.59 ± 0.06) at 30- and 45-days post-surgery, respectively. The depth of the bone defects (mm) decreased significantly (p < 0.05) in the treated group (2.26 ± 0.12 and 0.008 ± 0.002) compared with the untreated group (4.05 ± 0.05 and 2.16 ± 0.07) at 30- and 45-days post-surgery, respectively. Throughout the period of study, there was a significant increase (p < 0.05) in the radiographic density of the bone defects (px) in the treated group (474 ± 17.88) compared with that in the control group (619.6 ± 6.85). SEM results revealed complete closure of the bone defects in the treated group. Thus, implantation of bone defects with the CS/PVA/GO/nano TiO2 hydrogel represents a promising bone graft substitute for accelerating bone healing.
Achieving stable Zn-ion batteries operating under high charging–discharging rates and a high depth of discharge (DOD) remains challenging due to intensified dendrite growth and side reaction. This work introduces a novel hygroscopic vanadium metal–organic framework (V-MOF) as a multifunctional protective layer to achieve an outstanding Zn anode. The as-fabricated battery can remain stable and high performance with high DOD of 85.5% and fast discharging rate of 50 mAh/cm2. The hygroscopic V-MOF nature removes solvated shells and captures water as bonded/iced water within its structure, significantly suppressing side reactions. In addition, the V-MOF coating optimized the electrical field, inhibited the cracks, and reduced the Zn dendrite formation even at a high rate of 50 mAh/cm2, due to the construction of electrolyte-philic and smooth surface. Consequently, the hygroscopic Zn/V-MOF symmetrical cells achieve exceptional performance over 1000 h under 50 mA/cm2 (50 mAh/cm2) with 85.5% DOD. The Zn/V-MOF||V2O3/NC cell shows a capacity of 267 mAh/g at 0.5 A/g with excellent rate capability (100 mAh/g @20 A/g). In addition, it achieves an outstanding lifetime over 3300 cycles @ 5 A/g. The results at high rates with high DOD highlight the magnificent potential of hygroscopic V-MOF to achieve outstanding Zn anode and large-scale aqueous batteries.