Tuning the shell thickness of N-doped interconnected hollow carbon sphere for the electrochemical sensing of antibiotic drug chloramphenicol.

N-doped hollow carbon spheres (NHCSs) with different shell thicknesses are constructed using various amounts of SiO2 precursor. An interconnected framework with diminished wall thickness ensures an efficient and continuous electron transport which helps to enhance the performance of NHCS. Improvement of the electrocatalytic performance was shown in the determination of antibiotic drug chloramphenicol (CAP) due to the unique hollow thin shell morphology, ample defect sites, accessible surface area, higher surface-to-volume ratio and an synergistic effect. Boosted electrocatalytic activity of 1.5 N-doped HCS (1.5 NHCS) was applied to detect CAP with a linear range and detection limit of 1-1150 µM and 0.098 µM (n = 3), respectively, with superior storage stability and considerable sensitivity. These results suggest that the proposed work can be successfully applied to the determination of CAP in milk and water samples.

Synthesis of Graphdiyne Hollow Spheres and Multiwalled Nanotubes and Applications in Water Purification and Raman Sensing.

Controlling the structure of graphdiyne (GDY) is crucial for the discovery of new properties and the development of new applications. Herein, the microemulsion synthesis of GDY hollow spheres (HSs) and multiwalled nanotubes composed of ultrathin nanosheets is reported for the first time. The formation of an oil-in-water (O/W) microemulsion is found to be a key factor controlling the growth of GDY. These GDY HSs have fully exposed surfaces because of the avoidance of overlapping between nanosheets, thereby showing an ultrahigh specific surface area of 1246 m2 g-1 and potential applications in the fields of water purification and Raman sensing.

Enhanced Visible-Light Photocatalytic Activity of Bismuth Ferrite Hollow Spheres Synthesized via Evaporation-Induced Self-Assembly.

Semiconductor hollow spheres have garnered significant attention in recent years due to their unique structural properties and enhanced surface area, which are advantageous for various applications in catalysis, energy storage, and sensing. The present study explores the surfactant-assisted synthesis of bismuth ferrite (BiFeO3) hollow spheres, emphasizing their enhanced visible-light photocatalytic activity. Utilizing a novel, facile, two-step evaporation-induced self-assembly (EISA) approach, monodisperse BiFeO3 hollow spheres were synthesized with a narrow particle size distribution. The synthesis involved Bi/Fe citrate complexes as precursors and the triblock copolymer Pluronic P123 as a soft template. The BiFeO3 hollow spheres demonstrated outstanding photocatalytic performance in degrading the emerging pollutants Rhodamine B and metronidazole under visible-light irradiation (100% degradation of Rhodamine B in <140 min and of metronidazole in 240 min). The active species in the photocatalytic process were identified through trapping experiments, providing crucial insights into the mechanisms and efficiency of semiconductor hollow spheres. The findings suggest that the unique structural features of BiFeO3 hollow spheres, combined with their excellent optical properties, make them promising candidates for photocatalytic applications.

ZnO-CeO2 Hollow Nanospheres for Selective Determination of Dopamine and Uric Acid.

ZnO-CeO2 hollow nanospheres have been successfully synthesized via the hard templating method, in which CeO2 is used as the support skeleton to avoid ZnO agglomeration. The synthesized ZnO-CeO2 hollow nanospheres possess a large electrochemically active area and high electron transfer owing to the high specific surface area and synergistic effect of ZnO and CeO2. Due to the above advantages, the resulting ZnO-CeO2 hollow spheres display high sensitivities of 1122.86 µA mM-1 cm-2 and 908.53 µA mM-1 cm-2 under a neutral environment for the selective detection of dopamine and uric acid. The constructed electrochemical sensor shows excellent selectivity, stability and recovery for the selective analysis of dopamine and uric acid in actual samples. This study provides a valuable strategy for the synthesis of ZnO-CeO2 hollow nanospheres via the hard templating method as electrocatalysts for the selective detection of dopamine and uric acid.

Alloying-Induced Synthesis of Amorphous PdZnS Hollow Spheres as Enhanced Oxygen Reduction Catalysts.

Amorphous alloys have multiple advantages in electrocatalysis, yet the isotropic nature makes their syntheses a great obstacle in application. In this work, it is shown that the Zn2+ can interfere with the crystallization of Pd-base structures to form amorphous alloy materials. By simply adjusting the Zn2+ content, unique PdZnS amorphous hollow spheres (AHS) with various compositions and degrees of crystallinity can be obtained through a facile one-pot wet chemical method. Owing to both the amorphous nature and hollow morphologies, the PdZnS AHSs possess appealing activities and stabilities as oxygen reduction catalysts. Typically, the Pd20 ZnS10 AHSs exhibit the highest half-wave potential (E1/2 ) of 0.940 V (vs reversible hydrogen electrode), and such E1/2 only negatively shifts 25 mV after 60 000 cycles.

Hydrothermal Synthesis of Bismuth Ferrite Hollow Spheres with Enhanced Visible-Light Photocatalytic Activity.

In recent years, semiconductor hollow spheres have gained much attention due to their unique combination of morphological, chemical, and physico-chemical properties. In this work, we report for the first time the synthesis of BiFeO3 hollow spheres by a facile hydrothermal treatment method. The mechanism of formation of pure phase BiFeO3 hollow spheres is investigated systematically by variation of synthetic parameters such as temperature and time, ratio and amount of precursors, pressure, and calcination procedures. The samples were characterized by X-ray powder diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and UV-vis diffuse reflectance spectroscopy. We observe that the purity and morphology of the synthesized materials are very sensitive to synthesis parameters. In general, the chemically and morphologically very robust hollow spheres have diameters in the range of 200 nm to 2 µm and a wall thickness of 50-200 nm. The synthesized BiFeO3 hollow spheres were applied as catalysts in the photodegradation of the model pollutant Rhodamine B under visible-light irradiation. Notably, the photocatalyst demonstrated exceptionally high removal efficiencies leading to complete degradation of the dye in less than 150 min at neutral pH. The superior efficiencies of the synthesized material are attributed to the unique features of hollow spheres. The active species in the photocatalytic process have been identified by trapping experiments.

Core-Shell Structured C@SiO2 Hollow Spheres Decorated with Nickel Nanoparticles as Anode Materials for Lithium-Ion Batteries.

Silicon oxide is regarded as a promising anode material for lithium-ion batteries owing to high theoretical capacity, abundant reserve, and environmental friendliness. Large volumetric variations during the discharging/charging and intrinsically poor electrical conductivity, however, severely hinder its application. Herein, a core-shell structured composite is constructed by hollow carbon spheres and SiO2 nanosheets decorated with nickel nanoparticles (Ni-SiO2 /C HS). Hollow carbon spheres, as mesoporous cores, not only significantly facilitate the electron transfer but also prominently enhance the mechanical robustness of anode materials, which separately improves the rate performance and the cyclic durability. Besides, ultrathin SiO2 nanosheets, as hierarchical shells, provide abundant electrochemical active surface for capacity increment. Moreover, nickel nanoparticles boost the transport capacity of electrons in SiO2 nanosheets. Such a unique architecture of Ni-SiO2 /C HS guarantees an enhanced discharge capacity (712 mAh g-1 at 0.1 A g-1 ) and prolonged cyclic durability (352 mAh g-1 at 1.0 A g-1 after 500 cycles). The present work offers a possibility for silica-based anode materials in the application of next-generation lithium-ion batteries.

Multi-layered nano-hollow spheres for efficient electromagnetic wave absorption.

Ferrite nano-hollow spheres (NHS) are of great significance to improve electromagnetic (EM) wave absorption performance. Herein, the deposition of dielectric SiO2and ferrimagnetic CoFe2O4(CFO) layers on MnFe2O4(MnFO) NHS are found as an effective strategy to enhance EM wave attenuation. EM wave absorption properties of as-synthesized bare and bi-layered samples are investigated within a widely-used frequency range of 1-17 GHz. MnFO@CFO bi-layered NHSs exhibit an excellent reflection loss (RL) of -47.0 dB at only 20 wt% filler content with an effective broad bandwidth (BW) of ∼2.2 GHz (frequency region for RL < -10 dB). The attenuation constant is observed to increase from 191.6 Np m-1to 457.8 Np m-1for bare MnFO and MnFO@CFO NHSs respectively. Larger interfacial area, additional pairs of dipole, higher magnetic anisotropy, internal reflections and scattering from NHSs are responsible for superior absorption properties of MnFO@CFO NHSs. Moreover, the best impedance matching,∣Zin/Z0∣ âˆ¼ 1, promotes the optimum RL in MnFO@CFO at 5.96 GHz. MnFO@SiO2bi-layered NHSs result in a sufficiently high RL âˆ¼ -30.0 dB with a composite absorber of a thickness of only 3 mm. Analysis from theλ/4 model for best matching thickness (tm) displays a good agreement between experimental and simulatedtmvalues. This study demonstrates optimized MnFO@CFO NHS as a highly promising low-cost and lightweight EM wave absorber suitable for practical high-frequency applications.

Design of Multi-Shelled Hollow Cr2 O3 Spheres for Metabolic Fingerprinting.

Schizophrenia (SZ) detection enables effective treatment to improve the clinical outcome, but objective and reliable SZ diagnostics are still limited. An ideal diagnosis of SZ suited for robust clinical screening must address detection throughput, low invasiveness, and diagnosis accuracy. Herein, we built a multi-shelled hollow Cr2 O3 spheres (MHCSs) assisted laser desorption/ionization mass spectrometry (LDI MS) platform for the direct metabolic profiling of biofluids towards SZ diagnostics. The MHCSs displayed strong light absorption for enhanced ionization and microscale surface roughness with stability for the effective LDI of metabolites. We profiled urine and serum metabolites (≈1 µL) with the enhanced LDI efficacy in seconds. We discriminated SZ patients (SZs) from healthy controls (HCs) with the highest area under the curve (AUC) value of 1.000 for the blind test. We identified four compounds with optimal diagnostic power as a simplified metabolite panel for SZ and demonstrated the metabolite quantification for clinic use. Our approach accelerates the growth of new platforms toward a precision diagnosis in the near future.

Construction of Co-Mn Prussian Blue Analog Hollow Spheres for Efficient Aqueous Zn-ion Batteries.

Prussian blue analogs (PBAs) are considered as reliable and promising cathode materials for aqueous Zn-ion batteries (AZIBs), but they suffer from low capacity and poor cycling stability due to insufficient active sites and structural damage caused by the ion insertion/extraction processes. Herein, a template-engaged ion exchange approach has been developed for the synthesis of Co-substituted Mn-rich PBA hollow spheres (CoMn-PBA HSs) as cathode materials for AZIBs. Benefiting from the multiple advantageous features including hollow structure, abundant active sites, fast Zn2+ ion diffusion, and partial Co substitution, the CoMn-PBA HSs electrode shows efficient zinc ion storage properties in terms of high capacity, decent rate capability and prolonged cycle life.

Mo2 C/C Hierarchical Double-Shelled Hollow Spheres as Sulfur Host for Advanced Li-S Batteries.

One of the major challenges regarding the sulfur cathode of Li-S batteries is to achieve high sulfur loading, fast Li ions transfer, and the suppression of lithium polysulfides (LiPSs) shuttling. This issue can be solved by the development of molybdenum carbide decorated N-doped carbon hierarchical double-shelled hollow spheres (Mo2 C/C HDS-HSs). The mesoporous thick inner shell and the central void of the HDS-HSs achieve high sulfur loading, facilitate the ion/electrolyte penetration, and accelerate charge transfer. The microporous thin outer shell suppresses LiPSs shuttling and reduces the charge/mass diffusion distance. The double-shelled hollow structure accommodates the volume expansion during lithiation. Furthermore, Mo2 C/C composition renders the HDS-HSs cathode with improved conductivity, enhanced affinity to LiPSs, and accelerated kinetics of LiPSs conversion. The structural and compositional advantages render the Mo2 C/C/S HDS-HSs electrode with high specific capacity, excellent rate capability, and ultra-long cycling stability in the composed Li-S batteries.

Graphitic Carbon Nitride Stabilizers Meet Microfluidics: From Stable Emulsions to Photoinduced Synthesis of Hollow Polymer Spheres.

Graphitic carbon nitride (g-CN) has been utilized as a heterogeneous catalyst, but is usually not very well dispersible. The amphiphilic character of g-CN can be altered by surface modifications of g-CN nanopowders. Introducing hydrophilicity or hydrophobicity is a promising avenue for producing advanced emulsion systems. In this study, a special surface-modified g-CN is used to form stable Pickering emulsions. Using a PDMS-based microfluidic device designed for stable production of both single and double emulsions, it is shown that surface-modified g-CNs allow the manufacture of unconventionally stable and precise Pickering emulsions. Shell thickness of the double emulsions is varied to emphasize the robustness of the device and also to demonstrate the extraordinary stabilization brought by the surface-modified carbon nitride used in this study. Due to the electrostatic stabilization also in the oil phase, double emulsions are centered. Finally, when produced from polymerizable styrene, hollow polymer microparticles are formed with precise and tunable sizes, where g-CN is utilized as the only stabilizer and photoinitiator.

One-Pot Fabrication of Pd Nanoparticles@Covalent-Organic-Framework-Derived Hollow Polyamine Spheres as a Synergistic Catalyst for Tandem Catalysis.

Facile fabrication of nanocatalysts consisting of metal nanoparticles (NPs) anchored on a functional support is highly desirable, yet remains challenging. Covalent organic frameworks (COFs) provide an emerging materials platform for structural control and functional design. Here, a facile one-pot in situ reduction approach is demonstrated for the encapsulation of small Pd NPs into the shell of COF-derived hollow polyamine spheres (Pd@H-PPA). In the one-pot synthetic process, the nucleation and growth of Pd NPs in the cavities of the porous shell take place simultaneously with the reduction of imine linkages to secondary amine groups. Pd@H-PPA shows a significantly enhanced catalytic activity and recyclability in the tandem dehydrogenation of ammonia borane and selective hydrogenation of nitroarenes through an adsorption-activation-reaction mechanism. The strong interactions of the secondary amine linkage with borane and nitroarene molecules afford a positive synergy to promote the catalytic reaction. Moreover, the hierarchical structure of Pd@H-PPA allows the accessibility of active Pd NPs to reactants.

The A818-6 system as an in-vitro model for studying the role of the transportome in pancreatic cancer.

BACKGROUND: The human pancreatic cancer cell line A818-6 can be grown in vitro either as a highly malignant, undifferentiated monolayer (ML) or as three-dimensional (3D) single layer hollow spheres (HS) simulating a benign, highly differentiated, duct-like pancreatic epithelial structure. This characteristic allowing A818-6 cells to switch from one phenotype to another makes these cells a unique system to characterize the cellular and molecular modifications during differentiation on one hand and malignant transformation on the other hand. Ion channels and transport proteins (transportome) have been implicated in malignant transformation. Therefore, the current study aimed to analyse the transportome gene expression profile in the A818-6 cells growing as a monolayer or as hollow spheres. METHODS & RESULTS: The study identified the differentially expressed transportome genes in both cellular states of A818-6 using Agilent and Nanostring arrays and some targets were validated via immunoblotting. Additionally, these results were compared to a tissue Affymetrix microarray analysis of pancreatic adenocarcinoma patients' tissues. The overall transcriptional profile of the ML and HS cells confirmed the formerly described mesenchymal features of ML and epithelial nature of HS which was further verified via high expression of E-cadherin and low expression of vimentin found in HS in comparison to ML. Among the predicted features between HS and ML was the involvement of miRNA-9 in this switch. Importantly, the bioinformatics analysis also revealed substantial number (n = 126) of altered transportome genes. Interestingly, three genes upregulated in PDAC tissue samples (GJB2, GJB5 and SLC38A6) were found to be also upregulated in ML and 3 down-regulated transportome genes (KCNQ1, TRPV6 and SLC4A) were also reduced in ML. CONCLUSION: This reversible HS/ML in vitro system might help in understanding the pathophysiological impact of the transportome in the dedifferentiation process in pancreatic carcinogenesis. Furthermore, the HS/ML model represents a novel system for studying the role of the transportome during the switch from a more benign, differentiated (HS) to a highly malignant, undifferentiated (ML) phenotype.

Multishelled Transition Metal-Based Microspheres: Synthesis and Applications for Batteries and Supercapacitors.

With the rapid growth of material innovations, multishelled hollow nanostructures are of tremendous interest due to their unique structural features and attractive physicochemical properties. Continued effort has been made in the geometric manipulation, composition complexity, and construction diversity of this material, expanding its applications. Energy storage technology has benefited from the large surface area, short transport path, and excellent buffering ability of the nanostructures. In this work, the general synthesis of multishelled hollow structures, especially with architecture versatility, is summarized. A wealth of attractive properties is also discussed for a wide area of potential applications based on energy storage systems, including Li-ion/Na-ion batteries, supercapacitors, and Li-S batteries. Finally, the emerging challenges and outlook for multishelled hollow structures are mentioned.

Uniform Mesoporous Anatase Hollow Spheres: An Unexpectedly Efficient Fabrication Process and Enhanced Performance in Photocatalytic Hydrogen Evolution.

Uniform mesoporous anatase hollow spheres with high crystallinity have been fabricated by an efficient method, in which biocompatible ethanedioic acid acts as the chelating agent during the Ostwald ripening process. The combination of high crystallinity, large surface area, and mesoporosity leads to an excellent photocatalytic activity. In solar water splitting, the hollow spheres exhibit remarkably enhanced photocatalytic performance that is 1.4 times of P25.

Metal-Organic Framework Derived Hierarchical Co/C@V2 O3 Hollow Spheres as a Thin, Lightweight, and High-Efficiency Electromagnetic Wave Absorber.

Developing high-efficiency electromagnetic (EM) wave absorbing materials with light weight, thin thickness, and wide absorption bandwidth is highly desirable for ever-developing electronic and telecommunication devices. Herein, hierarchical metal-organic framework (MOF)-derived Co/C@V2 O3 hollow spheres were designed and synthesized through a facile hydrothermal, precipitation, and pyrolysis method. The composite exhibits both excellent impedance matching and light weight due to the rational combination of hollow V2 O3 spheres and porous Co/C. Additionally, multiple components enable a large dielectric and magnetic loss of the composite, giving rise to enhanced EM wave absorption performance with a maximum reflection loss (RL) of -40.1 dB and a broad effective absorption bandwidth (RL < -10 dB) of 4.64 GHz at a small thickness of 1.5 mm. This work provides insights into the design of hierarchical hollow and porous composites as thin and lightweight EM wave absorbers with efficient absorption, which can also be extended to energy storage, catalysis, and sensing.

Enhanced resistive acetone sensing by using hollow spherical composites prepared from MoO3 and In2O3.

Hollow sphere composites were synthesized by a template-free hydrothermal method from MoO3 and In2O3. The spheres have a typical size of 800 ± 50 nm and were characterized by XRD, FESEM, TEM, XPS. Gas sensors based on samples with different Mo/In composite ratios were fabricated and their gas sensing properties were studied. The results show that a Mo:In ratio of 1:1 in the composite gives the highest response, typically at a working temperature of 250 °C. The response increases to 38 when exposed to 100 ppm acetone at 250 °C. This is 13.6 times better than when using pure MoO3. The sensor shows improved selectivity, response, repeatability and long-term stability. Typical features include a large specific surface area, and high levels of chemisorbed oxygen and defective oxygen sites. The N-N heterojunction theory was used to explain the improvement of gas sensing performance. Graphical abstract Schematic presentation of MoO3 and In2O3 composites and response test graph for 100 ppm acetone. The sensor based on this composite exhibits a very high response (38) to acetone at 250 °C and very fast response time (2 s).

A General Strategy for the Synthesis of PtM (M=Fe, Co, Ni) Decorated Three-Dimensional Hollow Graphene Nanospheres for Efficient Methanol Electrooxidation.

A universal sacrificial template-based synthesis strategy was reported to prepare three dimensional (3D) reduced oxide graphene supported PtM (M=Fe, Co, Ni) hollow nanospheres (PtM/RGO HNSs). The inner 3D wrinkle-free graphene skeleton can promote electron and ion kinetics, resulting in enhancement for the permeation of small organic molecule in fuel cells. As inspired by this, the 3D PtM (M=Fe, Co, Ni)/RGO HNSs exhibit clearly enhanced electrocatalytic activity and durability towards the methanol oxidation reaction (MOR) in acidic medium compared with a commercial Pt/C catalyst. This study provides a versatile approach of realizing controlled synthesis of 3D graphene-metal hybrid nanostructures irrespective of the components of the metal domains, and will pave the way for the design of hetero-nanostructures with optimized morphologies and functions.

Hierarchical TiO2 /SnO2 Hollow Spheres Coated with Graphitized Carbon for High-Performance Electrochemical Li-Ion Storage.

A self-templated strategy is developed to fabricate hierarchical TiO2 /SnO2 hollow spheres coated with graphitized carbon (HTSO/GC-HSs) by combined sol-gel processes with hydrothermal treatment and calcination. The as-prepared mesoporous HTSO/GC-HSs present an approximate yolk-double-shell structure, with high specific area and small nanocrystals of TiO2 and SnO2 , and thus exhibit superior electrochemical reactivity and stability when used as anode materials for Li-ion batteries. A high reversible specific capacity of about 310 mAh g-1 at a high current density of 5 A g-1 can be achieved over 500 cycles indicating very good cycle stability and rate performance.