Multishell Structures Research Articles

Phenolic multiple kinetics-dynamics and discrete crystallization thermodynamics in amorphous carbon nanostructures for electromagnetic wave absorption

The lack of a chemical platform with high spatial dimensional diversity, coupled with the elusive multi-scale amorphous physics, significantly hinder advancements in amorphous electromagnetic wave absorption (EWA) materials. Herein, we present a synergistic engineering of phenolic multiple kinetic dynamics and discrete crystallization thermodynamics, to elucidate the origin of the dielectric properties in amorphous carbon and the cascade effect during EWA. Leveraging the scalability of phenolic synthesis, we design dozens of morphologies from the bottom up and combine with in-situ pyrolysis to establish a nanomaterial ecosystem of hundreds of amorphous carbon materials. Based on controlled discrete crystallization, nano-curvature regulation of spatial inversion symmetry-breaking structures, and surface electric field enhancement from multi-shell structures, the multi-scale charge imbalance triggers intense polarization. Both experiments and theories show that each scale is essential, which collectively drives broadband absorption (8.46 GHz) and efficient dissipation (−54.77 dB) of EWA performance. Our work on the amorphous nanostructure platform and the cascade effect can contribute to uncovering the missing pieces in amorphous physics and EWA research.

Energetics and electronic structure of graphene nanoscrolls

Geometric structures and electronic properties of graphene nanoscrolls have been investigated using the density functional theory. A graphene nanoribbon with a width of 21.37 nm, corresponding to a zigzag ribbon with 100 zigzag C chains, prefers scrolled structures until the innermost shell radius of 0.6 nm, because of the competition between the energy gain by the inter-shell van der Waals interaction and the energy cost by the structural strain derived from curvature. The most preferable innermost shell radiuses are 1.3–1.5 nm for the ribbon studied here. The electronic structure of graphene nanoscrolls shows strong position dependence that is sensitive to the shape of nanoscrolls owing to the electrostatic potential modulation by their multi-shell structures.

Surface charge engineering for structural control of colloidal silica rod-decorated silica particles and their flexible integration into magnetic core–multishell structures

In this study, the effect of surface modification and the resulting surface charge of colloidal silica seeds on the growth of silica rods during an emulsion droplet-based process is investigated. Through electrostatic interactions between negatively charged poly(vinylpyrrolidone) (PVP) and seed surfaces, significant PVP adsorption occurs as the seed surfaces are modified with positively charged cationic substances and then aged with PVP. This surface charge-enhanced PVP adsorption promotes the anchoring of water emulsion droplets, serving as the starting point for the growth of silica rods on the seed surfaces and leading to a high yield of silica rod-decorated particles during emulsion droplet-based growth. The surface properties, including surface charge and hydrophobicity, can be further modified by applying different cationic modifiers, which influence the morphology, structural architecture, and yield of the final product. We further demonstrated the versatility of this approach by successfully generating silica rod-decorated magnetic core (Fe3O4)–multishell (silica/polystyrene/titania) particles. The findings of this study highlight the critical role of surface charge engineering in controlling the structure and morphology of silica rod-decorated silica particles as well as their integration into complex multicomponent systems.

Exploring energy mechanisms involved in the luminescence reduction due to Ce3+ doping via core-multishell upconversion nanoparticles highly doped with Ho3+ and Yb3+

Upconversion nanoparticles (UCNPs), particularly those that are highly doped, possess outstanding properties and have demonstrated tremendous application potential. However, novel fine-tuning strategies are urgently required to enhance the upconversion luminescence (UCL) performance of UCNPs. In this study, a series of core–multishell UCNPs highly doped with Ho3+ and Yb3+ ions were synthesized via the oleate route. The X-ray diffraction (XRD), transmission electron microscopy (TEM), and UCL spectra and decay times, and pump power dependency of the synthesized UCNPs were used to examine their morphology, size, and the UCL properties. Ce3+ ions were introduced to enhance Ho3+-based red UCL, and their doping strategy was also optimized based on summarized UCL trends and detailed UCL mechanism analysis. NaHoF4:Gd3+@NaGdF4:Yb3+,Ce3+@NaGdF4:Yb3+ UCNPs that had 10 mol% Ce3+ dopants in their middle shells exhibited better UCL properties than the larger traditional NaGdF4:Yb3+,Ce3+,Ho3+ UCNPs, probably because of the combined influence of the energy interactions between the Ce3+ ions and surface groups, sensitizing energy enhancement by active shells, and the positive cooperation between the Ce3+ ions and highly-doped core–shell structures. In this study, the phenomenon of UCL decrease resulting from Ce3+ ion doping was explored. Using unique core–multishell structures with highly-doped activators and sensitizers placed within and outside the structures, respectively, the UCL decrease due to Ce3+ ion doping was attributed to a competition for photons. Doping the UCNPs with Ce3+ ions near the UCNP surfaces favors Ho3+-based red UCL. Our study findings can deepen the understanding of the Ho3+-based UCL mechanisms and increase the potential uses of NaHoF4 materials in photo-induced therapy.

Boosted hydrogen evolution kinetics of heteroatom-doped carbons with isolated Zn as an accelerant

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present a practical strategy to rationally design a model catalyst with a single zinc (Zn) atom coordinated with nitrogen and sulfur atoms in a multilevel carbon matrix. The Zn site exhibits an atomic interface configuration of ZnN4S1, where Zn's electron injection effect enables thermal-neutral hydrogen adsorption on neighboring atoms, pushing the activity boundaries of carbon electrocatalysts toward electrochemical hydrogen evolution to an unprecedented level. Experimental and theoretical analyses confirm the low-barrier Volmer-Tafel mechanism of proton reduction, while the multishell hollow structures facilitate the hydrogen evolution even at high current intensities. This work provides insights for understanding the actual active species during hydrogen evolution reaction and paves the way for designing high-performance electrocatalysts.

From nano- to macroarchitectures: designing and constructing MOF-derived porous materials for persulfate-based advanced oxidation processes.

Persulfate-based advanced oxidation processes (PS-AOPs) have gained significant attention as an effective approach for the elimination of emerging organic contaminants (EOCs) in water treatment. Metal-organic frameworks (MOFs) and their derivatives are regarded as promising catalysts for activating peroxydisulfate (PDS) and peroxymonosulfate (PMS) due to their tunable and diverse structure and composition. By the rational nanoarchitectured design of MOF-derived nanomaterials, the excellent performance and customized functions can be achieved. However, the intrinsic fine powder form and agglomeration ability of MOF-derived nanomaterials have limited their practical engineering application. Recently, a great deal of effort has been put into shaping MOFs into macroscopic objects without sacrificing the performance. This review presents recent advances in the design and synthetic strategies of MOF-derived nano- and macroarchitectures for PS-AOPs to degrade EOCs. Firstly, the strategies of preparing MOF-derived diverse nanoarchitectures including hierarchically porous, hollow, yolk-shell, and multi-shell structures are comprehensively summarized. Subsequently, the approaches of manufacturing MOF-based macroarchitectures are introduced in detail. Moreover, the PS-AOP application and mechanisms of MOF-derived nano- and macromaterials as catalysts to eliminate EOCs are discussed. Finally, the prospects and challenges of MOF-derived materials in PS-AOPs are discussed. This work will hopefully guide the design and development of MOF-derived porous materials in SR-AOPs.

Controlled synthesis of transition metal oxide multi-shell structures and in situ study of the energy storage mechanism

Multi-shell transition metal oxide hollow spheres show great potential for applications in energy storage because of their unique multilayered hollow structure with large specific surface area, short electron and charge transport paths, and structural stability. In this paper, the controlled synthesis of NiCo2O4, MnCo2O4, NiMn2O4 multi-shell layer structures was achieved by using the solvothermal method. As the anode materials for Li-ion batteries, the three multi-shell structures maintained good stability after 650 long cycles in the cyclic charge/discharge test. The in situ transmisssion electron microscope characterization combined with cyclic voltammetry tests demonstrated that the three anode materials NiCo2O4, MnCo2O4 and NiMn2O4 have similar charge/discharge transition mechanisms, and the multi-shell structure can effectively buffer the volume expansion and structural collapse during lithium embedding/delithiation to ensure the stability of the electrode structure and cycling performance. The research results can provide effective guidance for the synathesis and charging/discharging mechanism of multi-shell metal oxide lithium-ion battery anode materials.

Thermal-/pH-triggered hollow mesoporous carbon nanocarrier for NIR-responsive drug release

Intelligent drug-delivery systems are considered one of the most important techniques for improving cancer treatment using existing over-the-counter medicines. However, metallic materials are always accompanied by metabolism problems, whereas chemotherapy produces several side effects in humans. Carbon-based materials exhibit exceptional features such as bio-affinity and bio-degradability. Herein, hollow mesoporous carbon nanoparticles (HMCs) are reported as effective nanocarriers of anti-cancer small drug molecules. Near IR (NIR) sources, which can penetrate most organs, induce thermal effects via non-invasive pathways. NIR radiation not only provides thermal therapy but also is compatible with temperature-sensitive coated responsive polymer shells. The template method was used to synthesize HMCs with size 200 ± 50 nm, under various conditions, to obtain suitably sized and hollow structures for liver-cancer treatment. Additional pH/thermal-bi-responsive poly(N-isopropylacrylamide) (PNIPAM) shells were further coated onto the HMCs to produce multiple shells that could trigger swelling motions in PNIPAM@HMCs, as confirmed via small-angle X-ray scattering (SAXS). NIR results demonstrated an extreme increase to the ∆T of 8.7 and 14.2 °C for HMC and PNIPAM@HMCs, respectively. The SAXS spectra analyzed using SasView simulations demonstrated the multi-shell structures of synthesized HMCs and the release mechanism of PNIPAM@HMCs. Based on the model simulation of SAXS, the different rates of polymer swelling indicated the core shrinkage (229.7 to 134.2 Å) and shell expansion (324.3 to 514.3 Å) at 37 °C and 42 °C, respectively. In addition, the first-order, Higuchi, Korsmeyer–Peppas, and Weibull mathematical models were used to verify the drug-release kinetics, and the model with the highest R2 value was considered most suitable for further application. This paper presents the first SAXS study on PNIPAM@HMCs release kinetics and related mechanisms. This phenomenon indicates NIR-induced PNIPAM@HMCs as an effective strategy for cancer treatment via doxorubicin release.

The construction of defect-rich CoP@CoP@(Co/Ni)2P triple-shell hollow nanospheres with boosted electrocatalytic hydrogen evolution performances over a wide pH range

The development of highly effective non-precious metal catalysts with high intrinsic activity and rich accessible catalysis centers are the relentless goals of the scientific community to lower energy consumption and production cost. In this work, a unique triple-shell CoP@CoP@(Co/Ni)2P hollow structure with rich defect structure has been successfully constructed, which presents remarkable activity against HER over a wide pH range. The overpotentials of 147 mV, 139 mV, and 144 mV are achieved at 10 mA cm−2 current density for CoP@CoP@(Co/Ni)2P in 1 M KOH, 0.5 M H2SO4, and 1 M phosphate-buffered saline (PBS) conditions, respectively. The excellent HER activity of CoP@CoP@(Co/Ni)2P can be attributed to their multi-shell hollow structure for abundant activity centers, and rich defect structure for the enhanced intrinsic activity. This work provides new insights into the design and synthesis of multi-shell hollow structures with diverse compositions and defect-rich catalysts for energy storage and conversion application.

Core-double-shell structure and heterojunction in CdS/SnS2 boosting fast carrier separation for ultrasensitive detection of carbohydrate antigen 125

Combining heterojunctions and advanced structures is an effective strategy for improving light capture capability and electron-hole pair separation of photoactive materials. In this work, we facilely constructed CdS/SnS2 with a unique core-double-shell structure (CS-CDSSs) using cobalt glycerate nanospheres as sacrificial templates. The one-step hydrothermal cation exchange method was used to construct energy-matched heterojunctions, simultaneously endowing CS-CDSSs with a distinctive morphology of coexisting core-shell and multi-shell structures. The enhanced photoconversion efficiency was attributed to (i) unique structural features and a narrow shell spacing; (ii) broadened optical response and shift toward the visible-light range; (iii) scattering/reflection effect of the incident light to increase light enrichment; and (iv) close contact at the interface between CdS and SnS2. Based on the excellent photoelectric conversion efficiency of CS-CDSSs, the fabricated photoelectrochemical (PEC) biosensors exhibit high performance with a wide linear range from 10−7 to 102 U·mL−1, and an ultralow detection limit of 5.48 × 10−8 U·mL−1 for carbohydrate antigen 125 (CA125). This novel strategy significantly improves the PEC performance of heterojunctions by preparing core-double-shell structures, which could provide more inspiration for constructing other functionalized photoactive materials.

A general strategy for preparing hollow spherical multilayer structures of Oxygen-Rich vacancy transition metal Oxides, especially high entropy perovskite oxides

The development of excellent synthetic strategies and exploration of the synthesis mechanisms of active site-rich high-entropy oxides are crucial for high-entropy materials. Herein, a universal synthetic method was designed to prepare La(Co0.2Mn0.2Fe0.2Ni0.2Cu0.2)O3 (HSM-HEPs) with hollow spherical multilayer structure (HSM) and rich oxygen vacancies. The tracking characterization was used during the synthesis of HSM-HEPs to clarify the formation of multi-shell, multi-vacancy, and single-phase crystal structures of HSM-HEPs. Three basic conditions were proposed to obtain vacancy-rich high-entropy materials. The experimental data showed excellent electrochemical activity and extraordinary stability of HSM-HEPs electrode materials owing to the formation of HSM structure, abundant oxygen vacancies, abundant elemental composition, and high specific surface area. When used as supercapacitor electrode materials, HSM-HEPs exhibited a high specific capacity of 625 F g−1 with an excellent capacity retention rate of 88 % after 10,000 cycles. Besides, HSM-HEPs achieved efficient water oxidation with an overpotential of 309 mV at 10 mA cm−2. Furthermore, the proposed strategy can be extended to the synthesis of metal oxides with various representative HSM crystal structures. Overall, the designed and tuned synthetic method looks promising for the formation of more active sites-high-entropy materials.

Hydrothermal synthesis of water-soluble Mn- and Cu-doped CdSe quantum dots with multi-shell structures and their photoluminescence properties.

Optical properties of semiconductor quantum dots (QDs) can be tuned by doping with transition metal ions. In this study, water-soluble CdSe/ZnS:Mn/ZnS QDs with the core/shell/shell structure were synthesized through a hydrothermal method, in which the surface of the CdSe core was coated with a ZnS:Mn shell and ZnS capping shell. Herein, the CdSe core QDs were prepared first and then doped with Mn2+; therefore, the QD size and doping level could be controlled independently and interference from the self-purifying effect could be avoided. When CdSe cores with diameters less than 1.9 nm were used, Mn-related photoluminescence (PL) was observed as the main PL band, whereas the band-edge PL was mainly observed when larger CdSe cores were used. Furthermore, using ZnS:Cu as the doping shell layer, CdSe/ZnS:Cu/ZnS and ZnSe/ZnS:Cu/ZnS nanoparticles were successfully synthesized, and Cu-related PL was clearly observed. These results indicate that the core/shell/shell QD structure with doping in the shell layer is a versatile method for synthesizing doped QDs.

Nanoconfinement Engineering over Hollow Multi-Shell Structured Copper towards Efficient Electrocatalytical C-C coupling.

Nanoconfinement provides a promising solution to promote electrocatalytic C-C coupling, by dramatically altering the diffusion kinetics to ensure a high local concentration of C1 intermediates for carbon dimerization. Herein, under the guidance of finite-element method simulations results, a series of Cu2 O hollow multi-shell structures (HoMSs) with tunable shell numbers were synthesized via Ostwald ripening. When applied in CO2 electroreduction (CO2 RR), the in situ formed Cu HoMSs showed a positive correlation between shell numbers and selectivity for C2+ products, reaching a maximum C2+ Faradaic efficiency of 77.0±0.3 % at a conversion rate of 513.7±0.7 mA cm-2 in a neutral electrolyte. Mechanistic studies clarified the confinement effect of HoMSs that superposition of Cu shells leads to a higher coverage of localized CO adsorbate inside the cavity for enhanced dimerization. This work provides valuable insights for the delicate design of efficient C-C coupling catalysts.

Robustness of the chiral-icosahedral golden shell I-Au60 in multi-shell structures.

Motivated by the recent theoretical discovery [S.-M. Mullins et al., Nat. Commun. 9, 3352 (2018)] of a surprisingly contracted 60-atom hollow shell of chiral-icosahedral symmetry (I-Au60) of remarkable rigidity and electronegativity, we have explored, via first-principles density functional theory calculations, its physico-chemical interactions with internal and external shells, enabling conclusions regarding its robustness and identifying composite forms in which an identifiable I-Au60 structure may be realized as a product of natural or laboratory processes. The dimensions and rigidity of I-Au60 suggest a templating approach; e.g., an Ih-C60 fullerene fits nicely within its interior, as a nested cage. In this work, we have focused on its susceptibility, i.e., the extent to which the unique structural and electronic properties of I-Au60 are modified by incorporation into selected multi-shell structures. Our results confirm that the I-Au60 shell is robustly maintained and protected in various bilayer structures: Ih-C60@I-Au60, Ih-Au32@I-Au60 2+, Au60(MgCp)12, and their silver analogs. A detailed analysis of the structural and electronic properties of the selected I-Au60 shell-based nanostructures is presented. We found that the I-Au60 shell structure is quite well retained in several robust forms. In all cases, the I-symmetry is preserved, and the I-Au60 shell is slightly deformed only in the case of the Ih-C60@I-Au60 system. This analysis serves to stimulate and provide guidance toward the identification and isolation of various I-Au60 shell-based nanostructures, with much potential for future applications. We conclude with a critical comparative discussion of these systems and of the implications for continuing theoretical and experimental investigations.

In-Situ Growth of Nucleus Geometry to Dual Types of Periodically Ringed Assemblies in Poly(nonamethylene terephthalate)

Monitoring of nucleus geometry and growth into dual types of periodically ring-banded morphology in poly(nonamethylene terephthalate) (PNT), respectively, Type-1 and Type-2, are done with detailed analyses using polarized-light optical microscopy (POM) in-situ CCD recording; the periodic assembly morphologies are characterized using atomic-force microscopy (AFM) and scanning electron microscopy (SEM). Different annealing treatments (Tmax = 110, 120, 130 °C) are accomplished at a crystallization temperature of 85 °C; effects on the nucleus geometry, number (25–10%) and volume fractions (33–15%) of Type-2 among two types of banded PNT spherulites are expounded. Growth of a specific type of periodically banded PNT spherulite is initiated from either highly elongated sheaf-like or well-rounded nuclei, with the final grown lamellae being self-packed as multi-shell structures. Nucleation geometry and crystallization parameters collectively lead to development of multiple types of banded PNT spherulites of different relative fractions.

Robust Electrodes for Flexible Energy Storage Devices Based on Bimetallic Encapsulated Core-Multishell Structures.

Developing flexible electrodes with high active materials loading and excellent mechanical stability is of importance to flexible electronics, yet remains challenging. Herein, robust flexible electrodes with an encapsulated core‐multishell structure are developed via a spraying‐hydrothermal process. The multilayer electrode possesses an architecture of substrate/reduced graphene oxide (rGO)/bimetallic complex/rGO/bimetallic complex/rGO from the inside to the outside, where the cellulosic fibers serve as the substrate, namely, the core; and the multiple layers of rGO and bimetallic complex, are used as active materials, namely, the shells. The inner two rGO interlayers function as the cement that chemically bind to two adjacent layers, while the two outer rGO layers encapsulate the inside structure effectively protecting the electrode from materials detachment or electrolyte corrosion. The electrodes with a unique core‐multishell structure exhibit excellent cycle stability and exceptional temperature tolerance (−25 to 40 °C) for lithium and sodium storage. A combination of experimental and theoretical investigations are carried out to gain insights into the synergetic effects of cobalt‐molybdenum‐sulfide (CMS) materials (the bimetallic complex), which will provide guidance for future exploration of bimetallic sulfides. This strategy is further demonstrated in other substrates, showing general applicability and great potential in the development of flexible energy storage devices.

Synthesis and energy applications of m ulti‐shell micro/n ano‐spheres

Nowadays, multishelled hollow materials having various compositions and structures have drawn huge attention of researchers. In comparison to the single-shelled hollow structures, which become advantageous and preferred due to their large void volume and high surface-to-volume ratio, it is considered that hollow materials with multi-shell structures can gain extra benefits from their specially constituted inner structures. This review article aims on the progress in the synthesis and energy applications of multishelled spherical nano-materials in last decade. The synthetic strategies include the hard templating, soft templating, sacrificial templating, and template-free technologies. The review further approaches toward the fundamentals of each of the synthetic strategies. Moreover, it addresses the challenges and the advantages of each of the synthetic strategies. This also emphasizes on the potential applications of the these specially structured micro- and nano-materials in the field of electrocatalysis, electrodes, lithium ion batteries, and solar cells. The correlation between the number of shells, geometric, and compositional structure with their properties and specific applications has also been addressed.

A co-rotational triangular finite element for large deformation analysis of smooth, folded and multi-shells

A six-node co-rotational curved triangular shell finite element with a novel rotation treatment for folded and multi-shell structures is presented. Different from other co-rotational triangular element formulations, rotations are not represented by axial (pseudo) vectors, but by components of polar (proper) vectors, of which additivity and commutativity lead to symmetry of the tangent stiffness matrices in both local and global coordinate systems. In the co-rotational local coordinate system, the two smallest components of the shell director are defined as the nodal rotational variables. Similarly, the two smallest components of each director in the global coordinate system are adopted as the global rotational variables for nodes located either on smooth shells or away from non-smooth shell intersections. At intersections of folded and multi-shells, global rotational variables are defined as three selected components of an orthogonal triad initially oriented along the global coordinate system axes. As such, the vectorial rotational variables enable simple additive update of all nodal variables in an incremental-iterative procedure, resulting in significant enhancement in computational efficiency for large deformation analysis. To alleviate membrane and shear locking phenomena, an assumed strain method is employed in obtaining the element tangent stiffness matrices and the internal force vector. The effectiveness of the presented co-rotational triangular shell element formulation is verified by analyzing several benchmark problems of smooth, folded and multi-shell structures undergoing large displacements and large rotations.

Delicate Control on the Shell Structure of Hollow Spheres Enables Tunable Mass Transport in Water Splitting

AbstractIn the study of structure–property relationships for rational materials design, hollow multishell structures (HoMSs) have attracted tremendous attention owing to the optimal balance between mass transfer and surface exposure. Considering the shell structure can significantly affect the properties of HoMSs, in this paper, we provide a novel one‐step strategy to continually regulate the shell structures of HoMSs. Through a simple phosphorization process, we can effectively modify the shell from solid to bubble‐like and even duplicate the shells with a narrow spacing. Benefitting from the structure merits, the fabricated CoP HoMSs with close duplicated shells can promote gas release owing to the unbalanced Laplace pressure, while accelerating liquid transfer for enhanced capillary force. It can provide effective channels for water and gas and thus exhibits a superior electrocatalytic performance in the hydrogen and oxygen evolution reaction.

Delicate Control on the Shell Structure of Hollow Spheres Enables Tunable Mass Transport in Water Splitting

In the study of structure-property relationships for rational materials design, hollow multishell structures (HoMSs) have attracted tremendous attention owing to the optimal balance between mass transfer and surface exposure. Considering the shell structure can significantly affect the properties of HoMSs, in this paper, we provide a novel one-step strategy to continually regulate the shell structures of HoMSs. Through a simple phosphorization process, we can effectively modify the shell from solid to bubble-like and even duplicate the shells with a narrow spacing. Benefitting from the structure merits, the fabricated CoP HoMSs with close duplicated shells can promote gas release owing to the unbalanced Laplace pressure, while accelerating liquid transfer for enhanced capillary force. It can provide effective channels for water and gas and thus exhibits a superior electrocatalytic performance in the hydrogen and oxygen evolution reaction.