Enhanced uranium extraction from seawater: from the viewpoint of kinetics and thermodynamics.

Uranium extraction from seawater (UES) is recognized as one of the seven pivotal chemical separations with the potential to revolutionize global paradigms. The forthcoming decade is anticipated to witness a surge in UES, driven by escalating energy demands. The oceanic reservoirs, possessing uranium quantities approximately 1000-fold higher than terrestrial mines, present a more sustainable and environmentally benign alternative. Empirical evidence from historical research indicates that adsorption emerges as the most efficacious process for uranium recovery from seawater, considering operational feasibility, cost-effectiveness, and selectivity. Over the years, scientific exploration has led to the development of a plethora of adsorbents with superior adsorption capacity. It would be efficient to design materials with a deep understanding of the adsorption from the perspective of kinetics and thermodynamics. Here, we summarize recent advancements in UES technology and the contemporary challenges encountered in this domain. Furthermore, we present our perspectives on the future trajectory of UES and finally offer our insights into this subject.

Revealing the Mechanism of sp-N Doping in Graphdiyne for Developing Site-Defined Metal-Free Catalysts.

Due to the limited reserves of metals, scientists are devoted to exploring high-performance metal-free catalysts based on carbon materials to solve environment-related issues. Doping would build up inhomogeneous charge distribution on surface, which is an efficient approach for boosting the catalytic performance. However, doping sites are difficult to control in traditional carbon materials, thus hindering their development. Taking the advantage of unique sp-C in graphdiyne (GDY), a new N doping configuration of sp-hybridized nitrogen (sp-N), bringing a Pt-comparable catalytic activity in oxygen reduction reaction is site-defined introduced. However, the reaction intermediate of this process is never captured, hindering the understanding of the mechanism and the precise synthesis of metal-free catalysts. After the four-year study, the fabrication of intermediate-like molecule is realized, and finally sp-N doped GDY via the pericyclic reaction is obtained. Compared with GDY doped with other N configurations, the designed sp-N GDY shows much higher catalytic activity in electroreduction of CO2 toward CH4 production, owing to the unique electronic structure introduced by sp-N, which is more favorable in stabilizing the intermediate. Thus, besides opening the black-box for the site-defined doping, this work reveals the relationship between doping configuration and products of CO2 reduction.

Hollow Nanomaterials in Advanced Drug Delivery Systems: From Single- to Multiple Shells.

Hollow-structured nanomaterials (HSNMs) have attracted increased interest in biomedical fields, owing to their excellent potential as drug delivery systems (DDSs) for clinical applications. Among HSNMs, hollow multi-shelled structures (HoMSs) exhibit properties such as high loading capacity, sequential drug release, and multi-functionalized modification and represent a new class of nanoplatforms for clinical applications. The remarkable properties of HoMS-based DDS can simultaneously satisfy and enhance DDSs for delivering small molecular drugs (e.g., antibiotics, chemotherapy drugs, and imaging agents) and macromolecular drugs (e.g., protein/peptide- and nucleic acid-based drugs). First, the latest research advances in delivering small molecular drugs are summarized and highlight the inherent advantages of HoMS-based DDSs for small molecular drug targeting, combining continuous therapeutic drug delivery and theranostics to optimize the clinical benefit. Meanwhile, the macromolecular drugs DDSs are in the initial development stage and currently offer limited delivery modes. There is a growing need to analyze the deficiency of other HSNMs and integrate the advantages of HSNMs, providing solutions for the safe, stable, and cascade delivery of macromolecular drugs to meet vast treatment requirements. Therefore, the latest advances in HoMS-based DDSs are comprehensively reviewed, mainly focusing on the characteristics, research progress by drug category, and future research prospects.

PEG-Functionalized Hollow Multishelled Structures with On-Off Switch and Rate-Regulation for Controllable Antimicrobial Release.

The construction of responsive antimicrobial carriers with multifunctional and controllable release is an attractive but challenging proposition. Recently developed hollow multishelled structures (HoMSs) offers structural advantages, such as easily modifiable surfaces and mutually influenced shells. Herein, we report a novel pH-responsive antimicrobial carrier having hierarchical shells as multilevel responsive bodies using polyethylene glycol (PEG) as a gated regulator. The interaction between PEG-functionalized shells endows them with a pH-responsive switch and rate-regulator capability. These features are present in the form of rapid release of molecules wrapped in the outer shell, and controlled diffusion of antimicrobials stored in the inner shell by electrostatic interaction, resulting in a long-lasting mildew resistance for up to 71 days. The versatility of the hierarchical interactions of HoMSs will inspire the design of promising smart drug carriers.

Accurately Localizing Multiple Nanoparticles in a Multishelled Matrix Through Shell-to-Core Evolution for Maximizing Energy-Storage Capability.

Robust and fast lithium energy storage with a high energy density is highly desired to accelerate the market adoption of electric vehicles. To realize such a goal requires the development of electrode materials with a high capacity, however, such electrode materials suffer from huge volume expansion and induced short cycling life. Here, using tin (Sn) as an example, an ideal structure is designed to effectively solve these problems by separately localizing multiple Sn nanoparticles in a nitrogen-doped carbon hollow multishelled structure with duplicated layers for carbon shell (Sn NPs@Nx C HoMS-DL). The fabricated composite can promote ion and electron diffusion owing to the conductive network formed by connected multiple shells and cores, effectively buffer the volume expansion, and maintain a stable electrode-electrolyte interface. Despite the challenging fabrication, such a structure is realized through an innovative and facile synthesis strategy of "in situ evolution of shell to core", which is applicable for diverse low-melting-point materials. As expected, such a structure enables the high-capacity electrode material to realize nearly its theoretical lithium-storage capability: the developed Sn NPs@Nx C HoMS-DL electrode maintains 96% of its theoretical capacity after 2000 cycles at 2C.

Highly Efficient Photothermal Conversion and Water Transport during Solar Evaporation Enabled by Amorphous Hollow Multishelled Nanocomposites.

Solar evaporation, which enables water purification without consuming fossil fuels, has been considered the most promising strategy to address global scarcity of drinkable water. However, the suboptimal structure and composition designs still result in a trade-off between photothermal conversion, water transport, and tolerance to harsh environments. Here, an ultrastable amorphous Ta2 O5 /C nanocomposite is designed with a hollow multishelled structure (HoMS) for solar evaporation. This HoMS results in highly efficient photoabsorption and photothermal conversion, as well as a decrease of the actual water evaporation enthalpy. A superfast evaporation speed of 4.02 kg m-2 h-1 is achieved. More importantly, a World Health Organization standard drinkable water can be achieved from seawater, heavy-metal- and bacteria-containing water, and even from extremely acidic/alkaline or radioactive water sources. Notably, the concentration of pseudovirus SC2-P can be decreased by 6 orders of magnitude after evaporation.

Hollow structures as drug carriers: Recognition, response, and release.

Hollow structures have demonstrated great potential in drug delivery owing to their privileged structure, such as high surface-to-volume ratio, low density, large cavities, and hierarchical pores. In this review, we provide a comprehensive overview of hollow structured materials applied in targeting recognition, smart response, and drug release, and we have addressed the possible chemical factors and reactions in these three processes. The advantages of hollow nanostructures are summarized as follows: hollow cavity contributes to large loading capacity; a tailored structure helps controllable drug release; variable compounds adapt to flexible application; surface modification facilitates smart responsive release. Especially, because the multiple physical barriers and chemical interactions can be induced by multishells, hollow multishelled structure is considered as a promising material with unique loading and releasing properties. Finally, we conclude this review with some perspectives on the future research and development of the hollow structures as drug carriers.

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.

Hollow Multishelled Structured SrTiO3 with La/Rh Co-Doping for Enhanced Photocatalytic Water Splitting under Visible Light.

La- and Rh-co-doped SrTiO3 (STO:La/Rh) hollow multishelled structures (HoMSs) are fabricated by adding La3+ and Rh3+ ions during the hydrothermal process of converting TiO2 HoMSs to STO HoMSs. STO:La/Rh HoMSs have successfully expanded the light absorption edge to 520 nm. Accompanied with the benefits of the unique hierarchical structure and relatively thin shells, STO:La/Rh HoMSs exhibit elevated light-harvesting capacity and charge separation efficiency. Compared with STO:La/Rh nanoparticles (NPs), STO:La/Rh HoMSs demonstrate enhanced photocurrent response, photocatalytic hydrogen evolution activity, and the quantum efficiency. Moreover, overall water splitting is realized by a Z-scheme system combining STO:La/Rh HoMSs with BiVO4 (BVO) nanosheets with 1 wt% Pt as the co-catalyst. Steady evolution of hydrogen and oxygen is performed under both visible light and simulated sunlight irradiation. The solar-to-hydrogen efficiency of double-shelled STO:La/Rh HoMS-BVO photocatalysts reaches 0.08%, which is twofold higher than STO:La/Rh NP-BVO photocatalysts.

Quasi-Epitaxial Growth of Magnetic Nanostructures on 4H-Au Nanoribbons.

Phase engineering of nanomaterials is an effective strategy to tune the physicochemical properties of nanomaterials for various promising applications. Herein, by using the 4H-Au nanoribbons as templates, four novel magnetic nanostructures, namely 4H-Au @ 14H-Co nanobranches, 4H-Au @ 14H-Co nanoribbons, 4H-Au @ 2H-Co nanoribbons, and 4H-Au @ 2H-Ni nanoribbons, are synthesized based on the quasi-epitaxial growth. Different from the conventional epitaxial growth of metal nanomaterials, the obtained Co and Ni nanostructures possess different crystal phases from the Au template. Due to the large lattice mismatch between Au and the grown metals (i.e., Co and Ni), ordered misfit dislocations are generated at the Co/Au and Ni/Au interfaces. Notably, a new super-structure of Co is formed, denoted as 14H. Both 4H-Au @ 14H-Co nanobranches and nanoribbons are ferromagnetic at room temperature, showing similar Curie temperature. However, their magnetic behaviors exhibit distinct temperature dependence, resulting from the competition between spin and volume fluctuations as well as the unique geometry. This work paves the way to the templated synthesis of nanomaterials with unconventional crystal phases for the exploration of phase-dependent properties.

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles.

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO2RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochemical cells.

Sequential drug release via chemical diffusion and physical barriers enabled by hollow multishelled structures.

Hollow multishelled structures (HoMSs), with relatively isolated cavities and hierarchal pores in the shells, are structurally similar to cells. Functionally inspired by the different transmission forms in living cells, we studied the mass transport process in HoMSs in detail. In the present work, after introducing the antibacterial agent methylisothiazolinone (MIT) as model molecules into HoMSs, we discover three sequential release stages, i.e., burst release, sustained release and stimulus-responsive release, in one system. The triple-shelled structure can provide a long sterility period in a bacteria-rich environment that is nearly 8 times longer than that of the pure antimicrobial agent under the same conditions. More importantly, the HoMS system provides a smart responsive release mechanism that can be triggered by environmental changes. All these advantages could be attributed to chemical diffusion- and physical barrier-driven temporally-spatially ordered drug release, providing a route for the design of intelligent nanomaterials.

Steering Hollow Multishelled Structures in Photocatalysis: Optimizing Surface and Mass Transport.

Hollow multishelled structures (HoMSs) provide a promising platform for fabricating photocatalysts, because the unique structure optimizes the effective surface and mass transport, showing enhanced light absorption, optimized mass transport and highly effective active sites exposed. Subsequently, the rational design on HoMS photocatalytsts is elaborated to boost the photocatalytic activity with efforts in all dimensions, from nanoscale to microscale. Breakthroughs in synthetic methodology of HoMSs have greatly evoked the prosperous photocatalytic researches for HoMSs since the developing of sequential templating approach in 2009. The dawn of HoMS photocatalyst is coming after revealing the temporal-spatial ordering property, which is also discussed in this paper with pioneer works demonstrating the greatly enhanced energy/mass transfer processes. Some insights into the key challenges and perspectives of HoMSs photocatalysts are also discussed. With the reviewed fate and future of HoMSs photocatalysts, hopefully new concepts and innovative works can be inspired to flourish this sun-rise field.

Dual-Defects Adjusted Crystal-Field Splitting of LaCo1-x Nix O3-δ Hollow Multishelled Structures for Efficient Oxygen Evolution.

To boost the performance for various applications, a rational bottom-up design on materials is necessary. The defect engineering on nanoparticle at the atomic level can efficiently tune the electronic behavior, which offers great opportunities in enhancing the catalytic performance. In this paper, we optimized the surface oxygen vacancy concentration and created the lattice distortion in rare-earth-based perovskite oxide through gradient replacement of the B site with valence alternated element. The dual defects make the electron spin state transit from low spin state to high spin state, thus decreasing the charge transport resistance. Furthermore, assembly the modified nanoparticle subunits into the micro-sized hollow multishelled structures can provide porous shells, abundant interior space and effective contact, which enables an enhanced mass transfer and a shorter charge transport path. As a result, the systemic design in the electronic and nano-micro structures for catalyst has brought an excellent oxygen evolution performance.

Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction.

Various kinds of amorphous materials, such as transition metal dichalcogenides, metal oxides, and metal phosphates, have demonstrated superior electrocatalytic performance compared with their crystalline counterparts. Compared to other materials for electrocatalysis, noble metals exhibit intrinsically high activity and excellent durability. However, it is still very challenging to prepare amorphous noble-metal nanomaterials due to the strong interatomic metallic bonding. Herein, the discovery of a unique thiol molecule is reported, namely bismuthiol I, which can induce the transformation of Pd nanomaterials from face-centered-cubic (fcc) phase into amorphous phase without destroying their integrity. This ligand-induced amorphization is realized by post-synthetic ligand exchange under ambient conditions, and is applicable to fcc Pd nanomaterials with different capping ligands. Importantly, the obtained amorphous Pd nanoparticles exhibit remarkably enhanced activity and excellent stability toward electrocatalytic hydrogen evolution in acidic solution. This work provides a facile and effective method for preparing amorphous Pd nanomaterials, and demonstrates their promising electrocatalytic application.

A Hollow Multi-Shelled Structure for Charge Transport and Active Sites in Lithium-Ion Capacitors.

The lithium-ion capacitor (LIC) has attracted tremendous research interest because it meets both the requirement on high energy and power densities. The balance between effective surface areas and mass transport is highly desired to fabricate the optimized electrode material for LIC. Now, triple-shelled (3S) Nb2 O5 hollow multi-shelled structures (HoMSs) were synthesized for the first time through the sequential templating approach and then applied for the anode of LIC. The unique structure of HoMSs, such as large efficient surface area, hierarchical pores, and multiple shells, provides abundant reaction sites, decreases the electron transport resistance, and increases the diffusion rate for ion transport. In this case, the best combination performance has been achieved among all the reported Nb2 O5 -based materials, which delivered an excellent energy and power densities simultaneously, and superb cycling stability.

When hollow multishelled structures (HoMSs) meet metal-organic frameworks (MOFs).

Hollow multishelled structures (HoMSs) have distinguished advantages, such as a large effective surface area, an optimized mass transport route, and a high loading capacity, but the fabrication of HoMSs has been a big challenge. In 2009, we developed a universal and facile method for HoMS fabrication, i.e., the sequential templating approach (STA). Progress in the synthetic methodology has enabled the study of HoMSs to develop and has made it a research hotspot in materials science. To date, HoMSs have shown their advantages in a wide range of applications, including catalysis, energy conversion and storage, drug delivery, etc. Based on the understanding in this field, we recently revealed the unique temporal-spatial ordering properties of HoMSs. Furthermore, we have been wondering if the structure of a HoMS can be modulated at the molecular level. Encouragingly, metal-organic frameworks (MOFs) are star materials with clearly defined molecular structures. The compositions, geometries, functionalities and topologies of MOFs have been well tuned by rational design. Integrating the unique properties of MOFs and HoMS could realize the systemic design of materials from the molecular to the micro-level, which would provide a series of advantages for various applications, such as developing high performance catalysts for cascade and/or selective catalysis, combining the reaction and separation process for multiple reactions, releasing drugs in a certain environment for smart medicine, and so on. We believe it is time to summarize the recent progress in the integration of MOFs and HoMSs, including HoMSs coated with MOFs, MOF-derived HoMSs, and MOFs with a hollow multishelled structure, and we also put forward our personal outlook in relation to the future opportunities and challenges in this emerging yet promising research field.

Hollow multishell structures exercise temporal-spatial ordering and dynamic smart behaviour.

A hollow multishell structure (HoMS) is an assembly of multiple shells with voids between the individual shells. Accessible through nanopores, these voids represent separate reaction environments in the same assembly, such that HoMSs have unique properties that are applicable to diverse fields. These applications have mostly exploited the large specific surface area, high loading capacity and/or buffering effect of HoMSs, benefiting the mass/energy transmission and effective surface area. In comparison, the temporal-spatial ordering of reactions, as well as the dynamic smart behaviour of HoMSs, have been less explored but are also emphasized in this Perspective. We first describe the synthesis of HoMSs and the thermodynamic and kinetic aspects of their formation. We then consider the composition and structural functionalization of each shell within a HoMS and then highlight how these enable applications based on temporal-spatial ordering and dynamic smart behaviour.

Efficient sequential harvesting of solar light by heterogeneous hollow shells with hierarchical pores.

In nature, sequential harvesting of light widely exists in the old life entity, i.e. cyanobacteria, to maximize the light absorption and enhance the photosynthesis efficiency. Inspired by nature, we propose a brand new concept of temporally-spatially sequential harvesting of light in one single particle, which has purpose-designed heterogeneous hollow multi-shelled structures (HoMSs) with porous shells composed of nanoparticle subunits. Structurally, HoMSs consist of different band-gap materials outside-in, thus realizing the efficient harvesting of light with different wavelengths. Moreover, introducing oxygen vacancies into each nanoparticle subunit can also enhance the light absorption. With the benefit of sequential harvesting of light in HoMSs, the quantum efficiency at wavelength of 400 nm is enhanced by six times compared with the corresponding nanoparticles. Impressively, using these aforementioned materials as photocatalysts, highly efficient photocatalytic water splitting is realized, which cannot be achieved by using the nanoparticle counterparts. This new concept of temporally-spatially sequential harvesting of solar light paves the way for solving the ever-growing energy demand.