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Effective intratumoral drug penetration is pivotal for successful cancer treatment. However, due to the disrupted capillary networks and poor perfusion in solid tumors, there exist challenges to realize autonomous directional drug penetration and controlled drug release within the tumor. Considering the specificity of glucose within tumor tissue, we draw inspiration from nature and engineer asymmetrical hollow structures exhibiting chemotaxis towards high glucose levels. By incorporating multiple shells into these structures, we enhance the local chemical concentration gradients, thereby improving cellular uptake and precise targeting. The advantages of anisotropic hollow multishell structure (a-HoMS) can be reflected from the diffusion coefficient and directivity, which increase by 73.4 % and 273 % respectively compared to conventional isotropic hollow spheres, achieving the most linear movement while ensuring the speed of movement. Furthermore, the multi-level porosity and temporal-spatial order of a-HoMS enable sequential drug delivery that inhibits angiogenesis with inducing cell apoptosis. After the eradication of localized tumor cells, the a-HoMS can automatically migrate to the alive tumor cells under the glucose gradient, inducing another cycle of drug delivery and chemotaxis, resulting in excellent antitumor efficacy. These anisotropic HoMS demonstrate intelligence, adaptability, and precision in tumor therapy, providing valuable insights for programmable treatment within tissues., (© 2024 Wiley-VCH GmbH.)

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 CO 2 toward CH 4 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 CO 2 reduction., (© 2022 Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

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., (© 2022 Wiley-VCH GmbH.)

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@N x 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@N x C HoMS-DL electrode maintains 96% of its theoretical capacity after 2000 cycles at 2C., (© 2022 Wiley-VCH GmbH.)

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 Ta 2 O 5 /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., (© 2021 Wiley-VCH GmbH.)

La- and Rh-co-doped SrTiO 3 (STO:La/Rh) hollow multishelled structures (HoMSs) are fabricated by adding La 3+ and Rh 3+ ions during the hydrothermal process of converting TiO 2 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 BiVO 4 (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., (© 2021 Wiley-VCH GmbH.)

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., (© 2021 Wiley-VCH GmbH.)

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., (© 2020 Wiley-VCH GmbH.)

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., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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) Nb 2 O 5 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 Nb 2 O 5 -based materials, which delivered an excellent energy and power densities simultaneously, and superb cycling stability., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Precise control of the micro-/nanostructures of nanomaterials, such as hollow multi-shelled structures (HoMSs), has shown its great advantages in various applications. Now, the crystal structure of building blocks of HoMSs are controlled by introducing the lattice distortion in HoMSs, for the first time. The lattice distortion located at the nanoscale interface of SnS 2 /SnO 2 can provide additional active sites, which not only provide the catalytic activity under visible light but also improve the separation of photoexcited electron-hole pairs. Combined with the efficient light utilization, the natural advantage of HoMSs, a record catalytic activity was achieved in solid-gas system for CO 2 reduction, with an excellent stability and 100 % CO selectivity without using any sensitizers or noble metals., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The crystal phase plays an important role in controlling the properties of a nanomaterial; however, it is a great challenge to obtain a nanomaterial with high purity of the metastable phase. For instance, the large-scale synthesis of the metallic phase MoS 2 (1T-MoS 2 ) is important for enhancing electrocatalytic reaction, but it can only be obtained under harsh conditions. Herein, a spatially confined template method is proposed to synthesize high phase-purity MoS 2 with a 1T content of 83 %. Moreover, both the confined space and the structure of template will affect the purity of 1T-MoS 2 ; in this case, this approach was extended to other similar spatially confined templates to obtain the high-purity material. The obtained ultrathin nanosheets exhibit good electrocatalytic activity and excellent stability in the hydrogen evolution reaction., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

As a rising star of carbon allotropes, graphynes (GYs) merely consist of sp- and sp 2 -hybridized carbon atoms, which endow them a large conjugated network and expanded 2D porous structure. With unique topological structure, GYs display unusual semiconducting properties, especially in the aspects of charge mobility and electron transport. Among the members of the GY family, only graphdiyne (GD) can be successfully synthesized in large quantities. The advanced properties of GD make it promising in various applications. Here, the recent progress in the synthesis of GD and GD-based composites is reviewed as well as their applications in photorelated and electrocatalytic applications. It is hoped that this Review will promote the development and applications of carbon chemistry.

Similar to heterostructures composed of different materials, possessing unique properties due to the synergistic effect between different components, the crystal-phase heterostructures, one variety of hetero-phase structures, composed of different crystal phases in monometallic nanomaterials are herein developed, in order to explore crystal-phase-based applications. As novel hetero-phase structures, amorphous/crystalline heterostructures are highly desired, since they often exhibit unique properties, and hold promise in various applications, but these structures have rarely been studied in noble metals. Herein, via a one-pot wet-chemical method, a series of amorphous/crystalline hetero-phase Pd nanosheets is synthesized with different crystallinities for the catalytic 4-nitrostyrene hydrogenation. The chemoselectivity and activity can be fine-tuned by controlling the crystallinity of the as-synthesized Pd nanosheets. This work might pave the way to preparing various hetero-phase nanostructures for promising applications., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hierarchical metal nanostructures containing 1D nanobuilding blocks have stimulated great interest due to their abundant active sites for catalysis. Herein, hierarchical 4H/face-centered cubic (fcc) Ru nanotubes (NTs) are synthesized by a hard template-mediated method, in which 4H/fcc Au nanowires (NWs) serve as sacrificial templates which are then etched by copper ions (Cu 2+ ) in dimethylformamide. The obtained hierarchical 4H/fcc Ru NTs contain ultrathin Ru shells (5-9 atomic layers) and tiny Ru nanorods with length of 4.2 ± 1.1 nm and diameter of 2.2 ± 0.5 nm vertically decorated on the surface of Ru shells. As an electrocatalyst for the hydrogen evolution reaction in alkaline media, the hierarchical 4H/fcc Ru NTs exhibit excellent electrocatalytic performance, which is better than 4H/fcc Au-Ru NWs, commercial Pt/C, Ru/C, and most of the reported electrocatalysts., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In recent decades, researchers have devoted tremendous effort into the rational design and controlled synthesis of metal nanomaterials with well-defined size, morphology, composition, and structure, and great achievements have been reached. However, the crystal-phase engineering of metal nanomaterials still remains a big challenge. Recent research has revealed that the crystal phase of metal nanomaterials can significantly alter their properties, arising from the distinct atomic arrangement and modified electronic structure. Until now, it has been relatively uncommon to synthesize metal nanomaterials with novel crystal phases in spite of the fact that these nanostructures would be promising for various applications. Here, the research progress regarding the fine control of noble metal (Au, Ag, Ru, Rh, Pd) and non-noble metal (Fe, Co, Ni) nanomaterials with novel crystal phases is reviewed. First, synthesis strategies and their phase transformations are summarized, while highlighting the peculiar characteristics of each element. The phase-dependent properties are then discussed by providing representative examples. Finally, the challenges and perspectives in this emerging field are proposed., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Inspired by the unique properties of ultrathin 2D nanomaterials and excellent catalytic activities of noble metal nanostructures for renewable fuel cells, a facile method is reported for the high-yield synthesis of ultrathin 2D PdCu alloy nanosheets under mild conditions. Impressively, the obtained PdCu alloy nanosheet after being treated with ethylenediamine can be used as a highly efficient electrocatalyst for formic acid oxidation. The study implicates that the rational design and controlled synthesis of an ultrathin 2D noble metal alloy may open up new opportunities for enhancing catalytic activities of noble metal nanostructures., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ultrathin Pd nanosheets (NSs) coated with submonolayered Ru, referred to as Pd@Ru NSs, are synthesized via a seed-mediated growth method. The underpotential deposition can be the driving force for the formation of Pd@Ru NSs. The Pd@Ru NSs exhibit superior catalytic properties in the reduction of 4-nitrophenol and the semihydrogenation of 1-octyne, compared to the pure Pd NSs and Ru NSs., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solar energy is commonly considered to be one of the most important forms of future energy production. This is due to its ability to generate essentially free power, after installation, with low environmental impact. Green plants, meanwhile, exhibit a process for light-to-charge conversion that provides a useful model for using solar radiation efficiently. Granum, the core organ in photosynthesis consists of a stack of ~10-100 thylakoids containing pigments and electrons acceptors. Imitating the structure and function of granum, stacked structures are fabricated with TiO(2) /graphene nanosheets as the thylakoids unit, and their photo-electric effect is studied by varying the number of layers present in the film. The photo-electric response of the graphene composites are found to be 20 times higher than that of pure TiO(2) in films with 25 units stacked. Importantly, the cathodic photocurrent changes to anodic photocurrent as the thickness increases, an important feature of efficient solar cells which is often ignored. Here graphene is proposed to perform similarly to the b6f complex in granum, by separating charges and transporting electrons through the stacked film. Using this innovation, stacked TiO(2) /graphene structures are now able to significantly increase photoanode thickness in solar cells without losing the ability to conduct electrons., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dye-sensitized solar cells (DSSCs) are promising low-cost, high-efficiency devices with low environmental impact. One of the important methods to improve their efficiencies involves increasing the light-harvesting efficiency. Earlier work has focused on varying the morphology of the photoanode. With such a hierarchical structured photoanode in hand, we modify herein the structure of the counter electrode to enhance the optical path length through the plasmonic and reflecttion effects. With the introduced topological gold layer, the photocurrent and efficiency are increased by 16 % and 18 %, respectively, due to the increased light collection. Besides, this effect is effective at both high and low levels of solar irradiation., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of multishelled ZnO hollow microspheres with controlled shell number and inter-shell spacing have been successfully prepared by a simple carbonaceous microsphere templating method, whose large surface area and complex multishelled hollow structure enable them load sufficient dyes and multi-reflect the light for enhancing light harvesting and realize a high conversion efficiency of up to 5.6% when used in dye-sensitized solar cells., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)