One‐Dimensional Hybrid Nanostructures for Heterogeneous Photocatalysis and Photoelectrocatalysis

Semiconductor‐based photocatalysis and photoelectrocatalysis have received considerable attention as alternative approaches for solar energy harvesting and storage. The photocatalytic or photoelectrocatalytic performance of a semiconductor is closely related to the design of the semiconductor at the nanoscale. Among various nanostructures, one‐dimensional (1D) nanostructured photocatalysts and photoelectrodes have attracted increasing interest owing to their unique optical, structural, and electronic advantages. In this article, a comprehensive review of the current research efforts towards the development of 1D semiconductor nanomaterials for heterogeneous photocatalysis and photoelectrocatalysis is provided and, in particular, a discussion of how to overcome the challenges for achieving full potential of 1D nanostructures is presented. It is anticipated that this review will afford enriched information on the rational exploration of the structural and electronic properties of 1D semiconductor nanostructures for achieving more efficient 1D nanostructure‐based photocatalysts and photoelectrodes for high‐efficiency solar energy conversion.     

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.     

Electron Tomography: A Unique Tool Solving Intricate Hollow Nanostructures

Innovations in nanofabrication have expedited advances in hollow‐structured nanomaterials with increasing complexity, which, at the same time, set challenges for the precise determination of their intriguing and complicated 3D configurations. Conventional transmission electron microscopy (TEM) analysis typically yields 2D projections of 3D objects, which in some cases is insufficient to reflect the genuine architectures of these 3D nano‐objects, providing misleading information. Advanced analytical approaches such as focused ion beam (FIB) and ultramicrotomy enable the real slicing of nanomaterials, realizing the direct observation of inner structures but with limited spatial discrimination. Electron tomography (ET) is a technique that retrieves spatial information from a series of 2D electron projections at different tilt angles. As a unique and powerful tool kit, this technique has experienced great advances in its application in materials science, resolving the intricate 3D nanostructures. Here, the exceptional capability of the ET technique in the structural, chemical, and quantitative analysis of hollow‐structured nanomaterials is discussed in detail. The distinct information derived from ET analysis is highlighted and compared with conventional analysis methods. Along with the advances in microscopy technologies, the state‐of‐the‐art ET technique offers great opportunities and promise in the development of hollow nanomaterials.     

Fundamentals of TiO2 Photocatalysis: Concepts,Mechanisms, and Challenges

Photocatalysis has been widely applied in various areas, such as solar cells, water splitting, and pollutant degradation. Therefore, the photochemical mechanisms and basic principles of photocatalysis, especially TiO₂ photocatalysis, have been extensively investigated by various surface science methods in the last decade, aiming to provide important information for TiO₂ photocatalysis under real environmental conditions. Recent progress that provides fundamental insights into TiO₂ photocatalysis at a molecular level is highlighted. Insights into the structures of TiO₂ and the basic principles of TiO₂ photocatalysis are discussed first, which provides the basic concepts of TiO₂ photocatalysis. Following this, details of the photochemistry of three important molecules (oxygen, water, methanol) on the model TiO₂ surfaces are presented, in an attempt to unravel the relationship between charge/energy transfer and bond breaking/forming in TiO₂ photocatalysis. Lastly, challenges and opportunities of the mechanistic studies of TiO₂ photocatalysis at the molecular level are discussed briefly, as well as possible photocatalysis models.     

Metal Oxide Hollow Nanostructures for Lithium‐ion Batteries

Metal oxide hollow structures have received great attention because of their many promising applications in a wide range of fields. As electrode materials for lithium‐ion batteries (LIBs), metal oxide hollow structures provide high specific capacity, superior rate capability, and improved cycling performance. In this Research News, we summarize the recent research activities in the synthesis of metal oxide hollow nanostructures with controlled shape, size, composition, and structural complexity, as well as their applications in LIBs. By focusing on hollow structures of some binary metal oxides (such as SnO₂, TiO₂, Fe₂O₃, Co₃O₄) and complex metal oxides, we seek to provide some rational understanding on the effect of nanostructure engineering on the electrochemical performance of the active materials. It is thus anticipated that this article will shed some light on the development of advanced electrode materials for next‐generation LIBs.     

Self‐Templating Approaches to Hollow Nanostructures

This current research progress on the fabrication of hollow nanostructures by using self‐templating methods is reviewed. After a brief introduction to the unique properties and applications of hollow nanostructures and the three general fabrication routes, the discussions are focused on the five main self‐templating strategies, including galvanic replacement, the Kirkendall effect, Ostwald ripening, dissolution–regrowth, and the surface‐protected hollowing process. Some newly developed synthetic routes are selected and discussed in detail. In conclusion, a summary and the perspectives on the directions that might lead the future development of this exciting field are presented.     

A Review of Photocatalysis using Self‐organized TiO2 Nanotubes and Other Ordered Oxide Nanostructures

Photocatalytic approaches, that is the reaction of light‐produced charge carriers at a semiconductor surface with their environment, currently attract an extremely wide scientific interest. This is to a large extent due to the high expectations: i) to convert sunlight directly into an energy carrier (H₂), ii) to stimulate chemical synthetic reactions, or iii) to degrade unwanted environmental pollutants. Since the early reports in 1972, TiO₂ has been the most investigated photocatalytic material by far; this originates from its outstanding electronic properties that allow for a wide range of applications. Not only the material, but also its structure and morphology, can have a considerable influence on the photocatalytic performance of TiO₂. In recent years, particularly 1D (or pseudo 1D) structures such as nanowires and nanotubes have received great attention. The present Review focuses on TiO₂ nanotube arrays (and similar structures) that grow by self‐organizing electrochemistry (highly aligned) from a Ti metal substrate. Herein, the growth, properties, and applications of these tubes are discussed, as well as ways and means to modify critical tube properties. Common strategies are addressed to improve the performance of photocatalysts such as doping or band‐gap engineering, co‐catalyst decoration, junction formation, or applying external bias. Finally, some unique applications of the ordered tube structures in various photocatalytic approaches are outlined.     

Lanthanide‐Doped Photoluminescence Hollow Structures: Recent Advances and Applications

Lanthanide‐doped nanomaterials have attracted significant attention for their preeminent properties and widespread applications. Due to the unique characteristic, the lanthanide‐doped photoluminescence materials with hollow structures may provide advantages including enhanced light harvesting, intensified electric field density, improved luminescent property, and larger drug loading capacity. Herein, the synthesis, properties, and applications of lanthanide‐doped photoluminescence hollow structures (LPHSs) are comprehensively reviewed. First, different strategies for the engineered synthesis of LPHSs are described in detail, which contain hard, soft, self‐templating methods and other techniques. Thereafter, the relationship between their structure features and photoluminescence properties is discussed. Then, niche applications including biomedicines, bioimaging, therapy, and energy storage/conversion are focused on and superiorities of LPHSs for these applications are particularly highlighted. Finally, keen insights into the challenges and personal prospects for the future development of the LPHSs are provided.     

A Composite Polymeric Carbon Nitride with In Situ Formed Isotype Heterojunctions for Highly Improved Photocatalysis under Visible Light

Introducing heterojunction is an effective way for improving the intrinsic photocatalytic activity of a graphitic carbon nitride (GCN) semiconductor. These heterostructures are mostly introduced by interfacing GCN with foreign materials that normally have entirely different physicochemical properties and show unfavorable compatibility, thus resulting in a limited improvement of the photocatalytic performance of the resultant materials. Herein, a composite polymeric carbon nitride (CPCN) that contains both melon‐based GCN and triazine‐based crystalline carbon nitride (CCN) is prepared by a simple thermal reaction between lithium chloride and GCN. Thanks to the intimate contact and good compatibility between GCN and CCN, an in situ formed heterojunction acts as a driving force for separating the photogenerated charge carriers in CPCN. As a result, CPCN exhibits a significantly improved photocatalytic performance under visible light irradiation, which is, respectively, 10.6 and 5.3 times as high as those of the GCN and CCN alone. This well designed isotype heterojunction by a coupling of CCN presents an effective avenue for developing efficient GCN photocatalysts.     

Complex Hollow Nanostructures: Synthesis and Energy‐Related Applications

Hollow nanostructures offer promising potential for advanced energy storage and conversion applications. In the past decade, considerable research efforts have been devoted to the design and synthesis of hollow nanostructures with high complexity by manipulating their geometric morphology, chemical composition, and building block and interior architecture to boost their electrochemical performance, fulfilling the increasing global demand for renewable and sustainable energy sources. In this Review, we present a comprehensive overview of the synthesis and energy‐related applications of complex hollow nanostructures. After a brief classification, the design and synthesis of complex hollow nanostructures are described in detail, which include hierarchical hollow spheres, hierarchical tubular structures, hollow polyhedra, and multi‐shelled hollow structures, as well as their hybrids with nanocarbon materials. Thereafter, we discuss their niche applications as electrode materials for lithium‐ion batteries and hybrid supercapacitors, sulfur hosts for lithium–sulfur batteries, and electrocatalysts for oxygen‐ and hydrogen‐involving energy conversion reactions. The potential superiorities of complex hollow nanostructures for these applications are particularly highlighted. Finally, we conclude this Review with urgent challenges and further research directions of complex hollow nanostructures for energy‐related applications.     

Surface‐Halogenation‐Induced Atomic‐Site Activation and Local Charge Separation for Superb CO2 Photoreduction

Solar‐energy‐driven CO₂ conversion into value‐added chemical fuels holds great potential in renewable energy generation. However, the rapid recombination of charge carriers and deficient reactive sites, as two major obstacles, severely hampers the photocatalytic CO₂ reduction activity. Herein, a desirable surface halogenation strategy to address the aforementioned concerns over a Sillén‐related layer‐structured photocatalyst Bi₂O₂(OH)(NO₃) (BON) is demonstrated. The surface halogen ions that are anchored on the Bi atoms by replacing surface hydroxyls on the one hand facilitate the local charge separation, and, on the other hand, activate the hydroxyls that profoundly boost the adsorption of CO₂ molecules and protons and facilitate the CO₂ conversion process, as evidenced by experimental and theoretical results collectively. Among the three series of BON‐X (X = Cl, Br, and I) catalysts, BON‐Br shows the most substantially enhanced CO production rate (8.12 µmol g^?1 h^?1) without any sacrificial agents or cocatalysts, ≈73 times higher than that of pristine Bi₂O₂(OH)(NO₃), also exceeding that of the state‐of‐the‐art photocatalysts reported to date. This work presents a surface polarization protocol for engineering charge behavior and reactive sites to promote photocatalysis, which shows great promise to the future design of high‐performance materials for clean energy production.     

Mechanistic Insight into the Yolk@Shell Transformation of MnO@Silica Nanospheres Incorporating Ni2+ Ions toward a Colloidal Hollow Nanoreactor

As an effort to develop a simple and versatile synthetic strategy that contributes to the evolution of hollow nanostructures with increasing complexity and functionality, this research is devoted to study the hollow transformation within a nanosized solid matrix. Through an in‐depth investigation of a hollowing process of MnO nanocrystals confined within a Ni²⁺ incorporating silica nanosphere, a very distinct transformation pathway can be explained that produces the yolk@shell nanostructure with a single Ni nanocrystal inside a silicate nanoshell. The yolk@shell structure is developed by a mechanism combining different processes, including the formation of a (Ni_0.1Mn_0.9)O mixed‐metal oxide and subsequent segregation of the reduced Ni. Furthermore, this study also devises a protocol to exploit the solid‐state‐synthesized powder for fabricating a colloidal hollow nanoreactor that can selectively catalyze the reduction of nitroarenes and be recycled via the magnetic process.     

La2CoFeO6竹节状中空纳米纤维的制备及其光催化性能

采用静电纺丝法制得La₂CoFeO₆竹节状中空纳米纤维光催化材料。La₂CoFeO₆纳米纤维具有稳定的一维结构, 由菱形晶型的La₂CoFeO₆纳米颗粒相互连接组成, 并存在明显的竹节状中空结构, 其比表面积可达98.7 m²/g。La₂CoFeO₆纳米纤维对自然光具有较高的利用率, 其禁带宽度为1.6 eV。在甲基橙溶液浓度为10 mg/L, pH为2, 催化剂用量为1.5 g/L条件下, 自然光光照2 h后, La₂CoFeO₆纳米纤维对甲基橙的降解率可达96.9%。     

中空氧化锌微球的制备及应用研究进展

中空ZnO微球具有密度低、比表面积大、渗透性好、光电性能优异等特点,受到科研工作者的广泛关注。综述了中空ZnO微球的制备方法及其应用领域,首先,主要阐述了硬模板法、软模板法、自模板法和无模板法4大类制备方法的研究进展,其次,介绍了中空ZnO微球在光催化、太阳能电池、气体传感器及生物医药等领域的应用进展,最后,对中空ZnO结构材料的发展前景进行了展望。     

Design of Hollow Nanostructures for Energy Storage,Conversion and Production

Hollow nanostructures have shown great promise for energy storage, conversion, and production technologies. Significant efforts have been devoted to the design and synthesis of hollow nanostructures with diverse compositional and geometric characteristics in the past decade. However, the correlation between their structure and energy‐related performance has not been reviewed thoroughly in the literature. Here, some representative examples of designing hollow nanostructure to effectively solve the problems of energy‐related technologies are highlighted, such as lithium‐ion batteries, lithium‐metal anodes, lithium–sulfur batteries, supercapacitors, dye‐sensitized solar cells, electrocatalysis, and photoelectrochemical cells. The great effect of structure engineering on the performance is discussed in depth, which will benefit the better design of hollow nanostructures to fulfill the requirements of specific applications and simultaneously enrich the diversity of the hollow nanostructure family. Finally, future directions of hollow nanostructure design to solve emerging challenges and further improve the performance of energy‐related technologies are also provided.