Bioinspired Synthesis of Monolithic and Layered Aerogels

Aerogels are the least dense and most porous materials known to man, with potential applications from lightweight superinsulators to smart energy materials. To date their use has been seriously hampered by their synthesis methods, which are laborious and expensive. Taking inspiration from the life cycle of the damselfly, a novel ambient pressure‐drying approach is demonstrated in which instead of employing low‐surface‐tension organic solvents to prevent pore collapse during drying, sodium bicarbonate solution is used to generate pore‐supporting carbon dioxide in situ, significantly reducing energy, time, and cost in aerogel production. The generic applicability of this readily scalable new approach is demonstrated through the production of granules, monoliths, and layered solids with a number of precursor materials.     

Hybrid Crystals Comprising Metal–Organic Frameworks and Functional Particles: Synthesis and Applications

Hybrid crystals containing encapsulated functional species exhibit promising novel physical and chemical properties. The realization of many properties critically depends on the selection of suitable functional species for incorporation, the rational control of the crystallinity of the host materials, and the manipulation of the distribution of the encapsulated species; only a few hybrid crystals achieve this. Here, a novel synthetic method enables the encapsulation of functional species within crystalline metal–organic frameworks (MOFs). Various kinds of single‐crystalline MOFs with incorporated particles are presented. The encapsulated particles can be distributed in a controllable manner, and the hybrid crystals are applied to the heterogeneous catalysis of the reduction of nitroarenes. These findings suggest a general approach for the construction of MOF materials with potential applications; by combining species and MOFs with suitable functionalities, new properties—not possible by other means—may arise.     

Amorphous Quantum Nanomaterials

In quantum materials, macroscopic behavior is governed in nontrivial ways by quantum phenomena. This is usually achieved by exquisite control over atomic positions in crystalline solids. Here, it is demonstrated that the use of disordered glassy materials provides unique opportunities to tailor quantum material properties. By borrowing ideas from single‐molecule spectroscopy, single delocalized π‐electron dye systems are isolated in relatively rigid ultrasmall (<10 nm diameter) amorphous silica nanoparticles. It is demonstrated that chemically tuning the local amorphous silica environment around the dye over a range of compositions enables exquisite control over dye quantum behavior, leading to efficient probes for photodynamic therapy (PDT) and stochastic optical reconstruction microscopy (STORM). The results suggest that efficient fine‐tuning of light‐induced quantum behavior mediated via effects like spin‐orbit coupling can be effectively achieved by systematically varying averaged local environments in glassy amorphous materials as opposed to tailoring well‐defined neighboring atomic lattice positions in crystalline solids. The resulting nanoprobes exhibit features proven to enable clinical translation.     

Recent Progress on Germanene and Functionalized Germanene: Preparation,Characterizations, Applications,and Challenges

A new family of single‐atom‐thick 2D germanium‐based materials with graphene‐like atomic arrangement, germanene and functionalized germanene, has attracted intensive attention due to their large bandgap and easily tailored electronic properties. Unlike carbon atoms in graphene, germanium atoms tend to adopt mixed sp²/sp³ hybridization in germanene, which makes it chemically active on the surface and allows its electronic states to be easily tuned by chemical functionalization. Impressive achievements in terms of the applications in energy storage and catalysis have been reported by using germanene and functionalized germanene. Herein, the fabrication of epitaxial germanene on different metallic substrates and its unique electronic properties are summarized. Then, the preparation strategies and the fundamental properties of hydrogen‐functionalized germanene (germanane or GeH) and other ligand‐terminated forms of germanene are presented. Finally, the progress of their applications in energy storage and catalysis, including both experimental results and theoretical predictions, is analyzed.     

Sharp V‐notches in viscoplastic solids: Strain energy rate density rule and fracture toughness

Different from Neuber's rule or Glinka's energy method which are always adopted to characterize the notch tip field under elastoplastic condition, in this paper, the strain energy rate density (SERD) rule is used for viscoplastic materials. In particular, based on the definition of generalized notch stress intensity factor (G‐NSIF) for sharp V‐notch in viscoplastic solids, the concept of SERD for sharp V‐notch in viscoplastic solids is presented. Subsequently, by taking as a starting point the SERD, the averaged strain energy density (SED) for sharp V‐notch in viscoplastic solids is derived with integration of time. The fracture toughness relation between sharp V‐notch specimens and crack specimen in viscoplastic materials is given based on the transformation of SERD. A numerical approach is presented to compute the SERD and SED based on finite element method. Some crucial comments on the G‐NSIF have been discussed. Some typical solutions for SERD and SED for sharp V‐notched specimens are investigated.     

Advanced triboelectric materials for liquid energy harvesting and emerging application

Triboelectric properties of materials play an essential role in liquid energy harvesting and emerging application. The triboelectric properties of materials can be controlled by chemical functionalization strategy, which can improve the utilization of liquid energy resources or reduce the hazards of electrostatic effects. Herein, the latest research progress in molecular modification based on chemical functionalization to control triboelectric properties of materials is systematically summarized. By introducing the mechanism of contact electrification between liquid and solid materials and the developmental history of liquid–solid contact electrification, the influence of solid surface charge density, wettability and liquid properties on contact electrification of liquid and solid materials is described. Research progress on chemical functionalization for improving the hydrophobicity of solid materials, surface charge density of solid materials and triboelectric properties of liquid materials is highlighted. The focus then turns to the significance of enhanced liquid–solid contact electrification in energy harvesting, self-powered sensors and metal corrosion protection. Recent advances in chemical functionalization strategies for weakening the triboelectric properties of solid and liquid materials are also highlighted. Finally, an outlook of the potential challenges for developing chemical functionalization strategies in the field of solid surface modification and liquid molecular modification is presented.     

A Functionalized Carbon Surface for High‐Performance Sodium‐Ion Storage

Sodium‐ion batteries (SIBs) are promising for large‐scale energy storage systems and carbon materials are the most likely candidates for their electrodes. The existence of defects in carbon materials is crucial for increasing the sodium storage ability. However, both the reversible capacity and efficiency need to be further improved. Functionalization is a direct and feasible approach to address this issue. Based on the structural changes in carbon materials produced by surface functionalization, three basic categories are defined: heteroatom doping, grafting of functional groups, and the shielding of defects. Heteroatom doping can improve the electrochemical reactivity, and the grafting of functional groups can promote both the diffusion‐controlled bulk process and surface‐confined capacitive process. The shielding of defects can further increase the efficiency and cyclic stability without sacrificing reversible capacity. In this Review, recent progresses in the ways to produce surface functionalization are presented and the related impact on the physical and chemical properties of carbon materials is discussed. Moreover, the critical issues, challenges, and possibilities for future research are summarized.     

Characterization of lattice defects in metallic materials by positron annihilation spectroscopy: A review

Positron is an excellent probe of lattice defects in solids. A thermallized positron delocalized in lattice can be trapped at open volume defects, e.g. vacancies, dislocations, grain boundaries etc. Positron annihilation spectroscopy is a non-destructive technique which enables characterization of open volume lattice defects in solids on the atomic scale. Positron lifetime and Doppler broadening of annihilation photo-peak are the most common observables related to positron annihilation process. Positron lifetime spectroscopy enables to identify defects in solids and to determine their concentrations while coincidence measurement of Doppler broadening provides information about local chemical environment of defects. This article provides a review of the state-of-art of defect characterization in bulk metallic materials by positron annihilation spectroscopy. Advanced analysis of positron annihilation data and recent developments of positron annihilation methodology are described and discussed on examples of defect studies of metallic materials. Future development in the field is proposed as well.     

Noble Metal‐Free Nanocatalysts with Vacancies for Electrochemical Water Splitting

The fast development of nanoscience and nanotechnology has significantly advanced the fabrication of nanocatalysts and the in‐depth study of the structural‐activity characteristics of materials at the atomic level. Vacancies, as typical atomic defects or imperfections that widely exist in solid materials, are demonstrated to effectively modulate the physicochemical, electronic, and catalytic properties of nanomaterials, which is a key concept and hot research topic in nanochemistry and nanocatalysis. The recent experimental and theoretical progresses achieved in the preparation and application of vacancy‐rich nanocatalysts for electrochemical water splitting are explored. Engineering of vacancies has shown to open up a new avenue beyond the traditional morphology, size, and composition modifications for the development of nonprecious electrocatalysts toward efficient energy conversion. First, an introduction followed by discussions of different types of vacancies, the approaches to create vacancies, and the advanced techniques widely used to characterize these vacancies are presented. Importantly, the correlations between the vacancies and activities of the vacancy‐rich electrocatalysts via tuning the electronic states, active sites, and kinetic energy barriers are reviewed. Finally, perspectives on the existing challenges along with some opportunities for the further development of vacancy‐rich noble metal‐free electrocatalysts with high performance are discussed.     

Emerging 2D Materials Produced via Electrochemistry

2D materials are important building blocks for the upcoming generation of nanostructured electronics and multifunctional devices due to their distinct chemical and physical characteristics. To this end, large-scale production of 2D materials with high purity or with specific functionalities represents a key to advancing fundamental studies as well as industrial applications. Among the state-of-the-art synthetic protocols, electrochemical exfoliation of layered materials is a very promising approach that offers high yield, great efficiency, low cost, simple instrumentation, and excellent up-scalability. Remarkably, playing with electrochemical parameters not only enables tunable material properties but also increases the material diversities from graphene to a wide spectrum of 2D semiconductors. Here, a succinct and critical survey of the recent progress in this research direction is presented, comprising the strategic design, exfoliation principles, underlying mechanisms, processing techniques, and potential applications of 2D materials. At the end of the discussion, the emerging trends, challenges, and opportunities in real practice are also highlighted.     

Self‐Powered Chemical Sensing Driven by Graphene‐Based Photovoltaic Heterojunctions with Chemically Tunable Built‐In Potentials

Ultralow power chemical sensing is essential toward realizing the Internet of Things. However, electrically driven sensors must consume power to generate an electrical readout. Here, a different class of self‐powered chemical sensing platform based on unconventional photovoltaic heterojunctions consisting of a top graphene (Gr) layer in contact with underlying photoactive semiconductors including bulk silicon and layered transition metal dichalcogenides is proposed. Owing to the chemically tunable electrochemical potential of Gr, the built‐in potential at the junction is effectively modulated by absorbed gas molecules in a predictable manner depending on their redox characteristics. Such ability distinctive from bulk photovoltaic counterparts enables photovoltaic‐driven chemical sensing without electric power consumption. Furthermore, it is demonstrated that the hydrogen (H₂) sensing properties are independent of the light intensity, but sensitive to the gas concentration down to the 1 ppm level at room temperature. These results present an innovative strategy to realize extremely energy‐efficient sensors, providing an important advancement for future ubiquitous sensing.     

Retrieving Grain Boundaries in 2D Materials

The coalescence of randomly distributed grains with different crystallographic orientations can result in pervasive grain boundaries (GBs) in 2D materials during their chemical synthesis. GBs not only are the inherent structural imperfection that causes influential impacts on structures and properties of 2D materials, but also have emerged as a platform for exploring unusual physics and functionalities stemming from dramatic changes in local atomic organization and even chemical makeup. Here, recent advances in studying the formation mechanism, atomic structures, and functional properties of GBs in a range of 2D materials are reviewed. By analyzing the growth mechanism and the competition between far-field strain and local chemical energies of dislocation cores, a complete understanding of the rich GB morphologies as well as their dependence on lattice misorientations and chemical compositions is presented. Mechanical, electronic, and chemical properties tied to GBs in different materials are then discussed, towards raising the concept of using GBs as a robust atomic-scale scaffold for realizing tailored functionalities, such as magnetism, luminescence, and catalysis. Finally, the future opportunities in retrieving GBs for making functional devices and the major challenges in the controlled formation of GB structures for designed applications are commented.     

Polymeric Graphene Bulk Materials with a 3D Cross‐Linked Monolithic Graphene Network

Although many great potential applications are proposed for graphene, till now none are yet realized as a stellar application. The most challenging issue for such practical applications is to figure out how to prepare graphene bulk materials while maintaining the unique two‐dimensional (2D) structure and the many excellent properties of graphene sheets. Herein, such polymeric graphene bulk materials containing three‐dimensional (3D) cross‐linked networks with graphene sheets as the building unit are reviewed. The theoretical research on various proposed structures of graphene bulk materials is summarized first. Then, the synthesis or fabrication of these graphene materials is described, which comprises mainly two approaches: chemical vapor deposition and cross‐linking using graphene oxide directly. Finally, some exotic and exciting potential applications of these graphene bulk materials are presented.     

Tailored Microstructures: Can a Dream come True?

The mechanical properties of crystalline solids are determined by the spatial distribution of chemical elements and crystal defects, which is referred to as microstructure. Microstructure changes during processing, and its evolution can be influenced by processing conditions and external fields. Advanced microstructure codes can cover the through‐process microstructural evolution and allow first predictions of terminal materials properties.     

Testing Metal‐Oxide Nanomaterials for Human Safety

Nanomaterials can display distinct biological effects compared with bulk materials of the same chemical composition. The physico‐chemical characterization of nanomaterials and their interaction with biological media are essential for reliable studies and are reviewed here with a focus on widely used metal oxide and carbon nanomaterials. Available rat inhalation and cell culture studies compared to original results suggest that hazard potential is not determined by a single physico‐chemical property but instead depends on a combination of material properties. Reactive oxygen species generation, fiber shape, size, solubility and crystalline phase are known indicators of nanomaterials biological impact. According to these properties the summarized hazard potential decreases in the order multi‐walled carbon nanotubes >> CeO₂, ZnO > TiO₂ > functionalized SiO₂ > SiO₂, ZrO₂, carbon black. Enhanced understanding of biophysical properties and cellular effects results in improved testing strategies and enables the selection and production of safe materials.     

Heterostructures Based on 2D Materials: A Versatile Platform for Efficient Catalysis

The unique structural and electronic properties of 2D materials, including the metal and metal‐free ones, have prompted intense exploration in the search for new catalysts. The construction of different heterostructures based on 2D materials offers great opportunities for boosting the catalytic activity in electo(photo)chemical reactions. Particularly, the merits resulting from the synergism of the constituent components and the fascinating properties at the interface are tremendously interesting. This scenario has now become the state‐of‐the‐art point in the development of active catalysts for assisting energy conversion reactions including water splitting and CO₂ reduction. Here, starting from the theoretical background of the fundamental concepts, the progressive developments in the design and applications of heterostructures based on 2D materials are traced. Furthermore, a personal perspective on the exploration of 2D heterostructures for further potential application in catalysis is offered.     

Arbitrarily oriented microcracks near the tip of an interface macrocrack in bonded dissimilar anisotropic materials

It is well known that microcracking in brittle materials results in a reduction of the stress intensity factor (SIF) and energy release rate (ERR). The reduced SIF or ERR represents crack tip shielding which is of significant interest to micromechanics and material science researchers. However, the effect of microcracking on the SIF and ERR is a complicated subject even for isotropic homogeneous materials, and becomes much more formidable in case of interface cracks in bonded dissimilar solids. To unravel the micromechanics of interface crack tip shielding in bonded dissimilar anisotropic solids, an interface crack interacting with arbitrarily oriented subinterface microcracks in bonded dissimilar anisotropic materials is studied. After deducing the fundamental solutions for a subinterface crack under concentrated normal and tangential tractions, the present interaction problem is reduced to a system of integral equations which is then solved numerically. A J‐integral analysis is then performed with special attention focused on the J₂‐integral in a local coordinate system attached to the microcracks. Theoretical and numerical results reassert the conservation law of the J‐integral derived for isotropic materials 1 , 2 also to be valid for bonded dissimilar anisotropic materials. It is further concluded that there is a wastage when the remote J‐integral transmits across the microcracking zone from infinity to the interface macrocrack tip. In order to highlight the influence of microstructure on the interfacial crack tip stress field, the crack tip SIF and ERR in several typical cases are presented. It is interesting to note that the Mode I SIF at the interface crack tip is quite different from the ERR in bonded dissimilar anisotropic materials.     

Carbon‐Nanotube‐Based Thermoelectric Materials and Devices

Conversion of waste heat to voltage has the potential to significantly reduce the carbon footprint of a number of critical energy sectors, such as the transportation and electricity‐generation sectors, and manufacturing processes. Thermal energy is also an abundant low‐flux source that can be harnessed to power portable/wearable electronic devices and critical components in remote off‐grid locations. As such, a number of different inorganic and organic materials are being explored for their potential in thermoelectric‐energy‐harvesting devices. Carbon‐based thermoelectric materials are particularly attractive due to their use of nontoxic, abundant source‐materials, their amenability to high‐throughput solution‐phase fabrication routes, and the high specific energy (i.e., W g^?1) enabled by their low mass. Single‐walled carbon nanotubes (SWCNTs) represent a unique 1D carbon allotrope with structural, electrical, and thermal properties that enable efficient thermoelectric‐energy conversion. Here, the progress made toward understanding the fundamental thermoelectric properties of SWCNTs, nanotube‐based composites, and thermoelectric devices prepared from these materials is reviewed in detail. This progress illuminates the tremendous potential that carbon‐nanotube‐based materials and composites have for producing high‐performance next‐generation devices for thermoelectric‐energy harvesting.