Quantum Emitters in Hexagonal Boron Nitride Have Spectrally Tunable Quantum Efficiency

Understanding the properties of novel solid‐state quantum emitters is pivotal for a variety of applications in research fields ranging from quantum optics to biology. Recently discovered defects in hexagonal boron nitride are especially interesting, as they offer much desired characteristics such as narrow emission lines and photostability. Here, the dependence of the emission on the excitation wavelength is studied. It is found that, in order to achieve bright single‐photon emission with high quantum efficiency, the excitation wavelength has to be matched to the emitter. This is a strong indication that the emitters possess a complex level scheme and cannot be described by a simple two or three‐level system. Using this excitation dependence of the emission, further insight to the internal level scheme is gained and it is demonstrated how to distinguish different emitters both spatially as well as in terms of their photon correlations.     

New Concepts and Applications in the Macromolecular Chemistry of Fullerenes

A new classification on the different types of fullerene‐containing polymers is presented according to their different properties and applications they exhibit in a variety of fields. Because of their interest and novelty, water‐soluble and biodegradable C₆₀‐polymers are discussed first, followed by polyfullerene‐based membranes where unprecedented supramolecular structures are presented. Next are compounds that involve hybrid materials formed from fullerenes and other components such as silica, DNA, and carbon nanotubes (CNTs) where the most recent advances have been achieved. A most relevant topic is still that of C₆₀‐based donor‐acceptor (D–A) polymers. Since their application in photovoltaics D–A polymers are among the most realistic applications of fullerenes in the so‐called molecular electronics. The most relevant aspects in these covalently connected fullerene/polymer hybrids as well as new concepts to improve energy conversion efficiencies are presented. The last topics disccused relate to supramolecular aspects that are in involved in C₆₀‐polymer systems and in the self‐assembly of C₆₀‐macromolecular structures, which open a new scenario for organizing, by means of non‐covalent interactions, new supramolecular structures at the nano‐ and micrometric scale, in which the combination of the hydrofobicity of fullerenes with the versatility of the noncovalent chemistry afford new and spectacular superstructures.     

Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal

The first experimental evidence for a giant, conventional barocaloric effect (BCE) associated with a pressure‐driven spin crossover transition near room temperature is provided. Magnetometry, neutron scattering, and calorimetry are used to explore the pressure dependence of the SCO phase transition in polycrystalline samples of protonated and partially deuterated [FeL₂][BF₄]₂ [L = 2,6‐di(pyrazol‐1‐yl)pyridine] at applied pressures of up to 120 MPa (1200 bar). The data indicate that, for a pressure change of only 0–300 bar (0–30 MPa), an adiabatic temperature change of 3 K is observed at 262 K or 257 K in the protonated and deuterated materials, respectively. This BCE is equivalent to the magnetocaloric effect (MCE) observed in gadolinium in a magnetic field change of 0–1 Tesla. The work confirms recent predictions that giant, conventional BCEs will be found in a wide range of SCO compounds.     

组合化学在无机功能材料中的研究进展

综述了近些年来,组合化学产业的历史背景、条件、基本方法、基本理论、以及在无机功能材料中的研究进展。     

Anionic Redox Chemistry as a Clue for Understanding the Structural Behavior in Layered Cathode Materials

The anionic redox chemistries of layered cathode materials have been in focus recently due to an intriguing phenomenon that cannot be described by the number of electrons of transition metal ions. However, even though several studies have investigated the anionic redox chemistry of layered materials in terms of the charge compensation, the relationship between the origin of the structural behavior and anionic redox chemistry in layered materials remains poorly understood. In addition, a simultaneous redox process of transition metal ions could occur through the d bands interaction. Here, it is demonstrated that the anionic redox chemistry is associated with the anisotropic structural behavior of the layered cathode materials albeit without providing additional capacities exceeding the theoretical values. These findings will provide a foundation of a new chapter in the understanding of the properties of materials.     

Bio‐inspired Materials Chemistry

Progress reports are a new type of article in Advanced Materials, dealing with the hottest current topics, and providing readers with a critically selected overview of important progress in these fields. It is not intended that the articles be comprehensive, but rather insightful, selective, critical, opinionated, and even visionary. We have approached scientists we believe are at the very forefront of these fields to contribute the articles, which will appear on an annual basis. The article below describes the latest advances in bio‐inspired materials chemistry.     

Bio‐inspired Materials Chemistry

Progress reports are a new type of article in Advanced Engineering Materials, dealing with the hottest current topics, and providing readers with a critically selected overview of important progress in these fields. It is not intended that the articles be comprehensive, but rather insightful, selective, critical, opinionated, and even visionary. We have approached scientists we believe are at the very forefront of these fields to contribute the articles, which will appear on an annual basis. The article below describes the latest advances in Bio‐inspired Materials Chemistry.     

Metal Immiscibility Route to Synthesis of Ultrathin Carbides,Borides, and Nitrides

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal‐carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum‐copper bilayer with corresponding precursor (C₂H₂, B powder, and NH₃). The ultrathin crystals are found on the copper surface (opposite of the metal–metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal–metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings.     

Materials Chemistry of Nanoultrasonic Biomedicine

As a special cross‐disciplinary research frontier, nanoultrasonic biomedicine refers to the design and synthesis of nanomaterials to solve some critical issues of ultrasound (US)‐based biomedicine. The concept of nanoultrasonic biomedicine can also overcome the drawbacks of traditional microbubbles and promote the generation of novel US‐based contrast agents or synergistic agents for US theranostics. Here, we discuss the recent developments of material chemistry in advancing the nanoultrasonic biomedicine for diverse US‐based bio‐applications. We initially introduce the design principles of novel nanoplatforms for serving the nanoultrasonic biomedicine, from the viewpoint of synthetic material chemistry. Based on these principles and diverse US‐based bio‐application backgrounds, the representative proof‐of‐concept paradigms on this topic are clarified in detail, including nanodroplet vaporization for intelligent/responsive US imaging, multifunctional nano‐contrast agents for US‐based multi‐modality imaging, activatable synergistic agents for US‐based therapy, US‐triggered on‐demand drug releasing, US‐enhanced gene transfection, US‐based synergistic therapy on combating the cancer and potential toxicity issue of screening various nanosystems suitable for nanoultrasonic biomedicine. It is highly expected that this novel nanoultrasonic biomedicine and corresponding high performance in US imaging and therapy can significantly promote the generation of new sub‐discipline of US‐based biomedicine by rationally integrating material chemistry and theranostic nanomedicine with clinical US‐based biomedicine.     

A Modular System for the Design of Stimuli‐Responsive Multifunctional Nanoparticle Aggregates by Use of Host–Guest Chemistry

A self‐assembly approach for the design of multifunctional nanomaterials consisting of different nanoparticles (gold, iron oxide, and lanthanide‐doped LiYF₄) is developed. This modular system takes advantage of the light‐responsive supramolecular host–guest chemistry of β‐cyclodextrin and arylazopyrazole, which enables the dynamic and reversible self‐assembly of particles to spherical nanoparticle aggregates in aqueous solution. Due to the magnetic iron oxide nanoparticles, the aggregates can be manipulated by an external magnetic field leading to the formation of linear structures. As a result of the integration of upconversion nanoparticles, the aggregates are additionally responsive to near‐infrared light and can be redispersed by use of the upconversion effect. By varying the nanoparticle and linker concentrations the composition, size, shape, and properties of the multifunctional nanoparticle aggregates can be fine‐tuned.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

Borohydride‐Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid‐State Electrolytes

Borohydride solid‐state electrolytes with room‐temperature ionic conductivity up to ≈70 mS cm^?1 have achieved impressive progress and quickly taken their place among the superionic conductive solid‐state electrolytes. Here, the focus is on state‐of‐the‐art developments in borohydride solid‐state electrolytes, including their competitive ionic‐conductive performance, current limitations for practical applications in solid‐state batteries, and the strategies to address their problems. To open, fast Li/Na/Mg ionic conductivity in electrolytes with BH₄ ^? groups, approaches to engineering borohydrides with enhanced ionic conductivity, and later on the superionic conductivity of polyhedral borohydrides, their correlated conductive kinetics/thermodynamics, and the theoretically predicted high conductive derivatives are discussed. Furthermore, the validity of borohydride pairing with coated oxides, sulfur, organic electrodes, MgH₂, TiS₂, Li₄Ti₅O₁₂, electrode materials, etc., is surveyed in solid‐state batteries. From the viewpoint of compatible cathodes, the stable electrochemical windows of borohydride solid‐state electrolytes, the electrode/electrolyte interface behavior and battery device design, and the performance optimization of borohydride‐based solid‐state batteries are also discussed in detail. A comprehensive coverage of emerging trends in borohydride solid‐state electrolytes is provided and future maps to promote better performance of borohydride SSEs are sketched out, which will pave the way for their further development in the field of energy storage.     

Combinatorial solid state chemistry by multitarget laser ablation: a way for the elaboration of new superconducting cuprates thin films?

Laser ablation by varying the number of consecutive laser pulses upon two targets, one superconducting YBa₂Cu₃O₇, the other insulating MCuO₂ (M=Sr, Ca), is used to build thin films of tuneable average compositions. Most of the samples are found to display high-T_c superconductivity with critical temperature generally higher than the 60 K of the ‘Cava phase’, the prototypic structure with two consecutive conducting CuO₂ planes and containing same types of atoms. The properties of the samples are not linearly dependent on the concentration of species coming from the insulating target. In addition, they depend not only on the ratio of the number of pulses on each target, but also on the number of consecutive pulses on each target. Thin films are characterized by temperature-dependent DC conductivity, X-ray diffraction, Castaing microprobe and infrared reflectivity spectroscopy. Present results suggest the robustness of high-T_c superconductivity, possibly related to a ‘Cava-phase-like’ skeleton.     

提高蛋白质晶体质量的研究进展

获得高质量蛋白质晶体一直是X射线衍射解析蛋白质结构的瓶颈问题,因此研究提高蛋白质晶体质量的方法具有非常重要的意义。近年来人们从影响蛋白质结晶过程的各个因素出发,发展了一系列提高蛋白质晶体质量的方法,如在亚稳区生长蛋白质晶体、利用特殊环境影响蛋白质晶体生长的动力学过程、利用去垢剂提高蛋白质晶体质量和分子工程改造蛋白质分子提高晶体质量等。分析和评述了这些方法影响蛋白质结晶过程的机理。     

Phase‐Change Hyperbolic Heterostructures for Nanopolaritonics: A Case Study of hBN/VO2

Unlike conventional plasmonic media, polaritonic van der Waals (vdW) materials hold promise for active control of light–matter interactions. The dispersion relations of elementary excitations such as phonons and plasmons can be tuned in layered vdW systems via stacking using functional substrates. In this work, infrared nanoimaging and nanospectroscopy of hyperbolic phonon polaritons are demonstrated in a novel vdW heterostructure combining hexagonal boron nitride (hBN) and vanadium dioxide (VO₂). It is observed that the insulator‐to‐metal transition in VO₂ has a profound impact on the polaritons in the proximal hBN layer. In effect, the real‐space propagation of hyperbolic polaritons and their spectroscopic resonances can be actively controlled by temperature. This tunability originates from the effective change in local dielectric properties of the VO₂ sublayer in the course of the temperature‐tuned insulator‐to‐metal phase transition. The high susceptibility of polaritons to electronic phase transitions opens new possibilities for applications of vdW materials in combination with strongly correlated quantum materials.