The Synergetic Innovation Center for Advanced Materials

Great attention has been given to metal–organic frameworks (MOFs)-derived solid bases because of their attractive structure and catalytic performance in various organic reactions. The extraordinary skeleton structure of MOFs provides many possibilities for incorporation of diverse basic functionalities, which is unachievable for conventional solid bases. The past decade has witnessed remarkable advances in this vibrant research area; however, MOFs for heterogeneous basic catalysis have never been reviewed until now. Therefore, a review summarizing MOFs-derived base catalysts is highly expected. In this review, we present an overview of the recent progress in MOFs-derived solid bases covering preparation, characterization, and catalytic applications. In the preparation section, the solid bases are divided into two categories, namely, MOFs with intrinsic basicity and MOFs with modified basicity. The basicity can originate from either metal sites or organic ligands. Different approaches used for generation of basic sites are included, and each approach is described with representative examples. The fundamental principles for the design and fabrication of MOFs with basic functionalities are featured. In the characterization section, experimental techniques and theoretical calculations employed for characterization of basic MOFs are summarized. Some representive experimental techniques, such as temperature-programmed desorption of CO2 (CO2-TPD) and infrared (IR) spectra of different probing molecules, are covered. Following preparation and characterization, the catalytic applications of MOFs-derived solid bases are dealt with. These solid bases have potential to catalyze some well-known “base-catalyzed reactions” like Knoevenagel condensation, aldol condensation, and Michael addition. Meanwhile, in contrast to conventional solid bases, MOFs show some different catalytic properties due to their special structural and surface properties. Remarkably, characteristic features of MOFs-derived solid bases are described by comparing with conventional inorganic counterparts, keeping in mind the current opportunities and challenges in this field.

Defect engineering in metal-organic frameworks (MOFs) is an exciting concept for tailoring material properties, which opens up novel opportunities not only in sorption and catalysis, but also in controlling more challenging physical characteristics such as band gap as well as magnetic and electrical/conductive properties. It is challenging to structurally characterize the inherent or intentionally created defects of various types, and there have so far been few efforts to comprehensively discuss these issues. Based on selected reports spanning the last decades, this Review closes that gap by providing both a concise overview of defects in MOFs, or more broadly coordination network compounds (CNCs), including their classification and characterization, together with the (potential) applications of defective CNCs/MOFs. Moreover, we will highlight important aspects of "defect-engineering" concepts applied for CNCs, also in comparison with relevant solid materials such as zeolites or COFs. Finally, we discuss the future potential of defect-engineered CNCs.

The recently proposed digital coding metasurfaces make it possible to control electromagnetic (EM) waves in real time, and allow the implementation of many different functionalities in a programmable way. However, current configurations are only space-encoded, and do not exploit the temporal dimension. Here, we propose a general theory of space-time modulated digital coding metasurfaces to obtain simultaneous manipulations of EM waves in both space and frequency domains, i.e., to control the propagation direction and harmonic power distribution simultaneously. As proof-of-principle application examples, we consider harmonic beam steering, beam shaping, and scattering-signature control. For validation, we realize a prototype controlled by a field-programmable gate array, which implements the harmonic beam steering via an optimized space-time coding sequence. Numerical and experimental results, in good agreement, demonstrate good performance of the proposed approach, with potential applications to diverse fields such as wireless communications, cognitive radars, adaptive beamforming, holographic imaging.

Metasurfaces have enabled a plethora of emerging functions within an ultrathin dimension, paving way towards flat and highly integrated photonic devices. Despite the rapid progress in this area, simultaneous realization of reconfigurability, high efficiency, and full control over the phase and amplitude of scattered light is posing a great challenge. Here, we try to tackle this challenge by introducing the concept of a reprogrammable hologram based on 1-bit coding metasurfaces. The state of each unit cell of the coding metasurface can be switched between '1' and '0' by electrically controlling the loaded diodes. Our proof-of-concept experiments show that multiple desired holographic images can be realized in real time with only a single coding metasurface. The proposed reprogrammable hologram may be a key in enabling future intelligent devices with reconfigurable and programmable functionalities that may lead to advances in a variety of applications such as microscopy, display, security, data storage, and information processing.Realizing metasurfaces with reconfigurability, high efficiency, and control over phase and amplitude is a challenge. Here, Li et al. introduce a reprogrammable hologram based on a 1-bit coding metasurface, where the state of each unit cell of the coding metasurface can be switched electrically.

Distant supervised relation extraction has been widely used to find novel relational facts from text. However, distant supervision inevitably accompanies with the wrong labelling problem, and these noisy data will substantially hurt the performance of relation extraction. To alleviate this issue, we propose a sentence-level attention-based model for relation extraction. In this model, we employ convolutional neural networks to embed the semantics of sentences. Afterwards, we build sentence-level attention over multiple instances, which is expected to dynamically reduce the weights of those noisy instances. Experimental results on real-world datasets show that, our model can make full use of all informative sentences and effectively reduce the influence of wrong labelled instances. Our model achieves significant and consistent improvements on relation extraction as compared with baselines.

The synthesis of lanthanide-activated phosphors is pertinent to many emerging applications, ranging from high-resolution luminescence imaging to next-generation volumetric full-color display. In particular, the optical processes governed by the 4f-5d transitions of divalent and trivalent lanthanides have been the key to enabling precisely tuned color emission. The fundamental importance of lanthanide-activated phosphors for the physical and biomedical sciences has led to rapid development of novel synthetic methodologies and relevant tools that allow for probing the dynamics of energy transfer processes. Here, we review recent progress in developing methods for preparing lanthanide-activated phosphors, especially those featuring 4f-5d optical transitions. Particular attention will be devoted to two widely studied dopants, Ce3+ and Eu2+. The nature of the 4f-5d transition is examined by combining phenomenological theories with quantum mechanical calculations. An emphasis is placed on the correlation of host crystal structures with the 5d-4f luminescence characteristics of lanthanides, including quantum yield, emission color, decay rate, and thermal quenching behavior. Several parameters, namely Debye temperature and dielectric constant of the host crystal, geometrical structure of coordination polyhedron around the luminescent center, and the accurate energies of 4f and 5d levels, as well as the position of 4f and 5d levels relative to the valence and conduction bands of the hosts, are addressed as basic criteria for high-throughput computational design of lanthanide-activated phosphors.

It remains challenging to fabricate strain-sensing materials and exquisite geometric constructions for integrating extraordinary sensitivity, low strain detectability, high stretchability, tunable sensing range, and thin device dimensions into a single type of strain sensor. A percolation network based on Ti3C2Tx MXene/carbon nanotube (CNT) composites was rationally designed and fabricated into versatile strain sensors. This weaving architecture with excellent electric properties combined the sensitive two-dimensional (2D) Ti3C2Tx MXene nanostacks with conductive and stretchable one-dimensional (1D) CNT crossing. The resulting strain sensor can be used to detect both tiny and large deformations with an ultralow detection limit of 0.1% strain, high stretchability (up to 130%), high sensitivity (gauge factor up to 772.6), tunable sensing range (30% to 130% strain), thin device dimensions (<2 μm), and excellent reliability and stability (>5000 cycles). The versatile and scalable Ti3C2Tx MXene/CNT strain sensors provide a promising route to future wearable artificial intelligence with comprehensive tracking ability of real-time and in situ physiological signals for health and sporting applications.

In this Review article, we systematically summarize the design and applications of various kinds of long-lived emissive probes for bioimaging and biosensing via time-resolved photoluminescence techniques. The probes reviewed, including lanthanides, transition-metal complexes, organic dyes, carbon and silicon nanoparticles, metal clusters, and persistent phosphores, exhibit longer luminescence lifetimes than that of autofluorescence from biological tissue and organs. When these probes are internalized into living cells or animals, time-gated photoluminescence imaging selectively collects long-lived signals for intensity analysis, while photoluminescence lifetime imaging reports the decay details of each pixel. Since the long-lived signals are differentiated from autofluorescence in the time domain, the imaging contrast and sensing sensitivity are remarkably improved. The future prospects and challenges in this rapidly growing field are addressed.

In recent years, emulsions stabilized by micro- or nanoparticles (known as Pickering emulsions) have attracted much attention. Micro- or nanoparticles, as the main components of the emulsion, play a key role in the preparation and application of Pickering emulsions. The existence of particles at the interface between the oil and aqueous phases affects not only the preparation, but also the properties of Pickering emulsions, affording superior stability, low toxicity, and stimuli-responsiveness compared to classical emulsions stabilized by surfactants. These advantages of Pickering emulsions make them attractive, especially in biomedicine. In this review, the effects of the characteristics of micro- and nanoparticles on the preparation and properties of Pickering emulsions are introduced. In particular, the preparation methods of Pickering emulsions, especially uniform-sized emulsions, are listed. Uniform Pickering emulsions are convenient for both mechanistic research and applications. Furthermore, some biomedical applications of Pickering emulsions are discussed and the problems hindering their clinical application are identified.

Organic afterglow materials, developed recently by breaking through the difficulties in modulating ultrafast-decayed excited states, exhibit ultralong-lived emission for persistent luminescence with lifetimes of several orders of magnitude longer than traditional fluorescent and phosphorescent emissions at room temperature. Their exceptional properties, namely ultralong luminescent lifetime, large Stokes shifts, facile excited state transformation, and environmentally sensitive emission, have led to a diverse range of advanced optoelectronic applications. Here, the organic afterglow is reviewed from the perspective of fundamental concepts on both phenomenon and mechanism, examining the technical challenges in relation to excited state tuning and lifetime elongation. In particular, the advances in material design strategies that afford a large variety of organic afterglow materials for a broad utility in optoelectronics including lighting and displays, anti-counterfeiting, optical recording, chemical sensors and bio-imaging are highlighted.

Two-dimensional (2D) materials of atomic thickness have emerged as nano-building blocks to develop high-performance separation membranes that feature unique nanopores and/or nanochannels. These 2D-material membranes exhibit extraordinary permeation properties, opening a new avenue to ultra-fast and highly selective membranes for water and gas separation. Summarized in this Minireview are the latest ground-breaking studies in 2D-material membranes as nanosheet and laminar membranes, with a focus on starting materials, nanostructures, and transport properties. Challenges and future directions of 2D-material membranes for wide implementation are discussed briefly.

In this review, we summarize the origin and advancements of iridium-catalyzed asymmetric allylic substitution reactions during the past two decades. Since the first report in 1997, Ir-catalyzed asymmetric allylic substitution reactions have attracted intense attention due to their exceptionally high regio- and enantioselectivities. Ir-catalyzed asymmetric allylic substitution reactions have been significantly developed in recent years in many respects, including ligand development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. In this review, an explicit outline of ligands, mechanism, scope of nucleophiles, and applications is presented.

Enriching the functionality of ferroelectric materials with visible-light sensitivity and multiaxial switching capability would open up new opportunities for their applications in advanced information storage with diverse signal manipulation functions. We report experimental observations of robust intralayer ferroelectricity in two-dimensional (2D) van der Waals layered α-In₂Se₃ ultrathin flakes at room temperature. Distinct from other 2D and conventional ferroelectrics, In₂Se₃ exhibits intrinsically intercorrelated out-of-plane and in-plane polarization, where the reversal of the out-of-plane polarization by a vertical electric field also induces the rotation of the in-plane polarization. On the basis of the in-plane switchable diode effect and the narrow bandgap (∼1.3 eV) of ferroelectric In₂Se₃, a prototypical nonvolatile memory device, which can be manipulated both by electric field and visible light illumination, is demonstrated for advancing data storage technologies.

Abstract The energy decomposition analysis (EDA) is a powerful method for a quantitative interpretation of chemical bonds in terms of three major expressions. The instantaneous interaction energy Δ E int between two fragments A and B in a molecule A–B is partitioned in three terms, namely, (1) the quasiclassical electrostatic interaction Δ E elstat between the fragments, (2) the repulsive exchange (Pauli) interaction Δ E Pauli between electrons of the two fragments having the same spin, and (3) the orbital (covalent) interaction Δ E orb , which comes from the orbital relaxation and the orbital mixing between the fragments. The latter term can be decomposed into contributions of orbitals with different symmetry, which makes it possible to distinguish between σ , π, and δ bonding. After a short introduction into the theoretical background of the EDA, we present illustrative examples of main group and transition metal chemistry. The results show that the EDA terms can be interpreted in a chemically meaningful way, thus providing a bridge between quantum chemical calculations and heuristic bonding models of traditional chemistry. © 2011 John Wiley &amp; Sons, Ltd. This article is categorized under: Structure and Mechanism &gt; Molecular Structures

The development of clean and renewable energy materials as alternatives to fossil fuels is foreseen as a potential solution to the crucial problems of environmental pollution and energy shortages. Hydrogen is an ideal energy material for the future, and water splitting using solar/electrical energy is one way to generate hydrogen. Metal-organic frameworks (MOFs) are a class of porous materials with unique properties that have received rapidly growing attention in recent years for applications in water splitting due to their remarkable design flexibility, ultra-large surface-to-volume ratios and tunable pore channels. This review focuses on recent progress in the application of MOFs in electrocatalytic and photocatalytic water splitting for hydrogen generation, including both oxygen and hydrogen evolution. It starts with the fundamentals of electrocatalytic and photocatalytic water splitting and the related factors to determine the catalytic activity. The recent progress in the exploitation of MOFs for water splitting is then summarized, and strategies for designing MOF-based catalysts for electrocatalytic and photocatalytic water splitting are presented. Finally, major challenges in the field of water splitting are highlighted, and some perspectives of MOF-based catalysts for water splitting are proposed.

Two-dimensional (2D) metal–organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti3C2Tx (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm–2 at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec–1 in 0.1 M KOH. These results outperform those obtained by the standard IrO2-based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic Ti3C2Tx nanosheets enabled the rapid charge and ion transfer across the well-defined Ti3C2Tx–CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc–air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

) have recently emerged as novel active materials for photovoltaic applications with power conversion efficiency over 22%. Conventional perovskite solar cells (PSCs); however, suffer the issue that lead is toxic to the environment and organisms for a long time and is hard to excrete from the body. Therefore, it is imperative to find environmentally-friendly metal ions to replace lead for the further development of PSCs. Previous work has demonstrated that Sn, Ge, Cu, Bi, and Sb ions could be used as alternative ions in perovskite configurations to form a new environmentally-friendly lead-free perovskite structure. Here, we review recent progress on lead-free PSCs in terms of the theoretical insight and experimental explorations of the crystal structure of lead-free perovskite, thin film deposition, and device performance. We also discuss the importance of obtaining further understanding of the fundamental properties of lead-free hybrid perovskites, especially those related to photophysics.

Abstract Due to the characteristics of optical rotation, selective emission of polarized light, and circular dichroism, circularly polarized luminescent materials have aroused extensive attentions, and they have exhibited wide optoelectronic applications, such as optical data storage, liquid crystal display, and backlights in 3D displays. Here, the research progress of circularly polarized luminescent materials for organic optoelectronic devices is summarized. First, the definition and measurement of the circularly polarized light, such as optical rotatory dispersion, circular dichroism, and circularly polarized luminescence, are systematically introduced. Subsequently, the design strategies for various kinds of circularly polarized luminescent materials, including luminescent lanthanide and transition‐metal complexes, small organic luminophores, conjugated polymers, supramolecules, and liquid crystals are summarized. These materials exhibit circularly polarized luminescence with different magnitudes of luminescence dissymmetry values ( g lum ). They are further applied in optoelectronic devices with excellent performance, and the influence factors on the g lum values of these materials are presented in detail. Finally, the current opportunities and challenges in this rapidly growing research field are discussed systematically. The circularly polarized luminescent materials with large g lum and high luminescence efficiency are very promising for applications in organic optoelectronic fields.

High-performance perovskite light-emitting diodes are achieved by an interfacial engineering approach, leading to the most efficient near-infrared devices produced using solution-processed emitters and efficient green devices at high brightness conditions. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Printed electronics are an important enabling technology for the development of low-cost, large-area, and flexible optoelectronic devices. Transparent conductive films (TCFs) made from solution-processable transparent conductive materials, such as metal nanoparticles/nanowires, carbon nanotubes, graphene, and conductive polymers, can simultaneously exhibit high mechanical flexibility, low cost, and better photoelectric properties compared to the commonly used sputtered indium-tin-oxide-based TCFs, and are thus receiving great attention. This Review summarizes recent advances of large-area flexible TCFs enabled by several roll-to-roll-compatible printed techniques including inkjet printing, screen printing, offset printing, and gravure printing using the emerging transparent conductive materials. The preparation of TCFs including ink formulation, substrate treatment, patterning, and postprocessing, and their potential applications in solar cells, organic light-emitting diodes, and touch panels are discussed in detail. The rational combination of a variety of printed techniques with emerging transparent conductive materials is believed to extend the opportunities for the development of printed electronics within the realm of flexible electronics and beyond.