Showing papers in "Chemical Society Reviews in 2021"

Transition metal nitrides for electrochemical energy applications.

Abstract: Transition metal nitrides (TMNs), by virtue of their unique electronic structure, high electrical conductivity, superior chemical stability, and excellent mechanical robustness, have triggered tremendous research interest over the past decade, and showed great potential for electrochemical energy conversion and storage. However, bulk TMNs usually suffer from limited numbers of active sites and sluggish ionic kinetics, and eventually ordinary electrochemical performance. Designing nanostructured TMNs with tailored morphology and good dispersity has proved an effective strategy to address these issues, which provides a larger specific surface area, more abundant active sites, and shorter ion and mass transport distances over the bulk counterparts. Herein, the most up-to-date progress on TMN-based nanomaterials is comprehensively reviewed, focusing on geometric-structure design, electronic-structure engineering, and applications in electrochemical energy conversion and storage, including electrocatalysis, supercapacitors, and rechargeable batteries. Finally, we outline the future challenges of TMN-based nanomaterials and their possible research directions beyond electrochemical energy applications.

Single-atom catalysis in advanced oxidation processes for environmental remediation.

Abstract: Emerging single atom catalysts (SACs), especially carbon-based SACs are appealing materials in environmental catalysis because of their ultrahigh performances, environmental friendliness, structural/chemical robustness, and the maximum utilization of active metal sites. The metal centres, carbon matrixes, and coordination characteristics collectively determine the electronic features of carbon-based SACs, and their behaviours in catalysing peroxide activation and efficiencies in advanced oxidation processes (AOPs). However, there is lack of a comprehensive and critical review reporting the successful marriage of carbon-based SACs in AOP-based remediation technologies. It is particularly necessary to systematically compare and reveal the catalytic sites and the associated mechanisms of carbon-based SACs in diverse AOP systems. In this review, we highlight the synthetic strategies, characterisation, and computation of carbon-based SACs, and for the first time, showcase their innovative applications in AOP technologies. We unveil the origins of versatile catalytic oxidation pathways in different AOP systems and the mechanisms of micropollutant degradation over carbon-based SACs, distinguished from the upsized counterparts (metals/oxides and carbon substrates). We also provide directions to the rational design of on-demand SACs for green chemistry and environmental sustainability. Also, we suggest a designated and integrated experimental/theoretical protocol for revealing the structure-catalysis relations of SACs in AOP applications, and propose the prospects for future opportunities and challenges.

Electrocatalysis for CO2 conversion: from fundamentals to value-added products

Abstract: The continuously increasing CO2 released from human activities poses a great threat to human survival by fluctuating global climate and disturbing carbon balance among the four reservoirs of the biosphere, earth, air, and water. Converting CO2 to value-added feedstocks via electrocatalysis of the CO2 reduction reaction (CO2RR) has been regarded as one of the most attractive routes to re-balance the carbon cycle, thanks to its multiple advantages of mild operating conditions, easy handling, tunable products and the potential of synergy with the rapidly increasing renewable energy (i.e., solar, wind). Instead of focusing on a special topic of electrocatalysts for the CO2RR that have been extensively reviewed elsewhere, we herein present a rather comprehensive review of the recent research progress, in the view of associated value-added products upon selective electrocatalytic CO2 conversion. We initially provide an overview of the history and the fundamental science regarding the electrocatalytic CO2RR, with a special introduction to the design, preparation, and performance evaluation of electrocatalysts, the factors influencing the CO2RR, and the associated theoretical calculations. Emphasis will then be given to the emerging trends of selective electrocatalytic conversion of CO2 into a variety of value-added products. The structure-performance relationship and mechanism will also be discussed and investigated. The outlooks for CO2 electrocatalysis, including the challenges and opportunities in the development of new electrocatalysts, electrolyzers, the recently rising operando fundamental studies, and the feasibility of industrial applications are finally summarized.

Recent progress in photosensitizers for overcoming the challenges of photodynamic therapy: from molecular design to application.

Abstract: Photodynamic therapy (PDT), a therapeutic mode involving light triggering, has been recognized as an attractive oncotherapy treatment. However, nonnegligible challenges remain for its further clinical use, including finite tumor suppression, poor tumor targeting, and limited therapeutic depth. The photosensitizer (PS), being the most important element of PDT, plays a decisive role in PDT treatment. This review summarizes recent progress made in the development of PSs for overcoming the above challenges. This progress has included PSs developed to display enhanced tolerance of the tumor microenvironment, improved tumor-specific selectivity, and feasibility of use in deep tissue. Based on their molecular photophysical properties and design directions, the PSs are classified by parent structures, which are discussed in detail from the molecular design to application. Finally, a brief summary of current strategies for designing PSs and future perspectives are also presented. We expect the information provided in this review to spur the further design of PSs and the clinical development of PDT-mediated cancer treatments.

Second near-infrared photothermal materials for combinational nanotheranostics

Abstract: Second near-infrared photothermal therapy (NIR-II PTT, 1000-1500 nm) has recently emerged as a new phototherapeutic modality with the advantages of deeper penetration, less energy dissipation and minimal normal-tissue toxicity over traditional first NIR PTT (750-1000 nm). However, suboptimal photothermal conversion and limited therapeutic efficacy remain the major challenges for NIR-II PTT. With the convergence in materials science, nanomedicine and biology, multifunctional NIR-II photothermal inorganic or organic materials have been extensively developed to combine NIR-II PTT with other therapeutic modalities for improved efficacies in treating life-threatening diseases including cancer and infection. This review summarizes the recent advances of NIR-II photothermal combinational theranostics pertinent to chemotherapy, immunotherapy, radiotherapy, and photodynamic, sonodynamic, chemodynamic, gene, gas, ionic, vascular and magnetothermal therapy. Potential obstacles and perspectives for future research and clinical translation of this new theranostic modality are also discussed.

Covalent organic frameworks: an ideal platform for designing ordered materials and advanced applications

Abstract: Covalent organic frameworks offer a molecular platform for integrating organic units into periodically ordered yet extended two- and three-dimensional polymers to create topologically well-defined polygonal lattices and built-in discrete micropores and/or mesopores. This polymer architecture is unique as it enables predesigning both primary- and high-order structures, greatly enhancing our capabilities of designing organic materials to produce predictable structures and to achieve unique properties and functions. Progress over the past 15 years in the design, synthesis and functional exploration of COFs has successively established the basis of the COF field and COFs have shown the great potential of chemistry in developing a class of amazing organic materials. In this review, we focus on analysing the historic developments of COFs to uncover a full materials and application picture by providing comprehensive yet clear guidance for molecular design, synthetic control and functional exploration. We scrutinise the structural components of COFs including building blocks, reactive sites and functional groups with the aim of finding the origins of structural designability and diversity, as well as multiple functionalities. We disclose strategies for designing and synthesising frameworks to construct various tailor-made interfaces, and for exploring skeletons and pores to design properties and functions. With well-defined skeletons, pores and interfaces that offer a chemical basis to trigger and control interactions with photons, excitons, phonons, polarons, electrons, holes, spins, ions and molecules, we illustrate the current status of our understandings of structure-property correlations, and unveil the principles for establishing a regime to design unique functions that originate from and are inherent to structures. We predict the key central issues in design and synthesis, the challenges in functional design and the future directions from the perspectives of chemistry, physics and materials science.

Electrocatalysis as an enabling technology for organic synthesis.

Abstract: Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and radical ion intermediates in a controlled fashion under mild conditions has inspired the development of a number of new electrochemical methodologies for the preparation of valuable chemical motifs. Particularly, recent developments in electrosynthesis have featured an increased use of redox-active electrocatalysts to further enhance control over the selective formation and downstream reactivity of these reactive intermediates. Furthermore, electrocatalytic mediators enable synthetic transformations to proceed in a manner that is mechanistically distinct from purely chemical methods, allowing for the subversion of kinetic and thermodynamic obstacles encountered in conventional organic synthesis. This review highlights key innovations within the past decade in the area of synthetic electrocatalysis, with emphasis on the mechanisms and catalyst design principles underpinning these advancements. A host of oxidative and reductive electrocatalytic methodologies are discussed and are grouped according to the classification of the synthetic transformation and the nature of the electrocatalyst.

Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction.

Abstract: A climax in the development of cost-effective and high-efficiency transition metal-based electrocatalysts has been witnessed recently for sustainable energy and related conversion technologies. In this regard, structure-activity relationships based on several descriptors have already been proposed to rationally design electrocatalysts. However, the dynamic reconstruction of the surface structures and compositions of catalysts during electrocatalytic water oxidation, especially during the anodic oxygen evolution reaction (OER), complicate the streamlined prediction of the catalytic activity. With the achievements in operando and in situ techniques, it has been found that electrocatalysts undergo surface reconstruction to form the actual active species in situ accompanied with an increase in their oxidation state during OER in alkaline solution. Accordingly, a thorough understanding of the surface reconstruction process plays a critical role in establishing unambiguous structure-composition-property relationships in pursuit of high-efficiency electrocatalysts. However, several issues still need to be explored before high electrocatalytic activities can be realized, as follows: (1) the identification of initiators and pathways for surface reconstruction, (2) establishing the relationships between structure, composition, and electrocatalytic activity, and (3) the rational manipulation of in situ catalyst surface reconstruction. In this review, the recent progress in the surface reconstruction of transition metal-based OER catalysts including oxides, non-oxides, hydroxides and alloys is summarized, emphasizing the fundamental understanding of reconstruction behavior from the original precatalysts to the actual catalysts based on operando analysis and theoretical calculations. The state-of-the-art strategies to tailor the surface reconstruction such as substituting/doping with metals, introducing anions, incorporating oxygen vacancies, tuning morphologies and exploiting plasmonic/thermal/photothermal effects are then introduced. Notably, comprehensive operando/in situ characterization together with computational calculations are responsible for unveiling the improvement mechanism for OER. By delivering the progress, strategies, insights, techniques, and perspectives, this review will provide a comprehensive understanding of the surface reconstruction in transition metal-based OER catalysts and future guidelines for their rational development.

Nitrate electroreduction: mechanism insight, in situ characterization, performance evaluation, and challenges.

Abstract: Excessive nitrate ions in the environment break the natural nitrogen cycle and become a significant threat to human health. So far, many physical, chemical, and biological techniques have been developed for nitrate remediation, but most of them require high post-processing costs and rigorous treatment conditions. In contrast, nitrate electroreduction is promising because it utilizes green electrons as reductants under ambient conditions. The recognition and mastering of the nitrate reaction mechanism is the premise for the design and synthesis of efficient electrocatalysts for the selective reduction of nitrate. In this regard, this review aims to provide an insight into the electrocatalytic mechanism of nitrate reduction, especially combined with in situ electrochemical characterization and theoretical calculations over different kinds of materials. Moreover, the performance evaluation parameters and standard test methods for nitrate electroreduction are summarized to screen efficient materials. Finally, an outlook on the current challenges and promising opportunities in this research area is discussed. This review provides a guide for development of electrocatalysts for selective nitrate reduction with a fascinating performance and accelerates the development of sustainable nitrogen chemistry and engineering.

Covalent organic frameworks (COFs) for electrochemical applications

Abstract: Covalent organic frameworks are a class of extended crystalline organic materials that possess unique architectures with high surface areas and tuneable pore sizes. Since the first discovery of the topological frameworks in 2005, COFs have been applied as promising materials in diverse areas such as separation and purification, sensing or catalysis. Considering the need for renewable and clean energy production, many research efforts have recently focused on the application of porous materials for electrochemical energy storage and conversion. In this respect, considerable efforts have been devoted to the design and synthesis of COF-based materials for electrochemical applications, including electrodes and membranes for fuel cells, supercapacitors and batteries. This review article highlights the design principles and strategies for the synthesis of COFs with a special focus on their potential for electrochemical applications. Recently suggested hybrid COF materials or COFs with hierarchical porosity will be discussed, which can alleviate the most challenging drawback of COFs for these applications. Finally, the major challenges and future trends of COF materials in electrochemical applications are outlined.

Recent progress of zero-dimensional luminescent metal halides

Abstract: Zero-dimensional (0D) all-inorganic/organic-inorganic metal halides, as emerging luminescent materials, have attracted unparalleled interest from versatile perspectives due to their unique crystallographic/electronic structures with isolated building units and fascinating optical characteristics. However, significant challenges still exist for 0D metal halides, including their chemical molecular design, photoluminescence (PL) mechanism, PL modification and applications. In this review, we summarize the 0D metal halides through the classification of all-inorganic and organic-inorganic hybrid metal halides, and further emphasize the unique role of B-site cations with different electronic configurations in the PL process. Furthermore, the PL mechanisms focusing on the self-trapped excitons (STEs) model and PL regulation engineering are examined to explore their extraordinary PL properties and further reveal new application prospects. This review aims to provide in-depth insight into the structure-luminescence-application relationship of 0D metal halides and pave the way for the realization of next-generation high-performance luminescent materials.

Understanding nanoparticle endocytosis to improve targeting strategies in nanomedicine

Abstract: Nanoparticles (NPs) have attracted considerable attention in various fields, such as cosmetics, the food industry, material design, and nanomedicine. In particular, the fast-moving field of nanomedicine takes advantage of features of NPs for the detection and treatment of different types of cancer, fibrosis, inflammation, arthritis as well as neurodegenerative and gastrointestinal diseases. To this end, a detailed understanding of the NP uptake mechanisms by cells and intracellular localization is essential for safe and efficient therapeutic applications. In the first part of this review, we describe the several endocytic pathways involved in the internalization of NPs and we discuss the impact of the physicochemical properties of NPs on this process. In addition, the potential challenges of using various inhibitors, endocytic markers and genetic approaches to study endocytosis are addressed along with the principal (semi) quantification methods of NP uptake. The second part focuses on synthetic and bio-inspired substances, which can stimulate or decrease the cellular uptake of NPs. This approach could be interesting in nanomedicine where a high accumulation of drugs in the target cells is desirable and clearance by immune cells is to be avoided. This review contributes to an improved understanding of NP endocytic pathways and reveals potential substances, which can be used in nanomedicine to improve NP delivery.

Recent progress in hot exciton materials for organic light-emitting diodes

Abstract: According to Kasha's rule, high-lying excited states usually have little effect on fluorescence. However, in some molecular systems, the high-lying excited states partly or even mainly contribute to the photophysical properties, especially in the process of harvesting triplet excitons in organic electroluminescent devices. In the current review, we focus on a type of organic light-emitting diode (OLED) materials called “hot exciton” materials, which can effectively harness the non-radiative triplet excitons via reverse intersystem crossing (RISC) from high-lying triplet states to singlet states (Tn → Sm; n ≥ 2, m ≥ 1). Since Ma and Yang proposed the hot exciton mechanism for OLED material design in 2012, there have been many reports aiming at the design and synthesis of novel hot exciton luminogens. Herein, we present a comprehensive review of the recent progress in hot exciton materials. The developments of the hot exciton mechanism are reviewed, the fundamental principles regarding molecular design are discussed, and representative reported hot exciton luminogens are summarized and analyzed, along with their structure–property relationships and OLED applications.

Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts

Abstract: Oxygen reduction and evolution reactions constitute the core process of many vital energy storage or conversion techniques. However, the kinetic sluggishness of the oxygen redox reactions and heavy reliance on noble-metal-based electrocatalysts strongly limit the energy efficiency of the related devices. Developing high-performance noble-metal-free bifunctional ORR and OER electrocatalysts has gained worldwide attention, where much important progress has been made during the last decade. This review systematically addresses the design principles to obtain high-performance noble-metal-free bifunctional oxygen electrocatalysts by emphasizing strategies of both intrinsic activity regulation and active site integration. A statistical analysis of the reported bifunctional electrocatalysts is further carried out to reveal the composition-performance relationship and guide further exploration of emerging candidates. Finally, perspectives for developing advanced bifunctional oxygen electrocatalysts and aqueous rechargeable metal-air batteries are proposed.

High-voltage liquid electrolytes for Li batteries: progress and perspectives

Abstract: Since the advent of the Li ion batteries (LIBs), the energy density has been tripled, mainly attributed to the increase of the electrode capacities. Now, the capacity of transition metal oxide cathodes is approaching the limit due to the stability limitation of the electrolytes. To further promote the energy density of LIBs, the most promising strategies are to enhance the cut-off voltage of the prevailing cathodes or explore novel high-capacity and high-voltage cathode materials, and also replacing the graphite anode with Si/Si-C or Li metal. However, the commercial ethylene carbonate (EC)-based electrolytes with relatively low anodic stability of ∼4.3 V vs. Li+/Li cannot sustain high-voltage cathodes. The bottleneck restricting the electrochemical performance in Li batteries has veered towards new electrolyte compositions catering for aggressive next-generation cathodes and Si/Si-C or Li metal anodes, since the oxidation-resistance of the electrolytes and the in situ formed cathode electrolyte interphase (CEI) layers at the high-voltage cathodes and solid electrolyte interphase (SEI) layers on anodes critically control the electrochemical performance of these high-voltage Li batteries. In this review, we present a comprehensive and in-depth overview on the recent advances, fundamental mechanisms, scientific challenges, and design strategies for the novel high-voltage electrolyte systems, especially focused on stability issues of the electrolytes, the compatibility and interactions between the electrolytes and the electrodes, and reaction mechanisms. Finally, novel insights, promising directions and potential solutions for high voltage electrolytes associated with effective SEI/CEI layers are proposed to motivate revolutionary next-generation high-voltage Li battery chemistries.

Recent advances in persistent luminescence based on molecular hybrid materials

Abstract: Molecular persistently luminescent materials have received recent attention due to their promising applications in optical displays, biological imaging, chemical sensing, and security systems. In this review, we systematically summarize recent advances in establishing persistently luminescent materials—specifically focusing on materials composed of molecular hybrids for the first time. We describe the main strategies for synthesizing these hybrid materials, namely: (i) inorganics/organics, (ii) organics/organics, and (iii) organics/polymer systems and demonstrate how molecular hybrids provide synergistic effects, while improving luminescence lifetimes and efficiencies. These hybrid materials promote new methods for tuning key physical properties such as singlet–triplet excited state energies by controlling the chemical interactions and molecular orientations in the solid state. We review new advances in these materials from the perspective of examining experimental and theoretical approaches to room-temperature phosphorescence and thermally-activated delayed fluorescence. Finally, this review concludes by summarizing the current challenges and future opportunities for these hybrid materials.

Fundamentals and applications of photo-thermal catalysis.

Abstract: Photo-thermal catalysis has recently emerged as an alternative route to drive chemical reactions using light as an energy source. Through the synergistic combination of photo- and thermo-chemical contributions of sunlight, photo-thermal catalysis has the potential to enhance reaction rates and to change selectivity patterns, even under moderate operation conditions. This review provides the fundamentals of localized surface plasmon resonance (LSPR) that explain the photo-thermal effect in plasmonic structures, describes the different mechanistic pathways underlying photo-thermal catalysis, suggests methodologies to disentangle the reaction mechanisms and proposes material design strategies to improve photo-thermal performance. Ultimately, the goal is to pave the way for the wide implementation of this promising technology in the production of synthetic fuels and chemicals.

Metal–organic frameworks and their derivatives as electrocatalysts for the oxygen evolution reaction

Abstract: Electrochemical water splitting is an appealing and promising approach for energy conversion and storage. As a key half-reaction of electricity-driven water splitting, the oxygen evolution reaction (OER) is a sluggish process due to the transfer of four protons and four electrons. Therefore, development of low-cost and robust OER electrocatalysts is of great importance for improving the efficiency of water splitting. Based on the merits of high surface area, rich pore structure, diverse composition and well-defined metal centers, metal-organic frameworks (MOFs) and their derivatives have been widely exploited as OER electrocatalysts. Herein, the current progress on MOFs and their derivatives for OER electrolysis is summarized, highlighting the design principle, synthetic methods and performance for MOF-based materials. In addition, the structure-performance relationships of MOFs and their derivatives toward the OER are discussed, providing valuable insights into rationally developing OER catalysts with high efficiency. The current scientific and technological challenges and future perspectives towards the purpose of sustainable industrial applications are addressed at the end.

High temperature proton exchange membrane fuel cells: progress in advanced materials and key technologies

Abstract: High temperature proton exchange membrane fuel cells (HT-PEMFCs) are one type of promising energy device with the advantages of fast reaction kinetics (high energy efficiency), high tolerance to fuel/air impurities, simple plate design, and better heat and water management. They have been expected to be the next generation of PEMFCs specifically for application in hydrogen-fueled automobile vehicles and combined heat and power (CHP) systems. However, their high-cost and low durability interposed by the insufficient performance of key materials such as electrocatalysts and membranes at high temperature operation are still the challenges hindering the technology's practical applications. To develop high performance HT-PEMFCs, worldwide researchers have been focusing on exploring new materials and the related technologies by developing novel synthesis methods and innovative assembly techniques, understanding degradation mechanisms, and creating mitigation strategies with special emphasis on catalysts for oxygen reduction reaction, proton exchange membranes and bipolar plates. In this paper, the state-of-the-art development of HT-PEMFC key materials, components and device assembly along with degradation mechanisms, mitigation strategies, and HT-PEMFC based CHP systems is comprehensively reviewed. In order to facilitate further research and development of HT-PEMFCs toward practical applications, the existing challenges are also discussed and several future research directions are proposed in this paper.

Engineering nanomedicine for glutathione depletion-augmented cancer therapy

Abstract: Glutathione (GSH), the main redox buffer, has long been recognized as a pivotal modulator of tumor initiation, progression and metastasis. It is also implicated in the resistance of platinum-based chemotherapy and radiation therapy. Therefore, depleting intracellular GSH was considered a potent solution to combating cancer. However, reducing GSH within cancer cells alone always failed to yield desirable therapeutic effects. In this regard, the convergence of GSH-scavenging agents with therapeutic drugs has thus been pursued in clinical practice. Unfortunately, the therapeutic outcomes are still unsatisfactory due to untargeted drug delivery. Advanced nanomedicine of synergistic GSH depletion and cancer treatment has attracted tremendous interest because they promise to deliver superior therapeutic benefits while alleviating life-threatening side effects. In the past five years, the authors and others have demonstrated that numerous nanomedicines, by simultaneously delivering GSH-depleting agents and therapeutic components, boost not only traditional chemotherapy and radiotherapy but also multifarious emerging treatment modalities, including photodynamic therapy, sonodynamic therapy, chemodynamic therapy, ferroptosis, and immunotherapy, to name a few, and achieved decent treatment outcomes in a large number of rodent tumor models. In this review, we summarize the most recent progress in engineering nanomedicine for GSH depletion-enhanced cancer therapies. Biosynthesis of GSH and various types of GSH-consuming strategies will be briefly introduced. The challenges and perspectives of leveraging nanomedicine for GSH consumption-augmented cancer therapies will be discussed at the end.

Robust superhydrophobicity: mechanisms and strategies

Abstract: Superhydrophobic surfaces hold great prospects for extremely diverse applications owing to their water repellence property The essential feature of superhydrophobicity is micro-/nano-scopic roughness to reserve a large portion of air under a liquid drop However, the vulnerability of the delicate surface textures significantly impedes the practical applications of superhydrophobic surfaces Robust superhydrophobicity is a must to meet the rigorous industrial requirements and standards for commercial products In recent years, major advancements have been made in elucidating the mechanisms of wetting transitions, design strategies and fabrication techniques of superhydrophobicity This review will first introduce the mechanisms of wetting transitions, including the thermodynamic stability of the Cassie state and its breakdown conditions Then we highlight the development, current status and future prospects of robust superhydrophobicity, including characterization, design strategies and fabrication techniques In particular, design strategies, which are classified into passive resistance and active regeneration for the first time, are proposed and discussed extensively

Propane dehydrogenation: catalyst development, new chemistry, and emerging technologies

Abstract: Propylene is an important building block for enormous petrochemicals including polypropylene, propylene oxide, acrylonitrile and so forth. Propane dehydrogenation (PDH) is an industrial technology for direct propylene production which has received extensive attention in recent years. With the development of dehydrogenation technologies, the efficient adsorption/activation of propane and subsequential desorption of propylene on the surfaces of heterogeneous catalysts remain scientifically challenging. This review describes recent advances in the fundamental understandings of the PDH process in terms of emerging technologies, catalyst development and new chemistry in regulating the catalyst structures and inhibiting the catalyst deactivation. The active sites, reaction pathways and deactivation mechanisms of PDH over metals and metal oxides as well as their dependent factors are also analysed and discussed, which is expected to enable efficient catalyst design for minimizing the reaction barriers and controlling the selectivity towards propylene. The challenges and perspectives of PDH over heterogeneous catalysts are also proposed for further development.

Metal-organic frameworks as photoluminescent biosensing platforms: mechanisms and applications.

Abstract: Biosensing is of vital importance for advancing public health through monitoring abnormalities in biological systems, which may be potentially associated with certain body dysfunctions. A wide range of luminescent materials have been actively pursued in the fabrication of biosensing platforms, particularly ones that can function in complex biological fluids with high selectivity and sensitivity. Recently, metal-organic frameworks (MOFs) have experienced rapid growth due to their tunable structures, large surface area, and being prone to surface engineering, etc. These virtues endow MOF materials with immense feasibility in the target-oriented construction of sensing platforms for specific applications. In this review, we extrapolated six sensing mechanisms for MOF-based photoluminescent biosensing platforms, including photoelectron transfer (PET), resonance energy transfer (RET), competition absorption (CA), structural transformation (ST), chemical conversion (CC), and quencher detachment (QD). Accordingly, recent progress of MOF-based materials in photoluminescence sensing of biomolecules, biomarkers, drugs, and toxins was highlighted. The objective of this review is to provide readers with an extensive overview of the design and synthesis of MOF materials for photoluminescence biosensing. The challenges and outlook are briefly discussed at the end.

Emerging photothermal-derived multimodal synergistic therapy in combating bacterial infections.

Abstract: Due to the emerging bacterial resistance and the protection of tenacious biofilms, it is hard for the single antibacterial modality to achieve satisfactory therapeutic effects nowadays. In recent years, photothermal therapy (PTT)-derived multimodal synergistic treatments have received wide attention and exhibited cooperatively enhanced bactericidal activity. PTT features spatiotemporally controllable generation of hyperthermia that could eradicate bacteria without inducing resistance. The synergy of it with other treatments, such as chemotherapy, photo-dynamic/catalytic therapy (PDT/PCT), immunotherapy, and sonodynamic therapy (SDT), could lower the introduced laser density in PTT and avoid undesired overheating injury of normal tissues. Simultaneously, by heat-induced improvement of the bacterial membrane permeability, PTT is conducive for accelerated intracellular permeation of chemotherapeutic drugs as well as reactive oxygen species (ROS) generated by photosensitizers/sonosensitizers, and could promote infiltration of immune cells. Thereby, it could solve the currently existing sterilization deficiencies of other combined therapeutic modes, for example, bacterial resistance for chemotherapy, low drug permeability for PDT/PCT/SDT, adverse immunoreactions for immunotherapy, etc. Admittedly, PTT-derived synergistic treatments are becoming essential in fighting bacterial infection, especially those caused by antibiotic-resistant strains. This review firstly presents the classical and newly reported photothermal agents (PTAs) in brief. Profoundly, through the introduction of delicately designed nanocomposite platforms, we systematically discuss the versatile photothermal-derived multimodal synergistic therapy with the purpose of sterilization application. At the end, challenges to PTT-derived combinational therapy are presented and promising synergistic bactericidal prospects are anticipated.

Two-dimensional materials in biomedical, biosensing and sensing applications

Abstract: Two-dimensional (2D) materials are at the forefront of materials research. Here we overview their applications beyond graphene, such as transition metal dichalcogenides, monoelemental Xenes (including phosphorene and bismuthene), carbon nitrides, boron nitrides along with transition metal carbides and nitrides (MXenes). We discuss their usage in various biomedical and environmental monitoring applications, from biosensors to therapeutic treatment agents, their toxicity and their utility in chemical sensing. We highlight how a specific chemical, physical and optical property of 2D materials can influence the performance of bio/sensing, improve drug delivery and photo/thermal therapy as well as affect their toxicity. Such properties are determined by crystal phases electrical conductivity, degree of exfoliation, surface functionalization, strong photoluminescence, strong optical absorption in the near-infrared range and high photothermal conversion efficiency. This review conveys the great future of all the families of 2D materials, especially with the expanding 2D materials' landscape as new materials emerge such as germanene and silicene.

Metallenes as functional materials in electrocatalysis.

Abstract: Metallenes, atomically thin layers composed primarily of under-coordinated metal atoms, have emerged as the newest members in the family of 2D nanomaterials. Furthermore, the remarkable physicochemical properties associated with metallenes coupled with the ease of applying chemical modifications result in exciting opportunities towards catalyst engineering for electrochemical conversions. Especially in recent years, interest around metallenes has grown, evidenced by the surge in available literature. As such, it is imperative to review the findings and present directions for the future. In this review, we highlight the techniques available for deriving metallenes and further discuss the modification strategies commonly employed in devising metallenes to better suit applications in electrocatalysis. We provide a rational understanding of how each strategy drives performance enhancements and present gaps in the knowledge, necessary for further advancements in the field.

The recent progress on metal-organic frameworks for phototherapy.

Abstract: Some infectious or malignant diseases such as cancers are seriously threatening the health of human beings all over the world. The commonly used antibiotic therapy cannot effectively treat these diseases within a short time, and also bring about adverse effects such as drug resistance and immune system damage during long-term systemic treatment. Phototherapy is an emerging antibiotic-free strategy to treat these diseases. Upon light irradiation, phototherapeutic agents can generate cytotoxic reactive oxygen species (ROS) or induce a temperature increase, which leads to the death of targeted cells. These two kinds of killing strategies are referred to as photodynamic therapy (PDT) and photothermal therapy (PTT), respectively. So far, many photo-responsive agents have been developed. Among them, the metal-organic framework (MOF) is becoming one of the most promising photo-responsive materials because its structure and chemical compositions can be easily modulated to achieve specific functions. MOFs can have intrinsic photodynamic or photothermal ability under the rational design of MOF construction, or serve as the carrier of therapeutic agents, owing to its tunable porosity. MOFs also provide feasibility for various combined therapies and targeting methods, which improves the efficiency of phototherapy. In this review, we firstly investigated the principles of phototherapy, and comprehensively summarized recent advances of MOF in PDT, PTT and synergistic therapy, from construction to modification. We expect that our demonstration will shed light on the future development of this field, and bring it one step closer to clinical trials.

Layered double hydroxide-based electrocatalysts for the oxygen evolution reaction: identification and tailoring of active sites, and superaerophobic nanoarray electrode assembly.

Abstract: The electrocatalytic oxygen evolution reaction (OER) is a critical half-cell reaction for hydrogen production via water electrolysis. However, the practical OER suffers from sluggish kinetics and thus requires efficient electrocatalysts. Transition metal-based layered double hydroxides (LDHs) represent one of the most active classes of OER catalysts. An in-depth understanding of the activity of LDH based electrocatalysts can promote further rational design and active site regulation of high-performance electrocatalysts. In this review, the fundamental understanding of the structural characteristics of LDHs is demonstrated first, then comparisons and in-depth discussions of recent advances in LDHs as highly active OER catalysts in alkaline media are offered, which include both experimental and computational methods. On top of the active site identification and structural characterization of LDHs on an atomic scale, strategies to promote the OER activity are summarised, including doping, intercalation and defect-making. Furthermore, the concept of superaerophobicity, which has a profound impact on the performance of gas evolution electrodes, is explored to enhance LDHs and their derivatives for a large scale OER. In addition, certain operating standards for OER measurements are proposed to avoid inconsistency in evaluating the OER activity of LDHs. Finally, several key challenges in using LDHs as anode materials for large scale water splitting, such as the issue of stability and the adoption of membrane–electrode-assembly based electrolysers, are emphasized to shed light on future research directions.

Stimuli-responsive polydopamine-based smart materials

Abstract: Stimuli responsiveness has long been a fascinating feature of smart material design. Polydopamine (PDA), a nature inspired polymeric pigment, exhibits excellent photo-responsive properties and has active surface functionality for loading various responsive motifs, making it a promising candidate for the construction of stimuli-responsive smart functional materials. PDA has long been considered as a robust coating material, but its responsive feature has rarely been emphasized in the past reviews. Herein, we present the first effort to summarize recent advances in the design strategies, responsive mechanisms, and diverse applications of stimuli-responsive PDA-based smart materials; the stimuli include light, pH, chemicals, temperature, humidity, electric fields, mechanical force, magnetic fields, and ultrasound. Moreover, the current trends, challenges, and future directions of stimuli-responsive PDA-based materials are also elaborated.

Fabrication of desalination membranes by interfacial polymerization: history, current efforts, and future directions

Abstract: Membrane desalination is a promising technology for addressing the global challenge of water scarcity by augmenting fresh water supply. Continuous progress in this technology relies on development of membrane materials. The state-of-the-art membranes used in a wide range of desalination applications are polyamide thin-film composite (TFC) membranes which are formed by interfacial polymerization (IP). Despite the wide use of such membranes in desalination, their real-world application is still hampered by several technical obstacles. These challenges of the TFC membranes largely stem from the inherent limitations of the polyamide chemistry, as well as the IP reaction mechanisms. In the past decade, we have witnessed substantial progress in the understanding of polyamide formation mechanisms and the development of new IP strategies that can potentially lead to the redesign of TFC membranes. In this Tutorial, we first present a brief history of the development of desalination membranes and highlight the major challenges of the existing TFC membranes. We then proceed to discuss the pros and cons of emerging IP-based fabrication strategies aiming at improving the performance of TFC membranes. Next, we present technical obstacles and recent efforts in the characterization of TFC membranes to enable fundamental understanding of relevant mechanisms. We conclude with a discussion of the current gap between industrial needs and academic research in designing high-performance TFC membranes, and provide an outlook on future research directions for advancing IP-based fabrication processes.