Functional MXenes: Progress and Perspectives on Synthetic Strategies and Structure-Property Interplay for Next-Generation Technologies.

MXenes are a class of 2D materials that include layered transition metal carbides, nitrides, and carbonitrides. Since their inception in 2011, they have garnered significant attention due to their diverse compositions, unique structures, and extraordinary properties, such as high specific surface areas and excellent electrical conductivity. This versatility has opened up immense potential in various fields, catalyzing a surge in MXene research and leading to note worthy advancements. This review offers an in-depth overview of the evolution of MXenes over the past 5 years, with an emphasis on synthetic strategies, structure-property relationships, and technological prospects. A classification scheme for MXene structures based on entropy is presented and an updated summary of the elemental constituents of the MXene family is provided, as documented in recent literature. Delving into the microscopic structure and synthesis routes, the intricate structure-property relationships are explored at the nano/micro level that dictate the macroscopic applications of MXenes. Through an extensive review of the latest representative works, the utilization of MXenes in energy, environmental, electronic, and biomedical fields is showcased, offering a glimpse into the current technological bottlenecks, such asstability, scalability, and device integration. Moreover, potential pathways for advancing MXenes toward next-generation technologies are highlighted.

Highly Biocompatible Antibacterial Hydrogel for Wearable Sensing of Macro and Microscale Human Body Motions.

Flexible electronics, like electronic skin (e-skin), rely on stretchable conductive materials that integrate diverse components to enhance mechanical, electrical, and interfacial properties. However, poor biocompatibility, bacterial infections, and limited compatibility of functional additives within polymer matrices hinder healthcare sensors' performance. This study addresses these challenges by developing an antibacterial hydrogel using polyvinyl alcohol (PVA), konjac glucomannan (KGM), borax (B), and flower-shaped silver nanoparticles (F-AgNPs), referred as PKB/F-AgNPs hydrogel. The developed hydrogel forms a hierarchical network structure, with a tensile strength of 96 kPa, 83% self-healing efficiency within 60 minutes, and 128% cell viability in Cell Counting Kit-8 (CCK-8) assays, indicating excellent biocompatibility. It also shows strong antibacterial efficacy against Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus). Blue light irradiation enhances its antibacterial activity by 1.3-fold for E. coli and 2.2-fold for S. aureus. The hydrogel's antibacterial effectiveness is assessed by monitoring changes in electrical conductivity, providing a cost-effective alternative to traditional microbial culture assays. The PKB/F-AgNPs hydrogel's flexibility and electrical conductivity enable it to function as strain sensors for detecting body movements and facial expressions. This antibacterial hydrogel underscores its potential for future human-machine interfaces and wearable electronics.

Step-Scheme SnO2/Zn3In2S6 Catalysts for Solar Production of Hydrogen Peroxide From Seawater.

Photocatalytic generation of H2O2, involving both oxygen reduction and water oxidation without sacrificial agents, necessitates maximized light absorption, suitable band structure, and efficient carrier transport. Leveraging the redox capacity this study designs and constructs a step-scheme heterostructured SnO2/Zn3In2S6 catalyst for H2O2 production from seawater under ambient conditions for the first time. This photocatalyst demonstrates a remarkable H2O2 production rate of 43.5 µmol g⁻¹ min⁻¹ without sacrificial agents, which can be increased to 80.7 µmol g⁻¹ min⁻¹ with additional O2 injection. Extensive in situ and ex situ characterizations, supported by theoretical calculations, reveal efficient carrier transport and robust redox ability, enabling complete photosynthesis of H2O2 at the oxidation and reduction sites in the S-scheme SnO2/Zn3In2S6 heterojunction. Furthermore, it is hypothesized that substituting SnO2 with other semiconductors such as TiO2, WO3, and BiVO4 can all form S-scheme and the results confirm the feasibility of such catalyst design. Additionally, it demonstrates the recycling and further utilization of the H2O2 produced. These findings offer new insights into the design of heterostructure catalyst architectures and present new opportunities for H2O2 production from seawater at ambient conditions without sacrificial agents.

A Functionally Asymmetric Janus Hygro-Photothermal Hybrid for Atmospheric Water Harvesting in Arid Regions.

Metal-organic frameworks (MOFs) are high-performance adsorbents for atmospheric water harvesting but have poor water-desorption ability, requiring excess energy input to release the trapped water. Addressing this issue, a Janus-structured adsorbent with functional asymmetry is presented. The material exhibits contrasting functionalities on either face - a hygroscopic face interfaced with a photothermal face. Hygroscopic aluminum fumarate MOF and photothermal CuxS layers are in-situ grown on opposite sides of a Cu/Al bimetallic substrate, resulting in a CuxS-Cu/Al-MOF Janus hygro-photothermal hybrid. The two faces serve as independent "factories" for photothermal conversion and water adsorption-desorption respectively, while the interfacing bimetallic layer serves as a "heat conveyor belt" between them. Due to the high porosity and hydrophilicity of the MOF, the hybrid exhibits a water-adsorption capacity of 0.161 g g-1 and a fast adsorption rate (saturation within 52 min) at 30% relative humidity. Thanks to the photothermal CuxS, the hybrid can reach 71.5 °C under 1 Sun in 20 min and desorb 97% adsorbed water in 40 min, exhibiting a high photothermal conversion efficiency of over 90%. CuxS-Cu/Al-MOF exhibits minimal fluctuations after 200 cycles, and its water-generation capacity is 3.21 times that of powdery MOF in 3 h in a self-designed prototype in one cycle.

Ultrathin Two-Dimensional Membranes Assembled by Ionic Covalent Organic Nanosheets with Reduced Apertures for Gas Separation.

Covalent organic frameworks (COFs) are a promising category of porous materials possessing extensive chemical tunability, high porosity, ordered arrangements at a molecular level, and considerable chemical stability. Despite these advantages, the application of COFs as membrane materials for gas separation is limited by their relatively large pore apertures (typically >0.5 nm), which exceed the sieving requirements for most gases whose kinetic diameters are less than 0.4 nm. Herein, we report the fabrication of ultrathin two-dimensional (2D) membranes through layer-by-layer (LbL) assembly of two kinds of ionic covalent organic nanosheets (iCONs) with different pore sizes and opposite charges. Because of the staggered packing of iCONs with strong electrostatic interactions, the resultant membranes exhibit features of reduced aperture size, optimized stacking pattern, and compact dense structure without sacrificing thickness control, which are suitable for molecular sieving gas separation. One of the hybrid membranes, TpEBr@TpPa-SO3Na with a thickness of 41 nm, shows a H2 permeance of 2566 gas permeation units (GPUs) and a H2/CO2 separation factor of 22.6 at 423 K, surpassing the recent Robeson upper bound along with long-term hydrothermal stability. This strategy provides not only a high-performance H2 separation membrane candidate but also an inspiration for pore engineering of COF or 2D porous polymer membranes.

Hydro-Assisted Self-Regenerating Brominated N-Alkylated Thiophene Diketopyrrolopyrrole Dye Nanofibers-A Sustainable Synthesis Route for Renewable Air Filter Materials.

With rising global concerns over the alarming levels of particulate pollution, a sustainable air quality management is the need of the hour. Air filtration research has gained momentum in recent years. However, the research perspective is still blinkered toward formulating new fiber systems for the energy-intensive electrospinning process to fabricate high quality factor air filters. A holistic approach on sustainable air filtration models is still lacking. The air filter model presented in this work uses a simple process involving water-induced self-organization and self-regeneration of nanofibers, and an easy recycling route after the filter life that not only facilitates reuse of the microfibrous scaffold holding the nanofibers but also allows renewal of nanofibers. Three generations of air filters are fabricated and tested, all having high particulate matter (PM)-adsorbing tendency, high filtration efficiency (>95%), and high Young's modulus (≈5 GPa). The renewable air filters offer a sustainable alternative to the present cost-intensive electrospun air filters.

Transparent Nanofibrous Mesh Self-Assembled from Molecular LEGOs for High Efficiency Air Filtration with New Functionalities.

Alarming levels of particulate matter pollution in air pose a serious health threat in several countries, therefore intriguing a strong need for an economic and a viable technology of air filtration. Current air purification technology is rather expensive with certain types even having the risk of emitting hazardous by-products. The authors have developed a multifunctional air filter inspired from the nasal hairs possessing an ability to specifically trap/exhale the foreign particles and allergens while still letting the air flow. This design is achieved by introducing different functionalities at different dimensional scale employing a bottom-up approach starting with an organic molecule which is further self-organized to form nanoparticles and ultimately to a nanofibrous mesh. While the molecular building block inherently possesses the property of shielding Ultraviolet (UV) rays, the nanofibrous mesh built up from it aids in trapping the particulate matter while maintaining good air flow. By controlling the concentration of the organic molecule, the formation of fibers has been enabled in the nanoscale regime to obtain high particle-capture possibilities. The self-assembled nanofibrous filter thus designed has achieved a high filtration efficiency of ≈90% for the PM 2.5 particle in congruence with the ability to block the harmful UV radiations.

Cobalt-Ion Superhygroscopic Hydrogels Serve as Chip Heat Sinks Achieving a 5 °C Temperature Reduction via Evaporative Cooling.

In the rapidly advancing semiconductor sector, thermal management of chips remains a pivotal concern. Inherent heat generation during their operation can lead to a range of issues such as potential thermal runaway, diminished lifespan, and current leakage. To mitigate these challenges, the study introduces a superhygroscopic hydrogel embedded with metal ions. Capitalizing on intrinsic coordination chemistry, the metallic ions in the hydrogel form robust coordination structures with non-metallic nitrogen and oxygen through empty electron orbitals and lone electron pairs. This unique structure serves as an active site for water adsorption, beginning with a primary layer of chemisorbed water molecules and subsequently facilitating multi-layer physisorption via Van der Waals forces. Remarkably, the cobalt-integrated hydrogel demonstrates the capability to harvest over 1 and 5 g g-1 atmospheric water at 60% RH and 95% RH, respectively. Furthermore, the hydrogel efficiently releases the entirety of its absorbed water at a modest 40°C, enabling its recyclability. Owing to its significant water absorption capacity and minimal dehydration temperature, the hydrogel can reduce chip temperatures by 5°C during the dehydration process, offering a sustainable solution to thermal management in electronics.

Symbiotic defect-reinforced bimetallic MOF-derived fiber components for solar-assisted atmospheric water collection.

Conversion of atmospheric water to sustainable and clean freshwater resources through MOF-based adsorbent has great potential for the renewable environmental industry. However, its daily water production is hampered by susceptibility to agglomeration, slow water evaporation efficiency, and limited water-harvesting capacity. Herein, a solar-assisted bimetallic MOF (BMOF)-derived fiber component that surmounts these limitations and exhibits both optimized water-collect capacity and short adsorption-desorption period is proposed. The proposed strategy involves utilizing bottom-up interface-induced assembly between carboxylated multi-walled carbon nanotube and hygroscopic BMOF on a multi-ply glass fiber support. The designed BMOF (MIL-100(Fe,Al)-3) skeleton constructed using bimetallic-node defect engineering exhibits a high specific surface area (1,535.28 m2/g) and pore volume (0.76 cm3/g), thereby surpassing the parent MOFs and other reported MOFs in capturing moisture. Benefiting from the hierarchical structure of fiber rods and the solar-driven self-heating interface of photothermal layer, the customized BMOF crystals realize efficient loading and optimized water adsorption-desorption kinetics. As a result, the resultant fiber components achieve six adsorption-desorption cycles per day and an impressive water collection of 1.45 g/g/day under medium-high humidity outdoor conditions. Therefore, this work will provide new ideas for optimizing the daily yield of atmospheric water harvesting techniques.

Artificial Photosynthetic System with Spatial Dual Reduction Site Enabling Enhanced Solar Hydrogen Production.

Although S-scheme artificial photosynthesis shows promise for photocatalytic hydrogen production, traditional methods often overly concentrate on a single reduction site. This limitation results in inadequate redox capability and inefficient charge separation, which hampers the efficiency of the photocatalytic hydrogen evolution reaction. To overcome this limitation, a double S-scheme system is proposed that leverages dual reduction sites, thereby preserving energetic photo-electrons and holes to enhance apparent quantum efficiency. The design features a double S-scheme junction consisting of CdS nanospheres decorated with anatase TiO2 nanoparticles coupled with graphitic C3 N4 . The as-prepared catalyst exhibits a hydrogen evolution rate of 26.84 mmol g-1  h-1 and an apparent quantum efficiency of 40.2% at 365 nm. This enhanced photocatalytic hydrogen evolution is ascribed to the efficient charge separation and transport induced by the double S-scheme. Both theoretical calculations and comprehensive spectroscopy tests (both in situ and ex situ) affirm the efficient charge transport across the catalyst interface. Moreover, substituting the reduction-type catalyst CdS with other similar sulfides like ZnIn2 S4 , ZnS, MoS2 and In2 S3 further confirms the feasibility of the proposed double S-scheme configuration. The findings provide a pathway to designing more effective double S-scheme artificial photosynthetic systems, opening up fresh perspectives in enhancing photocatalytic hydrogen evolution performance.

Catalyzing Artificial Photosynthesis with TiO2 Heterostructures and Hybrids: Emerging Trends in a Classical yet Contemporary Photocatalyst.

Titanium dioxide (TiO2 ) stands out as a versatile transition-metal oxide with applications ranging from energy conversion/storage and environmental remediation to sensors and optoelectronics. While extensively researched for these emerging applications, TiO2 has also achieved commercial success in various fields including paints, inks, pharmaceuticals, food additives, and advanced medicine. Thanks to the tunability of their structural, morphological, optical, and electronic characteristics, TiO2 nanomaterials are among the most researched engineering materials. Besides these inherent advantages, the low cost, low toxicity, and biocompatibility of TiO2 nanomaterials position them as a sustainable choice of functional materials for energy conversion. Although TiO2 is a classical photocatalyst well-known for its structural stability and high surface activity, TiO2 -based photocatalysis is still an active area of research particularly in the context of catalyzing artificial photosynthesis. This review provides a comprehensive overview of the latest developments and emerging trends in TiO2 heterostructures and hybrids for artificial photosynthesis. It begins by discussing the common synthesis methods for TiO2 nanomaterials, including hydrothermal synthesis and sol-gel synthesis. It then delves into TiO2 nanomaterials and their photocatalytic mechanisms, highlighting the key advancements that have been made in recent years. The strategies to enhance the photocatalytic efficiency of TiO2 , including surface modification, doping modulation, heterojunction construction, and synergy of composite materials, with a specific emphasis on their applications in artificial photosynthesis, are discussed. TiO2 -based heterostructures and hybrids present exciting opportunities for catalyzing solar fuel production, organic degradation, and CO2 reduction via artificial photosynthesis. This review offers an overview of the latest trends and advancements, while also highlighting the ongoing challenges and prospects for future developments in this classical yet rapidly evolving field.

Microphase-Separated Elastic and Ultrastretchable Ionogel for Reliable Ionic Skin with Multimodal Sensation.

Bioinspired artificial skins integrated with reliable human-machine interfaces and stretchable electronic systems have attracted considerable attention. However, the current design faces difficulties in simultaneously achieving satisfactory skin-like mechanical compliance and self-powered multimodal sensing. Here, this work reports a microphase-separated bicontinuous ionogel which possesses skin-like mechanical properties and mimics the multimodal sensing ability of biological skin by ion-driven stimuli-electricity conversion. The ionogel exhibits excellent elasticity and ionic conductivity, high toughness, and ultrastretchability, as well as a Young's modulus similar to that of human skin. Leveraging the ion-polymer interactions enabled selective ion transport, the ionogel can output pulsing or continuous electrical signals in response to diverse stimuli such as strain, touch pressure, and temperature sensitively, demonstrating a unique self-powered multimodal sensing. Furthermore, the ionogel-based I-skin can concurrently sense different stimuli and decouple the variations of the stimuli from the voltage signals with the assistance of a machine-learning model. The ease of fabrication, wide tunability, self-powered multimodal sensing, and the excellent environmental tolerance of the ionogels demonstrate a new strategy in the development of next-generation soft smart mechano-transduction devices.

Tailoring the whole-cell sensing spectrum with cyborgian redox machinery.

Whole-cell biosensors are an important class of analytical tools that offer the advantages of low cost, facile operation, and unique reproduction/regeneration ability. However, it has always been quite challenging to expand the sensing spectrum of the host. Here, a new approach to extend the cell sensing spectrum with biomineralized nanoparticles is developed. The nano-biohybrid design comprise biomineralized FeS nanoparticles firmly anchored onto the bacterium, Shewanella oneidensis MR-1, wherein the nanoparticles are wired to the cellular electron transfer machinery (MtrCAB/OmcA) of the bacterium, forming an artificial cyborgian redox machinery consisting of FeS-MtrCAB/OmcA-FccA. Strikingly, with this cyborgian redox machinery, the sensing spectrum of FeS hybridized S. oneidensis MR-1 cell is successfully expanded to enable whole-cell electrochemical detection of Vitamin B12, while an unhybridized native cell is incapable of sensing. This proof-of-concept nano-biohybrid design offers a new perspective on manipulating the microbial toolkit for an expanded sensing spectrum in whole-cell biosensors.

Enhancing Photocatalytic Hydrogen Evolution by Synergistic Benefits of MXene Cocatalysis and Homo-Interface Engineering.

Photocatalytic water splitting holds great promise as a sustainable and cost-effectiveness alternative for the production of hydrogen. Nevertheless, the practical implementation of this strategy is hindered by suboptimal visible light utilization and sluggish charge carrier dynamics, leading to low yield. MXene is a promising cocatalyst due to its high conductivity, abundance of active sites, tunable terminal functional groups, and great specific surface area. Homo-interface has perfect lattice matching and uniform composition, which are more conducive to photogenerated carriers' separation and migration. In this study, a novel ternary heterogeneous photocatalyst, a-TiO2 /H-TiO2 /Ti3 C2 MXene (MXTi), is presented using an electrostatic self-assembly method. Compared to commercial P25, pristine anatase, and rutile TiO2 , as-prepared MXTi exhibit exceptional photocatalytic hydrogen evolution performance, achieving a rate of 0.387 mmol h-1 . The significant improvement is attributable to the synergistic effect of homo-interface engineering and Ti3 C2 MXene, which leads to widened light absorption and efficient carrier transportation. The findings highlight the potential of interface engineering and MXene cocatalyst loading as a proactive approach to enhance the performance of photocatalytic water splitting, paving the way for more sustainable and efficient hydrogen production.

A Twin S-Scheme Artificial Photosynthetic System with Self-Assembled Heterojunctions Yields Superior Photocatalytic Hydrogen Evolution Rate.

Designing heterojunction photocatalysts imitating natural photosynthetic systems has been a promising approach for photocatalytic hydrogen generation. However, in the traditional Z-Scheme artificial photosynthetic systems, the poor charge separation, and rapid recombination of photogenerated carriers remain a huge bottleneck. To rationally design S-Scheme (i.e., Step scheme) heterojunctions by avoiding the futile charge transport routes is therefore seen as an attractive approach to achieving high hydrogen evolution rates. Herein, a twin S-scheme heterojunction is proposed involving graphitic C3 N4 nanosheets self-assembled with hydrogen-doped rutile TiO2 nanorods and anatase TiO2 nanoparticles. This catalyst shows an excellent photocatalytic hydrogen evolution rate of 62.37 mmol g-1 h-1 and high apparent quantum efficiency of 45.9% at 365 nm. The significant enhancement of photocatalytic performance is attributed to the efficient charge separation and transfer induced by the unique twin S-scheme structure. The charge transfer route in the twin S-scheme is confirmed by in situ X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) spin-trapping tests. Femtosecond transient absorption (fs-TA) spectroscopy, transient-state surface photovoltage (TPV), and other ex situ characterizations further corroborate the efficient charge transport across the catalyst interface. This work offers a new perspective on constructing artificial photosynthetic systems with S-scheme heterojunctions to enhance photocatalytic performance.

Ultrathin, Cationic Covalent Organic Nanosheets for Enhanced CO2 Electroreduction to Methanol.

Metalloporphyrins and metallophthalocyanines emerge as popular building blocks to develop covalent organic nanosheets (CONs) for CO2 reduction reaction (CO2 RR). However, existing CONs predominantly yield CO, posing a challenge in achieving efficient methanol production through multielectron reduction. Here, ultrathin, cationic, and cobalt-phthalocyanine-based CONs (iminium-CONs) are reported for electrochemical CO2 -to-CH3 OH conversion. The integration of quaternary iminium groups enables the formation of ultrathin morphology with uniformly anchored cobalt active sites, which are pivotal for facilitating rapid multielectron transfer. Moreover, the cationic iminium-CONs exhibit a lower activity for hydrogen evolution side reaction. Consequently, iminium-CONs manifest significantly enhanced selectivity for methanol production, as evidenced by a remarkable 711% and 270% improvement in methanol partial current density (jCH3OH ) compared to pristine CoTAPc and neutral imine-CONs, respectively. Under optimized conditions, iminium-CONs deliver a high jCH3OH of 91.7 mA cm-2 at -0.78 V in a flow cell. Further, iminium-CONs achieve a global methanol Faradaic efficiency (FECH3OH ) of 54% in a tandem device. Thanks to the single-site feature, the methanol is produced without the concurrent generation of other liquid byproducts. This work underscores the potential of cationic covalent organic nanosheets as a compelling platform for electrochemical six-electron reduction of CO2 to methanol.

Solar Energy Triggered Clean Water Harvesting from Humid Air Existing above Sea Surface Enabled by a Hydrogel with Ultrahigh Hygroscopicity.

Water scarcity is a ubiquitous problem with its magnitude expected to rise in the near future, and efforts to seek alternative water sources are on the rise. Harvesting water from air has intrigued enormous research interest among many groups with Scientific American listing this technology as the second most impactful technology that can bring about a massive change in people's lives. Though desalination offers a huge prospect in mitigating water crisis, its practicality is limited by exorbitant energy requirement. Alternatively, the air above sea water is moisture rich, with the quantity of vapor increasing at the rate of 0.41 kg m-2 . Herein, a method to sustainably harvest water from this moisture rich zone is demonstrated by employing a nanoporous superhygroscopic hydrogel, which is capable of absorbing water from highly humid atmospheres by over 420% (highest) of its own weight. The desorption process from the hydrogel, occurring at 55 °C (lowest), is triggered by natural sunlight (A.M 1.5) thereby ensuing an external energy-less water harvesting approach. The hydrogel exhibits excellent stability even after 1000 absorption/desorption cycles. Through multiple absorption/desorption cycles, it is possible to harvest over 10 L water per kg of hydrogel daily.

Portable Trilayer Photothermal Structure for Hybrid Energy Harvesting and Synergic Water Purification.

Many exciting developments have unfolded on the recently emerged research topic of solar-driven interfacial evaporation, which is a promising technology for water purification. However, the sole heat source, i.e., solar energy, has put a limit on the maximum achievable evaporation rate. Therefore, to boost the evaporation beyond the limit, we here in this work have put forth a new photothermal system with a trilayered structure (TLS) that is capable of simultaneously harvesting hybrid energy in addition to solar energy for enhanced evaporation. A carbon-based material with broad-band light absorption that can be facilely synthesized through dehydration effect is also reported. Demonstrations of TLS evaporator by recovering the free thermal energy from sources like ground surficial heat and waste heat from laboratory facility and building walls together with solar radiation have been carried out. A remarkable synergic evaporation rate exceeding 2.4 kg m-2 h-1 is achieved, and moreover, the hybrid heating makes evaporation independent of solar intermittency. Besides, a TLS integrated hybrid water-purification bottle with outstanding portability is further demonstrated, which is expected to be of great significance to the development of mobile water purification and safe water security in the future.

Photosynthetic apparatus of Rhodobacter sphaeroides exhibits prolonged charge storage.

Photosynthetic proteins have been extensively researched for solar energy harvesting. Though the light-harvesting and charge-separation functions of these proteins have been studied in depth, their potential as charge storage systems has not been investigated to the best of our knowledge. Here, we report prolonged storage of electrical charge in multilayers of photoproteins isolated from Rhodobacter sphaeroides. Direct evidence for charge build-up within protein multilayers upon photoexcitation and external injection is obtained by Kelvin-probe and scanning-capacitance microscopies. Use of these proteins is key to realizing a 'self-charging biophotonic device' that not only harvests light and photo-generates charges but also stores them. In strong correlation with the microscopic evidence, the phenomenon of prolonged charge storage is also observed in primitive power cells constructed from the purple bacterial photoproteins. The proof-of-concept power cells generated a photovoltage as high as 0.45 V, and stored charge effectively for tens of minutes with a capacitance ranging from 0.1 to 0.2 F m-2.