Hydrophilic 1T-WS2 Nanosheet Arrays toward Conductive Textiles for High-Efficient and Continuous Hydroelectric Generation and Storage.

Flexible hydroelectric generators (HEGs) are promising self-powered devices that spontaneously derive electrical power from moisture. However, achieving the desired compatibility between a continuous operating voltage and superior current density remains a significant challenge. Herein, a textile-based van der Waals heterostructure is rationally designed between conductive 1T phase tungsten disulfide@carbonized silk (1T-WS2@CSilk) and carbon black@cotton (CB@Cotton) fabrics with an asymmetric distribution of oxygen-containing functional groups, which enhances the proton concentration gradients toward high-performance wearable HEGs. The vertically staggered 1T-WS2 nanosheet arrays on the CSilk fabric provide abundant hydrophilic nanochannels for rapid carrier transport. Furthermore, the moisture-induced primary battery formed between the active aluminum (Al) electrode and the conductive textiles introduces the desired electric field to facilitate charge separation and compensate for the decreased streaming potential. These devices exhibit a power density of 21.6 µW cm-2, an open-circuit voltage (Voc) of 0.65 V sustained for over 10 000 s, and a current density of 0.17 mA cm-2. This performance makes them capable of supplying power to commercial electronics and human respiratory monitoring. This study presents a promising strategy for the refined design of wearable electronics.

Oriented Self-Assembly of Hierarchical Branch Organic Crystals for Asymmetric Photonics.

Organic hierarchical branch micro/nanostructures constituted by single crystals with inherent multichannel characteristics exhibit superior potential in regulating photon transmission for photonic circuits. However, organic branch micro/nanostructures with precise branch positions are extremely difficult to achieve due to the randomness of the nucleation process. Herein, by taking advantage of the dislocation stress field-impurity interaction that solute molecules deposit preferentially along the dislocation line, twinning deformation was introduced into microcrystals to induce oriented nucleation sites, and ultimately organic branch microstructures with controllable branch sites were fabricated. The growth mechanism of these controllable single crystals with an angle of 140° between trunk and branch is attributed to the low lattice mismatching ratio (η) of 4.8%. These as-prepared hierarchical branch single crystals with asymmetrical optical waveguide characteristics have been demonstrated as an optical logic gate with multiple input/out channels, which provides a route to command the nucleation sites and offers potential applications in the organic optoelectronics at the micro/nanoscale.

Thermochromic Ni(II) Organometallics With High Optical Transparency and Low Phase-Transition Temperature for Energy-Saving Smart Windows.

Thermochromic smart windows with rational modulation in indoor temperature and brightness draw considerable interest in reducing building energy consumption, which remains a huge challenge to meet the comfortable responsive temperature and the wide transmittance modulation range from visible to near-infrared (NIR) light for their practical application. Herein, a novel thermochromic Ni(II) organometallic of [(C2 H5 )2 NH2 ]2 NiCl4 for smart windows is rationally designed and synthesized via an inexpensive mechanochemistry method, which processes a low phase-transition temperature of 46.3 °C for the reversible color evolution from transparent to blue with a tunable visible transmittance from 90.5% to 72.1%. Furthermore, cesium tungsten bronze (CWO) and antimony tin oxide (ATO) with excellent NIR absorption in 750-1500 and 1500-2600 nm are introduced in the [(C2 H5 )2 NH2 ]2 NiCl4 -based smart windows, realizing a broadband sunlight modulation of a 27% visible light modulation and more than 90% of NIR shielding ability. Impressively, these smart windows demonstrate stable and reversible thermochromic cycles at room temperature. Compared with the conventional windows in the field tests, these smart windows can significantly reduce the indoor temperature by 16.1 °C, which is promising for next-generation energy-saving buildings.

Organic Branched Heterostructures with Optical Interconnects for Photonic Barcodes.

Optical interconnects exhibit superior potential in the precise regulation of photon transmission for organic photonic circuits. However, the rational design of well-defined organic heterostructures toward active optoelectronics remains challenging. Herein, we designed organic branched heterostructures (OBHs) with accurate spatial organization for optical interconnection. Notably, the precise regulation of OBHs has been controllably achieved including the trunk morphologies and the branched microwire number. Significantly, these as-prepared OBHs inherently exhibit the multichannel coupling outputs and the excitation position-dependent waveguide characteristics, leading to various outcoupling signals with tunable intensity and emission colors. The optical interconnects are realized due to the occurrence of exciton conversion and photon propagation between branch and trunk at the heterojunction, benefiting the application possibilities of two-dimensional (2D) optical barcodes.

Cascaded Excited-State Intramolecular Proton Transfer Towards Near-Infrared Organic Lasers Beyond 850†nm.

Near-infrared (NIR) organic solid-state lasers play an essential role in applications ranging from laser communication to infrared night vision, but progress in this area is restricted by the lack of effective excited-state gain processes. Herein, we originally proposed and demonstrated the cascaded occurrence of excited-state intramolecular proton transfer for constructing the completely new energy-level systems. Cascading by the first ultrafast proton transfer of <430 fs and the subsequent irreversible second proton transfer of ca. 1.6 ps, the stepwise proton transfer process favors the true six-level photophysical cycle, which supports efficient population inversion and thus NIR single-mode lasing at 854 nm. This work realizes longest wavelength beyond 850 nm of organic single-crystal lasing to date and originally exploits the cascaded excited-state molecular proton transfer energy-level systems for organic solid-state lasers.

2D Organic Photonics: An Asymmetric Optical Waveguide in Self-Assembled Halogen-Bonded Cocrystals.

Anisotropic organic molecular construction and packing are crucial for the optoelectronic properties of organic crystals. Two-dimensional (2D) organic crystals with regular morphology and good photon confinement are potentially suitable for a chip-scale planar photonics system. Herein, through the bottom-up process, 2D halogen-bonded DPEpe-F4 DIB cocrystals were fabricated that exhibit an asymmetric optical waveguide with the optical-loss coefficients of RBackward =0.0346 dB µm-1 and RForward =0.0894 dB µm-1 along the [010] crystal direction, which can be attributed to the unidirectional total internal reflection caused by the anisotropic molecular packing mode. Based on this crystal direction-oriented asymmetric photon transport, these as-prepared 2D cocrystals have been demonstrated as a microscale optical logic gate with multiple input/out channels, which will offer potential applications as the 2D optical component for the integrated organic photonics.

White-Emissive Self-Assembled Organic Microcrystals.

Organic semiconductor micro-/nanocrystals with regular shapes have been demonstrated for many applications, such as organic field-effect transistors, organic waveguide devices, organic solid-state lasers, and therefore are inherently ideal building blocks for the key circuits in the next generation of miniaturized optoelectronics. In the study, blue-emissive organic molecules of 1,4-bis(2-methylstyryl)benzene (o-MSB) can assemble into rectangular microcrystals at a large scale via the room-temperature solution-exchange method. Because of the Förster resonance energy transfer, the energy of the absorbed photons by the host matrix organic molecules of o-MSB can directly transfer to the dopant organic molecules of tetracene or 1,2:8,9-dibenzopentacene (DBP), which then emit visible photons in different colors from blue to green, and to yellow. More impressively, by modulating the doping molar ratios of DBP to o-MSB, bright white-emissive organic microcrystals with well-preserved rectangular morphology can be successfully achieved with a low doping ratio of 1.5%. These self-assembled organic semiconductor microcrystals with multicolor emissions can be the white-light sources for the integrated optical circuits at micro-/nanoscale.

Vertical Phase-Engineering MoS2 Nanosheet-Enhanced Textiles for Efficient Moisture-Based Energy Generation.

Flexible moisture-electric generators (MEGs) capture chemical energy from atmospheric moisture for sustainable electricity, gaining attention in wearable electronics. However, challenges persist in the large-scale integration and miniaturization of MEGs for long-term, high-power output. Herein, a vertical heterogeneous phase-engineering MoS2 nanosheet structure based silk and cotton were rationally designed and successfully applied to construct wearable MEGs for moisture-energy conversion. The prepared METs exhibit ∼0.8 V open-circuit voltage, ∼0.27 mA/cm2 current density for >10 h, and >36.12 µW/cm2 peak output power density, 3 orders higher than current standards. And the large-scale device realizes a current output of 0.145 A. An internal phase gradient between the 2H semiconductor MoS2 in carbonized silks and 1T metallic MoS2 in cotton fibers enables a phase-engineering-based heterogeneous electric double layer functioning as an equivalent parallel circuit, leading to enhanced high-power output. Owing to their facile customization for seamless adaptation to the human body, we envision exciting possibilities for these wearable METs as integrated self-power sources, enabling real-time monitoring of physiological parameters in wearable electronics.

Visualizing the interfacial-layer-based epitaxial growth process toward organic core-shell architectures.

Organic heterostructures (OHTs) with the desired geometry organization on micro/nanoscale have undergone rapid progress in nanoscience and nanotechnology. However, it is a significant challenge to elucidate the epitaxial-growth process for various OHTs composed of organic units with a lattice mismatching ratio of > 3%, which is unimaginable for inorganic heterostructures. Herein, we have demonstrated a vivid visualization of the morphology evolution of epitaxial-growth based on a doped interfacial-layer, which facilitates the comprehensive understanding of the hierarchical self-assembly of core-shell OHT with precise spatial configuration. Significantly, the barcoded OHT with periodic shells obviously illustrate the shell epitaxial-growth from tips to center parts along the seeded rods for forming the core-shell OHT. Furthermore, the diameter, length, and number of periodic shells were modulated by finely tuning the stoichiometric ratio, crystalline time, and temperature, respectively. This epitaxial-growth process could be generalized to organic systems with facile chemical/structural compatibility for forming the desired OHTs.

2D/2D Cs0.32 WO3 /CuS Nano-Heterojunctions for Simultaneous High-Efficiency Solar Desalination, Photocatalytic Decontamination, and Electricity Generation.

Desalination and power generation through solar energy harvesting is a crucial technology that can effectively address freshwater shortages and energy crises. However, owing to the complexity of the actual water environment, the thermal output capability of the photothermal material and the functional integration of the evaporation system need urgent improvement, to obtain high-quality fresh water and sufficient electricity. Herein, a 2D/2D cesium tungsten bronze/copper sulfide (2D/2D Cs0.32 WO3 /CuS) nano-heterojunction is developed and it is loaded into a cellulose-based hybrid hydrogel to construct a multifunctional evaporator. Benefiting from the more nonradiative recombination centers from deep-level defects, as well as shorter carrier migration distances and higher redox potentials in the Cs0.32 WO3 /CuS nano-heterojunction, this evaporator has a significant improvement in thermal output capacity, enabling both super-efficient seawater evaporation (4.22 kg m-2 h-1 ) and photodegradation of organic pollutants (removal rate ≈ 99%). Moreover, the evaporator exhibits long-term stability and sustainable self-cleaning property against salt accumulation. Remarkably, the thermoelectric module based on the Cs0.32 WO3 /CuS nano-heterojunction shows promising electricity generation performance (4.85 W m-2 ), which can power small appliances durably and stably, exceeding previously reported similar devices. This 2D/2D heterojunction-based solar evaporation system will provide a more reliable solution for efficient and sustainable freshwater-electricity co-generation in resource-limited areas.

Organic Photothermal Cocrystals: Rational Design, Controlled Synthesis, and Advanced Application.

Organic photothermal cocrystals, integrating the advantages of intrinsic organic cocrystals and the fascinating photothermal conversion ability, hold attracted considerable interest in both basic science and practical applications, involving photoacoustic imaging, seawater desalination, and photothermal therapy, and so on. However, these organic photothermal cocrystals currently suffer individual cases discovered step by step, as well as the deep and systemic investigation in the corresponding photothermal conversion mechanisms is rarely carried out, suggesting a huge challenge for their further developments. Therefore, it is urgently necessary to investigate and explore the rational design and synthesis of high-performance organic photothermal cocrystals for future applications. This review first and systematically summarizes the organic photothermal cocrystal in terms of molecular classification, the photothermal conversion mechanism, and their corresponding applications. The timely interpretation of the cocrystal photothermal effect will provide broad prospects for the purposeful fabrication of excellent organic photothermal cocrystals toward great efficiency, low cost, and multifunctionality.

MXene-Decorated Smart Textiles with the Desired Mid-Infrared Emissivity for Passive Personal Thermal Management.

Multifunctional and long-term stable wearable heating systems have attracted extensive attention from experts, yet smart textiles that only rely on harvesting the body's heat without additional energy still face huge challenges in practical applications. Herein, we rationally prepared the monolayer MXene Ti3C2Tx nanosheets via an in situ hydrofluoric acid generation method, which was further employed to construct a wearable heating system of MXene @ polyester polyurethane blend fabrics (MP textile) for the passive personal thermal management through a simple spraying process. Owing to the unique two-dimensional (2D) structure, the MP textile presents the desired mid-infrared emissivity, which could efficiently suppress the thermal radiation loss from the human body. Notably, the MP textile with an MXene concentration of 28 mg/mL exhibits a low mid-infrared emissivity of 19.53% at 7-14 µm. Significantly, these prepared MP textiles demonstrate an enhanced temperature of more than 6.83 °C compared with those of favorably traditional fabrics, involving the black polyester fabric, pristine polyester polyurethane blend fabric (PU/PET), and cotton, suggesting a charming indoor passive radiative heating performance. The temperature of real human skin covered by MP textile is 2.68 °C higher than that covered by cotton fabric. Impressively, these prepared MP textiles simultaneously possess attractive breathability, moisture permeability, mechanical strength, and washability, which provide new insight into human body temperature regulation and physical health.

Dynamic Epitaxial Growth of Organic Heterostructures for Polarized Exciton Conversion.

Highly spatial and angular precision in epitaxial-growth process is crucial for constructing organic low-dimensional heterostructures (OLDHs) with the desired substructures, which remains significant challenge owing to the unpredicted location of complex heterogeneous nucleation. Herein, a dynamic epitaxial-growth approach is developed along the tailored longitudinal/horizontal directions to create diverse OLDHs with hierarchical architectures. The controlled morphology evolution of seed crystals from kinetic to thermodynamic species is achieved via incrementally increasing the crystallization time from 0 to 600 s. Accordingly, the kinetic and thermodynamic seed crystals respectively present the specific lattice-matching crystal-planes of (100) and (011), which facilitates the longitudinal epitaxial-growth (LG) process for triblock heterostructures, and the horizontal epitaxial-growth (HG) process for axial-branch heterostructures. The dominant core/shell heterostructures are prepared via both LG and HG processes with a crystallization time of ≈30 s. Significantly, these prepared OLDHs realize the rationally polarized exciton conversion for optical logic gate application through the exciton conversion and photon propagation at the heterojunction. This strategy provides an avenue for the precise synthesis of OLDHs with anisotropy optical characters for integrated optoelectronics.

Stretchable photothermal membrane of NIR-II charge-transfer cocrystal for wearable solar thermoelectric power generation.

Harvesting sunlight into cost-effective electricity presents an enticing prospect for self-powered wearable applications. The photothermal materials with an extensive absorption are fundamental to achieve optical and thermal concentration of the sunlight for efficiency output electricity of wearable solar thermoelectric generators (STEGs). Here, we synthesize an organic charge-transfer (CT) cocrystal with a flat absorption from ultraviolet to second near-infrared region (200 to 1950 nanometers) and a high photothermal conversion efficiency (PCE) of 80.5%, which is introduced into polyurethane toward large-area nanofiber membrane by electrospinning technology. These corresponding membranes demonstrate a high PCE of 73.7% under the strain more than 80%. Sandwiched with carbon nanotube-based thermoelectric fibers, the membranes as stretchable solar absorbers of STEGs could supply a notably increase temperature gradient, processing a maximum output voltage density of 23.4 volts per square meter at 1:00 p.m. under sunlight. This strategy presents an important insight in heat management for wearable STEGs with a desired electricity output.

Organic Bilayer Heterostructures with Built-In Exciton Conversion for 2D Photonic Encryption.

Organic multilayer heterostructures with accurate spatial organization demonstrate strong light-matter interaction from excitonic responses and efficient carrier transfer across heterojunction interfaces, which are considered as promising candidates toward advanced optoelectronics. However, the precise regulation of the heterojunction surface area for finely adjusting exciton conversion and energy transfer is still formidable. Herein, organic bilayer heterostructures (OBHs) with controlled face-to-face heterojunction via a stepwise seeded growth strategy, which is favorable for efficient exciton propagation and conversion of optical interconnects are designed and synthesized. Notably, the relative position and overlap length ratio of component microwires (LDSA /LBPEA = 0.39-1.15) in OBHs are accurately regulated by modulating the crystallization time of seeded crystals, resulting into a tailored heterojunction surface area (R = Loverlap /LBPEA = 37.6%-65.3%). These as-prepared OBHs present the excitation position-dependent waveguide behaviors for optical outcoupling characteristics with tunable emission colors and intensities, which are applied into two-dimensional (2D) photonic barcodes. This strategy opens a versatile avenue to purposely design OBHs with tailored heterojunctions for efficient energy transfer and exciton conversion, facilitating the application possibilities of advanced integrated optoelectronics.

Lattice-mismatch-free growth of organic heterostructure nanowires from cocrystals to alloys.

Organic heterostructure nanowires, such as multiblock, core/shell, branch-like and related compounds, have attracted chemists' extensive attention because of their novel physicochemical properties. However, owing to the difficulty in solving the lattice mismatch of distinct molecules, the construction of organic heterostructures at large scale remains challenging, which restricts its wide use in future applications. In this work, we define a concept of lattice-mismatch-free for hierarchical self-assembly of organic semiconductor molecules, allowing for the large-scale synthesis of organic heterostructure nanowires composed of the organic alloys and cocrystals. Thus, various types of organic triblock nanowires are prepared in large scale, and the length ratio of different segments of the triblock nanowires can be precisely regulated by changing the stoichiometric ratio of different components. These results pave the way towards fine synthesis of heterostructures in a large scale and facilitate their applications in organic optoelectronics at micro/nanoscale.

Segregated Array Tailoring Charge-Transfer Degree of Organic Cocrystal for the Efficient Near-Infrared Emission beyond 760 nm.

Harvesting the narrow bandgap excitons of charge-transfer (CT) complexes for the achievement of near-infrared (NIR) emission has attracted intensive attention for its fundamental importance and practical application. Herein, the triphenylene (TP)-2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 TCNQ) CT organic complex is designed and fabricated via the supramolecular self-assembly process, which demonstrates the NIR emission with a maximum peak of 770 nm and a photoluminescence quantum yield (PLQY) of 5.4%. The segregated stacking mode of TP-F4 TCNQ CT complex based on the multiple types of intermolecular interaction has a low CT degree of 0.00103 and a small counter pitch angle of 40° between F4 TCNQ and TP molecules, which breaks the forbidden electronic transitions of CT state, resulting in the effective NIR emission. Acting as the promising candidates for the active optical waveguide in the NIR region beyond 760 nm, the self-assembled TP-F4 TCNQ single-crystalline organic microwires display an ultralow optical-loss coefficient of 0.060 dB µm-1 . This work holds considerable insights for the exploration of novel NIR-emissive organic materials via an universal "cocrystal engineering" strategy.

Organic Charge-Transfer Cocrystals toward Large-Area Nanofiber Membrane for Photothermal Conversion and Imaging.

Organic photothermal materials integrating a high-efficiency light-heat conversion effect and high flexibility have generated immense interest in fundamental research and practical applications. Nevertheless, their practical applications still remain a challenge, owing to the complicated design, tedious synthesis, and limited programmable substrates. Herein, an organic charge-transfer cocrystal with a narrow energy gap of 0.33 eV and a high photothermal conversion efficiency (PCE) of 69.3% was rationally designed and synthesized via a facile self-assembly process, which was introduced into polyurethane for forming a large-area photothermal nanofiber membrane via electrospinning technology. Femtosecond transient absorption spectroscopy elucidates that the excellent PCE is attributed to the nonradiation transition process, including internal conversion and charge dissociation processes. Furthermore, the temperature of the as-prepared photothermal nanofiber membrane could quickly rise to 52 °C under laser irradiation with a power density of 0.183 W/cm2, suggesting a high PCE of 53.7%. This work successfully achieves the fabrication of a large-area photothermal membrane and the development of photothermal imaging.

Organic superstructure microwires with hierarchical spatial organisation.

Rationally designing and precisely constructing the dimensions, configurations and compositions of organic nanomaterials are key issues in material chemistry. Nevertheless, the precise synthesis of organic heterostructure nanomaterials remains challenging owing to the difficulty of manipulating the homogeneous/heterogeneous-nucleation process and the complex epitaxial relationships of combinations of dissimilar materials. Herein, we propose a hierarchical epitaxial-growth approach with the combination of longitudinal and horizontal epitaxial-growth modes for the design and synthesis of a variety of organic superstructure microwires with accurate spatial organisation by regulating the heterogeneous-nucleation crystallisation process. The lattice-matched longitudinal and horizontal epitaxial-growth modes are separately employed to construct the primary organic core/shell and segmented heterostructure microwires. Significantly, these primary organic core/shell and segmented microwires are further applied to construct the core/shell-segmented and segmented-core/shell type's organic superstructure microwires through the implementation of multiple spatial epitaxial-growth modes. This strategy can be generalised to all organic microwires with tailored multiple substructures, which affords an avenue to manipulate their physical/chemical features for various applications.

Smart Textiles Based on MoS2 Hollow Nanospheres for Personal Thermal Management.

Two-dimensional transition metal dichalcogenides are of particular interest in high-performance photothermal conversion, yet there remains a huge challenge in their practical application in smart textiles for healthcare, energy, and personal protection. Herein, we controllably prepared MoS2 hollow nanospheres with a high photothermal conversion efficiency of 36% via a microemulsion-hydrothermal method, which was further applied to construct photothermal fibers for personal thermal management after a hot-blast dip-drying process. Because of the prominent photothermal effect, the temperature of the photothermal fibers sharply increases from the room temperature value of 25.0 to 55.5 °C in 60 s under near-infrared illumination with a power density of 500 W/cm2. Furthermore, the photothermal fiber pad demonstrated an obvious temperature enhancement of 38.0 °C from a skin temperature of 22.0 °C after it was irradiated by natural sunlight for 60 s. Significantly, the antibacterial elimination rates of the photothermal fibers for Escherichia coli and Staphylococcus aureus are ∼99.9 and ∼99.8%, respectively. This strategy affords an avenue toward the practical application of photothermal materials in smart fibers for personal thermoregulation.