Effect of Spacer Length of Siloxane‐Terminated Side Chains on Charge Transport in Isoindigo‐Based Polymer Semiconductor Thin Films

A series of isoindigo‐based conjugated polymers (PII2F‐C_mSi, m = 3–11) with alkyl siloxane‐terminated side chains are prepared, in which the branching point is systematically “moved away” from the conjugated backbone by one carbon atom. To investigate the structure–property relationship, the polymer thin film is subsequently tested in top‐contact field‐effect transistors, and further characterized by both grazing incidence X‐ray diffraction and atomic force microscopy. Hole mobilities over 1 cm² V^?1 s^?1 is exhibited for all soluble PII2F‐C_mSi (m = 5–11) polymers, which is 10 times higher than the reference polymer with same polymer backbone. PII2F‐C₉Si shows the highest mobility of 4.8 cm² V^?1 s^?1, even though PII2F‐C₁₁Si exhibits the smallest π–π stacking distance at 3.379 Å. In specific, when the branching point is at, or beyond, the third carbon atoms, the contribution to charge transport arising from π–π stacking distance shortening becomes less significant. Other factors, such as thin‐film microstructure, crystallinity, domain size, become more important in affecting the resulting device's charge transport.     

Imidazolium Polyesters: Structure–Property Relationships in Thermal Behavior,Ionic Conductivity,and Morphology

New bis(ω‐hydroxyalkyl)imidazolium and 1,2‐bis[N‐(ω‐hydroxyalkyl)imidazolium]ethane salts are synthesized and characterized; most of the salts are room temperature ionic liquids. These hydroxyl end‐functionalized ionic liquids are polymerized with diacid chlorides, yielding polyesters containing imidazolium cations embedded in the main chain. By X‐ray scattering, four polyesters are found to be semicrystalline at room temperature: mono‐imidazolium‐C₁₁‐sebacate‐C₆ ( 4e ), mono‐imidazolium‐C₁₁‐sebacate‐C₁₁ ( 4c ), bis(imidazolium)ethane‐C₆‐sebacate‐C₆ ( 5a ), and bis(imidazolium)ethane‐C₁₁‐sebacate‐C₁₁ ( 5c ), all with hexafluorophosphate counterions. The other imidazolium polyesters, including all those with bis(trifluoromethanesulfonyl)imide (TFSI^?) counterions, are amorphous at room temperature. Room temperature ionic conductivities of the mono‐imidazolium polyesters (4 × 10^?6 to 3 × 10^?5 S cm^?1) are higher than those of the corresponding bis‐imidazolium polyesters (4 × 10^?9 to 8 × 10^?6 S cm^?1), even though the bis‐imidazolium polyesters have higher ion concentrations. Counterions affect ionic conduction significantly; all polymers with TFSI^? counterions have higher ionic conductivities than the hexafluorophosphate analogs. Interestingly, the hexafluorophosphate polyester, 1,2‐bis(imidazolium)ethane‐C₁₁‐sebacate‐C₁₁ ( 5c ), displays almost 400‐fold higher room temperature ionic conductivity (1.6 × 10^?6 S cm^?1) than the 1,2‐bis(imidazolium)ethane‐C₆‐sebacate‐C₆ analog ( 5a , 4.3 × 10^?9 S cm^?1), attributable to the differences in the semicrystalline structure in 5c as compared to 5a . These results indicate that semicrystalline polymers may result in high ionic conductivity in a soft (low glass tranition temperature, T_g) amorphous phase and good mechanical properties of the crystalline phase.     

Edge‐Fluorinated Graphene Nanoplatelets as High Performance Electrodes for Dye‐Sensitized Solar Cells and Lithium Ion Batteries

Edge‐selectively fluorinated graphene nanoplatelets (FGnPs) are prepared by mechanochemically driven reaction between fluorine gas (20 vol% in argon) and activated carbon species from graphitic C–C bonds unzipped by high‐speed stainless steel balls with a high kinetic energy. The fluorination at edges of the unzipped graphene nanoplatelets (GnPs) is confirmed by various analytical techniques while the content of fluorine in FGnPs is determined to be 3.0 and 3.4 at% by X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectroscopy, respectively. Because of the large difference in electronegativity between carbon (χ = 2.55) and fluorine (χ = 3.98) and the strong C–F bond, the edge‐fluorination of GnPs can provide the maximized charge polarization with an enhanced chemical stability. Thus, electrodes based on the resultant FGnPs demonstrate superb electrochemical performance with excellent stability/cycle life in dye‐sensitized solar cells (FF: 71.5%; J_sc: 14.44 mA cm^?2; V_oc: 970 mV; PCE: 10.01%) and lithium ion batteries (650.3 mA h g^?1 at 0.5 C, charge retention of 76.6% after 500 cycles).     

Flexible Solid‐State Supercapacitors with Enhanced Performance from Hierarchically Graphene Nanocomposite Electrodes and Ionic Liquid Incorporated Gel Polymer Electrolyte

High energy density, durability, and flexibility of supercapacitors are required urgently for the next generation of wearable and portable electronic devices. Herein, a novel strategy is introduced to boost the energy density of flexible soild‐state supercapacitors via rational design of hierarchically graphene nanocomposite (GNC) electrode material and employing an ionic liquid gel polymer electrolyte. The hierarchical graphene nanocomposite consisting of graphene and polyaniline‐derived carbon is synthesized as an electrode material via a scalable process. The meso/microporous graphene nanocomposites exhibit a high specific capacitance of 176 F g^?1 at 0.5 A g^?1 in the ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄) with a wide voltage window of 3.5 V, good rate capability of 80.7% in the range of 0.5–10 A g^?1 and excellent stability over 10 000 cycles, which is attributed to the superior conductivity (7246 S m^?1), and quite large specific surface area (2416 m² g^?1) as well as hierarchical meso/micropores distribution of the electrode materials. Furthermore, flexible solid‐state supercapacitor devices based on the GNC electrodes and gel polymer electrolyte film are assembled, which offer high specific capacitance of 180 F g^?1 at 1 A g^?1, large energy density of 75 Wh Kg^?1, and remarkable flexible performance under consecutive bending conditions.     

Supramolecular Self‐Assembly of Nanoconfined Ionic Liquids for Fast Anisotropic Ion Transport

Materials involving nanoconfinement of ionic liquids (ILs) have been pursued for functionalities and ionic devices. However, their complex synthesis, challenges to achieve long‐range order, and laborious tunability limit their practical implementation. Herein, these challenges are addressed by complexing surfactants to ILs, yielding a facile, modular, and scalable approach. Based on structural screening, ionic complexation of di‐n‐nonylamine to the terminal sulfonic acid of 1‐(4‐sulfobutyl)‐3‐methylimidazolium hydrogen sulfate IL is selected as a proof of concept. Spontaneous homeotropic smectic order over micrometers is observed, with alternating ionic and alkyl layers. The 1 nm thick ionic layers involve 2D crystalline internal order up to 150 °C, strongly promoting anisotropic ion transport (σ_||/σ_⊥ > 6500), and curiously, still allowing fluidity. High ionic conductivity of 35 mS cm^?1 and mesoscopic diffusion coefficient of ≈10^?5 cm² s^?1 at 150 °C along the ionic layers are observed. Fast anisotropic ion transport by simply complexing two components open doors to functional materials and applications.     

Highly Stretchable,High‐Mobility,Free‐Standing All‐Organic Transistors Modulated by Solid‐State Elastomer Electrolytes

Highly stretchable, high‐mobility, and free‐standing coplanar‐type all‐organic transistors based on deformable solid‐state elastomer electrolytes are demonstrated using ionic thermoplastic polyurethane (i‐TPU), thereby showing high reliability under mechanical stimuli as well as low‐voltage operation. Unlike conventional ionic dielectrics, the i‐TPU electrolyte prepared herein has remarkable characteristics, i.e., a large specific capacitance of 5.5 µF cm^?2, despite the low weight ratio (20 wt%) of the ionic liquid, high transparency, and even stretchability. These i‐TPU‐based organic transistors exhibit a mobility as high as 7.9 cm² V^?1 s^?1, high bendability (R_c, radius of curvature: 7.2 mm), and good stretchability (60% tensile strain). Moreover, they are suitable for low‐voltage operation (V_DS = ?1.0 V, V_GS = ?2.5 V). In addition, the electrical characteristics such as mobility, on‐current, and threshold voltage are maintained even in the concave and convex bending state (bending tensile strain of ≈3.4%), respectively. Finally, free‐standing, fully stretchable, and semi‐transparent coplanar‐type all‐organic transistors can be fabricated by introducing a poly(3,4‐ethylenedioxythiophene):polystyrene sulfonic acid layer as source/drain and gate electrodes, thus achieving low‐voltage operation (V_DS = ?1.5 V, V_GS = ?2.5 V) and an even higher mobility of up to 17.8 cm² V^?1 s^?1. Moreover, these devices withstand stretching up to 80% tensile strain.     

Dual Functions of Potassium Antimony(III)‐Tartrate in Tuning Antimony/Carbon Composites for Long‐Life Na‐Ion Batteries

Antimony holds a high‐specific capacity as a promising anode material for Na‐ion batteries (SIBs) and much research is focused on solving the poor cycling stability issue associated with its large volume expansion during alloying/dealloying processes. Here, self‐thermal‐reduction method is successfully applied to prepare antimony/carbon rods (Sb/C rods) utilizing potassium antimony(III)‐tartrate (C₈H₁₀O₁₅Sb₂K₂) as a dual source of carbon matrix and metallic antimony. According to theory calculations and experiment results, the formation process is explicitly explored as follows: C₈H₁₀O₁₅Sb₂K₂ → Sb₂O₃/C → Sb₂O₃/Sb/C → Sb/C rods. Notably, organic ligands in C₈H₁₀O₁₅Sb₂K₂ can be gradually turned into amorphous carbon with simultaneous reduction of Sb³⁺ to metal Sb. Moreover, potassium chloride acts as an activator and a template during the course of carbonization, and synchronous reduction is introduced. Consequently, an antimony/carbon electrode material denoted as Sb? O? C/C is formed, exhibiting a unique dual‐carbon‐modified structure and extensive Sb? O? C bridge bonds that give rise to outstanding cycling performance and rate capacity. Specifically, the capacity is maintained at 404 mA h g^?1 with 89% retention after 700 cycles at 500 mA g^?1. The low‐cost, self‐thermal‐reduction method and excellent electrode performances of electrode material make it attractive for large‐scale energy storage systems.     

Soft Processing of Graphene Nanosheets by Glycine‐Bisulfate Ionic‐Complex‐Assisted Electrochemical Exfoliation of Graphite for Reduction Catalysis

This study demonstrates a mild, environmentally friendly, and cost‐effective soft processing approach for the continuous synthesis of high‐quality, few‐layer graphene nanosheets. This has been achieved via electrochemical exfoliation of graphite, using an environmentally friendly glycine‐bisulfate ionic complex and was performed under ambient reaction conditions. Graphene nanosheets with 2–5 layers were obtained under optimized exfoliation conditions using a 15 wt% glycine‐bisulfate (aqueous) solution, with working biases of +1 V and +3 V applied for 5 min. The role of the glycine‐bisulfate ionic complex in the electrochemical exfoliation process was confirmed through comparison with a control experiment using only sulfuric acid as the electrolyte. A plausible electrochemical exfoliation mechanism that involves the formation of surface molecule nuclei via the polymerization of intercalated monomeric HSO₄^? and SO₄^2? ions is proposed. The ionic complex plays a key role in the anodic graphite exfoliation via electrochemical‐potential‐induced intercalation, leading to an efficient expansion of graphite sheets via the insertion of oxygen functional groups.     

An In Situ Simultaneous Reduction‐Hydrolysis Technique for Fabrication of TiO2‐Graphene 2D Sandwich‐Like Hybrid Nanosheets: Graphene‐Promoted Selectivity of Photocatalytic‐Driven Hydrogenation and Coupling of CO2 into Methane and Ethane

A novel, in situ simultaneous reduction‐hydrolysis technique (SRH) is developed for fabrication of TiO₂‐‐graphene hybrid nanosheets in a binary ethylenediamine (En)/H₂O solvent. The SRH technique is based on the mechanism of the simultaneous reduction of graphene oxide (GO) into graphene by En and the formation of TiO₂ nanoparticles through hydrolysis of titanium (IV) (ammonium lactato) dihydroxybis, subsequently in situ loading onto graphene through chemical bonds (Ti–O–C bond) to form 2D sandwich‐like nanostructure. The dispersion of TiO₂ hinders the collapse and restacking of exfoliated sheets of graphene during reduction process. In contrast with prevenient G‐TiO₂ nanocomposites, abundant Ti³⁺ is detected on the surface of TiO₂ of the present hybrid, caused by reducing agent En. The Ti³⁺ sites on the surface can serve as sites for trapping photogenerated electrons to prevent recombination of electron–hole pairs. The high photocatalytic activity of G‐TiO₂ hybrid is confirmed by photocatalytic conversion of CO₂ to valuable hydrocarbons (CH₄ and C₂H₆) in the presence of water vapor. The synergistic effect of the surface‐Ti³⁺ sites and graphene favors the generation of C₂H₆, and the yield of the C₂H₆ increases with the content of incorporated graphene. The work may open a new doorway for new significant application of graphene for selectively catalytic C–C coupling reaction     

Scalable Production of Graphene Inks via Wet‐Jet Milling Exfoliation for Screen‐Printed Micro‐Supercapacitors

The miniaturization of energy storage units is pivotal for the development of next‐generation portable electronic devices. Micro‐supercapacitors (MSCs) hold great potential to work as on‐chip micro‐power sources and energy storage units complementing batteries and energy harvester systems. Scalable production of supercapacitor materials with cost‐effective and high‐throughput processing methods is crucial for the widespread application of MSCs. Here, wet‐jet milling exfoliation of graphite is reported to scale up the production of graphene as a supercapacitor material. The formulation of aqueous/alcohol‐based graphene inks allows metal‐free, flexible MSCs to be screen‐printed. These MSCs exhibit areal capacitance (C_areal) values up to 1.324 mF cm^?2 (5.296 mF cm^?2 for a single electrode), corresponding to an outstanding volumetric capacitance (C_vol) of 0.490 F cm^?3 (1.961 F cm^?3 for a single electrode). The screen‐printed MSCs can operate up to a power density above 20 mW cm^?2 at an energy density of 0.064 µWh cm^?2. The devices exhibit excellent cycling stability over charge–discharge cycling (10 000 cycles), bending cycling (100 cycles at a bending radius of 1 cm) and folding (up to angles of 180°). Moreover, ethylene vinyl acetate‐encapsulated MSCs retain their electrochemical properties after a home‐laundry cycle, providing waterproof and washable properties for prospective application in wearable electronics.     

Layer‐by‐Layer Conjugated Extension of a Semiconducting Polymer for High‐Performance Organic Field‐Effect Transistor

A donor–acceptor (D–A) semiconducting copolymer, PDPP‐TVT‐29, comprising a diketopyrrolopyrrole (DPP) derivative with long, linear, space‐separated alkyl side‐chains and thiophene vinylene thiophene (TVT) for organic field‐effect transistors (OFETs) can form highly π‐conjugated structures with an edge‐on molecular orientation in an as‐spun film. In particular, the layer‐like conjugated film morphologies can be developed via short‐term thermal annealing above 150 °C for 10 min. The strong intermolecular interaction, originating from the fused DPP and D–A interaction, leads to the spontaneous self‐assembly of polymer chains within close proximity (with π‐overlap distance of 3.55 Å) and forms unexpectedly long‐range π‐conjugation, which is favorable for both intra‐ and intermolecular charge transport. Unlike intergranular nanorods in the as‐spun film, well‐conjugated layers in the 200 °C‐annealed film can yield more efficient charge‐transport pathways. The granular morphology of the as‐spun PDPP‐TVT‐29 film produces a field‐effect mobility (μ _FET) of 1.39 cm² V^?1 s^?1 in an OFET based on a polymer‐treated SiO₂ dielectric, while the 27‐Å‐step layered morphology in the 200 °C‐annealed films shows high μ _FET values of up to 3.7 cm² V^?1 s^?1.     

High‐Mobility Air‐Stable Solution‐Shear‐Processed n‐Channel Organic Transistors Based on Core‐Chlorinated Naphthalene Diimides

High charge carrier mobility solution‐processed n‐channel organic thin‐film transistors (OTFTs) based on core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are demonstrated. These OTFTs were prepared through a solution shearing method. Core‐chlorination of NDIs not only increases the electron mobilities of OTFTs, but also enhances their air stability, since the chlorination in the NDI core lowers the lowest unoccupied molecular orbital (LUMO) levels. The air‐stability of dichlorinated NDI was better than that of the tetrachlorinated NDIs, presumably due to the fact that dichlorinated NDIs have a denser packing of the fluoroalkyl chains and less grain boundaries on the surface, reducing the invasion pathway of ambient oxygen and moisture. The devices of dichlorinated NDIs exhibit good OTFT performance, even after storage in air for one and a half months. Charge transport anisotropy is observed from the dichlorinated NDI. A dichlorinated NDI with ?CH₂C₃F₇ side chains reveals high mobilities of up to 0.22 and 0.57 cm² V^?1 s^?1 in parallel and perpendicular direction, respectively, with regard to the shearing direction. This mobility anisotropy is related to the grain morphology. In addition, we find that the solution‐shearing deposition affects the molecular orientation in the crystalline thin films and lowers the d(001)‐spacing (the out‐of‐plane interlayer spacing), compared to the vapor‐deposited thin films. Core‐chlorinated NDI derivatives are found to be highly suitable for n‐channel active materials in low‐cost solution‐processed organic electronics.     

Phosphorescent Cationic Au4Ag2 Alkynyl Cluster Complexes for Efficient Solution‐Processed Organic Light‐Emitting Diodes

Cationic Au₄Ag₂ heterohexanuclear aromatic acetylides cluster complexes supported by bis(2‐diphenylphosphinoethyl)phenylphosphine (dpep) are prepared. The Au₄Ag₂ cluster structure originating from the combination of one anionic [Au(C≡CR)₂]^? with one cationic [Au₃Ag₂(dpep)₂(C≡CR)₂]³⁺ through the formation of Ag?acetylide η²‐bonds is highly stabilized by Au–Ag and Au–Au contacts. The Au₄Ag₂ alkynyl cluster complexes are moderately phosphorescent in the fluid CH₂Cl₂ solution, but exhibit highly intense phosphorescent emission in solid state and film. As revealed by theoretical computational studies, the phosphorescence is ascribable to significant ³[π (aromatic acetylide) → s/p (Au)] ³LMCT parentage with a noticeable Au₄Ag₂ cluster centered ³[d → s/p] triplet state. Taking advantage of mCP and OXD‐7 as a mixed host with 20 wt% dopant of phosphorescent Au₄Ag₂ cluster complex in the emitting layer, solution‐processed organic light‐emitting diodes (OLEDs) exhibit highly efficient electrophosphorescence with the maximum current, power, and external quantum efficiencies of 24.1 cd A^?1, 11.6 lm W^?1, and 7.0%, respectively. Introducing copper(I) thiocyanate (CuSCN) as a hole‐transporting layer onto the PEDOT:PSS hole‐injecting layer through the orthogonal solution process induces an obvious improvement of the device performance with lower turn‐on voltage and higher electroluminescent efficiency.     

High‐Performance Ultrathin Flexible Solid‐State Supercapacitors Based on Solution Processable Mo1.33C MXene and PEDOT:PSS

MXenes, a young family of 2D transition metal carbides/nitrides, show great potential in electrochemical energy storage applications. Herein, a high performance ultrathin flexible solid‐state supercapacitor is demonstrated based on a Mo_1.33C MXene with vacancy ordering in an aligned layer structure MXene/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) composite film posttreated with concentrated H₂SO₄. The flexible solid‐state supercapacitor delivers a maximum capacitance of 568 F cm^?3, an ultrahigh energy density of 33.2 mWh cm^?3 and a power density of 19 470 mW cm^?3. The Mo_1.33C MXene/PEDOT:PSS composite film shows a reduction in resistance upon H₂SO₄ treatment, a higher capacitance (1310 F cm^?3) and improved rate capabilities than both pristine Mo_1.33C MXene and the nontreated Mo_1.33C/PEDOT:PSS composite films. The enhanced capacitance and stability are attributed to the synergistic effect of increased interlayer spacing between Mo_1.33C MXene layers due to insertion of conductive PEDOT, and surface redox processes of the PEDOT and the MXene.     

DyeIonogels: Proton‐Responsive Ionogels Based on a Dye‐Ionic Liquid Exhibiting Reversible Color Change

Transparent, ion‐conducting, and flexible ionogels based on the room temperature ionic liquid (IL) 1‐butyl‐3‐methylimidazolium bis(trifluoromethane sulfonyl)imide [Bmim][N(Tf)₂], the dye‐IL (DIL) 1‐butyl‐3‐methylimidazolium methyl orange [Bmim][MO], and poly(methylmethacrylate) (PMMA) are prepared. Upon IL incorporation the thermal stability of the PMMA matrix significantly increases from 220 to 280 °C. The ionogels have a relatively high ionic conductivity of 10^?4 S cm^?1 at 373 K. Most importantly, the ionogels exhibit a strong and reversible color change when exposed to aqueous or organic solutions containing protons or hydroxide ions. The resulting material is thus a prototype of soft multifunctional matter featuring ionic conductivity, easy processability, response to changes in the environment, and a strong readout signal, the color change, that could be used in optical data storage or environmental sensing.     

Solution‐Processed Small‐Molecule Bulk Heterojunction Ambipolar Transistors

Solution‐processed small‐molecule bulk heterojunction (BHJ) ambipolar organic thin‐film transistors are fabricated based on a combination of [2‐phenylbenzo[d,d']thieno[3,2‐b;4,5‐b']dithiophene (P‐BTDT) : 2‐(4‐n‐octylphenyl)benzo[d,d ']thieno[3,2‐b;4,5‐b']dithiophene (OP‐BTDT)] and C₆₀. Treating high electrical performance vacuum‐deposited P‐BTDT organic semiconductors with a newly developed solution‐processed organic semiconductor material, OP‐BTDT, in an optimized ratio yields a solution‐processed p‐channel organic semiconductor blend with carrier mobility as high as 0.65 cm² V^?1 s^?1. An optimized blending of P‐BTDT:OP‐BTDT with the n‐channel semiconductor, C₆₀, results in a BHJ ambipolar transistor with balanced carrier mobilities for holes and electrons of 0.03 and 0.02 cm² V^?1 s^?1, respectively. Furthermore, a complementary‐like inverter composed of two ambipolar thin‐film transistors is demonstrated, which achieves a gain of 115.     

Low‐Temperature,Nontoxic Water‐Induced Metal‐Oxide Thin Films and Their Application in Thin‐Film Transistors

Here, a simple, nontoxic, and inexpensive “water‐inducement” technique for the fabrication of oxide thin films at low annealing temperatures is reported. For water‐induced (WI) precursor solution, the solvent is composed of water without additional organic additives and catalysts. The thermogravimetric analysis indicates that the annealing temperature can be lowered by prolonging the annealing time. A systematic study is carried out to reveal the annealing condition dependence on the performance of the thin‐film transistors (TFTs). The WI indium‐zinc oxide (IZO) TFT integrated on SiO₂ dielectric, annealed at 300 °C for 2 h, exhibits a saturation mobility of 3.35 cm² V^?1 s^?1 and an on‐to‐off current ratio of ≈10⁸. Interestingly, through prolonging the annealing time to 4 h, the electrical parameters of IZO TFTs annealed at 230 °C are comparable with the TFTs annealed at 300 °C. Finally, fully WI IZO TFT based on YO_x dielectric is integrated and investigated. This TFT device can be regarded as “green electronics” in a true sense, because no organic‐related additives are used during the whole device fabrication process. The as‐fabricated IZO/YO_x TFT exhibits excellent electron transport characteristics with low operating voltage (≈1.5 V), small subthreshold swing voltage of 65 mV dec^?1 and the mobility in excess of 25 cm² V^?1 s^?1.     

Facile “Spot‐Heating” Synthesis of Carbon Dots/Carbon Nitride for Solar Hydrogen Evolution Synchronously with Contaminant Decomposition

The use of solar energy to produce the clean hydrogen (H₂) energy from water splitting is a promising means of renewable energy conversion. High activation barriers for O₂ generation associated with the rate‐limiting steps require utilization of noble metal‐based cocatalysts, which complicates the fabrication procedure and compromises the stability of the catalyst. Here, a homogenous “spot heating” approach is designed via the ultrasonic cavitation effect for evenly embedding highly crystalline carbon quantum dots (CQDs) on 2D C₃N₄ nanosheets. Based on density functional calculations and electrochemical experiments, the optimal introduction of CQDs into C₃N₄ not only extends light absorption spectrum, but also reduces effective mass of electrons (e^?), facilitating photocarrier transport from excited sites. And, more importantly, the well‐organized CQDs with superior peroxidase mimetic activity can increase catalytic H₂ production through the process of (i) 2H₂O → H₂O₂ + H₂; (ii) H₂O₂→2 ? OH; (iii) ?OH + bisphenol A→ Final Products, with H₂ production rate (152 µmol g^?1 h^?1) several times higher than that for pure C₃N₄. This work demonstrates an ideal platform for efficient H₂ production with synergetic organic contaminant degradation, thereby opening possibilities for coupling energy conversion with environmental remediation.     

Versatile α,ω‐Disubstituted Tetrathienoacene Semiconductors for High Performance Organic Thin‐Film Transistors

Facile one‐pot [1 + 1 + 2] and [2 + 1 + 1] syntheses of thieno[3,2‐b]thieno[2′,3′:4,5]thieno[2,3‐d]thiophene (tetrathienoacene; TTA) semiconductors are described which enable the efficient realization of a new TTA‐based series for organic thin‐film transistors (OTFTs). For the perfluorophenyl end‐functionalized derivative DFP‐TTA , the molecular structure is determined by single‐crystal X‐ray diffraction. This material exhibits n‐channel transport with a mobility as high as 0.30 cm²V^?1s^?1 and a high on‐off ratio of 1.8 × 10⁷. Thus, DFP‐TTA has one of the highest electron mobilities of any fused thiophene semiconductor yet discovered. For the phenyl‐substituted analogue, DP‐TTA , p‐channel transport is observed with a mobility as high as 0.21 cm²V^?1s^?1. For the 2‐benzothiazolyl (BS‐) containing derivative, DBS‐TTA , p‐channel transport is still exhibited with a hole mobility close to 2 × 10^?3 cm²V^?1s^?1. Within this family, carrier mobility magnitudes are strongly dependent on the semiconductor growth conditions and the gate dielectric surface treatment.     

2D Heterostructure Membranes with Sunlight‐Driven Self‐Cleaning Ability for Highly Efficient Oil–Water Separation

Introducing solar energy into membrane filtration to decrease energy and chemicals consumption represents a promising direction in membrane fields. In this study, a kind of 0D/2D heterojunction is fabricated by depositing biomineralized titanium dioxide (TiO₂) nanoparticles with delaminated graphitic carbon nitride (g‐C₃N₄) nanosheets, and subsequently a kind of 2D heterostructure membrane is fabricated via intercalating g‐C₃N₄@TiO₂ heterojunctions into adjacent graphene oxide (GO) nanosheets by a vacuum‐assisted self‐assembly process. Due to the enlarged interlayer spacing of GO nanosheets, the initial permeation flux of GO/g‐C₃N₄@TiO₂ membrane reaches to 4536 Lm^?2 h^?1 bar^?1, which is more than 40‐fold of GO membranes (101 Lm^?2 h^?1 bar^?1) when utilized for oil/water separation. To solve the sharp permeation flux decline, arising from the adsorption of oil droplets, the a sunlight‐driven self‐cleaning process is followed, maintaining a flux recovery ratio of more than 95% after ten cycles of filtration experiment. The high permeation flux and excellent sunlight‐driven flux recovery of these heterostructure membranes manifest their attractive potential application in water purification.