Highly Efficient Organic Solar Cells with the Highly Crystalline Third Component as a Morphology Regulator.

The morphology of the active layer is crucial for highly efficient organic solar cells (OSCs), which can be regulated by selecting a rational third component. In this work, the highly crystalline nonfullerene acceptor BTP-eC9 is selected as the morphology regulator in OSCs with PM6:BTP-BO-4Cl as the main system. The addition of BTP-eC9 can prolong the nucleation and crystallization progress of acceptor and donor molecules, thereby enhancing the order of molecular arrangement. Meanwhile, the nucleation and crystallization time of the donor is earlier than that of the acceptors after introducing BTP-eC9, which is beneficial for obtaining a better vertical structural phase separation. The exciton dissociation, charge transport, and charge collection are promoted effectively by the optimized morphology of the active layer, which improves the short-circuit current density and filling factor. After introducing BTP-eC9, the power conversion efficiencies (PCEs) of the ternary OSCs are improved from 17.31% to 18.15%. The PCE is further improved to 18.39% by introducing gold nanopyramid (Au NBPs) into the hole transport layer to improve photon utilization efficiency. This work indicates that the morphology can be optimized by selecting a highly crystalline third component to regulate the nucleation and crystallization progress of the acceptor and donor molecules.

Highly Crystalline Multivariate Prussian Blue Analogs via Equilibrium Chelation Strategy for Stable and Fast Charging Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have been widely recognized as superior cathode materials for sodium-ion batteries (SIBs) owing to numerous merits. However, originating from the rapid crystal growth, PBAs still suffer from considerable vacancy defects and interstitial water, making the preparation of long-cycle-life PBAs the greatest challenge for its practical application. Herein, a novel equilibrium chelation strategy is first proposed to synthesize a high crystallinity (94.7%) PBAs, which is realized by modulating the chelating potency of strong chelating agents via "acid effect" to achieve a moderate chelating effect, forcefully breaking through the bottleneck of poor cyclic stability for PBAs cathodes. Impressively, the as-prepared highly crystalline PBAs represent an unprecedented level of electrochemical performance including ultra-long lifespan (10000 cycles with 86.32% capacity maintenance at 6 A g-1), excellent rate capability (82.0 mAh g-1 at 6 A g-1). Meanwhile, by pairing with commercial hard carbon, the as-prepared PBAs-based SIBs exhibit high energy density (350 Wh kg-1) and excellent capacity retention (82.4% after 1500 cycles), highlighting its promising potential for large-scale energy storage applications.

Hierarchically Periodic Macroporous Niobium Oxide Architecture for Enhanced Hydrogen Evolution.

The fabrication of periodic macroporous (PM) in Nb2O5 via morphological control is crucial for improving the photocatalytic hydrogen evolution efficiency. In this study, Nb2O5 with PM is synthesized using a straightforward colloidal crystal templating approach. This material features an open, interconnected macroporous architecture with nanoscale walls, high crystallinity, and substantial porosity. Extensive characterization reveals that this hierarchically structured Nb2O5 possesses abundant surface active sites and is capable of capturing light effectively, facilitating rapid mass transfer and diffusion of reactants and markedly suppressing the recombination of photoexcited charge carriers. Macroporous Nb2O5 exhibits superior water-splitting hydrogen evolution performance compared with its bulk and commercial counterparts, achieving a hydrogen production rate of 405 µmol g-1 h-1, surpassing that of bulk Nb2O5 (B-Nb2O5) and commercial Nb2O5 (C-Nb2O5) by factors of 5 and 33, respectively. This study proposes an innovative strategy for the design of hierarchically structured PM, thereby significantly advancing the hydrogen evolution potential of Nb2O5.

Temperature-dependent excitonic emission characteristics of highly crystallized carbon nitride nanosheets.

Highly-crystallized carbon nitride (HCCN) nanosheets exhibit significant potential for advancements in the field of photoelectric conversion. However, to fully exploit their potential, a thorough understanding of the fundamental excitonic photophysical processes is crucial. Here, the temperature-dependent excitonic photoluminescence (PL) of HCCN nanosheets and amorphous polymeric carbon nitride (PCN) is investigated using steady-state and time-resolved PL spectroscopy. The exciton binding energy of HCCN is determined to be 109.26 meV, lower than that of PCN (207.39 meV), which is attributed to the ordered stacking structure of HCCN with a weaker Coulomb interaction between electrons and holes. As the temperature increases, a noticeable reduction in PL lifetime is observed on both the HCCN and PCN, which is ascribed to the thermal activation of carrier trapping by the enhanced electron-phonon coupling effect. The thermal activation energy of HCCN is determined to be 102.9 meV, close to the value of PCN, due to their same band structures. Through wavelength-dependent PL dynamics analysis, we have identified the PL emission of HCCN as deriving from the transitions:σ*-LP,π*-π, andπ*-LP, where theπ*-LP transition dominants the emission because of the high excited state density of the LP state. These results demonstrate the impact of high-crystallinity on the excitonic emission of HCCN materials, thereby expanding their potential applications in the field of photoelectric conversion.

A Thermally Promoted Homogenous-Floating-Concentrating Strategy Synthesizing Highly Crystalline Triazine/hydroxyl-Rich COFs for 4-Nitrophenol Adsorption.

In this work, a "thermally promoted homogenous-floating-concentrating" strategy is reported for the rapid synthesis of highly crystalline triazine/hydroxyl-rich COFs under mild conditions, using for the effectively adsorbing 4-nitrophenol (4-NP) in aqueous solutions. This strategy originates from an optimized "homogenous-floating-concentrating" method as reported in the previous work. Both gradually improving concentration and heat treatment promote the condensation reaction between amino and aldehyde groups, resulting in high crystallinity and shorter reaction time. The obtained COFs demonstrate better crystallinity and higher surface area in comparison with the counterparts prepared by solvothermal strategy. A maximum surface area of 2391 m2 g-1 is achieved. The COFs exhibit excellent 4-NP adsorption capacity (Qmax = 1402.0 mg g-1 ), which is attributed to abundant triazine/hydroxyl-groups on the COF skeleton and their strong H-bonding interaction with 4-NP.

Ice-Assisted Synthesis of Highly Crystallized Prussian Blue Analogues for All-Climate and Long-Calendar-Life Sodium Ion Batteries.

For practical sodium-ion batteries, both high electrochemical performance and cost efficiency of the electrode materials are considered as two key parameters. Prussian blue analogues (PBAs) are broadly recognized as promising cathode materials due to their low cost, high theoretical capacity, and cycling stability, although they suffer from low-crystallinity-induced performance deterioration. Herein, a facile "ice-assisted" strategy is presented to prepare highly crystallized PBAs without any additives. By suppressing structure defects, the cathode exhibits a high capacity of 123 mAh g-1 with initial Coulombic efficiency of 87.2%, a long cycling lifespan of 3000 cycles, and significantly enhanced high/low temperature performance and calendar life. Remarkably, the low structure distortion and high sodium diffusion coefficient have been identified via in situ synchrotron powder diffraction and first-principles calculations, while its thermal stability has been analyzed by in situ heated X-ray powder diffraction. We believe the results could pave the way to the low-cost and large-scale application of PBAs in all-climate sodium-ion batteries.

A General Strategy for Kilogram-Scale Preparation of Highly Crystal-line Covalent Triazine Frameworks.

Scalable and eco-friendly synthesis of crystalline porous covalent triazine frameworks (CTFs) is essential to realize their broad industrial applications but remains a great challenge, which requires the fundamental understanding of the two-dimensional polymerization mechanism. Herein, we report a universal polyphosphoric acid (H6 P4 O13 )-catalyzed nitrile trimerization route to synthesize a series of highly crystalline CTFs with high specific surface areas. This new strategy enables the cost-effective large-scale fabrication of crystalline CTFs at kilogram level for the first time. Through density functional theory calculation and detailed controlled experiments, we reveal that the polyphosphate acid show much higher catalytic activity for trimerization reaction than its analogues such as P2 O5 and H3 PO4 . Furthermore, the crystalline CTFs with regular porosity and abundant triazine groups exhibit ultrahigh removal efficiency of micropollutants, indicating its great potential in environment remediation.

Plasma-Induced Nanocrystalline Domain Engineering and Surface Passivation in Mesoporous Chalcogenide Semiconductor Thin Films.

The synthesis of highly crystalline mesoporous materials is key to realizing high-performance chemical and biological sensors and optoelectronics. However, minimizing surface oxidation and enhancing the domain size without affecting the porous nanoarchitecture are daunting challenges. Herein, we report a hybrid technique that combines bottom-up electrochemical growth with top-down plasma treatment to produce mesoporous semiconductors with large crystalline domain sizes and excellent surface passivation. By passivating unsaturated bonds without incorporating any chemical or physical layers, these films show better stability and enhancement in the optoelectronic properties of mesoporous copper telluride (CuTe) with different pore diameters. These results provide exciting opportunities for the development of long-term, stable, and high-performance mesoporous semiconductor materials for future technologies.

Physical, Chemical and Rheological Characterization of Tuber and Starch from Ceiba aesculifolia subsp. parvifolia.

This work aimed to evaluate the physical, chemical and antioxidant properties of Ceiba aesculifolia subsp. parvifolia (CAP) tuber and determinate rheological, thermal, physicochemical and morphological properties of the starch extracted. The CAP tuber weight was 3.66 kg; the edible yield was 82.20%. The tuber presented a high hardness value (249 N). The content of carbohydrates (68.27%), crude fiber (15.61%) and ash (9.27%) from the isolated starch, reported in dry weight, were high. Phenolic compounds and flavonoid content of CAP tuber peel were almost 3-fold higher concerning the pulp. CAP tuber starch exhibited a pseudoplastic behavior and low viscosity at concentrations of 5-15%. Purity percentage and color parameters describe the isolated starch as high purity. Thermal characteristics indicated a higher degree of intermolecular association within the granule. Pasting properties describes starch with greater resistance to heat and shear. CAP tuber starch has X-ray diffraction patterns type A. The starch granules were observed as oval and diameters ranging from 5 to 30 µm. CAP tuber could be a good source of fiber and minerals, while its peel could be used for extracting bioactive compounds. Additionally, the starch separated from this tuber could be employed as a thickening agent in food systems requiring a low viscosity and subjected to high temperatures.

Isomeric Effect of Wide Bandgap Polymer Donors with High Crystallinity to Achieve Efficient Polymer Solar Cells.

Two highly crystalline polymer donors (PBTz4T2C-a, PBTz4T2C-b) with isomers (4T2C-a, 4T2C-b) are synthesized and applied in polymer solar cells. The developed polymers possess proper energy levels and complementary absorption with an efficient electron acceptor IT2F. It is interesting that the photophysical properties, crystallinity, and active layer morphology characteristic can be significantly changed by just slightly regulating the substitution position of the carboxylate groups. A series of simulation calculations of the two isomers are conducted in the geometry and electronic properties to explore the difference induced by the position adjustment of carboxylate groups. The results decipher that 4T2C-b moiety features much stronger intramolecular noncovalent S⋯O interactions compared to that of 4T2C-a, implying a higher coplanarity and much stronger crystallinity, and leading to excessive phase separation in PBTz4T2C-b:IT2F blend film. In contrast, PBTz4T2C-a with 4T2C-a moiety exhibits suitable crystallinity with a lower the highest occupied molecular orbital level, higher film absorption coefficient, and charge mobilities, resulting in a much higher power conversion efficiency of 11.02%. This research demonstrates that the molecular conformation is of great importance to be considered for developing high-performance polymer donors.

Solvent-Free Self-Assembly for Scalable Preparation of Highly Crystalline Mesoporous Metal Oxides.

Mesoporous metal oxides (MMOs) have been demonstrated great potential in various applications. Up to now, the direct synthesis of MMOs is still limited to the solvent induced inorganic-organic self-assembly process. Here, we develop a facile, general, and high throughput solvent-free self-assembly strategy to synthesize a series of MMOs including single-component MMOs and multi-component MMOs (e.g., doped MMOs, composite MMOs, and polymetallic oxide) with high crystallinity and remarkable porous properties by grinding and heating raw materials. Compared with the traditional solution self-assembly process, the avoidance of solvents in this method not only greatly increases the yield of target products and synthesis efficiency, but also reduces the environmental pollution and the consumption of cost and energy. We believe the presented approach will pave a new avenue for scalable production of advanced mesoporous materials for various applications.

Production of high crystallinity type-I cellulose from Komagataeibacter hansenii JR-02 isolated from Kombucha tea.

In this study, a bacterial cellulose (BC) producing strain was isolated from Kombucha tea and identified as Komagataeibacter hansenii JR-02 by morphological, physiological, and biochemical characterization and 16S rRNA sequence. Then, the media components and culture conditions for BC production were optimized. Result showed that the highest BC yield was 3.14 ± 0.22 and 8.36 ± 0.19 g/L after fermentation for 7 days under shaking and static cultivation, respectively. Moreover, it was interesting that JR-02 could produce BC in nitrogen-free medium with the highest yield of 0.76 ± 0.06 g/L/7days, and the possible nitrogen fixation gene nifH was cloned from its genomic DNA. The BC produced by JR-02 was type-I cellulose with high crystallinity and thermodynamic stability, which was revealed from Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis methods. The crystallinity of static and shaking cultured BC were 91.76% and 90.69%, respectively. The maximum rate of weight loss of static and shaking BC occurred at temperature of approximately 373.1 °C and 369.1 °C, respectively. Overall, these results indicated that K. hansenii JR-02 had great potential to produce high crystallinity type-I BC in manufacture.

Thickness Tolerance in Large-Area Organic Photovoltaics with Fluorine-Substituted Regioregular Conjugated Polymer.

Large areas and simple processing methods are necessary for the commercialization of organic photovoltaics (OPVs). However, the efficiency drop due to the variation in thickness of OPVs limits their large-scale applications. Regioregular polymers with good crystallinity and packing properties that exhibit high charge mobility and extraction ability can help overcome these limitations. In this study, a regioregular polymer named PDBD-2FBT was synthesized. The crystallinity and packing properties of PDBD-2FBT were enhanced by a simple thermal treatment. Using PDBD-2FBT material as a donor and Y6-HU as an acceptor, we fabricated binary blend OPV devices. The devices with optimized active layer thickness achieved a power conversion efficiency (PCE) of 14.14%. A PCE of 13.18% was maintained even in thick-film conditions (400 nm), and thickness tolerance was observed. Based on the thickness tolerance, a 5-line module measuring 36 cm2 was fabricated via the bar-coating method, and a PCE of approximately 10% was achieved.

Continuous and Scalable Synthesis of Prussian Blue Analogues with Tunable Structure and Composition in Surfactant-Free Microreactor for Stable Zinc-Ion Storage.

We represent a segmented flow surfactant-free microfluidic strategy for continuous synthesis of Prussian blue analogues (PBAs) with high dispersity and high crystallization. Representative zinc hexacyanoferrate (ZnHCF) nanocubes were successfully synthesized in a microfluidic reactor within a few minutes via the cooperation method and possessed lower contents of crystal water and Fe(CN)6 3- vacancies than that of synthesis in bulk solution. The nucleation and particle growth process can be precisely controlled by the exploration of different flow rates and reaction temperatures during the formation of ZnHCF nanocubes in segmented flow microfluidic reactors. High crystallinity, low crystal water and vacancies in the ZnHCF structure were presented at relatively high temperatures for the crystal growth process. High-quality ZnHCF with a low content of crystal water showed excellent electrochemical activity and stability towards zinc-ion storage. The continuous and scalable synthesis approach can be extended to the fabrication of other PBAs such as NiHCF, CoHCF, MnHCF, and CuHCF with high dispersity without using any surfactants. The controllable construction of PBAs with tunable properties in microfluidic reactors provides a promising direction to minimize the gap between commercial reality and laboratory research.

Triazine-Carbazole-Based Covalent Organic Frameworks as Efficient Heterogeneous Photocatalysts for the Oxidation of N-aryltetrahydroisoquinolines.

Covalent organic frameworks (COFs) have attracted growing interests as new material platform for a range of applications. In this study, a triazine-carbazole-based covalent organic framework (COF-TCZ) was designed as highly porous material with conjugated donor-acceptor networks, and feasibly synthesized by the Schiff condensation of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tr ianiline (TAPB) and 9-(4-formylphenyl)-9H-carbazole-3,6-dicarbaldehyde (CZTA) under the solvothermal condition. Considering the effect of linkage, the imine-linked COF-TCZ was further oxidized to obtain an amide-linked covalent organic framework (COF-TCZ-O). The as-synthesized COFs show high crystallinity, good thermal and chemical stability, and excellent photoactive properties. Two π-conjugated triazine-carbazole-based COFs with tunable linkages are beneficial for light-harvesting capacity and charge separation efficiency, which are empolyed as photocatalysts for the oxidation reaction of N-aryltetrahydroisoquinoline. The COFs catalyst systems exhibit the outstanding photocatalytic performance with high conversion, photostability and recyclability. Photoelectrochemical tests were employed to examine the behavior of photogenerated charge carriers in photo-illumination system. The control experiments provide further insights into the nature of photocatalysis. In addition, the current research also provided a valuable approach for developing photofunctional COFs to meet challenge in achieving the great potential of COFs materials in organic conversion.

High-Performance Organic Electrochemical Transistors Achieved by Optimizing Structural and Energetic Ordering of Diketopyrrolopyrrole-Based Polymers.

For optimizing steady-state performance in organic electrochemical transistors (OECTs), both molecular design and structural alignment approaches must work in tandem to minimize energetic and microstructural disorders in polymeric mixed ionic-electronic conductor films. Herein, a series of poly(diketopyrrolopyrrole)s bearing various lengths of aliphatic-glycol hybrid side chains (PDPP-mEG; m = 2-5) is developed to achieve high-performance p-type OECTs. PDPP-4EG polymer with the optimized length of side chains exhibits excellent crystallinity owing to enhanced lamellar and backbone interactions. Furthermore, the improved structural ordering in PDPP-4EG films significantly decreases trap state density and energetic disorder. Consequently, PDPP-4EG-based OECT devices produce a mobility-volumetric capacitance product ([µC*]) of 702 F V-1 cm-1 s-1 and a hole mobility of 6.49 ± 0.60 cm2 V-1 s-1 . Finally, for achieving the optimal structural ordering along the OECT channel direction, a floating film transfer method is employed to reinforce the unidirectional orientation of polymer chains, leading to a substantially increased figure-of-merit [µC*] to over 800 F V-1 cm-1 s-1 . The research demonstrates the importance of side chain engineering of polymeric mixed ionic-electronic conductors in conjunction with their anisotropic microstructural optimization to maximize OECT characteristics.

High-Crystallinity BiOCl Nanosheets as Efficient Photocatalysts for Norfloxacin Antibiotic Degradation.

Semiconductor photocatalysts are essential materials in the field of environmental remediation. Various photocatalysts have been developed to solve the contamination problem of norfloxacin in water pollution. Among them, a crucial ternary photocatalyst, BiOCl, has attracted extensive attention due to its unique layered structure. In this work, high-crystallinity BiOCl nanosheets were prepared using a one-step hydrothermal method. The obtained BiOCl nanosheets showed good photocatalytic degradation performance, and the degradation rate of highly toxic norfloxacin using BiOCl reached 84% within 180 min. The internal structure and surface chemical state of BiOCl were analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman, Fourier transform infrared spectroscopy (FTIR), UV-visible diffuse reflectance (UV-vis), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectra (XPS), and photoelectric techniques. The higher crystallinity of BiOCl closely aligned molecules with each other, which improved the separation efficiency of photogenerated charges and showed high degradation efficiency for norfloxacin antibiotics. Furthermore, the obtained BiOCl nanosheets possess decent photocatalytic stability and recyclability.

Rational redesign of thermophilic PET hydrolase LCCICCG to enhance hydrolysis of high crystallinity polyethylene terephthalates.

Polyethylene terephthalate (PET)-degrading enzymes represent a promising solution to the plastic pollution. However, PET-degrading enzymes, even thermophilic PETase, can effectively degrade low-crystallinity (∼8%) PETs, but exhibit weak depolymerization of more common, high-crystallinity (30-50%) PETs. Here, based on the thermophilic PETase, LCCICCG, we proposed two strategies for rational redesign of LCCICCG using the machine learning tool, Preoptem, combined with evolutionary analysis. Six single-point mutants (S32L, D18T, S98R, T157P, E173Q, N213P) were obtained that exhibit higher catalytic efficiency towards PET powder than wild-type LCCICCG at 75 °C. Additionally, the optimal temperature for degrading 39.07% crystalline PET increased from 65 °C in the wild-type LCCICCG to between 75 and 80 °C in the LCCICCG_I6M mutant that carries all six single-point mutations. Especially, the LCCICCG_I6M mutant has a significantly higher degradation effect on some commonly used bottle-grade plastic powders at 75-80 °C than that of wild type. The enzymatic digestion of ground 31.30% crystalline PET water bottles by LCCICCG_I6M yielded 31.91 ± 0.99 mM soluble products in 24 h, which was 3.64 times that of LCCICCG (8.77 ± 1.52 mM). Overall, this study provides a feasible route for engineering thermostable enzymes that can degrade high-crystallinity PET plastic.

Crystallization Regulation Engineering in the Carbon Nitride Nanoflower for Strong and Stable Electrochemiluminescence.

Cathode electrochemiluminescence (ECL) of C3N4 material has suffered from weak and unstable ECL emission for a long time, which greatly limits its practical application. Herein, a novel approach was developed to improve the ECL performance by regulating the crystallinity of the C3N4 nanoflower for the first time. The high-crystalline C3N4 nanoflower achieved a pretty strong ECL signal as well as excellent long-term stability compared to low-crystalline C3N4 when K2S2O8 was used as a co-reactant. Through the investigation, it is found that the enhanced ECL signal is attributed to the simultaneous inhibition of K2S2O8 catalytic reduction and enhancement of C3N4 reduction in the high-crystalline C3N4 nanoflower, which can provide more opportunities for SO4• - to react with electro-reduced C3N4• -, and a new "activity passivation ECL mechanism" was proposed, while the improvement of the stability is mainly ascribed to the long-range ordered atomic arrangements caused by structure stability in the high-crystalline C3N4 nanoflower. As a benefit from the excellent ECL emission and stability of high-crystalline C3N4, the C3N4 nanoflower/K2S2O8 system was employed as a Cu2+ detection sensing platform, which exhibited high sensitivity, excellent stability, and good selectivity with a wide linear range from 6 nM to 10 µM and a low detection limit of 1.8 nM.

Covalent Organic Frameworks Doped with Different Ratios of OMe/OH as Fluorescent and Colorimetric Sensors.

Improving the luminescence properties of covalent organic frameworks (COFs) has always been an important issue. Here, a series of COFs (([OMe]x -TzDa (TzDa is composed only by monomerics Tz and Da, OMe represents the incorporation of monomeric Dm)) with different ratios of OMe and OH were designed and synthesized. The photochemical behavior of [OMe]x -TzDa changed significantly due to the synergistic effect of aggregation induced emission (AIE), intramolecular charge transfer (ICT), and excited-state intramolecular proton transfer (ESIPT) effects. [OMe]2 -TzDa, which contained a ratio of 2/1 of OMe/OH, showed the strongest fluorescence emission in water and the best linear relationship for the detection of pH. Furthermore, [OMe]2 -TzDa was used to monitor HCl and NH3 gases and showed a color change, visible to the naked eye. Therefore, a "confidential pigment" was successfully made. Moreover, [OMe]2 -TzDa was also applied to detect N2 H4 . The work indicates the [OMe]2 -TzDa can serve as the first fluorescence sensor to detect pH, HCl and NH3 gases, which also shows a good response to N2 H4 .