In Situ Topochemical Transformation of ZnIn2S4 for Efficient Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran

Photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) coupled H₂ production offers a promising approach to producing valuable chemicals. Herein, an efficient in situ topological transformation tactic is developed for producing porous O-doped ZnIn₂S₄ nanosheets for HMF oxidation cooperative with H₂ evolution. Aberration-corrected high-angle annular dark-field scanning TEM images show that the hierarchical porous O-ZIS-120 possesses abundant atomic scale edge steps and lattice defects, which is beneficial for electron accumulation and molecule adsorption. The optimal catalyst (O-ZIS-120) exhibits remarkable performance with 2,5-diformylfuran (DFF) yields of 1624 µmol h⁻¹ g⁻¹ and the selectivity of >97%, simultaneously with the H₂ evolution rate of 1522 µmol h⁻¹ g⁻¹. Mechanistic investigations through theoretical calculations show that O in the O-ZIS-120 lattice can reduce the oxidation energy barrier of hydroxyl groups of HMF. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) results reveal that DFF^* (C₄H₂(CHO)₂O^*) intermediate has a weak interaction with O-ZIS-120 and desorb as the final product. This study elucidates the topotactic structural transitions of 2D materials simultaneously with electronic structure modulation for efficient photocatalytic DFF production.     

Imidazolium-Functionalized Diacetylene Amphiphiles: Strike a Lighter and Wear Polaroid Glasses to Decipher the Secret Code

The development of smart inks that change color and transparency in response to external stimuli is very important for various fields, from modern art to safety and anticounterfeiting technology. A uniaxially oriented diacetylene thin film on a macroscopic area is obtained by coating, self-assembling and topochemical photopolymerizing of imidazolium-functionalized diacetylenes (M-DA and T-DA) and 4,6-decadiyne ink (70 wt%:20 wt%:10 wt%) exhibiting a lyotropic smectic A liquid-crystalline phase at room temperature. The color and transparency of letters and symbols written with the DA-based secret inks change reversibly from blue to red as well as from colorless transparent to black opaque depending on the temperature and polarization axis. A secret code written with thermoresponsive and polarization-dependent secret inks consisting of imidazolium-functionalized diacetylenes is successfully deciphered by wearing polaroid glasses and holding a burning torch.     

Atomic force microscopy in the photochemistry of chalcones

The application of atomic force microscopy (AFM) to photodimerization of crystalline chalcones provides new insights into the detailed mechanisms of solid-state reactions on the molecular level. Well-directed long-range transport phenomena are found which reach far beyond the crystal lattice distances. Reactions occur in the surface region where the light is absorbed. Characteristic features are built up that depend on crystal structure and crystal face. This could not be foreseen by previous theories based solely on a topochemical postulate/principle. There is now a much more intimate correlation of crystal structure with solid-state reactivity and this is directly studied and proven experimentally by AFM. Even solid-state reactions which are in opposition to topochemistry can be studied and understood on a molecular basis. The three-dimensional resolution of undisturbed insulating surfaces which is obtained by AFM is not available by any other technique.     

Approaching Intra‐ and Interchain Charge Transport of Conjugated Polymers Facilely by Topochemical Polymerized Single Crystals

Charge transport of small molecules is measured well with scanning tunneling microscopy, conducting atomic force microscopy, break junction, nanopore, and covalently bridging gaps. However, the manipulation and measurement of polymer chains remain a long‐standing fundamental issue in conjugated polymers and full of challenge since conjugated polymers are naturally disordered materials. Here, a fundamental breakthrough in generating high‐quality conjugated‐polymer nanocrystals with extended conjugation and exceptionally high degrees of order using a surface‐supported topochemical polymerization method is demonstrated. In the crystal the conjugated‐polymer chains are extended along the long axis of the crystal with the side chains perpendicular to the long axis. Devices with conducting channels along the polymer chains show efficient charge transport, nearly two orders of magnitude greater than the interchain charge transport along the π–π stacking direction. This is the first example to clarify intra‐ and interchain charge transport based on an individual single crystal of conjugated polymers, and demonstrate the importance of intrachain charge transport in plastic electronics.     

熔盐法制备柱状铌酸钾钠粉体及其陶瓷

采用二步熔盐法合成了柱状铌酸钾钠粉体,并制备了致密的铌酸钾钠陶瓷。首先使用少量KSr_2Nb_5O_(15)粉体作为晶种,以Nb_2O_5、KCl与不同SrCO_3和Nb_2O_5的摩尔比(x=0.2,0.4,0.6和0.8)为原料合成了分散性较好的铌酸钾前驱体;然后将该前驱体通过化学拓扑反应制备出柱状的铌酸钾钠粉体;最后利用该粉体为原料,制备了铌酸钾钠陶瓷。测试结果表明,SrCO_3的添加有利于形成分散性良好的铌酸钾前驱体;Sr含量对钨青铜结构前驱体到钙钛矿结构铌酸钾钠的相转变有显著影响:当x≤0.4时,前驱体全部转化为钙钛矿相;x>0.4时,前驱体转变不完全;x=0.8时,前驱体几乎未发生转变。x=0.4时,合成的铌酸钾钠颗粒为微米级,长径比约为12,具有较高的烧结活性,为织构陶瓷的制备提供了一种合适的模板籽晶。     

Growth of NBT template particles through topochemical microcrystal conversion and their structural characterization

In this study, uniform rectangular plate‐like perovskite Na_0.5Bi_0.5TiO₃ templates were obtained by molten salt synthesis method in three steps. Perovskite plate‐like Na_0.5Bi_0.5TiO₃ templates were synthesized from bismuth‐layered Na_0.5Bi_4.5Ti₄O₁₅ by topochemical microcrystal conversion method at the third and final step. The most important point was that the plate‐like morphology remained as desired, but templates were obtained in cubic perovskite structure. The Na₂CO₃ excess in the third step was the main controlling parameter. The crystalline orientation of the particles was investigated by electron backscatter diffraction analysis. The results indicated that the particles are single crystalline in nature. In the case of the 90 mol% excess of the stoichiometric Na₂CO₃ ratio, the NBT platelets had highly regular, rectangular prismatic morphology and single‐crystal nature. The structure was also confirmed through high‐resolution transmission electron microscope and selected area electron diffraction analysis.     

CoFe–Cl Layered Double Hydroxide: A New Cathode Material for High‐Performance Chloride Ion Batteries

Chloride ion batteries (CIBs) are regarded as promising energy storage systems due to their large theoretical volumetric energy density, high abundance, and low cost of chloride resources. Herein, the synthesis of CoFe layered double hydroxide in the chloride form (CoFe–Cl LDH), for use as a new cathode material for CIBs, is demonstrated for the first time. The CoFe–Cl LDH exhibits a maximum capacity of 239.3 mAh g^?1 and a high reversible capacity of ≈160 mAh g^?1 over 100 cycles. The superb Cl^? ion storage of CoFe–Cl LDH is attributed to its unique topochemical transformation property during the charge/discharge process: a reversible intercalation/deintercalation of Cl^? ions in cathode with slight expansion/contraction of basal spacing, accompanied by chemical state changes in Co²⁺/Co³⁺ and Fe²⁺/Fe³⁺ couples. First‐principles calculations reveal that CoFe–Cl LDH is an excellent Cl^? ion conductor, with extremely low energy barriers (0.12?0.25 eV) for Cl^? diffusion. This work opens a new avenue for LDH materials as promising cathodes for anion‐type rechargeable batteries, which are regarded as formidable competitors to traditional metal ion‐shuttling batteries.     

拓扑化学法合成片状BaTiO3晶体

采用拓扑化学法,以KCl–NaCl、KCl–BaCl2等为熔盐体系,在900～1100℃制得BaTiO3片状晶体,分析了反应各参数对晶体微观形貌及性能的影响。热重、扫描电子显微镜、X射线衍射分析表明：在熔盐体系为KCl–BaCl2,反应物BaBi4Ti4O15与BaCO3的摩尔比为1：3.1,温度为950℃条件下,得到的BaTiO3晶体分布均匀、各向异性好、具有规则的片状外形,可以作为制备钙钛矿系织构化陶瓷的良好模板晶体。     

A low-cost and efficient pathway for preparation of 2D MoN nanosheets via Na2CO3-assisted nitridation of MoS2 with NH3

In this paper, an efficient and low-cost method was developed for producing isolated 2D MoN nanosheets via Na₂CO₃-assisted nitridation and exfoliation of natural 2H-MoS₂ by NH₃ at 700-800°C. It was found that, in the presence of Na₂CO₃, the nitridation of MoS₂ with NH₃ was a topochemical transformation. After heat treatment the mixture of MoS₂ and Na₂CO₃ in NH₃ at 700-800°C, layered MoN with intercalated Na₂S was obtained. Na₂CO₃ can dramatically promote the topochemical nitridation and exfoliation of MoS₂ in NH₃. At 750°C, the time for complete nitridation of (commercial) MoS₂ can be shortened to 2 hours, which is much shorter than 40 hours in the case without the addition of Na₂CO₃ as reported in the previous literature. After acid-washing, the intercalated Na₂S was removed, and the generated H₂S promoted the further separation of the MoN nanosheets. Finally, dispersed high crystalline 2D MoN nanosheets with thickness of a few nanometers were successfully produced. This method may be also applicable for the production of other 2D nitrides or carbides by nitridation or carbonization of various transition metal dichalcogenides (TMDs) with the assistance of sulfur-fixed agent.