Small
·
2024
·Vol. 20
·期 37
·2400549
·
IF 13
Yaoguo Shen,Mingliang Ding,Gang Chen,Yingjie Luo,Sangen Zhao,Junhua Luo
A large optical anisotropy is the most important parameter of birefringent crystals. Integrating π-conjugated groups with large polarizable anisotropy into target compounds is a common strategy for constructing brilliant birefringent crystals. However, the key problem is to enhance the density of the birefringence-active units and further arrange them parallelly. In this study, three novel birefringent crystals, C 9 H 7 NBrX (X = Cl, Br, NO 3 ), are successfully synthesized by introducing a new birefringence-active [C 9 H 7 NBr] + unit. Interestingly, these compounds feature similar layered structures but exhibit different optical anisotropies at 550 nm (0.277 for C 9 H 7 NBrCl, 0.328 for C 9 H 7 NBrBr, and 0.401 for C 9 H 7 NBrNO 3 ) owing to the different anions in them. Particularly, the small trigonal planar NO 3 anions perfectly fill the interstices of the π-conjugated [C 9 H 7 NBr] + groups with large optical anisotropy, with the resulting compound C 9 H 7 NBrNO 3 showing superior optical properties compared to the others. The above findings provide strategies for designing new optical materials with large birefringence by matching birefringence-active groups of different sizes. Additionally, a new theory for predicting and comparing the polarizability anisotropy of compounds is proposed, which would guide in exploring large birefringent crystals.
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JOURNAL OF CRYSTAL GROWTH
·
2024
·
IF 1.7
Jingyi Yu,Hao Sun,Cong Zheng,Weiwei Jiang,Nan Wang,Zhiqiang Li,Sumei Wu,Hualong Tao,Tingting Yao,Hualin Wang,Shimin Liu,Chaoqian Liu,Wanyu Ding,Zhihua Zhang
Pure TiO 2 , Sn/Cl co-doped TiO2 and Sn/Cl co-doped TiO 2 -ZnO were fabricated and compared by a novel one-pot method to improve the photocatalytic performance of pure TiO2, which accomplishes the construction of heterojunctions simultaneously with doping by volatile solid solution. TG-DSC, XRD, FTIR, XPS, SEM, EDS, TEM, SAED, UV–Vis, PL and EIS were characterized to investigate the influence mechanism of Sn/Cl co-doping and ZnO content (0, 25, 50, 75, and 100 mol.%) on the thermal effect, crystal structure, morphology, composition, charge transfer behavior and photocatalytic performance of samples. Results indicate that ZnO appears and SnO2 disappears simultaneously with anatase TiO2 as the main phase by increasing ZnO content, and the morphology is changed from irregular sphere to sphere-sheet and sphere-plate correspondingly. The photocatalytic degradation efficiency first increases and then decreases, and achieves the maximum value of 73 % by SCT/Z50 which has sphere-sheet heterostructure containing more hydroxyl radicals, under 15 W weak-UV light irradiations for 3 h using methyl orange (MO) as pollutant. The excellent photocatalytic performance is attributed to the structural and morphological effects of Sn/Cl co-doping and ZnO introduction, which can increase the electron-hole separation efficiency. The optimized composition also has great potential in practical photocatalytic application due to the commercial advantage that ZnO is much cheaper than TiO2.
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Matter
·
2024
·
IF 17.3
Pei Li,Shuo Yang,Jiaxiong Zhu,Shengnan Wang,Yue Hou,Huilin Cui,Ze Chen,Rong Zhang,Zhuoxi Wu,Yiqiao Wang,Zhiquan Wei,Xinghui Liu,Shaoce Zhang,Xinliang Li,Chunyi Zhi
Chlorine-based electrochemical energy storage is a promising candidate for sustainable battery technology. The anionic redox reaction of Cl 0/−1 is of interest due to its superior redox potential (1.36 V vs . standard hydrogen electrode [SHE]), capacity (756 mAh g −1 ), high power, and low cost. Although Cl chemistry has been used in aqueous batteries for a long time, its deployment in organic lithium batteries has been significantly impeded due to the insolubility of Cl − ions (<0.1 M). Scarce oxidizable Cl − blocks redox reactions and the inevitable lithium chloride (LiCl) film passivates electrodes on discharge. We report a eutectic effect to improve the Cl − solubility in organic electrolytes (2 M or higher) by mixing a series of N-/P-centered chloride salts with lithium bis(trifluoromethanesulfonyl)imide at specific ratios. Based on an optimized Cl − concentration, a Li-Cl 2 cell using I as a chemical fixation can achieve a three-electron transfer with a specific capacity of 702 mAh g −1 and an energy density of 1,116 Wh kg −1 .
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OPTICAL MATERIALS
·
2024
·
IF 3.8
Lin Chen,Xiong Shen,Jinhe Wei,Zhongming Wang,Fei Hu,Limin Bian,Qiuyun Ouyang
CsPb(Cl/Br) 3 perovskite nanocrystals (NCs) materials were synthesized by a hot injection method. To enhance the stability of the perovskite , CsPb(Cl/Br) 3 - multiwalled carbon nanotubes (CNTs) composites were synthesized by the insitu growth method. First, the successful composite of CNTs and perovskite has been proved by X-ray photoelectron spectroscopy (XPS). After CsPb(Cl/Br) 3 NCs have grew on CNTs, the exciton lifetime decays from 8.2 ns to 4.5 ns, suggesting the presence of an additional electron transfer pathway between CNTs and CsPb(Cl/Br) 3 NCs. The photoluminescence (PL) properties of perovskite NCs and CsPb(Cl/Br) 3 -CNTs were evaluated using temperature-dependent PL spectroscopy . The exciton binding energy of the CsPb(Cl/Br) 3 -CNTs composites (59.28 meV) is higher than that of the CsPb(Cl/Br) 3 NCs (51.79 meV), indicating a more stable exciton state within the CsPb(Cl/Br) 3 -CNTs structure. The PL stability experimental results reveal a notable enhancement in the stability of CsPb(Cl/Br) 3 -CNTs composites compared to CsPb(Cl/Br) 3 NCs. In addition, electrochemical tests of CsPb(Cl/Br) 3 -CNTs show a low resistance to charge transfer ( R ct ) alongside a favorable photocurrent response. This work has proved that the novel CsPb(Cl/Br) 3 -CNTs composites not only exhibit outstanding moisture and UV resistance but also demonstrate remarkable potential optoelectronic device applications.
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JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2025
·
IF 2.1
Honglin Xu,Ruilin Wang,Yongsheng Deng,Guofeng Dou,Xinyu Wang
The stable phase equilibrium of the reciprocal quaternary system of Na+, K+//VO3–, Cl––H2O at 298.15 K was investigated by an isothermal solution equilibrium method. The equilibrium liquid phase solubility data and physical property data [density (ρ), refractive index (nD), and pH] were determined, and the composition of the equilibrium solid phase was verified by X-ray diffraction. The phase diagram and physical property–composition diagrams were constructed based on the equilibrium solubility data and physical property data. The phase diagram contains three invariant points, seven isothermal univariant curves, and five crystalline phase regions. The study found that this quaternary system belongs to a complex system with the presence of the double salts. By comparing the experimental results with literature data, it was confirmed that at 298.15 K, the chemical formulas of the complex salt which formed by the quaternary system Na+, K+//VO3–, Cl––H2O were consistent with the complex salt chemical formula (Na2mKn(VO3)2m+n) proposed by the Druzynski group, thus verifying the reliability of this experiment. The results of this study will provide new experimental data for the thermodynamics of vanadium–water systems.
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COMBUSTION AND FLAME
·
2025
·
IF 6.2
Shubao Song,Lin Zhang,Meishuai Zou,Jiankun Shao
High-temperature gas-phase interactions between chlorine- and nitrogen-bearing species relevant to ammonium-perchlorate (AP) propellant combustion were elucidated by coupling shock-tube laser-absorption measurements with a detailed kinetic model. Time-resolved HCl concentration profiles were obtained for four argon-diluted surrogates—0.3 % NH 3 /0.3 % CCl 4 , 0.5 % NH 3 /0.3 % CCl 4 , 0.2 % NH 3 /0.2 % CCl 4 /0.2 % CH 4 , and 0.2 % NH 3 /0.2 % CCl 4 /0.2 % H 2 —over 1158–1506 K at near-atmospheric pressure. A kinetic model consisting of 164 species and 1358 reactions, assembled from state-of-the-art CCl 4 , H–Cl–O, NH 3 /C 0 –C 2 , and N–Cl sub-models, reproduced the new HCl data alongside literature ignition-delay and speciation measurements with excellent accuracy. Sensitivity and rate-of-production analyses reveal a temperature-robust control structure in which HCl forms almost entirely through Cl-atom abstraction from NH 3 , with Cl supplied by rapid CCl 4 dissociation; the barrierless Cl + H<=>HCl path dominates in H 2 -containing mixtures, whereas competition from Cl + CH 4 <=>CH 3 + HCl moderates HCl growth and channels carbon–nitrogen flux toward toxic HCN when CH 4 is present. Elevated temperature chiefly amplifies Cl production and suppresses NH 2 recombination, accelerating overall reactivity without altering the dominant pathways. The resulting benchmark HCl time-histories and rigorously validated model advance fundamental understanding of chlorine–nitrogen combustion chemistry and provide quantitative guidance for formulating halogenated energetic materials that maximise performance while limiting hazardous by-product formation. Importantly, the mechanism developed here may serve as a transferable gas-phase sub-model for future integration into comprehensive AP combustion frameworks, enabling more predictive simulations of real propellant systems.
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TALANTA
·
2025
·
IF 6.1
Liwu Gan,Xiaoying Feng,Suxin Zhou,Jinglin Chen,Juan Zheng,Gangfeng Ouyang
Functionalized metal organic framework (MOF) and covalent organic framework (COF) composites (MOF@COFs) with complementary advantages, hierarchical pores, pre-designable and tunable structures, are expected for remarkable adsorption of organic pollutants, yet to be explored. Herein, a kind of MOF@COF composite was synthesized by combining the parent MIL-68(In) and COF–V (10 %-MIL-68@COF–V), characterized with well-retained crystallinity and hierarchical pores. The parent materials and as-prepared MIL-68@COF-Vs were further fabricated as solid phase microextraction (SPME) coatings to study their extraction performance for Cl/Br-substituted organic pollutants. The 10 %-MIL-68@COF–V coated fiber exhibited the most outstanding enrichment performance for Cl/Br-substituted organic pollutants mainly due to the synthetic advantages, which was 1.1–196.5 times superior than that of the commercial PDMS coating. By combining it with gas chromatography-mass spectrometry (GC-MS), an ultrasensitive method was established, exhibiting wide linear ranges (1–5000 ng L −1 ), low LODs (0.17–0.29 ng L −1 ), and good reproducibility. The trace Cl/Br-substituted organic pollutants in marine water samples were successfully detected, verifying the practicability of the developed method in environmental monitoring.
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ACS Omega
·
2025
·
IF 4.3
SongYuChen Ma,Tao Liu,DeQi Wang,YinHui Li,WenJing Shi,FengSheng Li,Jie Liu
To address the quality issues arising from the uncontrollable morphological grain size in the preparation of CL-20/HMX cocrystals, a novel method for producing high-quality cocrystals with well-defined morphological grain sizes has been developed. The cocrystallization process was conducted using the solvent/nonsolvent method, wherein the mixing efficiency and solution supersaturation were precisely controlled through systematic optimization of key parameters, including solvent composition, solvent/nonsolvent ratio, reaction temperature, and stirring rate. Through systematic optimization of experimental parameters, three distinct rhombohedral CL-20/HMX cocrystal samples with uniform particle size distributions and well-defined morphologies were successfully prepared, exhibiting characteristic D50 values of 20, 63, and 130 μm. Comprehensive characterization revealed that SEM analysis demonstrated the cocrystals possess smooth surfaces and regular geometric shapes. Combined XRD and micro-CT analyses confirmed the high crystallinity of the cocrystals, particularly noting the reduced internal defects and superior crystal perfection in larger-grained samples. DSC measurements indicated enhanced thermal stability in cocrystals with larger particle sizes. Furthermore, sensitivity testing showed larger-grained cocrystals are less sensitive than smaller-grained ones, which can be attributed to the more compact internal structure of the crystals.
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ACS Applied Nano Materials
·
2025
·
IF 5.5
Zhifan Wang,Mengmeng Dai,Gang Yang,Xiao Zhang,Pengchao Shen,Chunxiang Zhao,Yongsheng Zhu
Perovskite nanocrystals have gained considerable attention owing to their outstanding photoluminescence and photodetection performance in various applications. However, the rigorous preparation conditions and lead toxicity of most lead halide perovskite nanocrystals still hamper practical application, which achieves efficient deep-red and near-infrared (NIR) emission also meeting the challenge. Herein, sub-25 nm Cl–-doped lead-free CsMnBr3 nanocrystals (NCs) were prepared via a moderate hot-injection method at room temperature and the resulting NCs showcased excellent photoluminescence property with reduced impurities. Furthermore, a substantial enhancement in photoluminescence quantum yield (PLQY) from 54.20% to 78.05% was achieved by manipulating the Cl– doping concentration, which is attributed to the weakened nonradiative recombination pathways induced by Cl–-mediated defect passivation. Consequently, we fabricated photoluminescent light-emitting diodes (LEDs) based on Cl–-doped CsMnBr3 nanocrystals and achieved NIR emissions of Nd3+, Yb3+, and Er3+ ions. These results reveal that Cl–-doped CsMnBr3 perovskites NCs can not only be facilely prepared via a simple room-temperature synthesis, but also demonstrate promising potential in various areas such as photoluminescent LEDs and near-infrared optoelectronic devices.
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OPTICAL MATERIALS
·
2024
·
IF 3.8
Wenzhi Wang,Liwei Wang,Shuo Song,Xinxin Guo,Hongyu Liu,Guangqiang Liu
All inorganic perovskite quantum dots (PQDs) have been studied extensively because of their excellent photoelectric properties. However, its poor stability and lead toxicity limit its practical application. At the same time, the complex synthesis conditions of the hot injection method also limited the preparation of large quantities. Here, we have successfully synthesized Mn-doped CsPb(Cl/Br) 3 PQDs with excellent thermal stability at room temperature by a simple supersaturation crystallization method. The synthesized Mn-doped CsPb(Cl/Br) 3 PQDs has good homogeneity and crystallinity. Meanwhile, Mn-doped CsPb(Cl/Br) 3 PQDs maintains the same crystal structure as CsPb(Cl/Br) 3 PQDs. Importantly, it was found that the activation energy of CsPb(Cl/Br) 3 PQDs after manganese doping increased from 65.1 meV to 222.8 meV through the high and low temperature PL test of 80 K–500 K. The crystal structure of CsPb(Cl/Br) 3 PQDs is more stable due to the introduction of manganese ion, and the thermal stability is significantly improved. In this study, manganese doped CsPb(Cl/Br) 3 PQDs with good crystallinity and thermal stability was rapidly synthesized by a simple supersaturation crystallization method at room temperature, which opened up a new way to improve the stability of PQDs and explore other non-toxic metal elements to replace Pb 2+ .
研究领域:
材料科学
·
纳米技术
·
化学
·
物理学
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Journal of Energy Storage
·
2024
·
IF 8.9
Yi Duan,Xiaopeng Qi,Xiangtao Bai,Tianwei Yu,Yanlong Wu,Zenghua Chang,Jiantao Wang
Argyrodite Li 6-x PS 5-x Cl 1+x with high ionic conductivity and excellent mechanical performance is an attractive solid electrolyte candidate for all-solid-state lithium batteries (ASSLBs). Adjusting Cl content is an effective strategy to enhance the ionic conductivity, however its effect on the thermal stability remain uncovered. Herein, our study shows that the increase of Cl content in Li 6-x PS 5-x Cl 1+x significantly enhances the ionic conductivity and electrochemical properties but significantly reduces its thermal stability. We reveal that the thermal stability of Li 6-x PS 5-x Cl 1+x is heavily dependent on its Cl content and can be significantly enhanced by elemental doping. LiNi 0.6 Co 0.2 Mn 0.2 O 2 based ASSLBs using Cl-rich argyrodite with pure phase shows better cycle performance. Achievements from this study could serve as a guidance for optimizing and applicating argyrodite solid electrolytes towards high-performance and safe ASSLBs.
研究领域:
材料科学
·
电化学
·
能源存储
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ENVIRONMENTAL RESEARCH
·
2022
·
IF 8.431
Sen Lu,Xuechuan Li,Yunkai Liao,Guan Zhang
Efficient removal of low-concentration ammonia from chlorinated wastewater is a challenge for decentralized wastewater treatment due to its notorious environmental effect and lethal influence on aquaculture. Photoelectrocatalytic (PEC) oxidation process is considered as an efficient and environment–friendly approach, whereas a low-cost and stable photoanode is crucial. In this study, TiO 2 nanotubes (TNTs) photoanode (Ar–TNT–500 °C) with excellent physicochemical and photoelectrochemical properties was prepared by optimizing the parameters of anodization, including the voltage/times of anodization and the atmosphere/temperature of heat treatment. During the synthesis, the electrochemical and heat treatment processes promoted the formation of oxygen vacancies (O V ) on the TNTs surface and enhanced its electrocatalytic activity. The optimized Ar–TNT–500 °C photoanode could selectively convert ammonia to N 2 (86%) and a small amount of nitrate (14%). Radical quenching and probe experiments confirmed that the ClO produced by rapid quenching of OH and Cl by free chlorine dominated the selective degradation of ammonia in the synergistic process of photocatalysis and electrocatalysis. The cycle of chlorine-based radicals (ClO and Cl ) and Cl − provided a continuous and efficient ammonia oxidation system, because chlorine-based radicals could efficiently and selectively oxidize ammonia and reduce the production of toxic (per) chlorate.
研究领域:
环境科学
·
材料科学
·
化学工程
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