CHEMICAL ENGINEERING JOURNAL
·
2018
·
IF 6.735
Wenfeng Han,Jinchao Wang,Lulu Chen,Luteng Yang,Shucheng Wang,Miao Xi,Haodong Tang,Wucan Liu,Weiyu Song,Jianjun Zhang,Ying Li,Huazhang Liu
Trifluoromethane is one of the most potent and stable greenhouse gases with global warming potential of 14,800 times higher than CO 2 (100-year time horizon). At present, it is destroyed by incineration or plasma at temperatures above 1200 K. For the first time, this work report that CHF 3 can be reverted to HCFC-22 via the intermolecular Cl/F exchange reaction of CHF 3 with CHCl 3 over AlF 3 catalyst under moderate conditions. As CHF 3 is produced during the manufacture of HCFC-22 via the fluorination of CHCl 3 in liquid phase, no additional feedstock and products are involved for the treatment of CHF 3 in this proposed process. At 593 K and atmospheric pressure, CHF 3 conversion levels of about 18%–20% are achieved and no significant deactivation is observed following time on stream of 100 h. In addition, the catalytic reaction mechanism is proposed. According to the experiments and DFT calculation, the intermolecular Cl/F exchange reaction of CHF 3 with CHCl 3 is mainly initiated by the breakage of C Cl. The present work provides a potential resource utilization route for the treatment of CHF 3 and other hydrofluorocarbons (HFCs).
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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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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2016
·
IF 2.567
Fan Tian,Huiping Zhao,Zan Dai,Gang Cheng,Rong Chen
Cl-incorporated BiOI nanostructures with different Cl/I molar ratios have been successfully fabricated via a facile room-temperature method in H2O/EG mixture solvent. Combined with FT-IR, Raman spectrum, XRD Rietveld refinements, and DFT calculation, the incorporated Cl ions are found mainly occupied on I sites, resulting in a hybrid valence band consisting of I 5p, O 2p, and Cl 3p orbitals, which deepens the valence band location of the materials and induces photogenerated holes with higher oxidation power. The incorporated Cl ions into the lattice also change the evolution of photogenerated electrons and holes, inducing the broadening of the bandgap but efficient production of photogenerated carriers. The enhanced oxidation power of Cl-incorporated BiOI products was evaluated by photocatalysis degradation of methylene blue, an organic dye for which pure BiOI shows negligible direct oxidation efficiency. Ascribed to the relatively low valence band maximum (VBM) and efficient generation of photoinduced electrons and holes, the incorporated products show distinct enhancement photocatalytic activities.
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Materials Science & Engineering C-Materials for Biological Applications
·
2015
·
IF 3.088
Manqing Yan,Hongjun Yang,Guangzhao Zhang
A novel biocompatible and biodegradable copolymer was synthesized by one-step hybrid copolymerization of ε -caprolactone (CL) and 2-( N , N -dimethylamino) ethyl methacrylate (DMAEMA) employing (1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phophoranylidenamino]-2Λ5,Λ5-catenadi(phosphazene) ( t -BuP 4 ) as a catalyst. The as-synthesized copolymer was betainizated resulting in a zwitterionic copolymer poly (CL- co - z DMAEMA) and the structure of the zwitterionic copolymer was confirmed by the FT-IR, NMR, and XPS measurements. The results of dynamic light scattering (DLS) show that this zwitterionic copolymer can self-assemble into stable micelles. The results of quartz crystal microbalance with dissipation (QCM- D ) analysis and MTT measurement suggest that this zwitterionic copolymer possess better protein resistance and lower cell cytotoxicity in vitro in comparison with the cationic copolymer. The pyrene solubilization measurement of copolymers poly (CL- co - z DMAEMA) indicates an excellent pyrene solubilization capacity. These zwitterionic polymer micelles can release drugs in response to specific signals, such as temperature, pH, and enzymes and have a potential application in drug delivery and gene therapy due to their good antifouling, low cytotoxicity and high pyrene solubilization.
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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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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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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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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 Environmental Chemical Engineering
·
2022
·
IF 7.968
Xiao Yu,Banghong Deng,Lixia Yang,Moliang Zou,Zhenglin Chen,Yixuan Fan,Zhihui Wei,Kai Chen,Mingxia Lu,Tiantian Ying,Jie Zhang,Weili Dai
Mn 2 O 3 is a conventional catalyst that is applied in photothermal catalytic oxidation of toluene while regular anions like SO 4 2- , Cl - , and NO 3 - from different Mn precursors are left in Mn 2 O 3 . When applied in toluene degradation, the declining activity of Mn 2 O 3 is always observable because the residual anions block the Mn 4+ /Mn 3+ active sites, shield the oxygen vacancies, and cube the production of active oxygen species (O 2 - , O - ). Herein, it is found that the residual SO 4 2- , Cl - , and NO 3 - make Mn 2 O 3 incapacitated in deeply oxidizing the intermediates and cutting off the reaction process, and their influence ranks in the order of SO 4 2- >Cl - >NO 3 - . Compared with pristine Mn 2 O 3 , the drops in CO 2 conversion efficiency account for 11 %, 60 %, and 73 %, respectively. Nevertheless, rinsing with water is an effective method to remove the residual anions, and the more the rinsing, the better the toluene mineralization degree. This work provides a profound cognition of the deactivation mechanism of SO 4 2- , Cl - , and NO 3 - and points out an effective way to abate their negative effect for the first time.
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Inorganic Chemistry Frontiers
·
2023
·Vol. 10
·期 11
·3319-3325
·
IF 7
Jing-Li Qi,Jiajing Wu,Yue Guo,Zhong-Ping Xu,Wenlong Liu,Sheng-Ping Guo
The emerging organic–inorganic hybrid metal halides feature unique optical and electronic properties, are easily grown and have flexible crystal structures, making them a class of promising next-generation nonlinear optical (NLO) and ferroelectric materials. Herein, we successfully synthesized two centimeter-level zero-dimensional copper halide organic–inorganic hybrids (C20H20P)CuX2 (X = Cl, Br) that are crystallized in the monoclinic noncentrosymmetric P21 space group. Their structures contain rare quasi-linear [CuX2]– anions and [C20H20P]+ cations. (C20H20P)CuCl2 and (C20H20P)CuBr2 crystals show phase-matchable NLO effects around 1.1 and 0.87 times that of benchmark KDP, respectively. These (C20H20P)CuX2 materials are the first NLO-active examples in the hybrid copper(I) halide family containing a quasi-linear CuX2 unit.
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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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