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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Decomposition mechanism of Cl-VOCs on Cu- and Fe-modified activated carbon in an O2-free atmosphere: The oxidation pathway and product distribution

Yuran Li,Zhicheng Xu,Jian Wang,Bin Wang,Tingyu Zhu

Activated carbon exhibits a high adsorption capacity for chlorinated volatile organic compounds (Cl-VOCs), while the desorption of Cl-VOCs is not desirable in the thermal regeneration progress of activated carbon. Chlorobenzene was selected as the model substance to explore whether Cl-VOCs can be oxidized as expected in the regeneration atmosphere of O 2 -free at the temperature range of 150–450 °C. The modification of activated carbon by Cu or Fe has been shown to considerably improve the decomposition activities. According to the breakthrough curves and detection results from XPS and in situ DRIFTS, the decomposition mechanism of C 6 H 5 Cl on Cu and Fe active sites is illustrated. The adsorbed C 6 H 5 Cl is firstly dechlorinated to form C 6 H 6 and *Cl, and then it was found there are two pathways for the C 6 H 6 oxidation. C 6 H 6 is indirectly oxidized to form C 6 H 5 OH and benzoquinone species, or directly ring-opened to generate ethylene and 1,3-butadiene, and further oxidized to produce CO 2 , CO and H 2 O. The C 6 H 6 oxidation is determined by the decomposition of acetate on Cu/AC, but the decomposition of benzoquinone and maleate on Fe/AC. The Fe 3 O 4 and Fe 2 O 3 active sites have a higher dechlorination activity but accelerate the deposition of FeCl 2 , FeCl 3 and organic Cl-containing components. The CuO active center has a higher oxidation performance with a higher CO 2 selectivity. About 83.0–83.5% of adsorbed chlorobenzene has been oxidized, and the main Cl-containing product is HCl accounting for approximately 77.8–81.0%, a small amount of Cl forms polychlorinated organic compounds or metal chlorides occupying 2.0–5.7%. As the regeneration temperature decreases, the total amount of Cl-containing species is reduced due the lower oxidation and dechlorination activity of catalysts. The decomposition products of Cl-VOCs in the thermal regeneration process of activated carbon were clarified and quantified, which provides a theoretical basis to control Cl-VOCs in regeneration gas.

CAS / MDL: 10031-43-3 7782-61-8
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2020 · IF 2.369

Vapor-Pressure Measurement of Ternary System CaCl2 + [Emim]Br + H2O, CaCl2 + [Emim]Cl + H2O, CaCl2 + [Emim]Ac + H2O, and CaCl2 + [Emim]NO3 + H2O

Yaqi Ding,Neng Gao,Yongping Wu,Yongmei Xuan,Guangming Chen

Calcium chloride (CaCl2) aqueous solution as a liquid desiccant has the disadvantage of low vapor pressure and easy crystallization. Ionic liquids (ILs) such as [Emim]Cl, [Emim]Ac, and [Emim]Br have been verified to have a good ability to reduce the vapor pressure. In this paper, the vapor pressures of four kinds of CaCl2 + ILs + H2O were measured, which were CaCl2 + [Emim]Br + H2O (mass ratio CaCl2/[Emim]Br = 2:1) at temperatures of between 311.10 and 394.45 K, CaCl2 + [Emim]Cl + H2O (mass ratio CaCl2/[Emim]Cl = 2:1) at temperatures of between 306.58 and 393.89 K, CaCl2 + [Emim]Ac + H2O (mass ratio CaCl2/[Emim]Ac = 2:1) at temperatures of between 304.93 and 382.71 K, and CaCl2 + [Emim]NO3 + H2O (mass ratio CaCl2/[Emim]NO3 = 2:1) at temperatures of between 312.46 and 391.80 K, with the mass fraction of solute ranging from 0.2 to 0.5. The Antonie-type equation was used to fit the measured results. The average absolute relative deviation (AARD %) values of the measured vapor pressures and calculated vapor pressures were 0.52, 0.40, 0.33, and 0.27%, which showed good consistency and accuracy. Comparing the vapor pressures of the different solutions at the same concentration, the following order of the four anions with the ability to reduce the vapor pressure of CaCl2 + H2O can be drawn at a mass fraction of 0.4: Br– > Cl– > NO3– > Ac–.

CAS / MDL: 10043-52-4 7647-14-5
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MICROCHIMICA ACTA · 2021 ·Vol. 188 ·期 10 ·1-9 · IF 5.833

N, Cl-doped carbon dots for fluorescence and colorimetric dual-mode detection of water in tetrahydrofuran and development of a paper-based sensor

Jia Jing,Lu Wenjing,Cui Sai,Dong Chuan,Shuang Shaomin

N, Cl-doped carbon dots (N, Cl-CDs) were prepared by hydrothermal method from rhodamine B (RhB) and ethylenediamine (EDA). The resulting N, Cl-CDs exhibited fascinating solvent dependence and strict excitation independence. As the polarity of the solvent increased (from tetrahydrofuran (THF) to water), the emission spectrum of N, Cl-CDs was redshifted and the fluorescence efficiency decreased, which were attributed to hydrogen bond-induced aggregation. Taking advantage of these attributes, the N, Cl-CDs were used as suitable probes for fluorescence and colorimetric dual-mode detection of water in THF. The linear relationship was 0.5–100% water with the detection limit down to 0.093%. Moreover, the sensing platform was converted into a paper-based sensor for handy, real-time, and visible humidity sensing. N, Cl-CDs/PVA films were fabricated and realized continuously tunable solid-state fluorescence, further expanding their practical application. Graphical abstract

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Advanced Optical Materials · 2019 ·Vol. 7 ·期 23 ·1901082 · IF 7.125

Halogen-Hot-Injection Synthesis of Mn-Doped CsPb(Cl/Br)3 Nanocrystals with Blue/Orange Dual-Color Luminescence and High Photoluminescence Quantum Yield

Daqin Chen,Su Zhou,Feifan Tian,Haitao Ke,Naizhong Jiang,Shujin Wang,Yongzhao Peng,Yue Liu

Recently, Mn 2+ -doped CsPb(Cl/Br) 3 perovskite nanocrystals (NCs), showing the advantages of dual-color emissions via exciton-to-dopant energy transfer and reduced usage of toxic Pb 2+ heavy metal ions by nontoxic Mn 2+ substitution, are widely explored. However, photoluminescence quantum yields (PLQYs) for Mn 2+ -doped CsPb(Cl/Br) 3 NCs still need to be further improved. Here, a halogen-hot-injection strategy is developed to prepare Mn:CsPb(Cl 0.6 Br 0.4 ) 3 NCs with the maximal PLQY of 65%. With this method, intense blue narrowband emission from excitonic recombination and orange broadband emission from Mn 2+ 4 T 1 → 6 A 1 transition can be simultaneously achieved. The competitive luminescence between perovskite NCs and Mn 2+ dopants is systematically investigated by controlling the injected halogen types and ratios. As a proof-of-concept experiment, the present Mn 2+ -doped CsPb(Cl/Br) 3 perovskite NCs with highly efficient dual-color emissions are demonstrated to be applicable as color converter in UV-excitable solid-state lighting.

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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2019 · IF 2.298

Study on the Phase Equilibrium of Na+, K+//Cl–, CO32––H2O and Single-Salt of Potassium Separation with the Aid of Compressed CO2

Zhongshu Li,Yuli Xue,Xiaoling Tan,Wenqing Li,Shaonan Xu,Ziyan Wang,Jian Wang,Lina Li,Shiding Miao

It is of great importance to separate potassium salts from carbonate-based lakes, especially the low-[K+] but high-[Na+] brine which has been discovered around the world. Here the phase diagram of the quaternary system Na+, K+//Cl–, CO32––H2O was experimentally studied at 298.15 K via the method of isothermal evaporation, and the results corrected the previous diagram reported by Blasdale (J. Am. Chem. Soc.1923, 45, 2935–2946). The type of salts appeared and their solubility during the evaporation, and the density vs composition diagram and the pH values were plotted based on the experimental data. It was found that there were six invariant points, seven univariant curves, and five crystallization fields in the equilibrium phase diagram. To extract single-salt of potassium, certain areas in the Na+, K+//Cl–, CO32––H2O diagram were chosen to be acidified by the compressed CO2, and potassium in the form of KHCO3 was precipitated from the mother solution. The compressed CO2 was able to avoid formation of NaKCO3·6H2O during evaporation of the original system Na+, K+//Cl–, CO32––H2O. Based on experiment data, the region area for potassium salt extraction was determined, and this area was suitable for extracting K+ salts from brines with a [Na+/K+] ratio even lower than 0.44. This strategy opened a new way to recovery of potassium with a maximum yield of 59.88% from the carbonate-chloride-based brine.

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Nanomaterials · 2019 ·Vol. 9 ·期 2 ·172 · IF 4.034

Highly Controllable Synthesis and DFT Calculations of Double/Triple-Halide CsPbX3 (X = Cl, Br, I) Perovskite Quantum Dots: Application to Light-Emitting Diodes

Xinyue Lao,Xiyu Li,Hans Ågren,Guanying Chen

Although all-inorganic CsPbX3(X = Cl, Br, I) perovskite quantum dots (PQDs) have evoked exciting new opportunities for optoelectronic applications due to their remarkable optical properties, their emission color tunability has not been investigated to any appreciable extent. In this work, double/triple CsPbX3perovskite quantum dots with precise ratios of Cl/Br or Br/I are synthesized and their luminescence (410–700 nm) is explored. A group of down-converted CsPbX3(X = Cl, Br, I) perovskite quantum dot light-emitting diode (LED) devices were constructed to demonstrate the potential use of such double/triple-halide CsPbX3perovskite quantum dots with full-spectrum luminescence. Based on density functional theory, we theoretically explored the properties of CsPbX3with double/triple anion atoms. The calculated band gaps provided strong support that the full-spectrum luminescence (410–700 nm) of double/triple CsPbX3can be realized with the change of the mixed-halide ratios, and hence that such PQDs are of potential use in optoelectronic devices.Keywords:perovskite quantum dots;light-emitting diode;density functional theory;band gap

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SEPARATION AND PURIFICATION TECHNOLOGY · 2015 · IF 3.091

Fabrication of new cellulose acetate blend imprinted membrane assisted with ionic liquid ([BMIM]Cl) for selective adsorption of salicylic acid from industrial wastewater

Zhihui He,Minjia Meng,Li Yan,Weihua Zhu,Fengquan Sun,Yongsheng Yan,Yan Liu,Shijuan Liu

Highly selective cellulose acetate (CA) blend imprinted membranes for salicylic acid (SA) was prepared by using phase inversion technique with sulfonated polysulfone (SPS) as a functional polymer, polyethylene glycol-4000 (PEG 4000) and ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as the additives. The membranes were characterized by several techniques including SEM, Raman, contact angle, membrane flux, and SA adsorption–desorption techniques. The SEM micrographs showed that the cross-sectional morphology of CA membranes was affected by polymer blend composition and applications of additives. Compared with the pure CA membrane the CA/SPS(90/10)   +   [BMIM]Cl membranes showed low contact angle, high membrane flux, strong adsorption capacity and high permeation selectivity. The experimental data of adsorption kinetic for CA/SPS(90/10)   +   [BMIM]Cl were well fitted to the pseudo-second-order kinetic model using multiple regression analysis. The selectivity coefficients of CA/SPS(90/10)   +   [BMIM]Cl-MIM for SA in relation to competition analogs p -hydroxybenzoic acid ( p -HB) and phenol were 5.8549 and 5.9062, respectively, which suggested that CA/SPS(90/10)   +   [BMIM]Cl-MIM had high selectivity and binding affinity for the template SA. Overall results suggest that [BMIM]Cl can be considered as an effective additive for CA imprinted membranes in the treatment of SA-contained water.

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SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

Lab-on-cloth integrated with gravity/capillary flow chemiluminescence (GCF-CL): towards simple, inexpensive, portable, flow system for measuring trivalent chromium in water

Rui Liu,Peng Zhang,Huijie Li,Chunsun Zhang

Flow chemiluminescence (CL) is widely applied for detection of heavy metal ions in environment, but it is seldom used in economical, practical, or affordable settings because non- and minimally instrumented flow driving is difficult to achieve. Here, we first report a gravity and capillary force-driven flow CL (GCF-CL) lab-on-cloth device, toward development of low-cost, easy-to-use, portable, minimally-instrumented platform for determination of trivalent chromium [Cr(III)] in water, where a difference in height between two zones on cloth creates a fast flow of CL trigger solution. Wax screen-printing was used to fabricate ultra-low-cost cloth-based devices, and the light emitted from the Cr(III)-catalysed oxidation of luminol by H 2 O 2 was imaged using an inexpensive portable CCD camera. Under optical conditions, Cr(III) could be determined over the range of 0.01–100   mg/L, with a detection limit of 6.2   μg/L, an analysis time of less than 30   s per sample, and RSDs of 6.2%, 3.1% and 1.7% for 0.05, 0.5 and 5   mg/L Cr(III) (n   =   5). The proposed GCF-CL lab-on-cloth was successfully applied for measuring Cr(III) in water samples, with recoveries of 100.67-111.70% and RSDs of 4.73–6.88%. Thus, the presented method should have the potential for portable field applications in environmental and public health fields.

CAS / MDL: 10025-73-7
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Insight into the roles of Cl− for the degradation of Acid Red 14 in an electrochemical advanced oxidation system: Mechanisms and DFT studies

Tongqing Wu,Zhihui Hu,Jiaqi Yang,Yan Jia,Zekun Dong,Yu Tang,Yan Zhang

Textile wastewater was typically characterized by high concentrations of chloride ions, with Acid Red 14 (AR14) representing a significant pollutant. Nevertheless, research into the degradation of AR14 by electrochemical advanced oxidation processes (EAOPs) had largely overlooked the influence of chloride ions. In this regard, the EC-Chlorine-MMO/Ti system was designed, and the degradation mechanism of AR14 was subjected to meticulous investigation. The adopted anode was composed of Ti/IrO 2 -Ta 2 O 5 (mixed metal oxide, MMO). It demonstrated superior efficiency in degrading AR14 within a sodium chloride (NaCl) electrolyte, registering an apparent kinetic constant rate approximately 16.76 times greater than that observed within a sodium perchlorate (NaClO 4 ) electrolyte. The optimal chloride ion concentration was identified as 0.04 mol/L. Besides, alkaline conditions were not conducive to the degradation of AR14. It was noteworthy that the electrochemical byproducts chlorite (ClO 2 − ), chlorate (ClO 3 − ), perchlorate (ClO 4 − ), and trihalomethane (THMs) were not produced in the solution treated by the EC-Chlorine-MMO/Ti system. Electron paramagnetic resonance (EPR) spectroscopy, probe, and quenching experiments identified that hydroxyl radicals ( • OH), superoxide radicals (O 2 •− ), and dichloride radicals/chlorine monoxide radicals (Cl 2 •− / ClO • ) were the major reactive species. Of these, • OH played a pivotal role in AR14 degradation. Additionally, the three principal degradation pathways of AR14 were deduced by LC-MS analysis, UV–vis spectra, density-functional theory (DFT) calculations, and excitation-emission matrix (EEM) fluorescence spectroscopy. Furthermore, the generation mechanism of reactive species and the proposed mechanism of AR14 degradation by the EC-Chlorine-MMO/Ti system were presented. The study made a significant contribution to the understanding of the electrochemical reactions occurring in textile wastewater and provided valuable insights into the rational control of electrolytic conditions for the treatment of saline wastewater.

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CHEMISTRY OF MATERIALS · 2024 · IF 7.2

Broadband Near-Infrared Luminescence from Mo4+ in Zero-Dimensional Perovskite Cs2Zr(Cl,Br)6 with an Exceptionally High Quantum Efficiency and Thermal Stability

Zhongyuan Li,Mengdi Xu,Wuqi Liu,Xuesong Wang,Ye Li,Xianju Zhou,Zhen Fang,Lixin Ning

Broadband near-infrared (NIR) luminescent materials hold the key to next-generation, smart, NIR light sources. The emerging halide perovskite materials are regarded as promising candidates for optoelectronics because of their superior optical properties and easy solution processability. However, it remains a major challenge to realize efficient and thermally stable broadband NIR luminescence in these materials. Herein, we report a novel strategy to achieve broadband NIR luminescence by utilizing the transitions from the lowest 1T2 level of Mo4+ to the components of its 3T1 ground state in the soft Cs2Zr(Cl,Br)6 lattice. The multiple transitions, each occurring within the (4d2) t22 crystal-field configuration and containing zero-phonon and vibronic contributions, superimpose on each other to generate the broadband NIR emission. The emission spectrum encompasses the long wavelength region from 800 to 1400 nm centered at 970 nm with a full width at half-maximum of 170 nm. More importantly, the title NIR phosphor shows an exceptional quantum efficiency (66.9%) and thermal stability (67%@150 °C). The as-fabricated NIR phosphor-converted light-emitting diode shows great potential as an NIR lighting source. This research opens a new horizon for realizing high-performance broadband NIR luminescence by exploiting multiple electronic transitions of activators in the soft lattice.

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Journal of Energy Chemistry · 2023 · IF 13.1

Synergy of I-Cl co-occupation on halogen-rich argyrodites and resultant dual-layer interface for advanced all-solid-state Li metal batteries

Han Yan,Ruifeng Song,Ruonan Xu,Shulin Li,Qiaoquan Lin,Xinlin Yan,Zhenyu Wang,Chuang Yu,Long Zhang

The (electro)chemical stability and Li dendrite suppression capability of sulfide solid electrolytes (SEs) need further improvement for developing all-solid-state Li batteries (ASSLBs). Here, we report advanced halogen-rich argyrodites via I and Cl co-occupation on the crystal lattice. Notably, a proper I content forms a single phase, whereas an excessive I causes precipitation of two argyrodite phases like a superlattice structure. The resultant synergistic effect of the optimized composition allows to gain high ionic conductivities at room temperature and −20 °C, and enhances the (electro)chemical stability against Li and Li dendrite suppression capability. The Li|argyrodite interface is very sensitive to the ratio of I and Cl. A LiCl- and LiI-rich double-layer interface is observed from the cell using the SE with optimized composition, whereas too high I content forms only a single interface layer with a mixture of LiI and LiCl. This double-layer interface is found to effectively mitigate the Li/SE reaction. The proper designed argyrodite enables ASSLBs to achieve good electrochemical properties at a broad temperature range regardless of the electrode materials. This co-occupation strategy provides a novel exploration for advanced halogen-rich argyrodite system.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Pillar[5]arene functionalized Au NPs and BiOX (Cl/Br/I) heterojunction constructed the enhanced photo-electrochemical sensor for ultrasensitive detection of serotonin

Jin Wang,Xu Guo,Qixiang Zhou,Yan Cai,Bing Lu,Yang Wang,Yong Yao

The functional photoelectric materials based on bismuth oxyhalides (BiOX, X = Cl, Br and I) have been widely used in the field of photo-electrochemistry (PEC) due to their excellent physical, chemical and optical properties. Herein, a series of BiOX nanoflowers conjugated water-soluble pillar[5]arenes functionalized Au (Au@WP5/BiOX) modified PEC sensor are constructed and investigated for the PEC detection of serotonin. Upon exploring the physical properties, such as size, visible light absorption capacity, band gap and impedance, of the three BiOX materials, it is discovered that BiOBr is more effective in detecting 5-HT due to its high redox ability, moderate band gap (∼2.03 eV), and low impedance. BiOBr can provide a high and stable starting photocurrent compared to the other two bismuth oxyhalides. When used in acidic or neutral environments, 5-HT with a positive charge can undergo electrostatic adsorption and host-guest complexation behavior with WP5, which has a negative charge. By using WP5, the recognition ability of the material to 5-HT molecules can be enhanced, and the adsorption of 5-HT molecules on Au@WP5/BiOBr can be accelerated. The local surface plasmon resonance effect (LSPR) of gold nanoparticles (Au NPs) can accelerate the electrochemical reaction rate and charge transfer rate, which ultimately leads to the amplification of the photocurrent signal. As a result, the 5-HT detection sensor based on Au@WP5/BiOBr has a wide detection range from 0.01 to 100 μM and a low detection limit of 3 nM (S/N = 3) compared to other sensors, including Au@WP5/BiOCl and Au@WP5/BiOI. The proposed PEC sensor also exhibits good stability and selectivity, making it a promising strategy for detecting biological small molecules using pillar[5]arene functionalized PEC active materials.

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