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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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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Scalable and room-temperature preparation of Cs2HfCl6 double perovskites with recorded photoluminescence efficiency and robust stability

Jialiang Jiang,Jinju Zheng,Hui Fu,Hao Zhang,Deliu Ou,Qiaochu Chen,Kai Wang,Sheng Cao,Jialong Zhao,Zhentao Du,Weiyou Yang

Vacancy-ordered double perovskites (DPs) are promising candidates for modern white light-emitting-diodes (WLEDs) due to their low toxicity and unique optical properties. However, the grand challenge is that DPs synthesized at room temperature (RT) typically have a low photoluminescence quantum yield (PLQY), most of which reported below 51 %, making them impractical for applications. Here, we present a facile strategy for the mass production of Bi 3+ and Te 4+ co-doped Cs 2 HfCl 6 (CHC) DPs at RT, to realize single-component dual-band emission with a high color rendering index. It is witnessed that the rationally designed ligand [Hmim]Cl facilitates a strong chemical interaction between the ligand and DPs. This interaction allows [Hmim]Cl to coordinate with undercoordinated Hf 4+ ions and provide excess chloride ions to the surface of the DPs. Consequently, it effectively controls the crystallization of DPs, protects them against moisture, reduces surface defects, and increases the migration barrier of halogen ions. As a result, the DPs exhibit excellent overall performance with robust photostability and a superior PLQY of 96.4 %, which is ∼ 2 times the highest reported value for similar DPs synthesized at RT. Current work presents a potential pathway for the mass production of high-quality DPs under mild conditions, leading to the development of signal-component WLEDs.

研究领域: 材料科学 · 光电技术 · 纳米技术
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Selective fluoride removal from groundwater using CNT-CeO2 electrodes in capacitive deionization (CDI)

Xun Liu,Danyal Rehman,Yufei Shu,Bei Liu,Li Wang,Li Li,Mengxia Wang,Kunkun Wang,Qi Han,Linlin Zang,John H. Lienhard,Zhongying Wang

Selective capacitive deionization (SCDI) is a promising process for preferentially removing specific ions from waters with complex compositions. The selectivity towards certain species in CDI is most frequently achieved through novel electrode materials with high affinities towards targeted species. In this study, we investigate the selective removal of fluoride ions from groundwater containing concentrated co-existing chloride ions. A carbon nanotube-CeO 2 (CNT-CeO 2 ) electrode is employed for the electro-sorption of fluoride ions. Our findings are compelling: when processing a mixed F − /Cl − solution comprising 10 mg/L F − and 100 mg/L Cl − , the CNT-CeO 2 electrode is seen to reduce the concentration of F − ions to 1.5 mg/L in just 150 min, amounting to an 85 % F − removal efficiency, while the Cl − removal efficiency remains below 2 %. Importantly, this translates to a F − /Cl − separation factor of up to 4.16 when using the CeO 2 -based electrodes, which is 40 times higher than that achieved with conventional activated carbon (AC) electrodes. Furthermore, the energy consumption for treating actual groundwater using scaled-up equipment is impressively low at approximately 0.2 kWh/m 3 . The high affinity of CNT-CeO 2 towards fluoride is attributed to the intercalation Faraday capacitance initiated by the reaction between F − with CeO 2 , as verified by the electrochemical quartz crystal microbalance (EQCM). Moreover, EQCM results show a substantial increase in both mass and current as the potential increased beyond 0.8 V vs Ag/AgCl, implying that the current surge is not a result of water splitting but rather the adsorption of F − onto the CNT-CeO 2 electrode. The addition of CNTs substantially increases the conductivity of CeO 2 electrodes and restricts the aggregation of CeO 2 , thereby accelerating ion diffusion and promoting selective adsorption characteristics. Importantly, our electro-driven approach demonstrates excellent adsorption–desorption over 20 cycles. This comprehensive study advances the technological development of selective CDI, while providing new insights for fluoride removal in groundwater.

研究领域: 环境工程 · 水处理 · 电化学 · 材料科学
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ELECTROCHIMICA ACTA · 2026 · IF 5.8

Cation-specific modulation of electrochemical oscillation and corrosion film dynamics in the Cu/H3PO4/Cl- system: Ni2+-stabilizing, Al3+-accelerating, and Na+-neutral effects

Peng Wu,Yuanyuan Ma,Hongyu Wang,Jianghong Wu,Sheng Fan,Yu Zheng,Yongfeng Li,Lifeng Ding

The electrochemical oscillation (EO) exhibited by Cu anodes during dissolution in H 3 PO 4 /Cl - mixed electrolytes significantly influence the efficacy of processes such as metal surface treatment, precision electroplating, and electrochemical mechanical polishing(ECMP). While Cl - ions have been identified as the key factor inducing oscillations, the mechanism governing their interaction with coexisting cations remains unclear. This study, integrating electrochemical analysis, anodic film surface characterisation, and density functional theory (DFT) calculations, reveals the decisive regulatory role of cations in oscillation mechanisms and corrosion film properties. The findings indicate that, when the influence of Cl - ion concentration is excluded, Na + ions primarily fulfil charge-balancing functions, while Ni 2+ and Al 3+ ions exert synergistic regulatory effects at the active interface. Ni 2+ ions form pure CuCl films through strong adsorption, prolonging oscillation periods. Conversely, Al 3+ ions promote the formation of CuCl/Cu(II)/AlO 4 /Al(OH) x composite films, accelerating film dissolution and shortening periods. The specificity of cations directly determines the stability and dissolution kinetics of films on the Cu anode surface. This study establishes the role of cations as key variables in the electrolytic process, providing a theoretical foundation for understanding EOs and passivation mechanisms.

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Green Energy & Environment · 2026 · IF 16.7

Modulating Electron Density of Ce Site via a Ce–O–Bi configuration on Ce-BiOX (X = Cl, Br, I) to Boost Hydrogen Peroxide Electrosynthesis

Na Wang,Wenting Lu,Fengyan Han,Weiping Xiao,Xiaofei Yang

The electron density of Ce active center is modulated via constructing the Ce–O–Bi configuration in Ce-doped BiOX (X = Cl, Br, I). • Halogen-induced differences in electronegativity and ionic radius effectively modulate Bi–O lattice symmetry and electronic properties. • The optimal 2.5%Ce-BOB catalyst delivers excellent H 2 O 2 selectivity, high production yield and favorable 2e - ORR kinetics. • In-situ electro-generated H 2 O 2 realizes efficient electro-Fenton degradation of organic dye pollutants. The selectivity of two-electron oxygen reduction reaction (2e - ORR) is predominantly determined by the adsorption strength of the key intermediate *OOH on the catalyst active sites, which has often been tuned by 3d transition-metal doping. Herein, we fabricate rare earth Ce doped bismuth oxyhalide (BiOX, X = Cl, Br, I) catalysts. The built in Ce–O–Bi local configuration triggers efficient charge rearrangement and tunes the surface electron density of Ce active centers. Meanwhile, the differences in ionic radius and electronegativity among halogen species can modulate the symmetry of the Bi–O lattice, thereby forming a typical volcano-type correlation between the bond length and 2e - ORR catalytic performance. The synergistic effect of Ce doping and halogen modulation endows the 2.5%Ce-BOB catalyst with optimal 2e - ORR performance. It delivers a H 2 O 2 selectivity of over 90% within the potential range of 0.2-0.6 V and achieves a H 2 O 2 production rate of 2631.4 mmol g -1 h -1 at 0.1 V. Furthermore, this optimized catalyst demonstrates potential application in organic wastewater treatment, where the degradation efficiency of methylene blue (MB) reaches approximately 95% in 40 min and that of rhodamine B (RhB) approaches 99% in 15 min. This work provides new insights into the rational design of electrocatalysts and environmental applications of electrosynthesized H 2 O 2 via the synergistic regulation of rare-earth metal doping and halogen modulation. The synergistic strategy integrating Ce-doping and halogen modulation finely tailors the electronic environment of Ce active centers, endowing the 2.5%Ce-BOB electrocatalyst with favorable H 2 O 2 selectivity, considerable production capacity and effective electro-Fenton degradation of organic dyes. Download: Download high-res image (284KB) Download: Download full-size image

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WATER RESEARCH · 2024 · IF 11.4

Wane-and-wax mechanism of nitrogenous disinfection byproducts with constant Cl/N peak under UV/chlorine treatment: Implication for new drinking water disinfection strategy

Jinxiu Lou,Lu Yin,Feilong Dong,Zhanfei He,Huijie Lu,Shuangxi Fang,Xiangliang Pan

Nitrogenous disinfection byproducts (N-DBPs) are notorious for their serious health risks, yet nitrate (NO 3 - ) mediates N-DBPs generation during UV/chlorine treatment remains unexplored. This study investigated the interaction of chlorine and NO 3 - on N-DBPs formation and developed a specific fragment-based screening method using UPLC-QTOF-MS to explore the underlying mechanism. Results showed that the chlorine-to-nitrogen (Cl/NO 3 - -N) molar ratio significantly affects dichloroacetonitrile (DCAN) and dichloroacetamide (DCAM) generation, with peak concentrations at a Cl/NO 3 - -N molar ratio of around 15. NO 3 - promotes the production of HO • , which positively correlates with DCAN and DCAM concentrations, also peaking at this ratio. Utilizing our developed method, three key hydroxyl-substituted intermediates that circumvent the previously reported “limiting-steps” in DCAN formation were identified. This reaction proceeds via a stepwise mechanism involving hydroxylation and chlorine substitution to produce hydroxyl-phenylacetonitrile and hydroxyl-chlorine-phenylacetonitrile. The conversion rate of hydroxyl-chlorine-phenylacetonitrile to DCAN was 8.6 times higher at Cl/NO 3 - -N molar ratio of 15 compared to conditions without NO 3 - , attributed to the weakened bond strength of the side chain, as supported by density functional theory calculations. This study provides novel insights into the mechanistic pathways of DCAN and DCAM formation, critical for developing more effective drinking water disinfection technologies to control N-DBPs.

研究领域: 环境科学 · 饮用水处理 · 化学动力学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Nanoscale · 2024 ·Vol. 17 ·期 1 ·567-574 · IF 5.8

Synergistic role of Cl− and Br− ions in growth control and mechanistic insights of high aspect ratio silver nanowires for flexible transparent conductive films

Jia-Lei Xu,Rui-Dong Shi,Hai-ping Zhou,Guo-Tao Xiang,Zi-Dong Zhou,Yong-Da Hu,Jin-Ju Chen

Silver nanowires (AgNWs) with high aspect ratios are pivotal for the production of flexible transparent conductive films (TCFs). The growth of AgNWs is significantly influenced by the strong affinity of halogen ions for silver ions. This affinity plays a crucial role in the controlled deposition of silver along the nanowire axis. By precisely controlling the concentrations of Cl− and Br− ions, we have successfully synthesized AgNWs with remarkable lengths of 96 μm and diameters of 40 nm, achieving an impressive aspect ratio of 2400. Utilizing density functional theory and molecular dynamics simulations, we investigate the impact of these ions on the growth of AgNWs. Our findings reveal that halogen ions strongly adsorb onto the Ag (100) plane in the radial direction, with Cl− ions promoting anisotropic growth and Br− ions effectively limiting the nanowire diameter, thus achieving high aspect ratio AgNWs. The resulting TCFs exhibit a high transmittance of 95.0% at 550 nm and a low sheet resistance of 14.7 Ω sq−1. Moreover, when integrated into a flexible transparent heater, these TCFs demonstrate a high heating rate of 12.1 °C s−1. The development of AgNWs is poised to significantly enhance the performance and versatility of flexible TCFs.

研究领域: 材料科学 · 纳米技术 · 表面化学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2020 · IF 4.65

Strongly enhanced photoluminescence and X-ray excited optical luminescence of the hydrothermally crystallized (Sr,Mn)5(PO4)3(F,Cl) nanorods by composition modulating

Zhihao Wang,Mengxiao Zhang,Jiao He,Yongan Tang,Tingchao He,Qiang Sun,Dianyuan Fan,Yu Wang

The development of emitting materials that present both photoluminescence (PL) and X-ray excited optical luminescence has recently been attracting rising research interest for visualization applications. We introduced in this study the hydrothermally crystallized (Sr 1- x Mn x ) 5 (PO 4 ) 3 F 1- y Cl y ( x  = 0–0.05, y  = 0–0.40) nanorods with favorable PL and X-ray excited optical luminescence properties after composition modulating. The effects of solution pH and Cl − incorporation on structure and morphology of the products were firstly unveiled. (Sr 1- x Mn x ) 5 (PO 4 ) 3 F gives green emission at ∼548 nm ( 4 T 1 ( 4 G) → 6 A 1 ( 6 S)) under either 402 nm excitation or X-ray irradiation, and the optimal PL and X-ray excited optical luminescence were observed at x  = 0.03. The replacement of F − by larger Cl − led to the generation of an amount of Frenkel defects (the dislocated F − and anion vacancies V F . ) along the c -axis, benefit from which the (Sr 0.97 Mn 0.03 ) 5 (PO 4 ) 3 F 1- y Cl y samples present enhanced PL and X-ray excited optical luminescence intensities by factors of 1.6 and 7.4, respectively, and the corresponding optimal y values are determined to be 0.20 and 0.30. Fluorescence decay analysis found steadily shortened fluorescent lifetime for Mn 2+ at higher Mn 2+ and Cl − concentrations, and the underlying mechanism was discussed. The (Sr,Mn) 5 (PO 4 ) 3 (F,Cl) apatite material, with enhanced PL and X-ray excited optical luminescence, may find novel applications for both lighting and scintillating.

研究领域: 材料科学 · 光学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Competitive coordination initiated one-pot synthesis of core–shell Bi-MOF@BiOX (X = I, Br and Cl) heterostructures for photocatalytic elimination of mixed pollutants

Dingliang Dai,Jianhao Qiu,Guanglu Xia,Yong Tang,Zhonghao Wu,Jianfeng Yao

Core-shell Bi-MOF@BiOX (X = I, Br and Cl) hybrids were fabricated by a one-pot solvothermal strategy via regulating the concentration and type of halogen ions in the Bi-based CAU-17 synthesis. By virtue of the competitive coordination effect to Bi 3+ between CAU-17 and BiOX, CAU-17 was converted into another Bi-MOF with similar structures and compositions. Moreover, Bi 3+ plays the role of “bridge” and endows an intimate interface contact between BiOX and the Bi-MOF, which immensely expedites the charge and mass transportation. The obtained Bi-MOF@BiOX hierarchical heterostructures were applied to photocatalytic elimination of solo and mixed pollutants (Cr(VI)/tetracycline and Cr(VI)/o-nitrophenol), and exhibited favorable performances. Choosing Bi-MOF@BiOI as a typical example, the corresponding performances for Cr(VI) reduction, tetracycline and o-nitrophenol degradation in their solo systems are 14, 10, 8 times higher than those of CAU-17, and 13, 7, 5 times higher than those of BiOI under visible light, respectively. Of note, the above photocatalytic performances could be further improved in the coexisting environment of Cr(VI) and tetracycline or o-nitrophenol, which is attributed to the elevated charge separation efficiency caused by the timely consumption of photo-excited electrons and holes. This work gives some insights into the delicate design of MOF photocatalysts and their applications in environmental restoration.

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