Science China-Chemistry
·
2025
·
IF 9.7
Kang Kai,Wang Qiuxiang,Huang Hongpu,Zhuang Xinxin,Cai Junlin,Wang Tao,Wang Xue,Xie Zhaoxiong,Xie Shuifen
Despite utilization of state-of-the-art Cu-based catalysts, achieving high selectivity and stability in multicarbon (C 2+ ) compounds production through electrocatalytic CO 2 reduction reaction (CO 2 RR) remains a critical and challenging objective. Here we employ lattice chlorine-doped Cu 2 O nanocubes (Cl d -Cu 2 O NCs) with well-defined {100} facets as a model catalyst to demonstrate that halogen doping can serve as a versatile and effective strategy for modulating surface charge distribution, thereby enhancing asymmetric C–C coupling toward high-selectivity C 2+ products in CO 2 RR. Compared to Cl-free Cu 2 O NCs, Cl d -Cu 2 O NCs exhibit a greatly enhanced C 2+ Faraday efficiency, i.e., ∼85% at −1.1 V (versus the reversible hydrogen electrode). Additionally, the Cl d -Cu 2 O NCs demonstrate significantly enhanced long-term durability, attributed to better preservation of the cubic morphology and more stable Cu δ + states. In-situ electrochemical studies reveal that Cl d -Cu 2 O NCs facilitate the formation of the key asymmetric *COH and *OCCOH intermediates, ultimately leading to higher C 2+ products. Density functional theory (DFT) calculations confirm that the introduced Cl-dopants disrupt the charge balance of the Cu 2 O(100) surface, enriching the Cl-adjacent Cu atoms with more electrons compared to those near O atoms. This unbalanced charge distribution significantly reduces the free energy of the rate-determining step for asymmetric C–C coupling from the *CO to *OCCOH on Cl-doped Cu 2 O (100) surface, requiring only 1.04 eV, in contrast to 1.50 eV on pristine Cu 2 O(100) surface. This study provides valuable insights into the surface charge modulation of Cu 2 O catalysts via halogen doping for enhancing asymmetric C–C coupling and C 2+ production in CO 2 RR.
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ELECTROCHIMICA ACTA
·
2026
·
IF 5.8
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
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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JOURNAL OF ALLOYS AND COMPOUNDS
·
2020
·
IF 4.65
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
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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INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Wenli Song,Bing Zhang,Wenli Zhou,Jilin Zhang,Liping Yu,Shixun Lian
All-inorganic perovskite quantum dots (PQDs, CsPbX3, X = Cl, Br, and I) show outstanding application prospects in the field of photoelectric devices. In recent years, the development of PQDs has greatly improved their stability to water, oxygen, and light. However, thermal quenching of PQDs greatly limits their practical application. Herein, we embed PQDs into ATiO3 (A = Ca, Ba, and Sr) of three different mesoporous spherical structures to explore the effect on thermal quenching of PQDs. Because of the unique mesoporous hollow microsphere structure and low thermal conductivity of SrTiO3, it can effectively block the heat transfer and improve the thermal quenching of PQDs. The photoluminescence (PL) intensity of CsPbBr3@SrTiO3 composites is 72.6% of the initial intensity after heating to 120 °C. Moreover, the PL intensity of CsPbBr3@SrTiO3 composites remains about 80% of the initial value even when stored in air for 20 days or irradiated by 365 nm UV light for 48 h. A neutral white light-emitting diode is assembled by a blue chip, CsPbBr3@SrTiO3 composites, and red phosphor of K2SiF6:Mn4+, which has a color temperature of 5389 K and a color gamut covered 133% of National Television Standards Committee (NTSC).
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PubMed
高影响因子
CHEMOSPHERE
·
2023
·
IF 8.8
Xiandong Wang,Yu Liu,Xinghui Zhang,Wenqing Tu,Qiyu Wang,Shuai Liu,Miao Zhang,Yongming Wu,Bixian Mai
As emerging alternatives to perfluorooctane sulfonate (PFOS), 6:2 chlorinated polyfluoroalkyl ether sulfonic acid (6:2 Cl-PFESA) and sodium p -perfluorous nonenox-benzenesulfonate (OBS) were frequently detected in the four freshwater fish species collected from Poyang Lake. Median concentrations of 6:2 Cl-PFESA and OBS in fish tissues were 0.046–6.0 and 0.46–5.1 ng/g wet weight, respectively. The highest concentrations of 6:2 Cl-PFESA was found in fish livers, whereas OBS was found in the pancreas, brain, gonads, and skin. The tissue distribution pattern of 6:2 Cl-PFESA is similar to that of PFOS. The tissue/liver ratios of OBS were higher than those of PFOS, suggesting that OBS has a greater tendency to transfer from the liver to other tissues. The logarithmic bioaccumulation factors (log BAFs) of 6:2 Cl-PFESA in three carnivorous fish species were greater than 3.7, whereas those of OBS were less than 3.7, indicating that 6:2 Cl-PFESA had a strong bioaccumulation potential. Notably, sex- and tissue-specific bioaccumulation of OBS has also been observed in catfish. Most tissues (except the gonads) exhibited higher OBS concentrations in males than in females. However, no differences were found for 6:2 Cl-PFESA and PFOS. Maternal transfer efficiency of OBS was higher than that of 6:2 Cl-PFESA and PFOS in catfish ( p < 0.05), indicating that OBS presents a higher risk of exposure to males and offspring through maternal offloading.
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Journal of Environmental Chemical Engineering
·
2022
·
IF 7.968
Zhengquan Yan,Lin Xing,Lin Zhao,Xinyi Zhang,Yingfan Zhang,Yulian Tang,Xuemei Zhou,Lei Hu,Nianlei Zhu
In this work, to efficiently eliminate the threat of toxic Cl − and Hg 2+ , a kind of AgRu bimetal mesoporous nanozyme co-stabilized by β-cyclodextrin and graphene oxide (AgRu@β-CD-co-GO) was first developed by a homogeneous redox and assembly method. The mesoporous microstructure and a large number of hydroxyl groups and GO aryl rings endowed AgRu@ β-CD-co-GO with superior peroxidase-mimic performance and enough active spots to adsorb more toxic Cl − and Hg 2+ . Under optimal conditions (pH 4.0, 350 μL 1.5 mM TMB and 200 μL 1.0 M H 2 O 2 and incubated for 30 min at 25 °C), AgRu@ β-CD-co-GO could accelerate the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) into blue oxTMB in the presence of H 2 O 2 . Toxic Cl − or Hg 2+ would exclusively alter its peroxidase-like activity, accompanied with the characteristic UV–vis absorption intensity at 653 nm ( A 653 ) decreased and color changed from blue to colorless. AgRu@ β-CD-co-GO was successfully applied for visual detection of Cl − and Hg 2+ and enriched removal of them after their detection. The detection limits were low to be 3.2 × 10 −10 mol∙L −1 for Hg 2+ and 6.4 × 10 −8 mol/L for Cl − . After detection, more than 94.9% Hg 2+ and 93.8% Cl − could be removed by only a simple filtration. The mechanisms for peroxidase-mimic activity of AgRu@ β-CD-co-GO and its exclusive recognition of Hg 2+ and Cl − were proposed.
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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2022
·Vol. 97
·期 10
·2805-2814
·
IF 3.709
Shuaibin Zhang,Bochao Yan,Zhihui Chen,Suping Zhang
BACKGROUND Levulinic acid, an important platform compound, is extensively used in textiles, dyes, antifreeze, animal feed, solvents and food additives. However, the use of lignocellulosic biomass to produce levulinic acid is difficult because of poor accessibility to cellulose and low hydrolytic yield. Thus a viable hydrolysis strategy and a suitable catalyst must be developed. RESULTS In this study, a bifunctional solid acid catalyst (HTC-SO 3 H) containing both cellulose binding sites ( Cl, COOH and OH) and catalytic sites ( SO 3 H) was prepared by a carbonization–grafting–oxidization method. X-ray photoelectron spectroscopy and Fourier transform infrared characterization confirmed the existence of Cl and the successful modification of the SO 3 H grafted hydrothermal carbon. The hydrogen bonds formed between cellulose and the binding sites ( Cl, OH and COOH) in the catalyst showed synergistic effects with the catalytic sites ( SO 3 H), leading to efficient hydrolysis of the furfural residue. A total of 74.81% (non-magnetic) and 70.18% (magnetic) levulinic acid yields were obtained after hydrolysis at 190 °C and 180 min in γ-valerolactone–H 2 O (1:1, v/v). Magnetic catalysts were synthesized using a co-precipitation method. Catalysts were recycled without any obvious reduction in catalytic activity. CONCLUSION Using sucralose as a raw material, the as-synthesized bifunctional solid acid catalyst improved the accessibility to cellulose and increased levulinic acid yield. Moreover, the grafted SO 3 H formed by hydroxyl hydration condensation exhibited superior stability. This study provides a valuable strategy for the efficient hydrolysis of lignocellulosic biomass. © 2022 Society of Chemical Industry (SCI).
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Advanced Optical Materials
·
2018
·Vol. 7
·期 4
·1801323
·
IF 7.43
Jiarui Hao,Xingyu Qu,Lei Qiu,Guogang Li,Yi Wei,Gongcheng Xing,Hongquan Wang,Chunjie Yan,Ho Seong Jang,Ziyong Cheng,Jun Lin
Currently, poor luminescence stability seriously impedes the practical application of inorganic halide perovskite (CsPbX 3 , X = Cl, Br, and I) quantum dots (QDs) in optoelectronic devices. In present work, CsPbX 3 QDs are successfully assembled on natural mineral halloysite nanotubes (HNTs) for improving the luminescence performances. Monodispersed CsPbX 3 QDs are arranged on two edges of HNTs in a highly ordered manner, which possibly originates from the electrostatic interaction between halogen ion and surface hydroxyl (Sur OH 2 + ) on the section face of HNTs. As expected, the photoluminescence (PL) performances of CsPbX 3 @HNTs nanocomposites are obviously improved. The PL intensity still can be maintained even 80% when working at 100 °C. Almost no emission degradation is observed after storing in an open ambient condition for 28 days. Moreover, the PL intensity also maintains 82% of room temperature (RT) intensity after continuously being illuminated by 365 nm UV lamps for 144 h. Excellent white light with Commission Internationale de l'Eclairage (CIE) chromaticity coordinates (0.34, 0.32) of the white light-emitting diodes (w-LEDs) fabricated by CsPbBr 3 @HNTs, CsPbBr 1.2 Cl 1.8 @HNTs, and CsPbBr 1.2 I 1.8 @HNTs phosphors are achieved. This work opens up a new insight in achieving stable CsPbX 3 QD-based multifunctional materials by designing nanocomposites with natural clay mineral.
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CHEMISTRY OF MATERIALS
·
2018
·
IF 9.89
Fei Li,Ying Liu,Hongliang Wang,Qian Zhan,Quanlin Liu,Zhiguo Xia
The control of surface properties of all inorganic cesium lead halide perovskite (CsPbX3; X = Cl, Br, or I) quantum dots (QDs) is essential to achieve excellent stability and high photoluminescence quantum yields (PLQYs). Herein, a facile method was performed to simultaneously enhance the stability and PLQYs of CsPbX3 QDs by a ZnX2/hexane solution post-treatment. We show that the halogen defect on the surface of CsPbX3 QDs can be treated in a controlled way, whereby the “black dots” that adhered on the surface as observed by transmission electron microscopy have be completely removed, resulting in enhanced stability and photoluminescence. The PLQYs of CsPbCl3, CsPbBr3, and CsPbI3 increased from 4, 58, and 63% to 86, 93, and 95%, respectively, and the origin of the “black dots” as well as their transformation mechanism has been demonstrated. As a result, the poly(dimethylsiloxane) composite films created by encapsulating stable and nearly defect-free green-emitting CsPbBr3, the red-emitting K2SiF6:Mn4+ phosphor, and a blue emission GaN chip were prepared and used to fabricate a remote-type white light-emitting diode device, which exhibits a high luminescence efficiency (≤98 lm/W) and a wide color gamut (∼130% of the National Television Standard Committee standard), suggesting the potential for liquid crystal display backlight application.
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APPLIED GEOCHEMISTRY
·
2017
·
IF 2.581
Wei Zhang,Li Zhou,Hongfeng Tang,Heping Li,Wenlei Song,Gang Xie
The solubility of fluorite in hydrothermal conditions is important in ore forming and geothermal processes and groundwater utilization. However, a quantitative description of the geochemical behavior of fluorite under hydrothermal conditions has not been previously reported. In this work, the solubility of fluorite in Na-K-Cl solutions at temperatures up to 260 °C and ionic strengths up to 4 M was determined by experiments and modeling. The solubility products obtained in this work at 30 and 50 °C under ambient pressure and those from literature were used to regress the density model parameters for fluorite solubility product calculation at high temperature. The Pitzer interaction model was adopted to calculate the activity coefficient . The fluorite solubility determined in KCl solution at 250 °C under vapor saturated pressure and that from the literature were combined with the low-temperature thermodynamic properties of heat capacity and osmotic coefficient to obtain the binary parameters of NaF and KF at temperatures up to 260 °C. A thermodynamic model was then developed for calculating the fluorite solubility in Na-K-Cl solution at temperatures up to 260 °C, under vapor saturated pressure and ionic strengths up to 4 M. As calculated from this model, fluorite solubility measured at 200 °C and 0.1 M NaCl was well predicted. Both temperature and ionic strength had significant effects on fluorite solubility, and fluorite exhibited a similar dissolution pattern in both NaCl and KCl solution. When the concentration was lower than 2 M, the solubility of fluorite first increased with temperature, reached a maximum at approximately 100 °C, and then decreased. When the concentration was higher than 2 M, the solubility of fluorite increased monotonically with temperature.
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