ACS ES&T Water
·
2025
·
IF 4.3
Xuecong Qian,Luwei Li,Jinhao Duan,Shilong Wang,Yun Liu,Da Wang,Haijun Cheng,Jun Ma
In aqueous systems, Mn(II) oxidation by chlorine involves both electron and proton transfer. However, the slow proton transfer due to water molecule’s limited proton acceptance capacity leads to low Mn(II) oxidation efficiency under near-neutral conditions. Pyridine (pKa = 5.25), a strong proton acceptor, was selected to investigate electron–proton transfer principles in Mn(II) oxidation. Kinetic studies show that pyridine enhances Mn(II) oxidation efficiency by chlorine under neutral to alkaline conditions (pH 7.0–9.5), with maximal enhancement observed when pH approaches pyridine’s pKa. A high kinetic isotope effect (up to 6.9) and an E1/2-pH slope near the Nernstian value in cyclic voltammetry experiments confirm that pyridine induces a concerted electron–proton transfer (CEPT) pathway. Density functional theory calculations reveal that the pyridine-induced CEPT pathway is thermodynamically more favorable than stepwise electron transfer followed by proton transfer (ETPT) and proton transfer followed by electron transfer (PTET) pathways, explaining the enhanced oxidation efficiency. Similarly, in pyridine-free systems, increasing pH from 7.0 to 9.5 promotes Mn(II) oxidation efficiency through an OH–-mediated pathway switching from ETPT to PTET and CEPT pathways. This study demonstrates the controlling role of proton transfer in the Mn(II) oxidation process, providing theoretical guidance for the rational selection or design of Mn-removal catalysts.
研究领域:
环境化学
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物理化学
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无机化学
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化学动力学
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电化学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2018
·
IF 3.927
Xiaoyong Yang,Fengping Jie,Bingjie Wang,Zhishan Bai
Environmental pollution by industrial effluents polluted with hazardous heavy metals has great concern. A novel microemulsion system (sodium dodecanoate/pentan-1-ol/heptane/NaCl) was prepared for the treatment of cobalt (Co) and manganese (Mn) wastewater. The effects of the batch extraction conditions were systematically studied and the extraction efficiency of Co(II) and Mn(II) were 98.2% and 97.5% respectively at the optimal conditions. Utilizing the centrifugal reinforcement of the annular centrifugal extractor (ACE), the continuous extraction of cobalt and manganese wastewater by microemulsion could be achieved. Under the optimized operation conditions: the motor speed of 1988 rpm, a flow ratio of 1/5, and a total flow rate of 48 L/h, the maximum extraction efficiency reached up to 99.9% for Co(II) and 99.1% for Mn(II), respectively. The stripping of Co(II) and Mn(II) from the microemulsion phase was also conducted using hydrogen chloride solution, indicating a high stripping efficiency. The investigation of synergistic extraction with microemulsion and ACE proposed an efficient treatment for Co and Mn wastewater.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2022
·
IF 13.599
Xiaoling Cui,Jinlong Sun,Dongni Zhao,Jingjing Zhang,Jie Wang,Hong Dong,Peng Wang,Junwei Zhang,Shumin Wu,Linhu Song,Ningshuang Zhang,Chunlei Li,Shiyou Li
By optimizing electrolyte formulation to inhibit the deposition of transition metal ions (TMIs) on the surface of the graphite anode is an effective way to improve the electrochemical performance of lithium-ion batteries. At present, it is generally believed the formation of an effective interfacial film on the surface of the anode electrode is the leading factor in reducing the dissolution of TMIs and prevent TMIs from being embedded in the electrode. It ignores the influence of the solvation structures in the electrolyte system with different composition, and is not conducive to the design of the electrolyte formulation from the perspective of changing the concentration and the preferred solvent to inhibit the degradation of battery performance caused by TMIs deposition. In this work, by analyzing the special solvation structures of the high-concentration electrolyte, we study the main reason why high-concentration electrolyte inhibits the destructive effect of Mn (II) on the electrochemical performance of LIBs. By combining the potential-resolved in-situ electrochemical impedance spectroscopy technology (PRIs-EIS) and density functional theory (DFT) calculation, we find that Mn (II) mainly exists in the form of contact ions pairs (CIPs) and aggregates (AGGs) in high-concentration electrolyte. These solvation structures can reduce the destructive effect of Mn (II) on battery performance from two aspects: on the one hand, it can rise the lowest unoccupied orbital (LUMO) value of the solvation structures of Mn (II), thereby reducing the chance of its reduction; on the other hand, the decrease of Mn 2+ ions reduction can reduce the deposition of metallic manganese in the solid electrolyte interphase (SEI), thereby avoiding the continuous growth of the SEI. This study can be provided inspiration for the design of electrolytes to inhibit the destructive effect of TMIs on LIBs.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry C
·
2022
·Vol. 10
·期 44
·16773-16780
·
IF 8.067
Jiawei Lin,Muwei Zhang,Niu Sun,Shihui He,Xusheng Zhang,Zhongnan Guo,Jing Zhao,Quanlin Liu,Wenxia Yuan
Zero-dimensional (0D) tetrahedral Mn(II) hybrids as narrow-band green emitters show great potential for the backlighting of liquid crystal displays. However, the factors influencing the full-width at half-maximum (fwhm) of green emission in the 0D Mn hybrid systems still need to be understood in depth. In this work, the regulation of the fwhm of green-emitting tetrahedral Mn(II) hybrids has been investigated from the structural distortion and hydrogen bond strength points of view. Two 0D Mn-based OIMHs with cyclic organic cations, (MDPA)2MnBr4 (1, MDPA = N-methyldiphenylaminium) and (MTPP)2MnBr4 (2, MTPP = methyltriphenylphosphonium), have been synthesized. Both of them contain isolated [MnBr4]2− tetrahedra and show green emission at 540 and 518 nm upon 450 nm excitation. It is found that the fwhm of compound 2 (48 nm) is much narrower than that of 1 (62 nm), and we demonstrate that it is associated with the smaller distortion of the Mn(II) tetrahedron in 2. Furthermore, Hirshfeld surface calculations suggest that this smaller distortion could be contributed by the weak hydrogen bonds between the organic cations and the [MnBr4]2− units in 2 compared to that in 1. We found that the other tetrahedral Mn(II) bromides reported in previous literature also show this behavior. Meanwhile, the triboluminescence emission is observed in both 1 and 2, ascribed to the polarized charges on the crystal surface. A white light-emitting diode device was fabricated using compound 2 with a high PLQY (55.66% upon 450 nm). Our work not only provides an insight to understand in depth the role of structural distortion and hydrogen bond strength in regulating the fwhm of the Mn(II) tetrahedron, but also provides feasible rules to explore the new narrow-band green-emitting OIMHs.
研究领域:
材料科学
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光电
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固体化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
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IF 13.2
Jia Zhao,Heng Zhang,Mengfan Luo,Hongyu Zhou,Zehua Wang,Jialong Yin,Chuanshu He,Peng Zhou,Jing Zhang,Bo Lai
Ferrate (Fe(VI)) activation by Mn(II) has been proven as a powerful technology due to the high catalytic activity of Mn(II) and the generation of multiple intermediates. However, the reactivity and stability of these intermediates greatly differ, thus necessitating the precise regulation of redox pathways towards the generation of the most desirable intermediates. In this study, we utilized ligand engineering to finely tune the redox pathways between Fe(VI) and Mn(II). Mn(II) complexing with ethylenediaminetetraacetic acid (EDTA) and nitrotriacetic acid (NTA) switched the redox pathways from generating Mn(IV) to more robust intermediates and enhanced the decontamination ability of Fe(VI). Ligand-to-metal charge transfer promoted the electron migration from Mn(II) complexes to Fe(VI), generating Fe(V) and Mn(III) intermediates. Then, complexing regulated the transformation of Mn(III) to generate different reactive species. Specifically, Mn(II)-EDTA activated Fe(VI) through Fe(IV)/Fe(V) and Mn(V), whereas the Fe(VI)-Mn(II)-NTA system relied on Mn(VII). Owing to the weaker chelating effect of NTA, unstable Mn(III)-NTA was successively oxidized via Mn(V) to Mn(VII). In contrast, the stronger stability of EDTA suppressed the excessive oxidation of Mn(V)-EDTA, boosting pollutant interception of reactive species. Accordingly, the Fe(VI)-Mn(II)-EDTA process delivered stronger activation and wider applicability, diminishing contaminant toxicity and resisting background interference. This study provides valuable insights into Fe(VI) activation induced by transition metal complexes and serves as a reference for selecting efficient strategies to avoid excessive consumption of oxidative capacity.
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产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2026
·
IF 10.6
Zhe Xu,Weilan Zhen,Chengfeng Liu,Jiantong Zhou,Taicheng An
The speciation compatibility of Cu-ligand complexes and catalytic oxidation systems fundamentally governs their decomplexation efficiency, exhibiting pronounced ligand concentration dependence. While contemporary methodologies predominantly focus on stoichiometric Cu(II)-ligand complexes, their efficacy in treating wastewater with ligand excess remains technologically contentious. This study demonstrates the Mn(II)/peroxymonosulfate (PMS) process as a robust solution for the elimination of Cu(II)-ligand complexes even in excessive ligand environments. Using Cu(II)-EDTA as the representative complex, 90% decomplexation was achieved within 1 and 5 min at [EDTA] 0 :[Cu] ratios of 1:1 and 2:1, respectively, surpassing reported decomplexation approaches such as UV/H 2 O 2 , UV/peroxydisulfate (PDS), and Co 2+ /PMS. Mechanistic investigations through oxidation species characterization and product analysis revealed a successive decarboxylation of EDTA by non-radical pathway, i.e., high valence metals and singlet oxygen, enhancing process selectivity while minimizing oxidant consumption ([PMS] 0 :[EDTA] 0 = 30:1). The system exhibits dual mechanistic regimes: (i) instantaneous decomplexation under ligand-deficient conditions via PMS activation by in-situ formed CuO through alkaline precipitation, and (ii) cascade decomplexation for ligand-rich systems involving Mn-Cu synergistic destruction of excessive EDTA prior to CuO-catalyzed degradation of residual ligand. Such synergism is believed to stem from the electron transfer from Cu(II) to Mn(V/VI), forming reactive Cu(III) for decomplexation through intramolecular electron transfer. The Mn(II)/PMS system also exhibited the applicability in treating various Cu(II)-ligand complexes and real wastewater. This work establishes a practical strategy for reliable treatment of industrial wastewater containing non-stoichiometric Cu-ligand complexes.
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DOI
高影响因子
Inorganic Chemistry Frontiers
·
2025
·
IF 6.4
Jia Liu,Long Yu,Xiaoyun Yi,Xin Li,Ziqing Liu,He Wang,Linwei Yang,Xin Yang,Suhua Wang
Low-dimensional lead-free Mn(II)-based organic–inorganic metal halides (OIMHs) are promising luminescent materials, yet molecular-level fine-tuning of organic structures to achieve high quantum yield and functional red-light emission remains challenging. In this study, three Mn(II)-based OIMHs were designed and synthesized using aminomethyl-pyridine isomers as cations. The results show that when 3-(aminomethyl)pyridine (3-AMPY) is employed as the organic ligand, its π-conjugated framework and enhanced molecular polarity facilitate the formation of a highly ordered and rigid zero-dimensional octahedral hybrid architecture, which achieves a high photoluminescence quantum yield (PLQY) of 63.42% with bright orange-red emission at 614 nm. In contrast, 2-AMPY and 4-AMPY counterparts only demonstrate weak red emission with low PLQY of 14.05% and 9.23%, respectively. Notably, (4-AMPY)4Mn3Br15 exhibits sensitive and irreversible red-to-green emission switching upon thermal treatment due to phase transition. To leverage this thermoresponsive luminescence behavior, a heating-assisted digital encryption system has been developed for complex information. This work reveals how cation substitution regulates the OIMH structure–property relationship and enriches the family of lead-free metal halides for anti-counterfeiting, information security, and optoelectronic applications.
研究领域:
材料科学
·
发光材料
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光电子学
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防伪技术
·
无机化学
✓ 已验证
产品关联
DOI
高影响因子
Laser & Photonics Reviews
·
2023
·
IF 11
Wen Li,Yunyun Li,Ying Wang,Zhengyang Zhou,Chao Wang,Yiyang Sun,Jianyong Sheng,Jiawen Xiao,Qian Wang,Shunsuke Kurosawa,Maksym Buryi,David John,Karin Paurová,Martin Nikl,Xiaoping OuYang,Yuntao Wu
The urgency for cost-effective, high-resolution, flexible X-ray imaging detectors is generating great demand for scintillators with low-temperature processability, high scintillation yield, and negligible afterglow. X-ray imaging materials are currently dominated by inorganic scintillators in the form of rigid films and bulk crystals, which have inherent limitations including high-temperature, complex synthesis, and considerable challenges toward advanced nonplanar imaging. Here, high-performance and flexible X-ray scintillators based on novel zero-dimensional (0D) (BTPP) 2 MnX 4 (BTPP = benzyltriphenylphosphonium; X = Cl, Br) halides are reported. They emit bright green light originating from the 4 T 1 - 6 A 1 transition of Mn 2+ under X-ray excitation. In particular, (BTPP) 2 MnBr 4 single crystals exhibit excellent air- and radiation-stability, a high scintillation yield of 53 000 photons MeV −1 , a low detection limit of 89.9 nGy air s −1 , and an ultralow afterglow comparable to commercial Bi 4 Ge 3 O 12 (BGO) single crystals. Moreover, the (BTPP) 2 MnCl 4 @polydimethylsiloxane (PDMS) flexible scintillation screens achieve a high spatial resolution of 14.1 lp mm −1 and realize high-quality imaging results of nonplanar objects. This study demonstrates that the flexible scintillation screens based on low-dimensional Mn(II) hybrid halides have significant potential for low-dose and high-resolution X-ray imaging applications.
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产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2023
·
IF 13.6
Yang Zong,Hua Zhang,Hao Liu,Jun Xu,Zhengwei Zhou,Xiaomeng Zhang,Ting Zhang,Deli Wu
Mn(II) is among the most efficient catalysts for the periodate (PI)-based oxidation process . In-situ formed colloidal MnO 2 simultaneously serves as the catalyst and oxidant during the degradation of organic contaminants by PI. Here, it is revealed that the complexation of Mn(II) by ethylene diamine tetraacetic acid (EDTA) further enhances the performance of PI-based oxidation in the selective degradation of organic contaminants. As evidenced by methyl phenyl sulfoxide probing, 18 O-isotope labeling, and mass spectroscopy , EDTA complexation modulates the reaction pathway between Mn(II) and PI, triggering the generation of high-valent manganese–oxo (Mn V –oxo) as the dominant reactive species. PI mediates the single-electron oxidation of Mn(II) to Mn(III), which is stabilized by EDTA complexation and then further oxidized by PI via the oxygen-atom transfer step, ultimately producing the Mn V –oxo species. Ligands analogous to EDTA, namely, [S,S]-ethylenediaminedisuccinic acid and L -glutamic acid N , N -diacetic acid, also enhances the Mn(II)/PI process and favors Mn V –oxo as the dominant species. This study demonstrates that functional ligands can tune the efficiency and reaction pathways of Mn(II)-catalyzed peroxide and peroxyacid-based oxidation processes.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2025
·
IF 5.4
Yang Zhang,Hanjun Wu,Zhenyue Zhang,Wenda Guo,Junxia Yu,Rongying Zeng,Ruan Chi,Zhiquan Pan
In this work, Ca-Al LDHs were modified via co-precipitation method utilizing two distinct chemical forms of adipic acid (adipate salt and adipic acid) as intercalation agents, with the resulting materials denoted as At-LDHs (adipate-intercalated LDHs) and Aa-LDHs (adipic acid-intercalated LDHs). The results indicated that At-LDHs and Aa-LDHs all exhibit a sheet-like porous structure stacked with each other. Due to the different synthesis conditions, the sheet structure of Aa-LDHs is smaller than that of At-LDHs. The kinetic and isotherm simulation results indicated that the capture capacity of At-LDHs for Mn 2 + was up to 227.53 mg·g −1 when the pH value was 7, while that of Aa-LDHs for naphthol green B reached to 132.73 mg·g −1 at a pH value of 9. The kinetic and thermodynamic simulation results indicated that the capture of Mn 2+ by At-LDHs conformed to the pseudo-first-order kinetic model and the Langmuir isotherm model, and the capture of naphthol green B by Aa-LDHs conformed to the Elovich kinetic model and the Temkin isotherm model. In addition, the capture process of both was a spontaneous exothermic reaction. Benefiting from the excellent adsorption properties of At-LDHs composites (Ion exchange, electrostatic attraction, adsorption precipitation, functional group chelation), the adsorption effect on Mn 2+ was better. Aa-LDHs have good adsorption effect on naphthol green B in solution through electrostatic attraction, dipole-dipole hydrogen bond, Yoshida hydrogen bond and n-π interaction. At-LDHs and Aa-LDHs have great potential to be employed as the materials for the removal of organic and inorganic composite pollutants from wastewater.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
WATER RESEARCH
·
2026
·
IF 12.8
Tianming Zheng,Peifang Wang,Bin Hu,Chongchong Liu,Ruoxi Zhen
Aquaculture activities discharge large amounts of antibiotics, with protein-like dissolved organic matter (DOM) coexisting in wastewater, whose impact on FF degradation remains unclear. An efficient advanced oxidation process (AOP) was established by Mn(II), nitrilotriacetic acid (NTA), and peroxymonosulfate (PMS) for degrading the typical aquaculture antibiotic florfenicol (FF), achieving removal efficiency of (97.38±1.02)% within 20 min primarily via Mn(V)= O , in which •OH, •SO 4 - , and 1 O 2 made minor contributions. The inhibitory effects of fishery amino acids on FF degradation followed the order: poly lysine > tryptophan > methionine > lysine. Based on electrochemical measurements and density functional theory (DFT) calculations, tryptophan and methionine competed for PMS binding sites, with methionine being preferentially oxidized by Mn(V)= O , thereby delaying FF degradation. Primary degradation pathways involved defluorination, dechlorination, and aromatic ring hydroxylation, exhibiting a reduced toxicity. Overall, this study developed a sustainable strategy to remove typical fishery antibiotics, highlighting the critical role of Mn(V)= O and the interference mechanism of protein-like DOM.
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DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2019
·
IF 5.155
Haitao Li,Qiang Gao,Guanshuai Wang,Bo Han,Kaisheng Xia,Chenghang Zhou
Developing high-performance heterogeneous Fenton-like catalyst and understanding its intrinsic catalytic properties are of fundamental and practical significance. In this work, a mesoporous Mn(II)-doped CeO 2 (MCO) with monodisperse spherical morphology and large surface area (141.8 m 2 g −1 ) was fabricated through a simple hydrothermal–calcination process, and further utilized as the heterogeneous catalyst for oxidative degradation of organic pollutants in the presence of H 2 O 2 . The density functional theory (DFT) simulations were carried out to study the H 2 O 2 decomposition process on the MCO surface. It was revealed that the Mn(II) doping in the CeO 2 could significantly promote the complex of the surface Ce sites and H 2 O 2 molecules. More importantly, the manganese dopants could serve as electron reservoirs, capable of reversibly donating and accepting electrons, which facilitated the electron transfer between Ce and H 2 O 2 . Owing to the electron reservoir properties of manganese, this MCO showed significantly enhanced catalytic efficiency in comparison to pure CeO 2 . Moreover, the catalytic activity of MCO almost kept unchanged after reuse several times, demonstrating its long-circulating characteristics. This study provides new and important insights into the electron transfer pathway involved in the heterogeneous Fenton-like process.
研究领域:
材料科学
·
环境科学
·
催化化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）