JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Lingqian Ye,Hao Fu,Jianeng Ji,Zhiqiang Wu,He Ren,Yu Zhang,Minjie Shi,Jun Yang
The Mn-based Prussian blue analogs (PBAs) have garnered significant attention due to their high specific capacity, stemming from the unique multi-electron reactions with Na + . However, the structural instability caused by multi-ion insertion impacts the cycle life, thus limiting their further application in aqueous sodium-ion batteries (ASIBs). To address this issue, this work employed an in situ epitaxial solvent deposition method to homogeneously grow Ni hexacyanoferrate (NiHCF) on the surface of MnPBA, which can effectively overcome the de-intercalation instability. The resulting heterostructured MnPBA@NiHCF integrates the multiple redox-active centers of MnPBA with the confinement ability of the outer NiHCF layer, thereby maintaining overall structural stability. As a cathode material for ASIBs, MnPBA@NiHCF achieves a reversible specific capacity of 66.2 mAh/g after 200 cycles at 1 A/g, significantly outperforming the single-component MnPBA and NiHCF, respectively. Moreover, it demonstrates ultralong cycling stability with only 0.0002 % capacity fade per cycle over 20,000 cycles at 10 A/g. Extensive kinetic analyses further confirm its superior Na + diffusion behaviors with disclosed redox mechanism through the comprehensive in situ Raman and ex situ analysis. A full cell built with a polyimide (PI) anode achieved an energy density of up to 59.9 Wh kg −1 , displaying a power output of 1200.4 W kg −1 and exceptional cycle stability. This work provides innovative insights for developing stable PBA cathodes for ASIB applications.
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INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Kaiyun Zhang,Wenxiu He,Fanyan Zeng,Yuhe Huang,Taiyang Wang,Meilan Xie,Dui Ma,Yang Pan
Addressing the kinetic mismatch and structural instability challenges in sodium-ion hybrid capacitor (SIHC) anodes, this study develops an N-doped carbon composite integrating amorphous Mn–S with adjacent low-nucleated MnS (a–Mn-S/MnSLN@NC). This architecture synergistically enhances mechanical stress buffering and charge transfer kinetics via the isotropic dynamic bonding of a–Mn-S and the high-affinity sites of MnSLN. The 3D C–S–Mn covalent bonds in the a–Mn-S stabilize MnSLN through atomic anchoring, homogenizing volume strains and exposing uncoordinated S active sites to elevate Na+ adsorption density. Theoretical calculations reveal that the proximity-induced d–p orbital hybridization reconstructs the electron-donor characteristics of S sites, creating an asymmetric electronic configuration. The electron-rich a–Mn-S serves as efficient Na+ trapping centers, while the electron-deficient MnSLN facilitates rapid electron transfer. This configuration endows the composite with superior Na+ adsorption energy and charge transfer efficiency over pure MnS. Consequently, the a–Mn-S/MnSLN@NC anode delivers a high reversible capacity of 597 mAh g–1 at 0.1 A g–1 and retains 90.5% capacity after 3500 cycles at 10.0 A g–1. The assembled SIHCs achieve exceptional energy/power densities (186 Wh kg–1 and 9576 W kg–1). This work elucidates the mechanism of adjacent asymmetric configurations for enhanced Na+ storage, offering a novel strategy for designing high-performance SIHCs.
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CHEMISTRY-A EUROPEAN JOURNAL
·
2024
·Vol. 30
·期 25
·e202400088
·
IF 3.9
Xin Li,Xin Lai,Qingquan Kong,Xuguang An,Jing Zhan,Xiaolei Li,Xiaonan Liu,Weitang Yao
P2-type layered manganese-based oxides have attracted considerable interest as economical, cathode materials with high energy density for sodium-ion batteries (SIBs). Despite their potential, these materials still face challenges related to sluggish kinetics and structural instability. In this study, a composite cathode material, Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @Na 3 V 2 O 2 (PO 4 ) 2 F was developed by surface-coating P2-type Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 with a thin layer of Na 3 V 2 O 2 (PO 4 ) 2 F to enhance both the electrochemical sodium storage and material air stability. The optimized Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @5wt %Na 3 V 2 O 2 (PO 4 ) 2 F exhibited a high discharge capacity of 176 mA h g −1 within the 1.5-4.1 V range at a low current density of 17 mA g −1 . At an increased current density of 850 mA g −1 within the same voltage window, it still delivered a substantial initial discharge capacity of 112 mAh g −1 . These findings validate the significant enhancement of ion diffusion capabilities and rate performance in the P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 material conferred by the composite cathode. Graphical We propose a composite cathode material, Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @Na 3 V 2 O 2 (PO 4 ) 2 F, featuring synergistic modification through doping and coating. The optimized Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @5wt %Na 3 V 2 O 2 (PO 4 ) 2 F exhibited a high discharge capacity of 176 mAh g −1 within the 1.5–4.1 V range at a low current density of 17 mA g −1 . At an increased current density of 850 mA g −1 within the same voltage window, it still delivered a substantial initial discharge capacity of 112 mAh g −1 .
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2024
·
IF 4.1
Kai Lin,Zuming He,Long Shen,Jiangbin Su,Zhengyi Huang,Yongmei Xia,Yong Wang
To address the issue of poor cycling performance and capacity of Mn-based Prussian Blue analogues (PBAs) as sodium ion battery cathodes due to the solubility of Mn ions, this study utilizes the strong chelating property of EDTA 2− with Mn ions to hydrothermally modify the sodium-rich monoclinic Na 1.75 Mn[ Fe ( CN ) 6 ] 0.94 ·2.25H 2 O synthesized under high salt conditions, in order to enhance its capacity and stability. The modified Na 1.93 Mn[Fe(CN) 6 ]•2·.38H 2 O exhibits a discharge capacity of 156.16 mAh/g at 10 mA g −1 (91.86 % of the theoretical capacity), it still retains the highest discharge capacity (70.23 mAh/g) after 500 cycles at 100 mA g −1 . Based on experimental analysis, the improvement in the electrochemical performance of PBAs was attributed to three main factors: (1) enhanced Na content; (2) suppression of defects; and (3) improved crystal structure.
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Fuel Cells
·
2017
·Vol. 17
·期 5
·723-729
·
IF 1.706
Y. Yi,J. Huo,W. Wang
Molecular simulation method was firstly used for analyzing the energy of aluminum alloy systems alloyed by Mg, Ga, Zn and Mn. Based on the analyses, Al-Mg, Al-Ga, Al-Zn, Al-Mn alloys were metallurgically prepared. The structures, electrochemical activities and utilization ratios were characterized by X-ray diffraction patterns (XRD), anodic polarization measurement and galvanostatic discharge. The calculated energies of the aluminum alloy systems increase in the following order: Al< Al-Mn < Al-Mg < Al-Zn < Al-Ga. The absolute values of the open circuit potentials of the alloys measured in alkaline solution rank in the following orders: φ Al-Ga alloy > φ Al-Zn alloy > φ Al-Mg alloy > φ Al-Mn alloy and the order is consistent with the calculated energies. The results indicate that molecular simulation based on the first-principles is a useful method in the alloying design and thermodynamic performance prediction. Alloy additives Zn and Ga effectively change the open circuit potential of metal aluminum to a more negative potential. In addition, alloy additive Zn increases the charge transfer resistance of Al→Al 3+ , which decreases the discharge current density. Alloy additive Mg diminishes the grain size of the alloy and notably enhances the discharge current density. Alloy additive Mn improves the utilization ratio remarkably when discharging in alkaline solution.
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MICROCHEMICAL JOURNAL
·
2026
·
IF 5.2
Wen Qing Jia,Ting Ting Li,Jian Bing Li,Zhen Chen,Hui Xi Li,Lei Han
It is a pressing necessity to establish a valid approach for precise and sensitive monitoring of the acetylcholinesterase (AChE) activity and its inhibitor, organophosphorus pesticides (OPs), for public health and food safety. Herein, a dual-mode colorimetric sensor was designed for sensitive and accurate sensing of AChE and OPs based on Mn metal-organic gels (Mn-MOGs)-derived multifunctional nanozyme. The nanozyme was synthesized by pyrolyzing the Mn-MOGs, which show superior oxidase (OXD)-like and laccase (LAC)-like activities. It can catalyze the 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation into blue TMB (oxTMB) and 2,4-dichlorophenol to generate the red quinone imine (QI). The OXD-like and LAC-like activities can be inhibited by the thiocholine generated from AChE hydrolysis of acetylthiocholine (ATCh), causing a significant reduction in the absorption of oxTMB and QI. OPs can restrain the AChE activity, which prevents the hydrolysis of ATCh, causing the recovery of absorption of oxTMB and QI. Thus, a dual-mode colorimetric sensor was designed for sensing of AChE and OPs. Moreover, this sensor was also utilized to detect OPs in real samples with satisfactory results. This study not only provides a valid way for sensitive and accurate monitoring of AChE and OPs but also affords new insights for designing multifunctional nanozymes used to develop multimodal sensors.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2020
·
IF 3.99
Hui Liu,Hao Guo,Wenqin Yao,Longwen Zhang,Mingyue Wang,Tian Fan,Wenhu Yang,Wu Yang
MOF-derived hydroxides provide a promising platform for high performance supercapacitors as electrode materials. Herein, a novel manganese-nickel double hydroxide (MnNiDH) composite with special morphology has been successfully prepared by alkalizing the precursor Mn/Ni-MOF-74. Obtaining electrode material inherits the spear-shaped morphology of the precursor well and possesses a smaller particle size by potassium hydroxide treatment. The smaller particle size and rich microporous structure can shorten the ion or proton transport path, thereby improve its electrochemical activity and utilization. Benefiting from these specific properties, the resultant MnNiDH composite demonstrates a high specific capacitance of 2498 F g −1 at a current density of 1A g −1 . The assembled aqueous device exhibits high energy density of 58.53Wh kg −1 , meanwhile the all-solid-state device also displays energy density of 30.63 Wh kg −1 based on the outstanding voltage window of 0∼2.1 V. These results suggest that as-synthesized MnNiDH hold great potential for practical applications in the energy storage field.
研究领域:
材料科学
·
储能
·
电化学
·
纳米材料
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·Vol. 65
·期 28
·15176-15189
·
IF 3.9
Wu Zuhao,Wu Shengji,Han Zhongxi,Li Siyue,Wang Hui,Yin Haoyong,Liu Juanjuan,Zhou Jie
Cerium-based
composite oxides have been intensively investigated
for the elimination of elemental mercury (Hg 0 ) from natural
gas and flue gas. Because of distinct operational conditions, the
required types of active oxygen species in composite oxides differ
substantially between these two atmospheric environments. Nevertheless,
the diversity of oxygen species has led to considerable debate regarding
the active sites responsible for the Hg 0 removal. The exploration
of these oxygen species is essential as it directly guides the rational
design of active sites in sorbents. In this work, we designed and
synthesized sorbents with different oxygen species and systematically
investigated the contributions of these oxygen species in the Hg 0 removal reaction. Cu–Mn–Ce (CMC) composite
oxides were successfully prepared by the coprecipitation method. Characterization
results indicate that the incorporation of Cu and Mn ions into the
CeO 2 lattice indeed significantly increases the concentration
of oxygen vacancies and releasable lattice oxygen. The Hg 0 removal efficiencies of CMC for natural gas and flue gas can be
maintained above 90.0% and 99.0%, respectively, even under a high
gas hourly space velocity of 480,000 h –1 . Furthermore,
CMC exhibits superior cyclic stability and high SO 2 resistance
for Hg 0 removal. Combined with the results from adsorption
tests and characterization, it can be concluded that the surface-active
oxygen species determine the catalytic oxidation and adsorption efficiency
of Hg 0 , while the releasable lattice oxygen species ensure
the continuous supply of active oxygen under extremely oxygen-deficient
conditions.
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TALANTA
·
2026
·
IF 6.7
Linying Cheng,Xiang Liu,Zixin Zhang,Jing Liu,Jianru Tang,Xiaohua Zhu,Youyu Zhang,Meiling Liu
Copper ions (Cu 2+ ) are essential micronutrients but become hazardous when accumulated in excess, necessitating reliable, sensitive, and field-deployable detection methods. Herein, we report a fluorescent Mn-based MOF nanozyme (Mn-TCPP) that exhibits intrinsic oxidase-like activity, capable of catalyzing the oxidation of non-fluorescent o -phenylenediamine (OPD) to fluorescent 2,3-diaminophenazine (DAP) with an emission peak at 560 nm, while the Mn-TCPP itself displays characteristic fluorescence at 655 nm. Upon exposure to Cu 2+ , the stronger affinity of Cu 2+ toward the porphyrinic TCPP ligand displaces Mn 2+ from the framework, forming Cu-TCPP. This metal-exchange process simultaneously quenches the 655 nm fluorescence of the MOF and attenuates its oxidase-mimicking activity, whereas free Cu 2+ in solution independently catalyzes OPD oxidation, further enhancing the 560 nm emission. Leveraging this dual-response mechanism, we develop a ratiometric fluorescence sensing strategy for Cu 2+ detection based on the intensity ratio F 560 /F 655 . The calibration curve follows a linear equation: F 560 /F 655 = 0.201x-0.001 (0.2-10 μM, R 2 = 0.985) and y = 0.002x+2.061 (10-100 μM, R 2 = 0.994) with the limit of detection (LOD) of 81 nM (S/N = 3). The sensor exhibits excellent selectivity over competing metal ions, and the method reliability is validated by standard addition recovery experiments in real water and rice samples. Furthermore, the Mn-TCPP nanozyme is embedded into an agarose hydrogel matrix, enabling visual, instrument-free monitoring of Cu 2+ contamination: increasing Cu 2+ concentrations induce a discernible fluorescence color transition from orange to yellow under 365 nm illumination. This work presents a tunable MOF platform that exploits competitive targets synchronous modulation of fluorescence and enzyme-mimicking activity, providing a robust, selective, and field-deployable ratiometric sensor for Cu 2+ .
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MICROCHIMICA ACTA
·
2026
·Vol. 193
·期 10
·693
·
IF 5.4
Li Sirui,Wang Shanshan,Chang Guorui,Yang Yaoxing,Feng Hui,Xue Haoqian,Zhang Li,Luo Manlin,Liu Jing,Li Bowen,Xu Shuxia
To enable rapid and reliable on-site monitoring of organophosphorus pesticides a novel portable dual-mode biosensor has been developed which integrates electrochemical and colorimetric detection into a single freeze-dried bioactive capsule. This innovative design supports instrument-free operation and provides dual-signal cross-validation. The sensor is based on a newly synthesized Mn/Ce bimetallic metal-organic framework (MOF) nanozyme with high oxidase-like activity, co-immobilized with acid phosphatase (ACP) within a mannitol- and sucrose-stabilized lyophilized capsule to ensure long-term stability and field readiness. In the presence of malathion, the pesticide selectively inhibits ACP, thereby restoring the MOF's catalytic activity and enabling the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). The resulting signal is detected both visually and through chronoamperometry after conversion to a yellow diimine product. This approach achieves a wide linear detection range of 1–2000 nM and an exceptionally low detection limit of 0.06 nM for malathion, along with high accuracy evidenced by recoveries of 93.31%-104.03% in real water samples. This work establishes a field-deployable and user-friendly sensing platform that combines innovative material design with integrated dual-mode detection, offering a robust and practical strategy for on-site environmental monitoring. Graphical
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MOLECULAR CRYSTALS AND LIQUID CRYSTALS
·
2026
·
IF 0.7
Hu Wang,Hua Shi,Pengxiao Guo,Li Sun,Chaochuang Yin,Yinyan Wang,Kang Chen,Yadong Zhou
A new Mn(II) complex, Mn(C36H34N2O8)·2CH3OH (1), containing a sexidentate N2O4 bis-Schiff base ligand, was synthesized and structurally characterized. X-ray analysis revealed that Mn(II) is hexacoordinated by two imine N atoms, two ether O atoms, and two carboxylate O atoms in a distorted octahedral geometry. DFT calculations at the B3LYP/6–311G** level were used to examine atomic charges, frontier molecular orbitals, molecular electrostatic potential, QTAIM, ELF, IRI, and Hirshfeld surfaces, providing detailed insight into its electronic structure. Molecular docking with CT-DNA suggested that the complex may act as a DNA-binding agent with potential biomedical applications.
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ENVIRONMENTAL RESEARCH
·
2026
·
IF 8.2
Jianying Huang,Yun Xing,Dechen Kong,Xiaohua Jing
The discharge of pharmaceutical wastewater containing antibiotics and the accumulation of metallurgical solid waste represent two pressing environmental challenges. This study presents a novel “waste-to-resource” solution by molecularly engineering the neutralization slag from vanadium extraction into a Mn-functionalized hydroxyapatite precursor (Mn-HAP-VNR) for enhanced antibiotic removal. Systematic optimization of hydrothermal synthesis identified a condition (pH 7, 0.7 M (NH 4 ) 2 HPO 4 , Ca/Mn=2:1), yielding Mn-HAP-VNR with exceptional Langmuir maximum adsorption capacities of 322.58 mg·g -1 for norfloxacin (NOR) and 214.79 mg·g -1 for tetracycline (TC), significantly outperforming the undoped material and many reported adsorbents. Comprehensive characterization confirmed the successful isomorphous substitution of Ca 2+ by Mn 2+ within the HAP lattice. The introduced Mn 2+ sites were identified as key active sites; based on experimental measurements, Mn doping enhanced the adsorption capacity by over 213% for TC and 628% for NOR compared to undoped HAP. Adsorption isotherms and kinetics were best described by the Langmuir and pseudo-second-order models, respectively, indicating monolayer chemisorption as the dominant mechanism. In-depth spectroscopic analyses (FTIR and Raman) deciphered the distinct chemisorption pathways: NOR primarily coordinates via a bidentate complex between its deprotonated carboxylate group and surface Mn 2+ /Ca 2+ sites, whereas TC engages through synergistic interactions involving its phenolic hydroxyl and ketone carbonyl groups. Thermodynamic studies corroborated the endothermic and spontaneous nature of the process. This work not only demonstrates the superior performance of a waste-derived adsorbent but also elucidates the molecular-level engineering mechanism, establishing a viable closed-loop strategy for the valorization of industrial residue into a high-performance, tailor-made material for targeted water decontamination.
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