NANOTECHNOLOGY
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2025
·Vol. 36
·期 14
·145601
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IF 2.8
Xinyu Shi,Libo Deng,Lingna Sun,Qianling Zhang,Xiangzhong Ren,Yongliang Li
Manganese dioxide (MnO2) is recognized as a promising candidate for the oxygen evolution reaction (OER); however, its practical application is hindered by limited active sites and low electrical conductivity. Fluorine (F), known for its strong electron affinity and electronegativity, can modulate the surface electronic structure and physicochemical properties of catalysts. In this study, we synthesized MnO2 nanosheets and fluorine-doped MnO2 (F-MnO2) using simple hydrothermal and ion-exchange methods. We then assessed the influence of fluorine doping on the intrinsic OER activity and stability of these catalysts, as well as their underlying catalytic mechanisms. By manipulating the amount of fluorine introduced and the fluorination temperature, we explored the relationship between varying fluorine concentrations and OER performance. The experimental results show that F-MnO2 exhibits higher OER activity than pristine MnO2. At a current density of 10 mA cm–2, the overpotential required for F-MnO2 is merely 320 mV, substantially lower than that of pristine MnO2. This enhanced performance is ascribed to fluorine doping, which leads to an increased quantity of active Mn3+ centers and oxygen vacancies, along with an expanded electrochemically active surface area. Furthermore, F-MnO2 displays improved stability during the testing period. It maintains long-term stability for over 25 h, further corroborating the catalyst's excellent anti-oxidation and anti-corrosion properties in alkaline water electrolysis.
研究领域:
材料科学
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电化学
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INORGANIC CHEMISTRY
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2024
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IF 4.3
Fu Wan,Ruiqi Liu,Yaoyang Xia,Kaida Hu,Yu Lei,Changding Wang,Sida Zhang,Shufan Li,Da Yang,Yujie Zheng,Weigen Chen
Rechargeable Zn-MnO2 batteries using mild water electrolytes have garnered significant interest owing to their impressive theoretical energy density and eco-friendly characteristics. However, MnO2 suffers from huge structural changes during the cycles, resulting in very poor stability at high charge–discharge depths. Briefly, the above problems are caused by slow kinetic processes and the dissolution of Mn atoms in the cycles. In this paper, a 2D homojunction electrode material (δ/ε-MnO2) based on δ-MnO2 and ε-MnO2 has been prepared by a two-step electrochemical deposition method. According to the DFT calculations, the charge transfer and bonding between interfaces result in the generation of electronic states near the Fermi surface, giving δ/ε-MnO2 a more continuous distribution of electron states and better conductivity, which is conducive to the rapid insertion/extraction of Zn2+ and H+. Moreover, the strongly coupled Mn–O–Mn interfacial bond can effectively impede dissolution of Mn atoms and thus maintain the structural integrity of δ/ε-MnO2 during the cycles. Accordingly, the δ/ε-MnO2 cathode exhibits high capacity (383 mAh g–1 at 0.1 A g–1), superior rate performance (150 mAh g–1 at 5 A g–1), and excellent cycling stability over 2000 cycles (91.3% at 3 A g–1). Profoundly, this unique homojunction provides a novel paradigm for reasonable selection of different components.
研究领域:
材料科学
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能源存储与转换
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Journal of Physical Chemistry C
·
2025
·
IF 3.2
Shixue Zhong,Yan Xin,Li’e Mo,Bijiao He,Fang Zhang,Chen Zhao,Linhua Hu,Huajun Tian
Manganese-based layered compounds offer promising cathode materials for aqueous zinc-ion batteries (AZIBs) due to their high safety, low cost, and environmental friendliness. However, their sluggish reaction kinetics, poor conductivity, and irreversible manganese dissolution result in severe capacity fading. Herein, a simple two-step method is successfully proposed to intercalate Ba2+ ions into layered manganese oxide (Ba-MnO2), which were utilized as cathode materials for AZIBs. Ba2+ ions have been innovatively introduced into the MnO2 cathode, generating abundant oxygen vacancies. Notably, the incorporated Ba2+ spontaneously forms an in situ BaSO4 layer during charging, which functions as a protective cathode electrolyte interface. These improvements promote the conductivity and ion diffusion of MnO2, enabling a reversible MnO2/Mn2+ deposition/dissolution reaction. The Zn//Ba-MnO2 full battery delivers a high capacity of 355 mA h g–1 at 0.3 C and maintains an ultrastable cycling stability of over 1200 cycles even at 3 C. This work provides an innovative strategy and a profound understanding of designing high-performance cathodes for AZIBs.
研究领域:
材料科学
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电化学
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能源存储
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Small
·
2024
·
IF 13
Weixuan Wang,Zhiyuan Bai,Baojun Wang,Xiaorui Yang,Juan Liu,Hao Li,Yaogang Li,Qinghong Zhang,Chengyi Hou,Kerui Li,Hongzhi Wang
Electrochromic (EC) battery technology shows great potential in future “zero-energy building” by controlling outdoor solar transmission to tune heat gain as well as storing the consumed energy to reuse across other building systems. However, challenges still exist in exploring an electrochemical system to satisfy requirements on both ultra-long optical memory (also called bistability) without continuous power supply and high energy density. Herein, an EC battery is proposed to demonstrate ultra-long bistability (>760 h) based on the reversible deposition and dissolution of manganese oxide (MnO 2 ) without the addition of any mediators. A porous low-barrier hydroxylated titanium dioxide (TiO 2 ) interface is incorporated to synergistically enrich Mn 2+ -affinity active sites for deposition and effectively reduce the electron transport barrier of MnO 2 for dissolution, thereby significantly improving the reversibility, high optical modulation (60.2% at 400 nm), and energy density (352 mAh m −2 ). The modification strategy is also verified on the cathode-less button cells with a much higher average coulombic efficiency (99.9%) compared to the batteries without the porous hydroxylated TiO 2 interface (74.6%). These achievements lay a foundation for advancements in both electrochromism and Zn-Mn aqueous batteries.
研究领域:
材料科学
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能源技术
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CHEMICAL ENGINEERING JOURNAL
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2026
·
IF 12.5
Jiang Dai,Yibo Zhang,Shidong Li,Shaohua Zhu,Shuhan Jin,Weina Xu,Lei Zhang
Iron doping regulates lattice strain to stabilize the manganese dioxide framework. • Modifying the local structure suppresses manganese dissolution during cycling. • Strain modulation accelerates calcium storage kinetics and improves robustness. • The optimized cathode delivers high capacity and long cycle life. Calcium-ion batteries (CIBs) have attracted increasing attention owing to the natural abundance and potentially low cost of calcium resources. However, practical CIBs cathodes are broadly hindered by sluggish Ca 2+ diffusion, large polarization, and structural instability upon repeated (de)intercalation. Among Mn-based candidates, α-MnO 2 exhibits a low Ca 2+ diffusion barrier, yet its structure suffers irreversible damage during Ca 2+ insertion/extraction. Herein, we propose a Fe-doping strategy to reconstruct the tunnel skeleton of Mn octahedra in α-MnO 2 , which toughens the lattice and regulates its electronic properties, thereby inhibiting the Jahn-Teller effect and preventing Mn dissolution. The strategic incorporation of Fe induces targeted lattice strain, maintaining the long-range skeletal integrity while precisely modifying short-range local distortions. This strain-driven regulation significantly expedites Ca 2+ transport, yielding a diffusion coefficient of 1.24 × 10 −9 cm 2 s −1 , which is the highest recorded value among Mn-based CIB cathodes. Consequently, the optimized Fe-doped α-MnO 2 delivers high rate performance, achieving capacities of 201, 161, 145, 132, and 111 mAh g −1 at 0.1, 0.2, 0.3, 0.5, and 1.0 A g −1 , respectively. Furthermore, it exhibits a long-term cycle life by retaining 74 mAh g −1 after 3000 cycles at 1 A g −1 , providing a rational design paradigm for advanced Mn-based cathodes in CIBs.
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ACS Applied Polymer Materials
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2026
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IF 5.2
Juntong Meng,Yongshuo Zhang,Xiongfei Du,Wei Zhang,Tiantian Li,Xinya Wang,Mingxing Chen
Formaldehyde (HCHO), a hazardous volatile organic compound (VOC) in indoor environments, urgently requires efficient abatement strategies. MnO2 is renowned for its excellent catalytic activity and enables effective degradation of HCHO at low temperatures. In this study, MnO2 nanorods (NRs) were successfully grown on polypropylene (PP) nonwoven fabric via hydrothermal synthesis, yielding MnO2 NRs @ PP composite material with integrated HCHO removal, antibacterial, and photocatalytic functions. pH value and temperature critically regulated MnO2 morphology. Increasing pH raised the aspect ratio of MnO2 NRs, which transitioned to MnO2 nanoparticles (NPs) when the pH value was above pH 3.5. Higher temperatures promoted MnO2 NRs formation, yet beyond 150 °C, excessive refinement led to MnO2 NRs agglomeration and partial PP fiber melting. Optimal performance was achieved at pH 3.5 and 150 °C, where the composite exhibited a high HCHO removal efficiency of 55.1% along with notable antibacterial and photocatalytic properties. This work provides a feasible synthesis strategy for multifunctional composites that can be applied in indoor air purification and environmental remediation.
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ACS Applied Materials & Interfaces
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2026
·
IF 7.8
Xinyi Guo,Mengmeng Wang,Danyang Qu,Hao Cui,Jiajing Gong,Qinglin Shen,Yang Han,Xingqi Pan,Zhenbao Liu,Meilin Shi
Sonodynamic therapy (SDT) offers a noninvasive strategy for tumor ablation through ultrasound-activated sonosensitizers that generate reactive oxygen species (ROS); however, its therapeutic efficacy is often limited by tumor hypoxia. Herein, we report the rational design of a multifunctional theranostic nanoplatform, HA-MnO2-TCPP nanoflowers, that integrates active tumor targeting, dual ROS amplification, and magnetic resonance imaging (MRI) guidance for synergistic sonodynamic and chemodynamic therapy. The MnO2 nanoflowers were loaded with the sonosensitizer 4-carboxyphenyl porphyrin (TCPP) and surface-modified with hyaluronic acid (HA). This design enables CD44 receptor-mediated tumor targeting and tumor microenvironment-responsive degradation. Upon exposure to the mildly acidic and reductive tumor microenvironment, MnO2 is reduced to Mn2+, leading to glutathione depletion, in situ oxygen generation, and alleviation of hypoxia, while the released Mn2+ catalyzes Fenton-like reactions to generate highly toxic hydroxyl radicals (•OH) and simultaneously serves as an efficient T1-weighted MRI contrast agent. Meanwhile, TCPP enhances singlet oxygen (1O2) generation upon ultrasound activation, enabling effective sonodynamic therapy. Through the coordinated activation of SDT and CDT under MRI guidance, HA-MnO2-TCPP nanoparticles achieve precise and efficient tumor suppression without reliance on photothermal mechanisms. This work provides a robust paradigm for tumor microenvironment-responsive nanotheranostics and highlights the potential of ultrasound-activated strategies for precision cancer therapy.
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JOURNAL OF POWER SOURCES
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2026
·
IF 8.4
Ying Li,Fangyuan Qiu,Wanyou Huang,Xuesong Tian,Limei Wang,Ruixia Chu,Hang Li,Yibo Gao
Developing low-cost, high-performing non-noble-metal catalysts for the oxygen reduction reaction (ORR) to replace Pt-based catalysts for practical metal-air batteries remains an enormous challenge. Herein, Co 3 O 4 /α-MnO 2 /C composite catalysts with different mass ratios are synthesized, and a heterostructured Co 3 O 4 /α-MnO 2 /C catalyst is successfully constructed. Benefiting from the synergistic interaction between Co 3 O 4 and α-MnO 2 , together with the enhanced conductivity imparted by the carbon support, the catalyst exhibits outstanding electrocatalytic activity. Furthermore, derivative analysis of the LSV curves is employed to accurately determine the ORR onset potential and half-wave potential, providing a quantitative approach for evaluating the electrochemical activity of the Co 3 O 4 /α-MnO 2 /C catalyst. Furthermore, a Zn-air battery driven by the Co 3 O 4 /α-MnO 2 /C catalyst shows excellent electrochemical performance, delivering a high open-circuit voltage of 1.458 V and long-term cycling stability for 300 h. Notably, its overall performance is close to that of commercial Pt/C catalysts. This work highlights the considerable promise of non-noble-metal catalysts for renewable energy storage and conversion applications.
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
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2026
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IF 4.8
Yong Zhu,Cuifeng Jiang,Jinjiang Yao,Xinmeng Wu
Resolving the aggregation of osmium (Os) nanozyme is important for improving its catalytic activity. Herein, Os nanoparticles-Bovine serum albumin-MnO 2 composite nanosheets (OsNPs-BSA-MnO 2 ) were synthesized by loading Os NPs on BSA-MnO 2 nanosheets. The Os NPs well dispersed on the surface of the nanosheets. The composite exhibited specific peroxidase-like activity with negligible oxidase-like activity. The catalytic mechanism was proved due to the generation of ·OH. Steady-state kinetics revealed stronger affinity for both H 2 O 2 and 3,3′,5,5′-tetramethylbenzidine (TMB) substrate. Interestingly, OsNPs-BSA-MnO 2 composite nanosheets exhibited a much lower activation energy than other osmium-based nanozymes, indicating superior catalytic performance. Moreover, ascorbic acid could effectively inhibit the catalytic activity of composite nanosheet. Thus, a colorimetric method for ascorbic acid detection was established with the limit of detection (LOD) of 1.69 μM and excellent selectivity. For practical application, ascorbic acid in Water-soluble C100 and fetal bovine serum was detected with satisfactory recoveries
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APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Wenjing Zhou,Fan Zhang,Liming Xu,Danqin Li,Jie Li,Jiashuo Lv,Yufei Hu,Meisi Yu,Furui Lin,Danhua Zhu,Jian Hou,Weiqiang Zhou
Ce-doped MnO 2 with oxygen vacancies modulates Pt electronic structure. • Pt/Ce-MnO 2 /MWCNTs shows 9.69 A mg Pt -1 for methanol oxidation under light. • Electron-rich Pt surface shows weakened CO adsorption at 0.94 V vs. RHE. • Synergy of defect engineering and photocatalysis boosts MOR durability. The development of efficient and CO-tolerant anode catalysts is critical for advancing direct methanol fuel cells (DMFCs). Herein, we report a rationally designed photoelectrocatalyst comprising ultrafine Pt nanoparticles anchored on Ce-doped MnO 2 supported by highly conductive multi-walled carbon nanotubes (Pt/Ce-MnO 2 /MWCNTs). Ce incorporation induces abundant oxygen vacancies within the amorphous MnO 2 matrix, which modulate the local electronic structure and facilitate strong metal-support interactions. This results in electron-enriched Pt surfaces with weakened CO adsorption, as evidenced by negative shifts in Pt 4f binding energies and improved CO stripping performance. Under simulated solar illumination, the Pt/Ce-MnO 2 /MWCNTs catalyst delivers a mass activity of 9.69 A mg Pt -1 toward methanol oxidation, representing a 46.6% enhancement over that under dark conditions and exceeding undoped Pt/MnO 2 /MWCNTs and commercial Pt/C catalysts. This performance is attributed to the synergistic interplay of (i) oxygen-vacancy-mediated electronic modulation, (ii) efficient charge transport via the MWCNT network, and (iii) photoexcited charge carriers from Ce-MnO 2 that actively participate in oxidizing poisoning intermediates. The catalyst also exhibits CO tolerance with an onset potential of 0.94 V and good long-term durability, retaining 82.3% of its initial activity after 500 cycles. This work demonstrates strategies for designing high-performance DMFC anodes through defect engineering and light harvesting. Download: Download high-res image (150KB) Download: Download full-size image
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ACS Applied Energy Materials
·
2025
·
IF 5.5
Zihao Song,Zhen Du,Yong Yang,Wensheng Wang,Yaqin Huang
Manganese dioxide (MnO2) emerges as a promising cathode active material for aqueous zinc-ion batteries (AZIBs) due to its inherent safety and environmental friendliness. However, various crystalline forms of MnO2 (e.g., α- or β-MnO2) exhibit low structural stability or limited ion diffusion, resulting in poor cycling stability, particularly under high current density. Herein, a MnO2 polymorph (PM-MnO2) is constructed via the in situ doping of trace potassium ions (K+) into β-MnO2, remarkably addressing these challenges. By leveraging the high structural stability of the β-MnO2 phase and the facilitated ion diffusion in α-MnO2 phases, PM-MnO2 with a low atomic ratio of K to Mn of only 0.02 demonstrates excellent electronic and ionic conductivity, thereby achieving enhanced charge storage kinetics as a cathode material. The assembled AZIBs exhibit a high specific capacity of 295.3 mA h g–1 at a charge–discharge rate of 10 C (1 C = 308 mA h g–1), with an average capacity decay rate of only 0.017% per cycle over 3000 cycles, indicating significant potential for practical applications. This research provides experimental insight into how K+ doping affects the crystal structure of MnO2 and highlights the crucial role of polymorphic materials in enhancing the performance of MnO2-based AZIBs.
研究领域:
材料科学
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能源存储与转换
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Chuanxi Zhao,Zhi Zhu,Kai Chang,Shijie Wang,Jiasheng Huang,Qin Wang,Lan Xia,Chunfei Zhang,He Miao
As one of the most successful aqueous zinc-based batteries, the alkaline Zn-MnO 2 batteries (AZMBs) suffer from the low utilization of MnO 2 . This work proposes a simple approach to address this issue by optimizing the graphite contents and microstructures in the cathode. It is found that the cathode of AZMB containing 9 wt% graphite exhibits the best electrochemical performances, achieving the discharge capacities of 240.6 mAh and 196.25 mAh at 10 and 25 mA, increasing by 7.7 % and 9.0 % compared to that of the commercial AZMBs, respectively. Additionally, by adopting the fully-expanded graphite with large specific surface area and thin thickness, the discharge capacities of AZMB increase by 8.7 % and 8.8 % at 10 and 25 mA, compared to that of the commercial AZMBs, respectively. The improving discharge properties of AZMBs with proper graphite content and microstructure can be ascribed to the high conversion rate of MnO 2 into the discharge product of MnOOH due to the improved conductive network. This work provides a valuable insight for the development of the aqueous Zn-based batteries.
研究领域:
材料科学
·
电化学
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