Small
·
2025
·Vol. 21
·期 19
·2411490
·
IF 12.1
Yujia Zhang,Fuliang Guo,Ao Li,Zhixiong Li,Pengcheng Yuan,Jing Xu,Zhiwei Hu,Liang Yin,Huiling Zhao,Ying Bai,Hong Li
Heteroatoms doping would validly stabilize the structure of Li-rich material and elevate electrochemical performance. For the synthesized Li-rich material, the conventional ex situ doping strategy can only incorporate heteroatoms in the outer particles, diminishing benefits for the internal structure of secondary particles. Recently, in situ doping has been employed to influence topological lithiation and achieve well-distribution in the bulk structure. However, the mechanisms of in/ex situ doping on elevating electrochemical performance for Li-rich material are ambiguous. Herein, by introducing magnesium (Mg 2+ ) ions on the precursor and synthesized Li-rich material, the in situ Mg doping (LRO-Mg1) and the ex situ Mg doping (LRO-Mg2) samples are successfully designed. Characterizations shows that Mg ion tend to incorporate into the Li-rich bulk structure for in situ doping, while they enrich in the surface for ex situ doping. Electrochemical measurement manifest that the in situ Mg doping Li-rich cathode exhibits more elevated high-rate performance, while the ex situ doping Li-rich cathode exhibits more elevated specific capacity, illuminating that enhances bulk structure of Li-rich cathode through in situ doping strategy is more effective than the surface modification (ex situ doping). Ex situ doping may be more effective for surface treatment, contributing to specific capacity improvement.
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ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Jie Qu,Dong Wang,Zu-guang Yang,Zhen-guo Wu,Lang Qiu,Xiao-dong Guo,Jun-tao Li,Ben-he Zhong,Xian-chun Chen,Shi-xue Dou
Composite cathodes have attracted great attention due to the integrated advantages of each pure structure. Also, the component ratio deserves a careful modulation to further improve the corresponding electrochemical performance. Mn-based layer–tunnel hybrid composite became a focus in sodium-ion batteries due to the superiority in terms of high performance, low cost, and nontoxicity. In the previous reports, the structure modulation was carried out via changing the synthesis condition, varying the transition-metal-element ratio, and different ion doping. Also, it is still challenging to explore a more feasible method to simplify the adjustment process. Herein, we introduced Mg2+ into Na sites or transition-metal sites in Na0.6MnO2 and first discovered the doping-site-variation-induced structural adjustment phenomenon. Specifically, Mg doping in transition-metal sites could be beneficial for the growth of the P2-type structure, while layer/tunnel component ratio decreased when locating Mg2+ in Na sites. The P2–O2 phase transformations could be effectively suppressed by locating Mg2+ in both sites in high-voltage regions and thus improve the cycling performance. The designed material, Na0.6Mn0.99Mg0.01O2, could attain a decent capacity of 100 mA h g–1 at 1000 mA g–1 and a satisfied retention of 76.6% after 500 cycles. Additionally, ex situ X-ray diffraction analysis experiments verify the excellent structural stability of Mg-substituted samples during charge–discharge processes. Moreover, the Na0.6Mn0.99Mg0.01O2 also displays superior sodium-ion full-cell properties when merged with hard carbon anode. Thus, this research may indicate a proper novel thread for designing high-performance composite electrodes.
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ACS Applied Energy Materials
·
2018
·
IF 0
Tesfaye Tadesse Gebremariam,Fuyi Chen,Qiao Wang,Jiali Wang,Yaxing Liu,Xiaolu Wang,Adnan Qaseem
The exploration and rational design of cost-effective, highly active, and durable catalysts for oxygen electrochemical reaction is crucial to actualize the prospective technologies such as metal–air batteries and fuel cells. Herein manganese cobalt oxide nanoparticles anchored on carbon nanofibers and wrapped in a nitrogen-doped carbon shell (MCO/CNFs@NC) is successfully prepared. Benefiting from the synergistic effect between the core nanoparticles and nitrogen-doped carbon shell, MCO/CNFs@NC catalyst exhibits oxygen reduction reaction (ORR) activity with comparable onset potential (1.00 V vs RHE) and half-wave potential (0.76 V vs RHE) which is only about 40 mV lower than that of the state of art Pt/C catalyst. Furthermore, the MCO/CNFs@NC catalyst exceeds the Pt/C catalyst by a great margin in terms of stability in alkaline media. Additionally, MCO/CNFs@NC catalyst is strongly tolerant to methanol crossover, promising its applicability as cathode catalyst in alcohol fuel cells. Moreover, MCO/CNFs@NC catalyst exhibits the oxygen evolution reaction (OER) activity with low overpotential of 0.41 V at the current density of 10 mA cm–2 and ORR/OER potential gap (ΔE) as low as 0.88 V, suggesting its strong bifunctionality. The Zn–air battery based on MCO/CNFs@NC catalyst is found to deliver a specific capacity of 695 mA h g–1Zn and an energy density of 778 W h kg–1Zn at a current density of 20 mA cm–2. The mechanically rechargeable Zn–air battery based on MCO/CNFs@NC catalyst is also found to function continually by only reloading the consumed Zn anode and electrolyte. Furthermore, the electrically rechargeable battery based on MCO/CNFs@NC catalyst is found to function for more than 220 cycles with negligible loss of voltaic efficiency. Moreover, MCO/CNFs@NC is found to display a supercapacitive nature with a good discharge capacity of 478 F g–1 at a discharge current density of 1 A g–1.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Wenbo Li,Jinyang Dong,Yong Zhao,Jiayu Zhao,Haoyu Wang,Ning Li,Yun Lu,Jianan Hao,Yujia Wu,Youyou Fang,Yali Li,Qiongqiong Qi,Yuefeng Su,Feng Wu,Lai Chen
Li-rich Mn-based (LMR) layered oxides are considered promising cathode materials for high energy–density Li-ion batteries. Nevertheless, challenges such as irreversible oxygen loss at the surface during the initial charge, alteration of the bulk structure, and poor rate performance impede their path to commercialisation. Most modification methods focus on specific layers, making the overall impact of modifications at various depths on the properties of materials unclear. This research presents an approach by using doping to adjust both surface and bulk properties; the materials with surface and bulk fluoride anion doping are synthesised to explore the connection between doping depth, structural and electrochemical stability. The surface-doped material significantly improves the initial Coulombic efficiency (ICE) from 77.85% to 85.12% and limits phase transitions, yet it does not enhance rate performance. Conversely, doping in bulk stands out by improving both rate performance and cyclic stability: it increases the specific discharge capacity by around 60 mAh g −1 and enhances capacity retention from 57.69% to 82.26% after 300 cycles at 5C. These results highlight a notable dependence of material properties on depth, providing essential insights into the mechanisms of surface and bulk modifications.
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JOURNAL OF HAZARDOUS MATERIALS
·
2026
·
IF 10.6
Fenghua Shen,Chaolong Liu,Jie Yu,Kaisong Xiang,Bangwei Bai,Xin Liang,Guangpeng Sun,Shide Li,Hui Liu
To address the issues of low activity and poor stability of manganese-based catalysts in the catalytic degradation of refractory volatile organic compounds such as chlorobenzene (CB), this study designed a sodium-doped Mn-Cu bimetallic catalyst supported on hydroxyl-rich pseudo-boehmite (PB), denoted as Na-CuMnO x /PB, depending on the route of “support hydroxylation, bimetallic synergy, and alkali metal modification”. The catalyst achieved highly efficient degradation of CB under room temperature with the non-thermal plasma assistance. The PB support significantly increased surface hydroxyl groups and acidity. MnO x /PB showed a degradation efficiency of 85.14 %, superior to the 73.98 % achieved by a conventional Al 2 O 3 -supported catalyst. Cu doping promoted the formation of a Mn-Cu synergistic structure, increasing the surface-adsorbed oxygen to 56.59 % and the Mn(IV)/Mn(III) ratio to 0.63, thereby improving the degradation efficiency to 92.02 %. However, chlorine deposition (Cl content: 3.91 %) caused rapid deactivation. After Na modification, the Na-CuMnO x /PB catalyst exhibited a further increased Mn(IV)/Mn(III) ratio of 0.79, enhanced weak basic and acidic sites. The abundant surface hydroxyl groups and alkaline sodium hydrolysis facilitated HCl generation, achieving an HCl selectivity of 40.95 % with surface chlorine deposition as low as 0.59 %, thereby enabling the catalyst to maintain a degradation efficiency of 95.95 % over 16 h. Mechanism studies revealed the crucial roles of acid-base sites, reactive oxygen species, and metal valence states in CB degradation. The bimetallic system promotes the redox cycling between Cu(II)/Cu(I) and Mn(IV)/Mn(III), enabling continuous regeneration of active species. This work provides new insights for designing highly active and chlorine-tolerant catalysts for low-temperature purification of chlorine-containing VOCs.
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Journal of Water Process Engineering
·
2026
·
IF 6.7
Xiao Liu,Runze He,Jiachen Song,Xinyu Hou,Fei Wang
With the growing severity of environmental pollution, the treatment of organic wastewater and waste plastic bottles has become global concerns. This study explored the feasibility of synthesizing metal-organic composite catalysts using waste PET plastic by a microwave one-step synthesis process with only 4 h. Comprehensive characterizations confirmed that the bimetallic Cu/Mn-PET catalyst outperformed monometallic counterparts and pure BDC-derived catalysts, featuring a more regular polyhedral morphology, good crystallinity and excellent stability. XPS valence state analysis uncovered pronounced synergistic interactions between Cu and Mn. Notably, despite a relatively low specific surface area (11.75 m 2 /g), Cu/Mn-PET featured the highest active site density and exhibited minimal interfacial charge transfer resistance in electrochemical measurements. When combined with PMS-AOPs technology, Cu/Mn-PET achieved nearly 100% degradation efficiency for various pollutants (dyes, antibiotics, phenolic compounds) under optimized conditions, accompanied by substantial mineralization (TOC removal rates above 56.36%). Additionally, the Cu/Mn-PET catalyst also showed strong recyclability with low metal leaching concentrations, as well as good salt tolerance. Furthermore, it was proved that the catalytic mechanism of Cu/Mn-PET involved the combined action of free radical reactions and non-free radical reactions, but the non-free radical based 1 O 2 played a dominant role. Thus, a green and efficient PET microwave one-step conversion technology has been developed to prepare a bimetallic organic composite catalyst with high catalytic activity and stability successfully, which hold significant implications for environmental protection and resource utilization.
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ADVANCED FUNCTIONAL MATERIALS
·
2026
·
IF 19.9
Hongbo Liang,Mengfan Pei,Shuo Zhuo,Rui Xie,Hui Lin,Wenkai Song,Zirui Guo,Xigao Jian,Fangyuan Hu
The high activation barriers for sodium polysulfide conversion during the charge–discharge processes of room-temperature sodium–sulfur batteries lead to sluggish reaction kinetics, thereby resulting in limited practical specific capacities. This simultaneously triggers the shuttle effect, leading to a rapid decay in specific capacity. In this study, we propose a hierarchical (crystalline-atomic) catalytic strategy, where the hierarchical catalyst features both manganese oxide crystalline sites and Mn single-atom sites. The two catalytic sites selectively anchor the sulfur and metal moieties of sodium polysulfides, respectively, exerting a “tearing” effect that weakens the chemical bonds and lowers the activation energy, thereby accelerating the polysulfide conversion. The cathode material synthesized using this method retains a specific capacity of 309 mAh g −1 after 2000 cycles at a current density of 2C, indicating that hierarchical parallel catalysis can effectively mitigate the shuttle effect and accelerate the reaction kinetics. Therefore, this work demonstrates the practical potential of hierarchical parallel catalysis in metal-sulfur batteries and provides a new approach for catalyst design in this domain.
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ACS Applied Materials & Interfaces
·
2026
·
IF 7.8
Xiaoyu Gui,Weiliang Li,Wenbo Liu,Zhongyuan Pei,Zhiqiang Zhao,Canrong Cao,Guifa Long,Kai Wan,Zhiyong Fu,Zhenxing Liang
Despite the high specific capacity of P′2-NaxMnO2 (NMO), its practical application is severely hindered by rapid capacity decay caused by drastic structural evolution. Herein, a P′2-[Na0.57KxZn0.10-x]Mn0.90Ti0.10O2 (NKxZMTO) cathode featuring K+ and Zn2+ as pillar cations is developed to mitigate O2–-O2– electrostatic repulsion and suppress detrimental phase transition. Physicochemical characterization and theoretical calculations reveal that K+ and Zn2+ co-occupy the Nae site, acting as inert pillars in the Na layers. While NMO undergoes an abrupt and irreversible OP4-P′2-P″2 triphase transition, NK0.02ZMTO maintains a high fraction of P layers within the OP4 phase and exhibits a mild and reversible P′2-OP4 biphase transition. This stabilized interlayer evolution arises from the combined effects of K+ and Zn2+: K+ enlarges the Na layer spacing owing to its large ionic radius, while Zn2+ reduces the electron density on O2– through its high positive charge, thereby simultaneously mitigating O2–-O2– electrostatic repulsion in accordance with Coulomb’s law. Benefiting from this structural stabilization, NK0.02ZMTO delivers superior cyclability (99.2% capacity retention after 150 cycles at 100 mA g–1) and a high specific capacity of 180 mAh g–1 at 10 mA g–1. This work provides an innovative strategy for designing highly stable cathode materials.
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ANALYTICA CHIMICA ACTA
·
2026
·
IF 6.1
Yi-Ting Chen,Xiao-Jun Dai,Xi- Qing Xu,Pei Liu,Wen-Ge Zhang,Wen-Rui Zhang,Shu-Xuan Li,Peng Wang,Chun-Hui Gong,Yi Yang
Background Iodide (I − ) serves as a key indicator for monitoring 131 I contamination in marine environments. However, rapid on-site detection remains challenging due to the short half-life of radionuclides and the complex nature of seawater. Traditional nanocatalysts exhibit limited catalytic activity under near-neutral conditions and poor selectivity in high-salinity environments. There is therefore an urgent need to develop a robust, instrument-free analytical platform that can meet on-site environmental monitoring requirements by combining high sensitivity with operational simplicity. Results In this study, Mn-modified MOF-808 (Mn/MOF-808) nanozymes were synthesised using a sustainable aqueous post-synthetic approach. The incorporation of Mn centers significantly altered the electronic structure of the MOF nodes, resulting in exceptional peroxidase-like activity across a wide pH range (3.5-8.0). We found that I − acts as a potent synergistic amplifier, greatly accelerating the catalytic oxidation of chromogenic substrates. The sensing system achieved an ultra-low limit of detection (LOD) of 0.63 nM for I − . To enable point-of-care testing (POCT), we developed a smartphone-integrated platform using a customised WeChat mini-program for digital image colorimetry. The test results showed no significant deviation from those obtained using the standard ICP-MS method. Significance This work presents a cost-effective ($0.104/test), rapid, and user-friendly approach for I − monitoring. The Mn/MOF-808 platform demonstrates superior anti-interference capability in various environmental water samples and simulated seawater (recoveries: 96.5%-103.2%). By bridging advanced nanozyme engineering with mobile digitization, this research offers a practical and scalable solution for real-time environmental monitoring and emergency diagnostics of radioactive contaminants, aligning with the principles of green analytical chemistry.
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BIORESOURCE TECHNOLOGY
·
2026
·
IF 8.2
Youn-Jun Lee,Chohee Yang,Deok Hyun Moon,Eilhann E. Kwon
CO 2 thermochemical treatment yielded MnO x -biochar and CO-rich syngas. • Micro- and mesopore development enhanced BPA adsorption by MnCCB (CO 2 ). • MnO x rich in Mn(IV) and Mn(III) promoted catalytic BPA oxidation. • Char gasification and oxygenate conversion increased yields of CO and H 2 . Adsorptive removal of aqueous organic pollutants is often limited by mass-transfer kinetics to the adsorbent surface. To address this constraint, integrated adsorption-oxidation processes have been widely explored as a strategic measure because they enable in situ degradation of adsorbent-bound organic pollutants, thereby regenerating active sites and prolonging removal performance. However, many such systems require energy inputs and chemical oxidants, which hinder practical implementation. Here, we evaluate MnO x -loaded corncob (CC) biochar produced under a CO 2 atmosphere (MnCCB (CO 2 )) as a bifunctional adsorption-oxidation material for bisphenol A (BPA) removal. Physicochemical characterization showed that CO 2 -assisted fabrication yielded MnO x with a higher oxidation state in MnCCB (CO 2 ) than that in the N 2 -derived analogue (MnCCB (N 2 )). MnCCB (CO 2 ) exhibited increased micro-/mesopore volume and a higher specific surface area. Consistent with these structural advantages, MnCCB (CO 2 ) achieved a BPA removal rate constant of 8.48 × 10 -2 min −1 , outperforming MnCCB (N 2 ) and pristine CC biochars produced under either N 2 or CO 2 . Beyond pollutant removal, Mn-catalyzed CO 2 mediated thermochemical treatment also enhanced syngas formation during MnCCB (CO 2 ) production. This improvement is attributed to selective catalytic reactions between bio-oil and CO 2 , during which CO 2 is converted to CO in the presence of MnO x . Overall, this work demonstrates the potential of CO 2 -assisted thermochemical treatment for the simultaneous production of functional biochar and syngas. Download: Download high-res image (121KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Jiamei Xiang,Yan Lu,Huizi Li,Rujuan Tang,Renjie Zhang
Constructing stable and highly active asymmetric Mn N 3 single-atomic sites integrated with Mn nanoclusters remains challenging. This work develops a facile secondary pyrolysis strategy to fabricate a porous dual-site catalyst (Mn SA /Mn NC -NC) featuring both single-atom Mn N 3 (Mn SA ) and Mn nanoclusters (Mn NC ) sites on nitrogen doped carbon black (NC). The Mn NC not only stabilizes the Mn SA but also enhances the overall conductivity and preserves the hierarchical porous framework, thereby maximizes dual-site exposure and mass transport. This synergy endows Mn SA /Mn NC -NC with outstanding activity for bifunctional oxygen catalysis with half-wave potential of 0.91 V and onset potential of 1.59 V, both surpassing those of commercial noble metal Pt/C and RuO 2 . A liquid zinc-air battery (LZAB) assembled with Mn SA /Mn NC -NC achieves a high power density of 218.0 mW cm −2 and stability exceeding 500 h. Density functional theory (DFT) calculations insightfully reveal the inherent mechanism that Mn NC not only stabilizes asymmetric Mn SA , but also precisely modulates the electronic structure and d-band energy levels, which kinetically optimizes the desorption behavior of reaction intermediates *OH and thermodynamically lowers the reaction energy barrier. This work verifies the critical role of nanoclusters on asymmetric single-atom sites, offering essential guidance to design of high performance catalysts for energy storage devices.
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Catalysts
·
2026
·Vol. 16
·期 2
·112
·
IF 4
Ping Lu,Yan Xie,Xin Zhou,Wei Lu,Qian Xu
The synthesis of Mn-TiO2/TiO2, together with its application as a photoanode for solar flow batteries (SFBs), is reported herein. Both the pure TiO2electrode and the Mn-TiO2/TiO2based composite electrode were prepared using the sol–gel spin-coating technique. The incorporation of a Mn-TiO2layer led to the enhancement of the built-in electric field within the composite photoanode. This enhancement not only improved the light-harvesting capability of the photoanode but also suppressed the recombination of charge carriers, consequently enhancing the photocatalytic efficiency. Furthermore, the optimal annealing temperature and the optimum TiO2loading were systematically controlled and optimized to maximize the photoelectric conversion efficiency of the composite photoanode. Ultimately, the optimized Mn-TiO2composite photoanode was integrated into a monolithic solar flow battery. The results demonstrate that the battery’s photocharging current density reaches 300 μA·cm−2. The photocharging current density was relatively increased by 150%.
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