COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2026
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IF 5.4
Guangwei Wu,Liu Yang,Bin Wang,Weiguo Tu,Hao Jiang,Xuejun Pan
Mn AOS controlled the partitioning of catechol interfacial redox pathways. • Low-Mn AOS birnessite sustained late-stage catechol depletion and Mn release. • Persistent organic radicals revealed single-electron transfer during catechol oxidation. • Radical accumulation was decoupled from catechol depletion and Mn release. • Anions and organic acids reshaped Mn AOS -dependent interfacial reactivity. Phenolic compounds are reactive components involved in organic carbon transformation and contaminant fate in soils and sediments. Manganese oxides are important natural oxidants, yet how the Mn average oxidation state (Mn AOS ) regulates phenolic interfacial oxidation on birnessite remains unclear. Here, four birnessite samples with different Mn AOS values were synthesized, and catechol was used as a representative o-diphenolic compound to probe Mn AOS -dependent interfacial redox processes. All samples retained the layered δ-MnO 2 phase, whereas decreasing Mn AOS from 3.39 to 3.28 altered layer stacking, pore structure, local Mn–O environments, and initial electrochemical responses. Catechol was rapidly depleted in all systems with simultaneous dissolved Mn release. HB3 and HB4 showed stronger sustained transformation in the middle-to-late stage, with C t /C 0 decreasing to 0.09 and 0.07 at 360 min, respectively, and dissolved Mn reaching 3.02 and 3.13 mg L −1 . EPR detected oxygen-centered semiquinone-like persistent organic radicals near g = 2.0046, but radical intensities were not fully synchronized with terminal catechol depletion or Mn release. Post-reaction Raman, FTIR, SEM, and XPS further indicated organic deposition, Mn valence reduction, and changes in the surface morphology and oxygen environment. Weakly alkaline conditions enhanced catechol transformation, whereas HCO 3 - , HPO 4 2- , and citric acid suppressed the reaction. Overall, Mn AOS -dependent differences were observed in the stage-dependent coupling among catechol transformation, dissolved Mn release, persistent organic radical accumulation, and surface evolution. These findings identify Mn AOS as an important descriptor of birnessite interfacial reactivity toward phenolic compounds. Download: Download high-res image (195KB) Download: Download full-size image
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Chuanming Zhang,Chunyang Shen,Zhenggang Huang,Hongxin Xu,Yaxiong Zeng,Baohong Guan
Ammonia nitrogen (NH 4 + -N), which exists in the dominant form of ammonium ion (NH 4 + ) under the pH of 6.5–8.5, is one of the regular indexes and the most important pollutants in drinking water. The selective conversion of NH 4 + -N into harmless substances is urgently needed and also a great challenge. Herein we propose a new NH 4 + -N conversion pathway based on a catalytic ozonation process with birnessite-type MnO 2 (δ-MnO 2 ) catalysts. The δ-MnO 2 exhibits a superior performance for NH 4 + -N (1.0 mg/L) removal in adsorption (8.26 %) and oxidation (44.6 %) as well as up to 95.2 % of N 2 selectivity, surpassing almost all the reported O 3 -based catalysts. Unlike the traditional radical oxidation, a singlet oxygen ( 1 O 2 )-dominated nonradical oxidation pathway is confirmed for the efficiently selective conversion of NH 4 + -N to N 2 through the successive dehydrogenation, leading to a 15.0-fold enhancement in NH 4 + -N oxidation rate compared with ozone oxidation. The Mn(III)/Mn(IV) redox sites and surface lattice oxygen in δ-MnO 2 act as the active sites promoting the decomposition of O 3 into •O 2 − and then 1 O 2 via electrons transfer. In application, δ-MnO 2 catalytic ozonation effectively removes NH 4 + -N in real drinking water and presents excellent stability. This work finds a nonradical reaction mechanism in catalytic ozonation for NH 4 + -N selective conversion to N 2 , and solidly solves the problem of low-concentration NH 4 + -N removal from drinking water under the limited pH of 6.5–8.5 condition.
研究领域:
环境科学
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水处理
·
催化
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污染物去除
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DOI
高影响因子
Advanced Materials Interfaces
·
2020
·Vol. 7
·期 12
·1902127
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IF 4.948
Shiwei Liu,Kai Li,Tao Hu,Xiaodong Wu,Haiyong Ao,Youtao Xie,Xuebin Zheng
The osteoblast-function associated integrin–ligand interactions are known to be dependent on divalent cations, but there is scarce information about the effect of Ca 2+ and Mg 2+ adsorption properties of an implant surface on integrin α 5 β 1 –fibronectin interactions and the subsequent osteoblast behavior. Cation adsorption properties are closely associated with the extent of structural defects in materials. Here, the birnessite-type MnO 2 coatings with different amounts of manganese vacancy ( V Mn ) are prepared on Ti substrates via hydrothermal treatment (denoted as 1M100-Ti, 5M100-Ti, and 5M120-Ti). The 5M120-Ti surface with hierarchical flower-like structure and the most stacked [MnO 6 ] layers possess the highest V Mn content, which is determined by the ratios of Mn 3+ /Mn 4+ and K/Mn. The increased V Mn content enhances the Ca 2+ and Mg 2+ adsorption properties of the birnessite coatings. When immersed in Ca 2+ /Mg 2+ aqueous solution, the birnessite coatings significantly promote fibronectin adsorption and the exposure of cell-binding domains on adsorbed fibronectin with 5M120-Ti showing the greatest enhancement. Accordingly, the 5M120-Ti surface provides more α 5 β 1 -integrin-specific instructions to MC3T3-E1 preosteoblasts capable of enhancing spreading and osteoblastic differentiation compared to two other samples. This study may provide a prospective approach of modulation of integrin–ligand interactions for controlling cell behavior by adjusting metal vacancies in metal oxides coatings.
研究领域:
材料科学
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生物医学工程
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细胞生物学
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Junxin Jia,Yaqi Jiao,Jiaying Gu,Chunnan Zhou,Qin Zhou,Hui Li,Sa Wang,Hongtao Shi,Li Li
Phenanthrene (PHE) is a typical polycyclic aromatic hydrocarbon (PAH) pollutant characterized by biological toxicity and environmental persistence. To enhance its degradation efficiency, a composite system combining birnessite with Novosphingobium sp. HDJX-2 was established to investigate the synergistic mechanism between minerals and functional bacteria. Gas chromatography-mass spectrometry (GC–MS), coupled with transcriptomic and metabolomic analyses, was employed to elucidate the molecular regulation and metabolic pathway reconstruction involved in PHE degradation in the composite system. The results demonstrated that PHE was metabolized by the strain through a series of reactions, including aromatic ring dioxygenation, ring cleavage, and decarboxylation, leading to the formation of acetyl-CoA via the phthalic acid pathway and ultimately achieving complete mineralization through the tricarboxylic acid (TCA) cycle. This degradation process was accompanied by extensive transcriptional regulation and metabolic pathway enrichment, with 967 differentially expressed genes and 125 significantly altered metabolites identified. Further analysis revealed the upregulation of genes associated with biofilm formation ( rcsA , 2.31-fold upregulation) and energy metabolism ( Rbs , 2.47-fold upregulation), along with enhanced pathways, such as arachidonic acid metabolism (1.85-fold upregulation) and riboflavin metabolism (1.13-fold upregulation). These changes contributed to improved membrane transport, oxidative stress response, and energy production, thereby significantly promoting PHE degradation. Notably, pathways related to amino acid metabolism and carbon fixation were significantly enriched, further enhancing the system's degradation capacity. This study established an efficient and stable mineral–microbial synergistic system and revealed its multilayered regulatory mechanisms in PAH bioremediation, offering theoretical insights and practical strategies for ecological restoration.
研究领域:
环境微生物学
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生物修复
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土壤污染
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组学科学
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环境化学
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Yunhao Hu,Depeng Zhang,Zhengkun Liu,Hanwen He,Hongyang Wang,Chao Deng,Sen Zhang
Aqueous Zn-ion batteries with high theoretical capacity, low price and high safety are promising energy storage devices. However, their development is restricted by manganese oxide (MnO 2 ) cathodes, which have the drawbacks of inferior electron conduction, irreversible dissolution and limited stability. Herein, a synergistic cation/anion (Ca/N) co-doping strategy is introduced to modulate the electric structure of birnessite-type MnO 2 (CACO–δ-MnO 2 ) to enhance its electron/ion-migration capability, improve structural stability and promote electrochemical performance. Theoretical analysis reveals that the synergistic effects of Ca/N co-doping considerably reduces the bandgap, decreases the adsorption energy and lowers the ion-diffusion energy barrier for CACO–δ-MnO 2 , thereby increasing its conductivity and ion-diffusion capability. Ex situ and in situ analyses reveal that the dual ions of the Zn 2+ and H + insertion mechanism and the superior structural stability of CACO–δ-MnO 2 during charging/discharging processes. Galvanostatic intermittent titration technique and electrochemical impedance spectroscopy results confirm its fast kinetics, low charge-transfer resistance and good stability. Moreover, electrochemical tests demonstrate its superior stability in high-rate and long-term cycling, which delivers a high capacity of 213.5 mAh g −1 following 2000 cycles at a high current density of 4 A g −1 . Integrated with the CACO–δ-MnO 2 cathode, the flexible Zn–MnO 2 battery demonstrates high flexibility and reliability in a wide temperature range (−20 °C–25 °C). Moreover, a long lifespan of 1000 cycles and a high capacity retention of 89.2 % are obtained for the flexible Zn–MnO 2 battery even at a low temperature of −20 °C. Therefore, this study not only introduces a novel Ca/N synergistic modulation strategy for high-performance δ-MnO 2 cathode but also propels the development of advanced Zn-ion batteries for various electronic items.
研究领域:
储能与转换
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电化学
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材料科学
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电池技术
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纳米材料
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DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
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2018
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IF 5.116
Xiaopeng Yang,Zhensong Qiao,Feng Liu,Shuhua Yang,Liqiang Zhang,Bingqiang Cao
In this work, we report a birnessite-MnO 2 /ramsdellite-MnO 2 /F_ SnO 2 (FTO) composite planar electrode with 3D peony-like micro-structure for micro-supercapacitors (m-SCs), which is prepared via an original series resistor electrochemical deposition (SRED) of MnO 2 and subsequent secondary-growth. The composite electrode achieves an excellent specific capacitance of 1261 F g -1 at 10 A g −1 and extraordinary cycling stability with a significant 304% capacity retention after 10000 GCD cycles. Different from conventional cases, even though it is Mn +4 , the MnO 2 prepared by the SRED would undergo a secondary-growth with phase transition process during the GCD cycling, which could dramatically improve the pseudocapacitance performance by surface/inner-surface and diffusion-controlled insertion capacity aspects. The mechanism is in-depth discovered by deconvolution of double-layer and Faradaic insertion capacity at different stages of the phase transition, and first principle calculation based on density functional theory (DFT). The secondary-growth process also offers a fabulous self-repairing feature of the SC electrode materials , which caters the maintenance-free and long-life requirement of the m-SCs application. Scan rate dependency of the bulk and the surface/near-surface pseudocapacitance is confirmed via de-convoluted the total capacities and the redox peaks of CV curves with different scan rates.
研究领域:
材料科学
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电化学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
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IF 14.229
Yang Liu,Hao Zhou,Ranran Cao,Xingyun Liu,Pengyi Zhang,Jingjing Zhan,Lifen Liu
Volatile organic compounds (VOCs) are notorious for global air pollution. It is key to find a material with high and stable activity to catalytically oxidize VOCs at low temperatures. In this paper, benzene, as a typical VOC contaminant, could be completely oxidized on a highly efficient and moisture-resistant birnessite MnO 2 at temperatures significantly lower than the reported values in literature. The best catalyst (H-MnO 2 (30-0.2-6)) could be tailored via a facile and green process by engineering a proper combination of treatment temperature (30 °C), HNO 3 aqueous concentration (0.2 M) and treatment period (6 h). The thus-obtained MnO 2 exhibited a stable removal efficiency of ˜94% for 318 ppm of benzene under a high space velocity of 120 L·g −1 h −1 and 1.5 vol.% H 2 O at 250 °C. XRD, SEM, (HR)TEM, EDS mapping, XPS, H 2 -TPR, O 2 -TPD and pyridine adsorption IR were combined with the deliberately designed C 6 H 6 -TPD, surface oxidation reaction of benzene and CO 2 -TPD to disclose the tremendous role of acid treatment in benzene oxidation. The increased acid sites and acidity of the acid-treated surface promoted the adsorption and activation of gaseous benzene, and the lattice oxygen and surface adsorbed oxygen became more facile and reactive due to the generated active oxygen vacancies via acid treatment, these two favorable factors together with the easy desorption of reaction products resulting in the excellent performance of the acid-treated sample. Finally, the acid treatment method can be extended to most of other crystal structures of manganese dioxides except α-MnO 2 .
研究领域:
环境科学
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材料科学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
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2025
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IF 7.2
Meiqing Chen,Wanxia Li,Bo Ruan,Yuxin Gu,Qingcheng Zhang,Hongling Bu,Peixin Du,Peng Yuan
The interaction between birnessite and dissolved organic matter(DOM) is critical for carbon sequestration and heavy metal immobilization. This study investigated humic acid (HA, a representative form of DOM) in mediating the formation of triclinite birnessite (TB) and elucidated the influence mechanisms for carbon sequestration and As(V) immobilization. HA significantly affected both the growth and structural properties of TB. HA induced TB structural transformation from lamellar-like to honeycomb-like, reduced surface negative charge, and increased specific surface area, oxygen vacancies and hydroxyl groups. HA-Mn(III) complexes and pore trapping enhance organic carbon sequestration synergistically. As(V) immobilization was improved by inner-sphere complexation (via hydroxyl coordination) and electrostatic attraction with the maximum adsorption capacities for HA-mediated birnessite (TB-2H) were 65.140 mg·g⁻¹ , 6.4-fold higher than pure TB. Besides, TB-2H shows low manganese release, high stability and good reusability. These findings achieves synergistic carbon sequestration and As(V) immobilization, providing an innovative strategy for environmental remediation.
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高影响因子
Journal of Physical Chemistry C
·
2020
·
IF 4.189
Abubakar Yusuf,Yong Sun,Yong Ren,Colin Snape,Chengjun Wang,Hongpeng Jia,Jun He
Defect engineering is an effective strategy to enhance the activity of catalysts for various applications. Herein, it was demonstrated that in addition to enhancing surface properties via doping, the influence of dopants on the surface–intermediate interaction is a critical parameter that impacts the catalytic activity of doped catalysts for low-temperature formaldehyde (HCHO) oxidation. The incorporation of Co into the lattice structure of δ-MnO2 led to the generation of oxygen vacancies, which promoted the formation of surface active oxygen species, reduced activation energy, and enhanced catalytic activity for low-temperature oxidation of HCHO. On the contrary, Cu doping led to a drastic suppression of the catalytic activity of δ-MnO2, despite its enhanced redox properties and slight increase in the surface concentration of active oxygen species, compared to pristine δ-MnO2. Diffuse reflectance infrared Fourier transform analysis revealed that in the presence of Cu, carbonate intermediate species accumulate on the surface of the catalysts, leading to partial blockage of active sites and suppression of catalytic activity.
研究领域:
材料科学
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环境科学
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高影响因子
Advanced Energy Materials
·
2018
·Vol. 9
·期 1
·1802739
·
IF 21.875
Ang Gao,Min Li,Nannan Guo,Daping Qiu,Yan Li,Senhao Wang,Xia Lu,Feng Wang,Ru Yang
Novel and low-cost rechargeable batteries are of considerable interest for application in large-scale energy storage systems. In this context, K-Birnessite is synthesized using a facile solid-state reaction as a promising cathode for potassium-ion batteries. During synthesis, an ion exchange protocol is applied to increase K content in the K-Birnessite electrode, which results in a reversible capacity as high as 125 mAh g −1 at 0.2 C. Upon K + exchange the reversible phase transitions are verified by in situ X-ray diffraction (XRD) characterization. The underlying mechanism is further revealed to be the concerted K + ion diffusion with quite low activation energies by first-principle simulations. These new findings provide new insights into electrode process kinetics, and lay a solid foundation for material design and optimization of potassium-ion batteries for large-scale energy storage.
研究领域:
材料科学
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电化学
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能量存储与转换
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电池技术
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DOI
高影响因子
Environmental Technology & Innovation
·
2025
·
IF 7.1
Changsheng Jin,Yin Gao,Jingjing Lu,Yuxi Liu,Baowei Hu
Soils contain abundant organic matter (OM) and Mn(oxyhydr)oxides (MnOs) composites, which primarily control the geochemical behavior of Cd. However, the impact of manganese phase transformation on the retention and availability of Cd remains unclear. Here, four organo-mineral composites were synthesized using birnessite (δ-Mn Ⅳ O 2 ), β-Mn Ⅲ,Ⅳ O 2 , γ-Mn Ⅲ OOH, and Mn Ⅱ,Ⅲ 3 O 4 with fulvic acid (FA), during adsorption to preformed MnOs with 5 wt% organic carbon loadings. The performance and underlying Cd(II) adsorption mechanism by resulting FA-MnO composites were explored. Results showed that δ-MnO 2 transformation decreases Cd(II) adsorption capacity by 23.02–45.44 % on the resulting FA-MnOs. This reduction was attributed to increased aggregation of MnO particles and competition from generated Mn(II/III) for available vacancy sites. Cd undergoes redistribution within the FA-MnOs during the transformation of δ-MnO 2 . The amount of Cd associated with MnOs decreases by 9.46–37.08 %, while OM bound-Cd increases by 2.82–10.49 %. FAδ-MnO 2 predominantly interacted with Cd(II) through tetravalent manganese, forming stable coordination or chemical bonds. In contrast, FAγ-MnOOH and FA-Mn 3 O 4 primarily interacted with Cd(II) through divalent manganese via electrostatic attraction and ion exchange, resulting in weaker binding stability. These findings provide new insights into the roles of manganese transformation in the geochemical cycling of Cd in soils.
研究领域:
环境科学
·
土壤学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Changye Mang,Jun Luo,Cheng Huang,Hao Jiang,Minjun Rao,Guanghui Li
Constructing a multi-component structure is an effective strategy to promote the formation of oxygen vacancies (OVs), which can enhance electron transition to improve the photocatalytic activity of materials. In this work, it was designed a series of novel photocatalysts supported on calcium silicate hydrates (C-S-H) via density functional theory calculation. These designed photocatalysts were then synthesized and marked as Bir@C-S-H, TiO 2 /Bir@C-S-H, and α-Fe 2 O 3 /TiO 2 /Bir@C-S-H, respectively. In comparison to other catalysts, α-Fe 2 O 3 /TiO 2 /Bir@C-S-H photocatalyst has a higher specific surface area, a lower band gap, more OVs, which can activate more dioxygen molecules, and more reactive radicals. The photocatalytic activity of as-synthesized photocatalysts was verified by using HCHO as the target pollutant. To the treatment of 80 ppm HCHO, the α-Fe 2 O 3 /TiO 2 /Bir@C-S-H exhibits 100% HCHO conversion corresponding gas hourly space velocity of 60 L/(g•h) with a relative humidity of 60% under visible light irradiation, while Bir@C-S-H and TiO 2 /Bir@C-S-H present 89.92% and 94.17% HCHO conversion, respectively at same conditions. This work demonstrates a more effective calcium silicate hydrate decorated by Fe, Ti co-modified birnessite heterostructures for HCHO oxidation, which can be directly used as decorative materials, providing a novel guidance for practical application.
研究领域:
材料科学
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环境科学
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DOI
高影响因子
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