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JOURNAL OF THE AMERICAN CERAMIC SOCIETY · 2025 ·Vol. 108 ·期 7 ·e20447 · IF 3.8

Unraveling Cs substitution-induced evolution in Fe-hollandite: Linking crystal chemistry to leaching resistance

Mingyang Zhao,Xiao Chen,Huiping Zhu,Songqin Xia,Yan Ma,Kyle S. Brinkman,Zhenfeng Tong

This study systematically explored the crystal chemistry of Fe-substituted hollandite (Fe-hollandite) solid solutions (Ba x Cs y )(Fe 2 x + y Ti 8−2 x − y )O 16 ( x + y = 1.33) yielding reliable results through meticulous Rietveld analysis of XRD data. Continuous Cs substitution triggered a monoclinic-tetragonal (M-T) phase transition, enhancing structural stability, as evidenced by increased tolerance factor ( t H ). The transition boundary, controlled by t H = .985, determines the symmetry of the hollandite phase. Unit cell parameters and the local bonding environment were refined, indicating enlarged tunnel sizes/cavities with higher Cs content, attributed to a larger ionic radius (Cs + vs. Ba 2+ ). Comparison between Cs/Ba-O bond distances and tunnel cross-section sizes confirmed effective A-site cation immobilization, hindered by oxygen bottlenecks. Additionally, a refined model was proposed and validated to predict lattice constants of Fe-hollandite precisely. Beyond crystal chemistry evolution with Cs substitution, leaching resistance in the same sample suites was assessed. As Cs content increased, normalized elemental release of A-site cations initially decreased until reaching a minimum at intermediate Cs substitution, then rose again. Ba 0.33 Cs 1.0 Fe 1.66 Ti 6.34 O 16 (i.e., HF5) displayed optimal leaching resistance. Variations in leaching resistance might be influenced by the distortion in [BO 6 ] octahedra and the bonding environment of tunnel cations. This comprehensive analysis highlights intricate correlations between crystal chemistry and leaching resistance, offering insights to guide the design of advanced crystalline nuclear waste forms with enhanced corrosion resistance.

研究领域: 材料科学 · 核废料处理
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CATALYSIS TODAY · 2018 · IF 4.667

Yolk-shell Fe/FeS@SiO2 particles with enhanced dispersibility, transportability and degradation of TBBPA

Luyao Ren,Liangzhong Li,Shuai Chen,Hui Li,Yongdi Liu,Liyang Zhou,Su Guo,YunJiang Yu

In this study, Fe/FeS@SiO 2 yolk-shell particles (Fe/FeS@SiO 2 YSPs) were synthesized, characterized, and applied to tetrabromobisphenol A (TBBPA) removal in simulated groundwater. The X-ray photoelectron spectroscopy, X-ray diffraction, Scanning electron microscopy, transmission electron microscopy and Brunauer Emmett Teller results revealed that Fe/FeS@SiO 2 YSPs possess special structures, including active cores, mesoporous networks, shells, hollow cavities and a large surface area (85 m 2 /g vs. 8 m 2 /g) compared to Fe/FeS. The mobility of the synthesized particles in porous media was simulated with sand column experiments. Fe/FeS@SiO 2 YSPs showed a much better transportability (83.02% of particles successfully transported through the column) than Fe/FeS particles (only 1.68%), related to the better suspension stability and much lower particle surface charge (−22.7 mV vs. −7.6 mV) at neutral pH. Improved TBBPA reduction performance in synthetic solution was observed for Fe/FeS@SiO 2 YSPs over bare Fe/FeS. The transformation pathway of TBBPA was studied in detail, revealing the formation of tri-BBPA, di-BBPA, mono-BBPA and BPA as the main products. In brief, thanks to the hollow mesoporous silica spheres (HMSS) coated on the surface of Fe/FeS particles, Fe/FeS@SiO 2 YSPs showed an enhanced dispersibility, transportability and degradation of TBBPA in simulated groundwater. The results in this study proved that Fe/FeS@SiO 2 YSPs are a promising material for in situ remediation of TBBPA in soil and groundwater.

CAS / MDL: 75-05-8 67-56-1 79-94-7
研究领域: 环境科学 · 材料科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2019 · IF 6.361

Adsorption behavior of arsenicals on MIL-101(Fe): The role of arsenic chemical structures

Zongchen Li,Xuemin Liu,Wei Jin,Qingsong Hu,Yaping Zhao

Arsenic species are regarded as typical water pollutants due to their toxicity. The chemical structures of arsenic species greatly influence their migration and transformation in the environment. Metal-organic frameworks (MOFs) are used as reliable adsorbents to control arsenic contamination, so it is urgently needed to study the effect of chemical structure of arsenic species during adsorption process. The adsorption behaviors of arsenate (As(V)) and its organic forms such as roxarsone (ROX), p-arsanilic acid (p-ASA) and dimethyl arsenate (DMA) by MIL-101(Fe), a type of highly porosity iron-based MOFs in aqueous environment were detailed investigated. The adsorption kinetics of those arsenic species on MIL-101(Fe) is rapid followed with pseudo-second-order kinetic model. MIL-101(Fe) exhibits excellent adsorption capacities for As(V), ROX, p-ASA and DMA with maximum adsorption capacities of 232.98, 507.97, 379.65 and 158.94 mg g −1 , respectively. The formed Fe O As inner-sphere coordination between arsenic species and the incomplete-coordinated cationic Fe in the MIL-101(Fe) cluster is the primary adsorption mechanism based on FTIR and XPS analysis. Substituent aromatic units in ROX and p-ASA strengthen the adsorption on MIL-101(Fe) through hydrogen bonds and π-π stacking interaction, resulting in higher adsorption capacities far beyond that of As(V) and DMA. The reusability of MIL-101(Fe) is limited by the strong Fe O As coordination. These results confirm MIL-101(Fe) a reliable adsorbent to control the aqueous arsenic species contamination and emphasize the significant role of the chemical structure of arsenic speciation on adsorption performances of MOFs.

研究领域: 环境科学 · 材料科学 · 化学
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Nano Research · 2024 · IF 9.5

Hollow structured Fe@C nanorods for boosting dehydrogenation properties of α-AlH3

Zhao Yuan,Wang Qingshuang,Yin Dongming,Wang Xiaoli,Li Shouliang,Wang Chunli,Liang Long,Zhao Shaolei,Wang Limin,Cheng Yong

α-AlH 3 is regarded as one of the most promising hydrogen storage materials due to its high hydrogen storage capacity (10.1 wt.%, 148 kg·m −3 ). However, in practical applications, the associated hydrogen release temperature remains relatively high. To effectively address this issue, hollow structured Fe@C nanorods derived from Fe-MOF are introduced as highly efficient catalyst to optimize the dehydrogenation properties of α-AlH 3 . Comparatively, the initial hydrogen release temperature of α-AlH 3 + 3 wt.% Fe@C is reduced to 94.2 °C, which is significantly lower than that of pure α-AlH 3 (137.8 °C). At 100 and 120 °C, it exhibits hydrogen capacities of 5.38 wt.% and 7.47 wt.%, respectively, whereas pure α-AlH 3 only delivers hydrogen capacities of 0.24 wt.% and 5.94 wt.% under the same temperatures. The density functional theory (DFT) calculations further indicate that the existence of Fe@C catalyst can make the length of Al–H bond increase, which is more conducive to the release of hydrogen. The results show that the synergistic effect of Fe and porous carbon in Fe@C nanorods can improve the hydrogen desorption kinetics of α-AlH 3 , providing a good prospect for the application of α-AlH 3 in hydrogen storage fields.

CAS / MDL: 110-17-8
研究领域: 材料科学 · 化学工程
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APPLIED SURFACE SCIENCE · 2019 · IF 5.155

Fe doped CoO/C nanofibers towards efficient oxygen evolution reaction

Weimo Li,Meixuan Li,Ce Wang,Yen Wei,Xiaofeng Lu

Rational design of highly efficient electrocatalyst for oxygen evolution reaction (OER) is essential to construct high-performance energy devices. In this study, we have developed an electrospinning, in situ polymerization and carbonization process to fabricate Fe doped CoO/C (Fe-CoO/C) nanofibers as efficient OER electrocatalysts. In the synthesized Fe-CoO/C nanofibers, ultrathin carbon layer can be used as conductive network to promote electron transfer and thus improve the electrocatalytic activity. At the same time, additional active sites, like bridged site, formed by Fe doping, also provides the catalyst excellent electrochemical activity in OER. The as-prepared Fe-CoO/C nanofibers exhibit an excellent OER activity with an overpotential of 362 mV at the current density of 10 mA cm −2 in an alkaline medium, which is comparable with the commercial RuO 2 catalyst. After 2500 cyclic voltammograms (CVs) cycles test, the catalyst still maintains the initial electrocatalytic activity, demonstrating a great durability. This strategy introduces both carbon layer and Fe doping to increase the conductivity and the density of active sites of CoO nanofibers, thus enhancing the electrocatalytic activity and stability. This work offers an efficient route to develop low-cost and highly active transitional metal oxide-based OER electrocatalyst for potential renewable electrochemical energy conversion and storage.

CAS / MDL: 109-97-7
研究领域: 材料科学 · 能源化学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2024 · IF 8.2

Efficient adsorption of short-chain perfluoroalkyl substances by pristine and Fe/Cu-loaded reed straw biochars

Na Liu,Yinhui Li,Minggu Zhang,Naiju Che,Xianliang Song,Yanli Liu,Chengliang Li

As the substitutes of legacy long-chain per-/polyfluoroalkyl substances (PFASs), short-chain PFASs have been widely detected in the environment. Compared to long-chain PFASs, short-chain PFASs have smaller molecules and are more hydrophilic. Therefore, they are more likely to experience long-distance transport and pose lasting environmental impacts. In this study, Fe-doped (R-Fe) and Cu-doped biochars (R-Cu) were prepared using reed straw biochar (R). The results showed that the PFBA and PFPeA sorption capacities of R-Fe were 25.81 and 43.59 mg g −1 , 1.65 and 1.55 times higher than those of R, respectively. The PFBA and PFPeA sorption capacities of R-Cu were 19.34 and 33.69 mg g −1 , 1.24 and 1.20 times higher than those of R, respectively. In addition, R, R-Fe, and R-Cu exhibited higher PFBA and PFPeA sorption capacities than the biochars previously reported. The excellent PFAS sorption performances of the biochars were attributed to the highly porous structure of R, which provided rich adsorption sites. Ion-pair sorption, pore filling, electrostatic interaction between the Fe/Cu and cationic groups on biochar and the anionic groups of PFASs, and hydrophobic interaction between the hydrophobic surface of biochar and the fluorinated tails of PFASs were the underlying sorption mechanisms. The biochars presented high removal rates (>86 %) of multiple PFASs (∑PFAS: 350 μg L −1 ) from synthetic wastewaters, including legacy and emerging PFASs of different chain lengths and with different functional groups. The biochars reported in this study are promising candidate adsorbents for treating waters contaminated with short-chain PFASs.

CAS / MDL:
研究领域: 环境科学 · 污染控制
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JOM · 2023 ·Vol. 76 ·期 2 ·969-975 · IF 2.6

Microstructure and Mechanical Properties of Fe-36Ni Alloy Prepared by a Two-Step Hydrogen Reduction Process

Liu Hanning,Liu Peidong,Tian Qinghua,Dong Zhaowang,Chen Yubing,Guo Xueyi

Fe-36Ni invar alloys (Invar 36 alloys), which have a low thermal expansion coefficient (CTE) and good mechanical properties, are typically produced through a high-pollution smelting process. A green and quick-process method for the two-step hydrogen reduction of a designed mixture of Fe 2 O 3 and NiO powders was developed to prepare Fe-36 wt.%Ni alloys. A dense Fe-36 wt.%Ni alloy with an oxygen content of 0.20 wt.% was successfully produced. A single γ -FeNi phase was identified at 1000°C, whereas grains and twins became more evident at 1100°C. The final alloy exhibited excellent mechanical properties at room temperature, showing a hardness of 154 HV, a tensile strength of 486 MPa, a yield strength of 251 MPa, and a fracture strain of 21%.

研究领域: 材料科学 · 冶金工程 · 结构合金
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Cu,Ce-containing phosphotungstates as laccase-like nanozyme for colorimetric detection of Cr(VI) and Fe(Ⅲ)

Yi Gu,Yang Jiao,Ya Ruan,Jing Yang,Yaling Yang

Herein, a nanocomposite of Cu,Ce-containing phosphotungstates (Cu,Ce-PTs) with outstanding laccase-like activity was fabricated via a one-pot microwave-assisted hydrothermal method. Notably, it was discovered that both Fe 3+ and Cr 6+ could significantly enhance the electron transfer rates of Ce 3+ and Ce 4+ , along with generous Cu 2+ with high catalytic activity, thereby promoting the laccase-like activity of Cu,Ce-PTs. The proposed system can be used for the detection of Fe 3+ and Cr 6+ in a range of 0.667–333.33 μg/mL and 0.033–33.33 μg/mL with a low detection limit of 0.135 μg/mL and 0.0288 μg/mL, respectively. The proposed assay exhibits excellent reusability and selectivity and can be used in traditional Chinese medicine samples analysis.

研究领域: 生物化学 · 环境科学 · 材料科学
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2025 ·Vol. 27 ·期 8 ·4278-4289 · IF 2.9

Efficient photocatalytic hydrogen production by employing a graphdiyne/NH2-MIL-88B(Fe) composite

Ziyu Li,Mei Li,Rongsheng Xu,Zhiliang Jin

The electron transfer rate in photocatalysts is one of the factors determining their hydrogen production activity. In this work, NH2-MIL-88B(Fe) (NFM) was synthesized using a one-step hydrothermal synthesis method and NFM/GDY-25 (NFMG-25) was successfully synthesized by loading graphdiyne (GDY) onto the surface of NFM. The hydrogen production performance and the mechanism of the prepared photocatalysts were systematically investigated using XRD, SEM, FT-IR, XPS, UV-Vis, PL and photoelectrochemical tests. The results showed that the hydrogen production of NFMG-25 reached 61.7 μmol in 5 hours. Photoelectrochemical and Mott–Schottky tests demonstrated that the composite catalyst exhibited high photogenerated carrier separation efficiency and single catalysts were n-type semiconductors. The conduction bands of NFM and GDY were −0.36 V and −0.56 V, respectively, while the valence bands were 1.90 V and 1.12 V. NFM acted as an electron acceptor and donor, which accelerated the transfer of the electrons, and enhanced the photocatalytic hydrogen production efficiency of the composite system. This study provides an effective method for using NFM in photocatalytic hydrogen production.

研究领域: 材料科学 · 能源科学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2022 · IF 4.598

An Fe-MOF/MXene-based ultra-sensitive electrochemical sensor for arsenic(III) measurement

Ping Xiao,Guodong Zhu,Xiaohong Shang,Bin Hu,Boshuang Zhang,Zhaoyu Tang,Jianmao Yang,Jianyun Liu

The Fe-metal organic framework decorated MXene (Fe-MOF/MXene) was in-situ synthesized by one-step hydrothermal method in the presence of MXene. Using Fe-MOF/MXene as modifier, the obtained Fe-MOF/MXene electrode presented excellent electrochemical activity due to the high surface area and good conductivity of MXene. A sensitive arsenite electrochemical sensor was fabricated based on the strong As-hydroxyl bonding at the Fe-MOF/MXene electrode, confirmed by X-ray photoelectron spectroscopy. Cyclic voltammetry characterization indicated that MXene facilitated the charge transfer with enhanced electrochemical response. The Fe-MOF/MXene modified electrode exhibited super-high current response to As(III) by square wave anodic stripping voltammetry, with extremely high sensitivity (8.94 µA·(ng·L −1 ) −1 ·cm −2 ) and super-low limit of detection (0.58 ng·L −1 ). The analysis of the real water demonstrated that the Fe-MOF/MXene-based sensor was feasible for the detection of As(III) in practical application.

研究领域: 材料科学 · 环境科学 · 分析化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Cu mediated defect manipulation in MIL-88A(Fe) for boosting photocatalytic N2 fixation

Runlai Liu,Qi Chen,Jinjing Qiu,Cheng Liu,Jionghua Wu,Jimmy C. Yu,Ling Wu

The construction of metal–organic frameworks that possesses the tunable metal active sites and synergistic effect for the reactant activation is an attractive strategy for the optimization of photocatalytic performance. Herein, a series of MIL-88A(Fe 1-x Cu x ) were synthesized for photocatalytic nitrogen reduction reaction (NRR). It was characterized that the Fe 2+ and oxygen vacancies were produced in MIL-88A(Fe) due to the partly reduction of ligand fumaric acid in synthesis process. The substitution of Fe 3+ with Cu 2+ induces charge imbalance and lattice distortion, further increasing the content of Fe 2+ and oxygen vacancies. The optimal sample MIL-88A(Fe 0.95 Cu 0.05 ) (CMA-5 %) exhibits the highest nitrogen fixation performance of 68.6 μmol·g −1 ·h −1 , which is 8 times higher than that of the pristine material. It is attributable to the synergistic effect of the abundant Fe 2+ and oxygen vacancies as active sites to promote N 2 coordination and photogenerated carrier separation, resulting in the efficient conversion of activated N 2 to NH 3 . Furthermore, the in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy provide clear evidence of the behavior of the N 2 adsorption and activation on the catalyst. Finally, we propose a potential mechanism at molecular level regarding the relationship between the synergistic effect and the nitrogen fixation activity.

CAS / MDL: 10125-13-0 110-17-8
研究领域: 材料科学 · 光催化 · 化学工程
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JOURNAL OF POLYMER SCIENCE · 2025 · IF 3.6

Sulfonated Fe-MOF Solid Acid Catalyst for High-Efficient Depolymerization of Polyamide 6

Yang Liu,Guodong Cao,Xuelong Zhu,Yi Zhang,Chenglu Liang,Yukun Chen

Upcycling the wasted polyamide 6 (PA6) to its monomer caprolactam via depolymerization is a promising way to build the resource cycling and alleviate the environmental pollution. High efficient catalyst for PA6 depolymerization is desirable and crucial. Herein, a sulfonated Fe-MOF catalyst was designed and performed as solid acid catalyst for the PA6 depolymerization for the first time. Results showed that a 100% conversion of PA6 solid to water-soluble liquid products can be achieved at temperatures of 250°C after only 1-h reaction. LC/MS results indicated that the water-soluble products were mainly composed of caprolactam and their oligomers. Without catalyst, nearly no water-soluble products can be obtained at the same condition. Moreover, a high selectivity of 90% caprolactam production in the water-soluble liquid products was achieved at 260°C, 5 h. The reaction rate constants at 240°C, 250°C, and 260°C were determined to be 0.024, 0.033, and 0.064, respectively, with a Ea value of 101.8 kJ/mol, showing positive temperature dependent relationship. The comparison of catalytic performances over sulfonated Fe-MOFs, FeCl 3 ·6H 2 O and the pristine un-sulfonated Fe-MOF suggested the synergistic contribution of Fe sites (Lewis acid centers) and the sulfonic acid sites to the catalytic performances. Graphical Water soluble liquid products (100 wt.%) with a high selectivity of 90% caprolactam can be achieved by the addition of Fe-MOF catalyst under a mild condition through the synergistic catalytic contribution of Fe sites (Lewis acid centers) and the sulfonic acid sites.

研究领域: 材料科学 · 环境科学 · 催化化学
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