ACS Applied Materials & Interfaces
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2023
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IF 9.5
Mengzhen Song,Jingru Han,Yingzhi Wang,Lungang Chen,YanYan Chen,Xiaoyuan Liao
Fe-based MOFs (Fe-MOFs) are deemed promising Fenton-like catalysts due to their well-developed pores and accessible active sites. However, their inferior catalytic activity, iron leaching, and low H2O2 utilization always hinder their application as Fe-based MOF catalysts. In this work, we manipulated the structure of Fe-oxo nodes in MIL-88B(Fe) via a CuI species substitution method, affording a mixed-valence (Cu-incorporated Fe-MOFs) with highly improved Fenton-like performance. It is found that the CuI serves as a shuttle to promote transfer between FeII/FeIII, inducing the formation of a larger amount of stable FeII sites, which was proven by experimental and DFT calculation results. A linear relationship was observed for the Fenton-like performance and the amount of CuI species for the catalysts. The corresponding value of the •OH formation is 2.17 eV for Cu-incorporated MIL-88B(Fe), which is significantly lower than that of MIL-88B(Fe) (2.69 eV). Meanwhile, the enriched CuI species suppress Fe species leaching during the catalytic reaction. The Fe-ion leakage of 0.4Cu@MIL-88B is very tiny (0.01–0.03 mg/L), significantly less than that of MIL-88B (2.00–3.02 mg/L). At the same time, H2O2 utilization for 0.4Cu@ MIL-88B(Fe) is 88%, which is almost 4.4 times that of pure MIL-88B(Fe). This work provides insights into the rational design of Fe-MOFs as promising Fenton-like catalysts for wastewater treatment.
研究领域:
环境科学
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材料科学
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DOI
PubMed
高影响因子
CATALYSIS LETTERS
·
2018
·Vol. 148
·期 7
·2095-2108
·
IF 2.911
Dong Zhengyu,Zhang Qian,Hong Junming,Chen Bor-Yann,Xu Qingqing
Abstract This first-attempt study used novel catalyst to activate persulfate (PS) with chitosan-stabilized zero-valent iron formed in microporous bead reactor for long-term acetaminophen (APAP) removal. As thermal conductivity of the metal was higher than that of organic polymer-chitosan, abundant micro-pores were formed in the proximity of zero-valence iron via heating and dehydration. Thus, the entire bead could be considered to be a “microporous reactor”. SEM, FTIR and XRD results indicated that APAP degradation was mainly taken place in such intra particulate micro pores rather than in suspended aqueous phase. This could effectively suppress the leaching of iron ions. As zero-valent iron was stably protected not to be corrosively attenuated, the catalyst exhibited persistently stable catalytic activity. Here, catalyst dosage, PS concentration, initial pH, and initial concentration of APAP were optimized for maximal performance of treatment. The optimal removal efficiency of APAP (98.5%) was achieved within 35 min with 2 mM PS and 2.0 g/L catalyst at neutral pH, and the iron leaching ratio was only 0.55%. Moreover, as metal leaching capability was not significantly altered, the catalyst could be used for long-term operation. Quenching experiment revealed that SO 4 ·− seemed to be the predominant active species dealing with APAP oxidation. In addition, two plausible routes of competitive reactions for APAP degradation were proposed via identification of degraded intermediates. As electroactive electron shuttles 1,4-dihydroxyl benzene was generated as intermediates to stimulate oxidation, APAP degradation would be more electrochemically favorable for promising efficiency. Graphical Abstract
研究领域:
环境科学
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化学工程
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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
Qibo Liu,Yi Wang,Xiaoguang Sang,Jingce Bi,Ningning Liu,Xia Zhang,Zhuopeng Wang,Yide Han
The agglomeration and leaching of metal species are critical issues for iron-based catalysts to remove tetracycline (TC) through peroxydisulfate (PDS) activation. In this work, iron-oxide species confined in cha cage of silicon aluminum phosphate zeolite (Fe-SAPO-34) was successfully synthesized by in-situ encapsulation method to address the above challenges. In Fe-SAPO-34/PDS system, approximately 92.6% TC was removed within 150 min at experimental conditions: [pH] = 3, [TC] = 20 mg/L, [Catalyst] = 0.10 g/L, [PDS] = 1 mM. Meanwhile, the biggest degradation rate constant is 0.03689 min −1 , which surpasses the counterpart systems. This result originates from the well dispersion of Fe-oxide species in Fe-SAPO-34, providing more active sites for TC degradation. As expected, the Fe-oxide species leaching concentration is ultra-low (0.018 mg/L) in Fe-SAPO-34/PDS system, which is attributed that SAPO-34 has a confinement effect of cha cage and eight-ring pore openings to limit its leaching. The radical quenching tests and electron paramagnetic resonance (EPR) technology verify singlet oxygen ( 1 O 2 ) is the primary reactive oxygen species (ROS) in Fe-SAPO-34/PDS system. Furthermore, two possible pathways for TC degradation are proposed in line with the intermediate identified by liquid chromatography-mass spectrometry (LC-MS).
研究领域:
环境科学
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催化材料
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
·
IF 15.1
Jieru Guo,Ge Song,Minghua Zhou
Iron-based catalysts usually have a narrow pH application range and are easy to agglomerate and inactivate in the heterogeneous electro-Fenton (Hetero-EF) process. In this work, FeN-carbon nanotubes (FeN-CNTs) catalysts with highly dispersed FeNx sites and tubular structures were synthesized. This FeN-CNTs/Hetero-EF process extended the pH application range to 3–11 with low metal leaching (0.4 mg/L at pH 3) and negligible homogeneous contribution. Compared with nitrogen-doped carbon (N-C, prepared with the same procedure but without FeCl 3 ⋅6H 2 O precursor), its pseudo-first order reaction rate constant was increased by 4.4 times, suggesting that the uniformly dispersed active site FeNx played a key role in the catalytic activation of H 2 O 2 and the efficient degradation of carbamazepine (CBZ). Effective CBZ removal (10 mg/L) could be achieved at low current density (1.25 mA/cm 2 ) and catalyst dosage (50 mg/L) in FeN-CNTs/Hetero-EF. The capture experiments and EPR tests confirmed the existence of various active species such as • OH and 1 O 2 , among which • OH played a dominant role in the degradation of CBZ. FeN-CNTs significantly improves the removal of pollutants under a wide pH range, showing broad application prospects.
研究领域:
环境科学
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催化化学
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高影响因子
JOURNAL OF POROUS MATERIALS
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2015
·Vol. 23
·期 2
·301-310
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IF 1.108
Ye Wei,Zhao Binxia,Gao Han,Huang Jiajun,Zhang Xiaoli
Fe,Zn,Al-pillared montmorillonite (Mt) were prepared by ion exchange reaction. Effect of the Fe/Zn molar ratio in Fe,Zn,Al-pillaring solution on the structural properties of Fe,Zn,Al-Mt was examined. Characterization studies were performed by N 2 -adsorption/desorption, ICP, FTIR, DR UV–Vis spectroscopy and XRD. The interlayer space, specific surface and volume of micropores of pillared-Mt was 18.8 Å, 157 m 2 g −1 and 0.114 cm 3 g −1 respectively. Besides, the catalytic performance of Fe,Zn,Al-Mt was analyzed through wet peroxide oxidation of Orange II under mild experimental condition. The results indicated that the catalytic performance of Fe,Zn,Al-Mt was affected by the Fe/Zn molar ratio as following pattern: the obtained pillared solids with lower Fe/Zn molar ratios exhibited better catalytic performance and less iron leaching during the reaction. Moreover, the introduction of zinc into Mt shortened the induction time of reaction and improved the catalytic behaviour. Throughout this work, the chemical oxygen demand removal of OII was 77.1 % after the solution treated by Fe,Zn,Al(3/7)-Mt (defined as the Fe/Zn molar ratio of 3/7 in the pillaring solution) catalyst at temperature of 60 °C and atmospheric pressure of 1 atm.
研究领域:
环境化学
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催化材料
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废水处理
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无机非金属材料
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表面科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2013
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IF 5.825
Yanbin Wang,Hongying Zhao,Mingfang Li,Jiaqi Fan,Guohua Zhao
Highly ordered mesoporous copper ferrite (meso-CuFe 2 O 4 ) with high surface area and large pore size was successfully fabricated and firstly proposed as a heterogeneous Fenton catalyst. It was synthesized through the nanocasting strategy by using KIT-6 as hard template. The morphology and physicochemical properties of meso-CuFe 2 O 4 were characterized by SEM, TEM, XRD, XPS, FT-IR, Raman spectra, etc. The obtained results showed that the surface area and the pore size of meso-CuFe 2 O 4 were 122 m 2 g −1 and 9.2 nm, respectively. The meso-CuFe 2 O 4 presented excellent catalytic activity for the degradation of imidacloprid, achieving almost complete removal of 10 mg L −1 imidacloprid after 5 h at the reaction conditions of 0.3 g L −1 catalyst and 40 mM H 2 O 2 . Kinetic analysis showed that the degradation of imidacloprid follows the pseudo-first order. The apparent rate constant for meso-CuFe 2 O 4 was 1.0445 h −1 , which was 1.5, 2 and 2.5 times than those of meso-CoFe 2 O 4 , con-CuFe 2 O 4 and nano-Fe 3 O 4 , respectively. The amount of hydroxyl radical ( OH) generated was directly proportional to the degradation efficiency of imidacloprid, suggesting the involvement of OH in oxidizing imidacloprid. The obtained results indicated that meso-CuFe 2 O 4 presented the highest activity, which was not only due to its ordered mesoporous structure with high surface area and large pore size, but also assigned to the redox recycle of Fe 2+ /Fe 3+ and Cu + /Cu 2+ in meso-CuFe 2 O 4 . The special effect of Cu was discussed in terms of the thermodynamically favorable Fe 3+ reduction by Cu + , regenerating the active species Fe 2+ . The meso-CuFe 2 O 4 presented very low iron leaching (<1 ppm) even in acidic condition and retained almost its high catalytic activity after 5 consecutive runs. Besides, meso-CuFe 2 O 4 possessed medium saturation magnetization, which had provided a potential advantage for the recovery and reuse of catalyst.
研究领域:
环境科学
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材料科学
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高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2017
·
IF 6.198
Xufang Qian,Meng Ren,Yao Zhu,Dongting Yue,Yu Han,Jinping Jia,Yixin Zhao
A novel α-FeOOH/mesoporous carbon (α-FeOOH/MesoC) composite prepared by in situ crystallization of adsorbed ferric ions within carboxyl functionalized mesoporous carbon was developed as a novel visible light assisted heterogeneous Fenton-like catalyst. The visible light active α-FeOOH nanocrystals were encapsulated in the mesoporous frameworks accompanying with surface attached large α-FeOOH microcrystals via C–O–Fe bonding. Assisting with visible light irradiation on α-FeOOH/MesoC, the mineralization efficiency increased owing to the photocatalytic promoted catalyzing H2O2 beyond the photothermal effect. The synergistic effect between α-FeOOH and MesoC in α-FeOOH/MesoC composite improved the mineralization efficiency than the mixture catalyst of α-FeOOH and MesoC. The iron leaching is greatly suppressed on the α-FeOOH/MesoC composite. Interestingly, the reused α-FeOOH/MesoC composites showed much higher phenol oxidation and mineralization efficiencies than the fresh catalyst and homogeneous Fenton system (FeSO4/H2O2). The XPS, XRD, FTIR, and textural property results reveal that the great enhancement comes from the interfacial emerged oxygen containing groups between α-FeOOH and MesoC after the first heterogeneous Fenton-like reaction. In summary, visible light induced photocatalysis assisted heterogeneous Fenton-like process in the α-FeOOH/MesoC composite system improved the HO• production efficiency and Fe(III)/Fe(II) cycle and further activated the interfacial catalytic sites, which finally realize an extraordinary higher degradation and mineralization efficiency.
研究领域:
环境科学
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材料科学
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催化化学
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PubMed
高影响因子
DALTON TRANSACTIONS
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2016
·Vol. 45
·期 19
·7952-7959
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IF 4.177
Qiao Sun,Min Liu,Keyan Li,Yitong Han,Yi Zuo,Junhu Wang,Chunshan Song,Guoliang Zhang,Xinwen Guo
A series of MIL-53(Fe)-type materials, Fe(BDC)(DMF,F), were prepared by using different ratios of n(FeCl3)/n(FeCl2), which have varied amounts of Fe2+ in their frameworks. From FeCl3 to FeCl2, the structures of the synthesized samples transform from MIL-53(Fe) to Fe(BDC)(DMF,F). Along with this structure transformation, the crystal morphology goes through a striking change from a small irregular shape to a big triangular prism. This phenomenon indicates that the addition of FeCl2 is beneficial for the formation of a Fe(BDC)(DMF,F) structure. The catalytic activity of these iron-containing MOFs was tested in phenol degradation with hydrogen peroxide as an oxidant at near neutral pH and 35 °C. The degradation efficiency of these samples increases gradually from MIL-53(Fe) to Fe(BDC)(DMF,F). 57Fe Mössbauer spectra reveal that Fe2+ and Fe3+ coexist in the Fe(BDC)(DMF,F) framework, and the highest amount of Fe2+ in the sample prepared with mixed FeCl3 and FeCl2 is 26.0%. The result illustrates that the amount of Fe2+ in the samples can be controlled using varied n(FeCl3)/n(FeCl2) in the feed. The diverse amount of Fe2+ in this series of FeMOF materials exactly explains the distinction of reaction efficiency. The iron leaching tests, structures of the fresh and used catalysts, and the data of the recycling runs show that the Fe-containing MOFs are stable in this liquid-phase reaction.
研究领域:
材料科学
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环境化学
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催化
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DOI
PubMed
高影响因子
CHEMICAL PHYSICS LETTERS
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2025
·
IF 3.1
Pengfei Liu,Fuwei Yang,Xingyu Xu,Manqing Zheng,Ming Liao,Yuqing Chen,Zhengqiu Yuan,Rui Zhang,Jiayin Li
This study develops a hierarchical diatomite-supported NiCoFe-LDH (De@NiCoFe-LDH) for peroxymonosulfate (PMS) activation to degrade ofloxacin (OFL). The analysis of SEM, XRD, FTIR, XPS and BET were used to characterize the samples. The as-prepared De@NiCoFe-LDH possesses a high specific surface area and abundant active sites, which contribute to its superior catalytic performance. Under the conditions of 0.2 g/L catalyst, 0.3 mM PMS, 20 mg L −1 OFL, and pH 5.2, 99.7 % of OFL was removed within 40 min, markedly outperforming the unsupported LDH. The removal fitted with the pseudo-first-order reaction kinetics well with rate constant of 0.1470 min −1 . ESR and quenching studies indicate that the OFL degradation proceeds via a mixed radical (SO₄• − , •OH, O₂• − ) / non-radical ( 1 O₂) mechanism, primarily driven by 1 O₂. Mechanism investigation suggested that the redox cycles of Ni 2+ /Ni 3+ , Co 2+ /Co 3+ and Fe 2+ /Fe 3+ on the surface of De@NiCoFe-LDH were crucial for PMS activation. In addition, the ideal reusability and versatility of De@NiCoFe-LDH as well as low-toxicity of treated water endowed the De@NiCoFe-LDH/PMS system with a wide range of applications.
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高影响因子
ENVIRONMENTAL RESEARCH
·
2025
·
IF 7.7
Li Song,Weiguo Zhang,Quan Liu,Xiao Zhang,Fuqiang Liu,Aimin Li
Various organic acids commonly coexist with Cr(VI) in wastewater. However, direct electron transfer between Cr(VI) and electron-rich organic acids is typically slow. Current Fe-based mediators primarily operate through the aqueous Fe(III)/Fe(II) cycle, which faces challenges in achieving efficient Fe recycling. To address the efficient removal of Cr(VI) and sodium citrate (Cit) composite pollutants (Cr(VI)-Cit), iron-loaded carbon nitride composites (Fe/CN) were synthesized via a combined loading-calcination approach. Crucially, coordination between carboxylate groups of Cit and undercoordinated Fe sites on Fe/CN formed photoactive complexes, effectively stimulating ligand-to-metal charge transfer (LMCT). This significantly enhanced the solid-phase Fe(III)/Fe(II) cycling efficiency, leading to a markedly increased Cr(VI) reduction rate constant ( k ) of 0.213 mg/(L·min). Furthermore, coordination with the N-rich matrix effectively inhibited Fe leaching, resulting in a post-reaction total Fe concentration below 0.5 mg/L. The formation of a Cr(VI)-Fe-Cit ternary cyclic complex effectively lowered the activation energy for Cr(VI) reduction by 81.3% compared to pristine CN. In the dark, intramolecular electron transfer within this complex generated Fe(II)-Cit species with a low electrode potential. Under irradiation, the photoactive Fe(III)-Cit complex generated Fe(II) via LMCT to reduce Cr(VI); concurrently, photogenerated electrons (e - ) and superoxide radicals (·O 2 - ) also contributed to Cr(VI) reduction. Reusability tests showed Fe/CN retained ∼90% Cr(VI) removal efficiency from actual wastewater over 5 cycles, demonstrating good stability under realistic conditions. This study provides valuable insights for the cost-effective and efficient remediation of Cr(VI)-organic acid complexes in real wastewater.
研究领域:
环境科学
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材料工程
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化学修复
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无机化学
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水处理技术
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产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Chao Zhang,Mengxiang Ye,Huaimeng Li,Zhenzhen Liu,Zhen Fu,Haimin Zhang,Guozhong Wang,Yunxia Zhang
Heterogeneous electro-Fenton is a promising technology for the degradation of organic contaminants. To ensure its effectiveness, it is in urgent demand to design cathode materials with the integrated capability of sufficient H 2 O 2 generation and subsequent activation into reactive oxygen species (ROS) together with catalytic stability. Herein, a composite constituted by Fe/Fe 3 C nanoparticles embedded into N-doped porous carbon (NPC), designated as Fe/Fe 3 C@NPC, was successfully fabricated from Fe 3+ -loaded poly(imine dioxime) (PIDO) membrane via the thermal treatment in N 2 atmosphere and employed as the heterogeneous electro-Fenton catalyst to degrade bisphenol A (BPA). By optimizing the pyrolysis temperature and loading level of iron species, the catalyst obtained at 800 °C (i.e. Fe/Fe 3 C@NPC-800) achieved almost 100% of BPA removal efficiency within 120 min via the electro-Fenton system, accompanied by 69.2% of the total organic carbon (TOC) removal rate. Furthermore, the proposed composite catalyst also exhibited satisfactory reusability and stability, as reflected by low decrease in removal efficiency after six successive degradation tests and limited iron leaching (<0.5 mg/L). This work might provide valuable instruction for the rational design of highly efficient and stable heterogeneous electro-Fenton catalysts for organic pollutant control.
研究领域:
环境科学
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催化
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水处理
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材料科学
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DOI
高影响因子
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