JOURNAL OF ALLOYS AND COMPOUNDS
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2025
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IF 6.3
Qiufan Sun,Yuxiang Zhu,Yan Wang,Zhengtao Jia,Xiang Zhong,Jianfeng Yao
Three isostructural MIL-68(M)-NH 2 frameworks (M = In, Fe, or Al) featuring different metal centers were synthesized to investigate their photocatalytic activities for nitrogen fixation. The influence of the metal oxo clusters on the crystalline structures, morphologies, and optical characteristics was examined. MIL-68(In)-NH 2 (MNI) with one-dimensional microrod structures has a larger surface area than bulk MIL-68(Fe)-NH 2 (MNF) and spherical MIL-68(Al)-NH 2 (MNA), and achieves an ammonia generation rate (140.34 μmol g cat −1 h −1 ) ca . 3.4 and 1.6 times higher than those of MNF (37.25 μmol g cat −1 h −1 ) and MNA (87.5 μmol g cat −1 h −1 ), respectively. The superior performance can be attributed to its high crystallinity, strong coordination between the In−oxo clusters and ligands, and microrod morphology, which enhance electron transfer, improve mass transport, and extend visible light absorption. Moreover, MNI shows greater stability in ethanol aqueous solution than other sacrificial reagents, such as methanol, potassium sulfite, and triethanolamine. While slight surface corrosion of the microrods occurs in methanol and potassium sulfite solutions, complete collapse is observed in triethanolamine.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Qiufan Sun,Yuxiang Zhu,Xiang Zhong,Meng Jiang,Yanchen Fan,Jianfeng Yao
In this work, MIL-68(In) functionalized with various ligand substitutions including amine, hydroxyl, bromine, nitro, and methyl groups was prepared, via a one-pot solvothermal reaction for visible-light photocatalytic ammonia synthesis. The diversity of ligands tunes the morphology, geometry, pore environment, and electronic structure of MIL-68(In)-based photocatalysts due to the polarity and intraframework interactions. Amine-inserted MIL-68(In) outperforms its counterparts, presenting a boosted nitrogen photofixation rate of 140.34 μmol gcat–1 h–1 with an apparent quantum efficiency of 5.69% at 420 nm. Further, the size of the batch solvothermal reactor and the amine group content also influence the photocatalytic activity. The combined experimental and theoretical results reveal that amine substituents improve the chemisorption of nitrogen molecules and the conversion of nitrogen into ammonia follows a dual pathway, i.e., a Mars–van Krevelen process and a ligand-to-metal charge transfer mechanism. This work provides a molecular engineering strategy via dual catalysis toward efficient ammonia production.
研究领域:
材料科学
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化学工程
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环境科学
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产品关联
DOI
PubMed
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 11
·3443
·
IF 4.927
Youjun Zhang,Licong Liu,Dixiong Yu,Jinglan Liu,Lin Zhao,Jinpeng Liu,Shuo Liu
A magnetic metal–organic framework nanocomposite (magnetic MIL-68(Ga)) was synthesized through a “one pot” reaction and used for heavy metal ion removal. The morphology and elemental properties of the nanocomposite were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), as well as zeta potential. Moreover, the factors affecting the adsorption capacity of the nanocomposite, including time, pH, metal ion type and concentration, were studied. It was found that the adsorption capacity of magnetic MIL-68(Ga) for Pb2+and Cu2+was 220 and 130 mg/g, respectively. Notably, the magnetic adsorbents could be separated easily using an external magnetic field, regenerated by ethylenediaminetetraacetic acid disodium salt (EDTA-Na2) and reused three times, in favor of practical application. This study provides a reference for the rapid separation and purification of heavy metal ions from wastewater.Keywords:MOF;magnetic separation;heavy metal ions;adsorption
研究领域:
环境科学
·
材料科学
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2015
·
IF 4.321
Tongtong Han,Yuanlong Xiao,Minman Tong,Hongliang Huang,Dahuan Liu,Luyan Wang,Chongli Zhong
A series of CNT@MIL-68(Al) composites with different carbon nanotubes (CNTs) loadings have been synthesized and characterized by SEM, TEM, PXRD, FT-IR, TGA, and N 2 adsorption. As evidenced from SEM and TEM images, the incorporation of CNTs can result in better dispersity of MIL-68(Al) in composites and smaller particle size than pure MIL-68(Al). Adding appropriate amounts of CNTs increases both the BET surface areas and the total volume of small micorpores (<16 Å), leading to largely improved performance of adsorptive removal of phenol from aqueous solution. In the industrial concentration range of phenol, the adsorption capacity of 0.75% CNT@MIL-68(Al) was improved up to 188.7% compared with the pristine MIL-68(Al), possibly due to the increase of small micropores introduced by the incorporation of CNTs. Regeneration experiments demonstrated that the composites are stable with good regenerability for at least five cycles. This work shows that the composites formed by the combination of CNTs and MOFs may find promising applications in liquid phase adsorption.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Cheng Liu,Mengning Chen,Yueling Chen,Qi Chen,Jionghua Wu,Sen Lin,Ling Wu,Jimmy C. Yu
This work develops a series of bimetallic MIL-68(InFe) MOF nanorods (NM(In 1-x Fe x )) mimicking the nitrogenase for biomimetic photocatalytic N 2 fixation. The partial substitution of In 3+ with Fe 3+ leads to the electron redistribution from In 3+ to Fe 3+ , generating electron-poor In 3+ (In (3+δ)+ ) sites and electron-rich Fe 3+ (Fe (3–δ)+ ) sites as an electron acceptor–donor combination to promote the N 2 activation by a π back-donation mechanism. The smaller size of the nanorods further provides more accessible active sites than the bulk counterpart. In cooperation with the H + released from the H 2 O, the activated N 2 molecules were reduced by photogenerated electrons to give NH 3 . The optimal sample NM(In 0.90 Fe 0.10 ) exhibited the highest NH 4 + production rate of 30.8 µmol·h −1 ·g −1 without any sacrificial agent, attributed to the presence of abundant In/Fe bimetallic sites for N 2 activation and enhanced charge mobility. This work provides new insights into rational design for artificial N 2 fixation systems by mimicking natural nitrogenase.
研究领域:
材料科学
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环境科学
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生物化学
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产品关联
DOI
高影响因子
RARE METALS
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2025
·
IF 11
Wang Dan-Dan,Xu Meng-Yang,Lin Zhao-Xin,Wu Jia-Hui,Yang Wei-Ting,Li Hong-Ji,Su Zhong-Min
The goal of photocatalytic CO 2 reduction is to obtain a single energy-bearing product with high efficiency and stability. Consequently, constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective. Here, we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived CdIn 2 S 4 /In 2 S 3 heterojunction that exhibited stable and high selectivity. Multiple characterizations of the CdIn 2 S 4 /In 2 S 3 heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites, a high visible-light utilization rate ( λ < 600 nm), efficient charge separation, and a prolonged charge-carrier lifetime. Moreover, an S-scheme charge transfer mechanism, based on the interleaved band between the two components, improved the reduction capability of the electrons. Benefiting from the compositional and structural synergy, the yield CO by CdIn 2 S 4 /In 2 S 3 -250 (CI-250) reached 135.62 μmol·g −1 ·h −1 , which was 49.32 times and 32.88 times higher than that of In 2 S 3 and CdIn 2 S 4 , respectively. The CdIn 2 S 4 /In 2 S 3 heterojunction exhibited a quantum efficiency of 4.23% with a CO selectivity of 71%. Four cycle tests confirmed the good stability and recyclability of the CI-250. This work provides a new approach for designing and preparing high-performance hollow MOFs-based photocatalysts for scalable and sustainable CO 2 reduction.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
JOURNAL OF POROUS MATERIALS
·
2021
·Vol. 29
·期 1
·181-192
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IF 2.496
Wang Li,Zhou Yu,Xu Qi,Wu Xian-Kun,Xu Guo-Dong,Guo Ji-Xiang,Fang Dong
The development of high efficient and cost-effective photocatalysts for organic matters degradation and hydrogen evolution is of great importance. In this study, heterojunction photocatalysts based In 2 S 3 and MIL-68(In) were synthesized by hydrothermal method. These composites exhibit excellent bi-functionality of photocatalytic Rhodamine B degradation and hydrogen evolution. And it was found that the photocatalytic performance of the composites was dependent on the ratio of In to S. The optimum catalyst In 2 S 3 /MIL-68(In)-1.5 exhibits much enhanced photocatalytic performance, offering a removal efficiency of 94.7% within 30 min for 20 ppm of Rhodamine B and a hydrogen evolution rate of 1618.8 µmol h −1 g −1 as a result of the synergist effect of heterojunction between the two components, promoting the charge separation. Besides, the mechanisms for photocatalytic degradation of Rhodamine B and photocatalytic hydrogen evolution were also proposed. This protocol could provide guiding information on the development of other functional photocatalysts.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Yiling Wu,Kaiji Xu,Jian Tian,Longmei Shang,Kok Bing Tan,Hao Sun,Kang Sun,Xiaoping Rao,Guowu Zhan
The efficient and economic conversion of CO2 and renewable H2 into methanol has received intensive attention due to growing concern for anthropogenic CO2 emissions, particularly from fossil fuel combustion. Herein, we have developed a novel method for preparing Ni/In2O3 nanocatalysts by using porous MIL-68(In) and nickel(II) acetylacetonate (Ni(acac)2) as the dual precursors of In2O3 and Ni components, respectively. Combined with in-depth characterization analysis, it was revealed that the utilization of MIL-68(In) as precursors favored the good distribution of Ni nanoparticles (∼6.2 nm) on the porous In2O3 support and inhibited the metal sintering at high temperatures. The varied catalyst fabrication parameters were explored, indicating that the designed Ni/In2O3 catalyst (Ni content of 5 wt %) exhibited better catalytic performance than the compared catalyst prepared using In(OH)3 as a precursor of In2O3. The obtained Ni/In2O3 catalyst also showed excellent durability in long-term tests (120 h). However, a high Ni loading (31 wt %) would result in the formation of the Ni-In alloy phase during the CO2 hydrogenation which favored CO formation with selectivity as high as 69%. This phenomenon is more obvious if Ni and In2O3 had a strong interaction, depending on the catalyst fabrication methods. In addition, with the aid of in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory (DFT) calculations, the Ni/In2O3 catalyst predominantly follows the formate pathway in the CO2 hydrogenation to methanol, with HCOO* and *H3CO as the major intermediates, while the small size of Ni particles is beneficial to the formation of formate species based on DFT calculation. This study suggests that the Ni/In2O3 nanocatalyst fabricated using metal–organic frameworks as precursors can effectively promote CO2 thermal hydrogenation to methanol.
研究领域:
催化化学
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材料科学
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环境科学
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DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2025
·
IF 6.3
Jun He,Xiaoyu Qi,Jingjing Liu,Hao Zhang,Zhongliao Wang,Deliang Li,Shuwang Duo
Triethylamine is a typical volatile toxic gas that can cause respiratory system diseases, blood diseases, and eye lesions upon prolonged inhalation. To mitigate this problem, a highly sensitive triethylamine sensor was achieved by loading the precious metal Au onto hexagonal hollow prisms of In 2 O 3 . Prominently, the microstructure of the hollow hexagonal prisms was derived from Material Institute Lavoisier(MIL)-68(In), which provided a larger specific surface area and more active sites. The sensing test results manifested that the sensor based on 0.6% Au/In 2 O 3 owned the best sensing performance among all samples, especially with the response value of 476.3 ( R a / R g ) towards 100 ppm triethylamine at 200°C, which was 37 times higher than that of pristine In 2 O 3 sensor. Additionally, the stability deviation value was less than 5.6% and the selectivity ( Response triethylamine / Response ethanol ) reached up to 28.8. Such distinguished characteristics can be attributed to the delicate hollow hexagonal prisms structure and the decoration of Au, which accelerated gas molecules transport and enhanced oxygen molecule adsorption and dissociation. This work may open up new visas for morphology manipulation of triethylamine sensing materials and intrinsic mechanism of performance enhancement.
研究领域:
材料科学
·
传感器技术
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环境监测
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产品关联
DOI
高影响因子
Materials
·
2022
·Vol. 15
·期 11
·3761
·
IF 3.748
Lei Wu,Doudou Qin,Fan Fang,Weifeng Wang,Wenying Zhao
Severe environmental pollution is caused by the massive discharge of complex industrial wastewater. The photocatalytic technology has been proved as an effective way to solve the problem, while an efficient photocatalyst is the most critical factor. Herein, a new photocatalyst MIL-68(Ga)_NH2was obtained by hydrothermal synthesis and were characterized by PXRD, FTIR,1H NMR, and TGA systematically. The result demonstrates that MIL-68(Ga)_NH2crystallized in orthorhombic system andCmcmspace group with the unit cell parameters:a= 36.699 Å,b= 21.223 Å,c= 6.75 Å,V= 5257.6 Å3, which sheds light on the maintenance of the crystal structure of the prototype material after amino modification. The conversion of Cr(VI) and binary pollutant Cr(VI)/RhB in wastewater under visible light stimulation was characterized by the UV-vis DRS. Complementary experimental results indicate that MIL-68(Ga)_NH2exhibits remarkable photocatalytic activity for Cr(VI) and the degradation rate reaches as high as 98.5% when pH = 2 and ethanol as hole-trapping agent under visible light irradiation with good reusability and stability. Owing to the synergistic effect between Cr(VI) and RhB in the binary pollutant system, MIL-68(Ga)_NH2exhibits excellent catalytic activity for both the pollutants, the degradation efficiency of Cr(VI) and RhB was up to 95.7% and 94.6% under visible light irradiation for 120 min, respectively. The possible removal mechanism of Cr(VI)/RhB based on MIL-68(Ga)_NH2was explored. In addition, Ga-based MOF was applied in the field of photocatalytic treatment of wastewater for the first time, which broadened the application of MOF materials in the field of photocatalysis.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2020
·
IF 6.182
Zhihui Lu,Xuefang Cao,Hong Wei,Wenting Huo,Qiquan Wang,Kebin Li
Metal organic frameworks (MOFs) have shown a great potential to act as heterogeneous Fenton-like catalysts. However, the lower catalytic efficiency and reaction rate are limiting their practical applications. Herein, a facile and efficient strategy was studied to boost the catalytic oxidation performance of MIL-68(Fe)-mediated Fenton-like process with the addition of a minor amount of bisulfite. The factors affecting the catalytic oxidation capacity of the MIL-68(Fe)/HSO 3 − /H 2 O 2 system were investigated using methyl orange (MO) as model pollutant. Under the optimal condition, the degradation rate of MO could be increased by 11.5 times compared to that in MIL-68(Fe)/H 2 O 2 system, and the total organic carbon (TOC) removal in 120 min reached 46.8%. The MIL-68(Fe)/HSO 3 − /H 2 O 2 system also displayed a wide applicable pH range. Besides MO, other organic contaminants such as acid red 18 (AR18), rhodamine B (RhB), methylene blue (MB), xylenol orange (XO) and tetracycline hydrochloride (TC) could be effectively degraded in the MIL-68(Fe)/HSO 3 − /H 2 O 2 system as well. The quenching tests and electron paramagnetic resonance (EPR) spectrometry confirmed that OH, SO 4 − , HO 2 , and 1 O 2 were the main reactive species for MO degradation in the MIL-68(Fe)/HSO 3 − /H 2 O 2 system. The coumarin fluorometry further disclosed that much more hydroxyl radicals were generated in the MIL-68(Fe)/HSO 3 − /H 2 O 2 system than in MIL-68(Fe)/H 2 O 2 system. Cyclic voltammetry analysis, on the other hand, indicated that the presence of HSO 3 − facilitated the Fe(III)/Fe(II) cycle in the MIL-68(Fe)/HSO 3 − /H 2 O 2 system. Based on these results, the enhancement mechanism of the Fenton-like MIL-68(Fe)/HSO 3 − /H 2 O 2 system was proposed. Finally, the cyclic experiments manifested the MIL-68(Fe)/HSO 3 − /H 2 O 2 system had good stability and reusability. This study suggests that the addition of bisulfite being an excellent approach to construct the Fe-MOFs mediated Fenton systems for eliminating organic contaminants in water with high efficiency.
研究领域:
环境科学
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催化化学
·
水处理技术
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产品关联
DOI
高影响因子
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2022
·
IF 4.831
Ning Wu,Hao Guo,Mingyue Wang,Liping Peng,Yuan Chen,Bingqing Liu,Zhilan Pan,Yinsheng Liu,Wu Yang
Ratio fluorescence has attracted much attention because of its self-calibration properties. However, it is difficult to obtain suitable fluorescent materials with well-resolved signals simultaneously under one excitation. In this work, we report a different strategy, using MIL-68(In)-NH 2 as both the fluorescence element and the scattered light unit, and coupling the fluorescence and the scattered light to construct the fluorescence and scattered light ratio system. Based on the optical properties and the second-order scattering (SOS) of the material nanoparticles , the synthesized MIL-68(In)-NH 2 can be used to realize the ratio detection of Hg 2+ . Because the scattering intensity of small particle MIL-68(In)-NH 2 is weak, SOS is not obvious. When Hg 2+ is introduced the coordination reaction between the amino nitrogen atoms of MIL-68(In)-NH 2 and Hg 2+ make the particles larger, resulting in the decrease of fluorescence and the enhancement of SOS. As a result, a novel Hg 2+ ratiometric detection method is developed by using the dual signal responses of the fluorescence and scattering. Under the optimal conditions (pH = 6, reaction time 5 min, room temperature , and the maximum excitation wavelength 365 nm), the linear range of the method is 0–100 μM, and the detection limit is 5.8 nM (Ksv = 9.89 × 10 9 M −1 ). In addition, the probe is successfully used to evaluate Hg 2+ in actual water samples. Compared with the traditional method of recording only the fluorescence signal, the proposed fluorescence-scattering method provides a new strategy for the design of ratiometric sensors.
研究领域:
材料科学
·
分析化学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）