VACUUM
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2025
·
IF 3.9
Zhuo Li,Huiling Du,Nan Kong,Na Cao,Kemeng Hu,Lan Yang,Xian Du
Carbon dioxide conversion represents a highly promising carbon reduction strategy, and photocatalytic conversion technology, characterized by greenness, non-toxicity, and sustainability, holds significant importance. However, enhancing CO 2 adsorption on photocatalysts and improving charge carrier separation efficiency remain substantial challenges. In this study, based on MIL-101, we designed a highly interconnected TiO 2 @MIL-101 bifunctional heterojunction by in-situ compositing TiO 2 on its surface through Ti-O-Cr bonding, aiming to achieve in-situ adsorption and conversion of carbon dioxide. This composite photocatalyst exhibits enhanced photocatalytic activity, with an average CO production rate of 35.39 μmol h −1 g −1 and a CH 4 production rate of 13.81 μmol h −1 g −1 . Compared to unmodified MIL-101 (Cr), these values are increased by 1.25-fold and 2.8-fold, respectively. Experimental results combined with DFT calculations demonstrate that the porous structure and high specific surface area of MIL-101 facilitate the diffusion of CO 2 on the photocatalyst surface and improve interfacial reaction kinetics. The synergistic effect between Ti-O-Cr bonds and the built-in electric field within the highly interconnected heterojunction accelerates the directional transfer of charge carriers at the heterointerfaces, effectively promoting the catalytic conversion of carbon dioxide.
研究领域:
材料科学
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光催化
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环境化学
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二氧化碳利用
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JOURNAL OF SOLID STATE CHEMISTRY
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2025
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IF 3.5
Guojian Ji,Chenyu Chu,Jiahua Cheng,Linya Fei,Anqi Xu,Tianle Zhang,Zhihui Zhang,Le Chen,Qunfeng Zou,Chuan Jiang
Metal-organic frameworks (MOFs) are advantageous for hydrogen storage owing to their tunable porosity. Two independent series were constructed: (i) MIL-101(Cr) functionalized with –NH 2 or –OH, and (ii) Li + -doped MIL-101 at controlled loadings. All samples retained their framework integrity. Textural analysis reveals a concentration-dependent, non-monotonic effect of Li + : at 0.015 wt%, Li + acts as an entrance unblocking (window reopening) effect, markedly increasing S BET and V total and strengthening the 1–2 nm window population; at 0.036 wt%, an optimal balance between reopened windows and accessible microporosity yields a peak H 2 uptake of 3.00 wt% (77 K, 100 kPa), surpassing both the parent framework and the –NH 2 derivative (2.37 wt%); at 0.296 wt%, partial occupation of cages/windows reduces accessibility. GCMC density maps and isosteric-heat data further corroborate that –NH 2 enhances polarity and strengthens host-guest interactions, whereas –OH blocks ultramicropores; moderate Li + simultaneously improves pore accessibility and introduces polarized adsorption sites. Overall, H 2 storage correlates more strongly with the coupling between accessible microporosity and pore-surface polarity than with S BET alone, highlighting dopant concentration as a key lever for optimizing MOF-based hydrogen storage.
研究领域:
材料科学
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氢能存储
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纳米多孔材料
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吸附
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ANALYTICAL CHEMISTRY
·
2023
·
IF 7.4
Yu-Fei Li,Can-Jun Zou,Xing-Biao Liu,Feng Gan,Ping-Ping Fang
The detection of pharmaceuticals has been a matter of concern among scientists and health researchers in the past few decades. However, it is still difficult to realize the sensitivity and selectivity detection of pharmaceuticals with similar structures. Herein, the pharmaceutical molecules of 2-mercaptobenzimidazole (MBI) and 2-mercaptobenzothiazole (MBT) with so similar structures can be selectively detected by surface-enhanced Raman spectroscopy (SERS) taking advantage of the fingerprint identification on Au/MIL-101(Cr), with sensitive detection limits of 0.5 ng·mL–1 for MBI and 1 ng·mL–1 for MBT. MBI is selectively enriched by Au/MIL-101(Cr) from the mixture solution and detected by SERS below 30 ng·mL–1. MBI can also be selectively detected in the serum samples with a detection limit of 10 ng·mL–1. Density functional theory calculations combined with the SERS experiments explained that the high sensitivity and selectivity are caused by the intrinsic differences in Raman intensity and different adsorption energies from the pharmaceutical molecules adsorbed on Au/MIL-101(Cr), respectively. This study provides an effective way to enrich and detect pharmaceutical molecules with similar structures.
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JOURNAL OF COORDINATION CHEMISTRY
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2023
·
IF 1.9
Jinyan Tan,Na Zhang,Ling Wang,Liduo Chen,Cuiqin Li,Jun Wang
Metal-organic framework MIL-125(Ti)-NH2 was prepared and coordinated with salicylaldehyde and NiCl2·6H2O to create a heterogeneous catalyst for ethylene polymerization. The structure of the products was characterized by a variety of physical methods, such as Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma mass spectrometry (ICP-MS), and nitrogen adsorption-desorption. The catalytic performance of MIL-125(Ti)-NH2-Sal-Ni was also investigated. The results showed that the reaction temperature, Al/Ni molar ratio, and ethylene pressure influenced on the catalytic activity and product selectivity. Under optimal reaction conditions, the catalytic activity of MIL-125(Ti)-NH2-Sal-Ni for ethylene oligomerization could reach 5.90 × 104 g·(mol Ni·h)−1 using cyclohexane as the solvent and MAO as the co-catalyst; the main products were C4 and C6. In addition, MIL-125(Ti)-NH2-Sal-Ni had good catalytic stability and recycling, which could be reused at least twice without significant loss of activity. Moreover, based on the evaluation of catalytic performance, the catalytic ethylene oligomerization mechanism of MIL-125(Ti)-NH2-Sal-Ni was also deduced.
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Molecular Catalysis
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2022
·
IF 5.089
Rongzhao Li,Chengtao Zhang,Shuo Li,Yupeng Du
Propane dehydrogenation is commonly operated at temperatures exceeding 600 °C due to thermodynamic requirements. However, high temperature accelerates the deactivation of catalysts because of the coke deposition. Therefore, it is quite necessary to develop catalysts with high catalytic activity and improved anti-coking ability. To this end, an Al-doped Cr 2 O 3 catalyst derived from MIL-101(Cr/Al) is prepared in this work. The preparation conditions, including the carbonization temperature of MIL-101 and the proportion of Cr/Al, are optimized via experimental studies. Meanwhile, the adsorption and dehydrogenation behaviors of propane on the catalyst are investigated using Density Functional Theory (DFT) methods. Findings indicate that the optimum carbonization temperature and Cr/Al proportion are 900 °C and 6:4, respectively. Under the reaction condition of P = 0.1 MPa, T = 580 °C and GHSV = 800 h −1 , the propane conversion and propylene selectivity on the Cr 6 /Al 4 catalyst are 19.5% and 92.0%, respectively. The activity stability of the Al-doped Cr 2 O 3 is elongated significantly due to the lower desorption energy of propene and higher energy barrier for the coke formation on the catalyst. In sum, the present work completed via experiments and DFT calculations will lead to a better understanding of the Al-doped Cr 2 O 3 catalyst and guide the rational design of anti-coking catalysts for propane dehydrogenation.
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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.
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Nanomaterials
·
2023
·Vol. 13
·期 14
·2072
·
IF 5.3
Xu Zhang,Bo Tian,Zhiheng Ma,He Wang,Zhixuan Cheng,Jiaqiang Xu
As a volatile air pollutant, formaldehyde can enter people’s living environment through interior decoration, furniture and paint, causing serious harm to human health. Therefore, it is necessary to develop a sensor for the real-time detection of formaldehyde in low concentrations. According to the chemical interaction between amino groups and formaldehyde, a MIL-101(Cr) aminated-material-based formaldehyde cantilever sensor was prepared, of which ethylenediamine- functionalized MIL-101(Cr) named ED-MIL-101(Cr)) showed the best gas sensing performance. Using quasi-in situ infrared spectroscopy, ED-MIL-101(Cr) was found bound to formaldehyde through a Schiff base. The adsorption enthalpy of formaldehyde-bound ED-MIL-101(Cr) was −52.6 kJ/mol, which corresponds to weak chemical adsorption, so the material showed good selectivity. In addition, ED-MIL-101(Cr) has the most active sites, so its response value to formaldehyde is larger and it takes longer to reach saturation adsorption than bare MIL-101(Cr). Through the research on the gas sensing performance of functionalized MIL-101(Cr) material, we found that it has a strong application potential in the field of formaldehyde monitoring, and the material performance can be quantitatively and accurately evaluated through combining calculation and experimentation for understanding the gas sensing mechanism.
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INORGANIC CHEMISTRY
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2023
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IF 4.6
Jun-Qing Ye,Yan-Zi Dai,Shu-Ying Xu,Pin-Xi Wang,Zhong-Hua Sun,Jun-Feng Qian,Qian Liang,Ming-Yang He,Qun Chen
The construction of efficient photocatalysts for water splitting to enable H2 evolution is pivotal to alleviate energy issues and environmental concerns. In this work, carbon dots (CDs) were prepared by employing “green solvent” ionic liquids as carbon sources and then combined with Pt/NH2-MIL-125, resulting in the emergence of a high-efficiency photocatalyst termed CDs-Pt/NH2-MIL-125 for the first time. This composite photocatalyst exhibited outstanding photocatalytic activity in H2 production under visible light irradiation. Notably, the H2 production rate of CDs100-Pt/NH2-MIL-125 reaches up to 951.4 μmol/g/h, which was 3.1 times that of Pt/NH2-MIL-125. The characterization results indicate that CDs and Pt uniformly dispersed on the surface of NH2-MIL-125 and fabricated a synergistic compact structure, providing a high BET surface area (985 m2 g–1) and a suitable band gap. Furthermore, the distinctive embeddable-dispersed CDs and Pt, as dual cocatalyst, can harvest light and facilitate the transfer of photogenerated electrons, thereby significantly augmenting the exploitation of visible light. The plausible mechanism of photocatalytic H2 evolution over the CDs-Pt/NH2-MIL-125 catalyst was also discussed. This work introduces a promising strategy for designing high-performance CDs-MOFs-based photocatalysts, an innovative step toward achieving efficient photocatalytic water splitting for H2 production.
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CHEMOSPHERE
·
2023
·
IF 8.8
Hao Li,Canyuan Lin,Ruhui Ma,Yuancai Chen
In this study, the selective adsorption of aromatic compounds on mesoporous MIL-53(Al) was investigated, and followed the order: Biphenyl (Biph) > Triclosan (TCS) > Bisphenol A (BPA) > Pyrogallol (Pyro) > Catechol (Cate) > Phenol (Phen), and exhibited high selectivity toward TCS in binary compounds. In addition to hydrophobicity and hydrogen bonding, π–π interaction/stacking predominated, and more evidently with double benzene rings. TCS-containing halogens could increase π interaction on the benzene rings via forming Cl–π stacking with MIL-53(Al). Moreover, site energy distribution confirmed that complementary adsorption mainly occurred in the Phen/TCS system, as evidenced by Δ Q pri (the decreased solid-phase TCS concentration of the primary adsorbate) < Q sec (the solid-phase concentrations of the competitor (Phen)) . In contrast , competitive sorption occurred in the BPA/TCS and Biph/TCS systems within 30 min due to Δ Q pri = Q sec , followed by substitution adsorption in the BPA/TCS system, but not for the Biph/TCS system, likely attributed to the magnitude of energy gaps (E g ) and bond energy of TCS (1.80 eV, 362 kJ/mol) fallen between BPA (1.74 eV, 332 kJ/mol) and Biph (1.99 eV, 518 kJ/mol) according to the density-functional theory of Gaussian models. Biph with a more stable electronic homeostasis than TCS lead to the occurrence of substitution adsorption in the TCS/BPA system, but not in the TCS/Biph system. This study provides insight into the mechanisms of different aromatic compounds on MIL-53(Al).
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY
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2022
·
IF 1.193
Linli HOU,Li WANG,Yonghai SONG,Limin LIU
A luminescent hydroxyl-functionalized MIL-53(Al) (OH-MIL-53(Al)) was prepared by one-step solvent thermal method for multiresponsive fluorescence sensor. The OH-MIL-53(Al) exhibited uniform nanospheres with average diameter of 150±20 nm, flexible three-dimensional frameworks, and good dispersion in water. The OH-MIL-53(Al) emitted green fluorescence with a maximum wavelength of 515 nm which showed good fluorescence quenching response for sensing F − and fluorescence enhancement response for water, with good day-to-day stability. The mechanism was based on protonation/deprotonation of hydroxyl group located on OH-MIL-53(Al). Good linear relationship could be found between the luminescence intensity of 515 nm and F − concentrations in the range of 0–60 µM with a determination limit of 70 nM. At the concentrations from 0% to 100%, the fitting curve for water content was in good agreement with the linear equation, and the detection limit was 0.10%. OH-MIL-53(Al) demonstrated excellent fluorescence sensing performance, indicating that it could be used as a multiresponsive sensor to practical application.
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RSC Advances
·
2022
·Vol. 12
·期 34
·21681-21689
·
IF 4.036
Na Cao,Jiayi Liu,Yuecheng Wang,Yingwu Zhou,Meng Zhao,Yujie Ban,Weishen Yang
The adsorption of bio-polyols from dilute aqueous solution is important but faces challenges in the sustainable bio-refinery process. One solution to increase adsorption efficiency is to leverage host–guest interactions between the polyols and materials to grant a preference for polyols. In this study, we synthesized MIL-53 and diverse OH-bonded variants, and studied their adsorption properties towards ethanediol, 1,3-propanediol and glycerol in water. Among the four materials, OH–MIL-53 exhibited fast adsorption kinetics and high capacity, and could be completely regenerated through ethanol elution. Hydrophobic interactions between the alkyl chains of the polyols and the organic linkers of OH–MIL-53 and hydrogen bonding interactions between their OH groups were identified. The synergistic effect of the host–guest interactions is responsible for the unique adsorption performances of OH–MIL-53 towards polyols, and particularly for 1,3-propanediol.
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Frontiers in Bioengineering and Biotechnology
·
2022
·
IF 6.064
Xie Dan,Wang Ruimeng,Fu Jinghao,Zhao Zhongxing,Li Min
Surface-enhanced Raman scattering (SERS) is an important and powerful analytical technique in chemical and biochemical analyses. Metal–organic frameworks (MOFs) can effectively capture volatile organic compounds (VOCs) with high adsorption capacity and fast kinetics, and the local surface plasmon resonance characteristics of gold nanoparticles can quickly and effectively distinguish different VOCs by SERS. Combining both, we designed a novel SERS substrate based on embedding gold nanoparticles (AuNPs) within MIL-101(Cr) for the recognition of various VOCs in the gaseous phase. Occupying of AuNPs inside MIL-101(Cr) increased the micropore-specific surface area of AuNPs@MIL-101(Cr), which enabled AuNPs@MIL-101(Cr) to absorb more toluene molecules and consequently realized its high detection sensitivity. The detection limits for toluene, 4-ethylbenzaldehyde, and formaldehyde were down to 6, 5, and 75, ppm respectively. Moreover, this substrate could be used for detecting different VOCs simultaneously. Finally, we discussed the enhancement of AuNPs outside and inside MIL-101(Cr) on the Raman signal.
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