CRYSTENGCOMM
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2016
·Vol. 18
·期 39
·7614-7619
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IF 3.849
Somboon Chaemchuem,Zhou Kui,Francis Verpoort
Lithium incorporation in metal–organic frameworks during solvothermal synthesis demonstrates a significant modification of the structure chemistry and surface properties of MOFs towards the adsorption selectivity of gas mixtures (CO2 and CH4) at ambient conditions. Variation of the lithium loading (xLi-MOF-5) led to tunability of the interpenetration resulting in materials with substantial differences in their properties. The behavior of xLi-MOF-5 was evaluated via phase identification based on XRD, functional group coordination using FTIR and adsorption measurements applying N2, CO2 and CH4 gas adsorption/desorption analysis. These efforts give rise to a new strategy to tailor MOFs for high efficiency CO2 adsorption and separation.
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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物理化学
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纳米技术
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
·
IF 19.7
Yunhong Pi,Quanming Chen,Qin Xu,Yating Han,Weilong Wang,Xiaolan Cai,Zhuowen Huang,Tiejun Wang
Microwave-enabled coordination reconstruction creates Ni–O–Sn–N motif in MOFs. • Ni sites and Sn relay nodes promote a short-range N→Sn→O→Ni LMCT pathway. • The electron-relay architecture enhances charge transfer and suppresses recombination. • Ni-Sn/e-NH 2 -UiO-66 delivers 293.6 mmolg cat −1 h −1 H 2 production with < 1% CO. • Operando studies and DFT support a formate-mediated photothermal reforming pathway. Engineering efficient ligand-to-metal charge transfer (LMCT) pathways in metal-organic frameworks (MOFs) is critical for enhancing photothermal redox catalysis but remains challenging due to limited electronic coupling between photosensitive ligands and catalytic metal centers. Here, we report a microwave-enabled coordination reconstruction strategy to construct cascaded LMCT pathways within NH 2 -UiO-66 for efficient photothermal methanol-to-hydrogen conversion. By sequentially anchoring high-density Ni sites and incorporating Sn species as electronic relay nodes, a directional N→Sn→O→Ni charge-transfer network is proposed inside the MOF scaffold. Microwave irradiation not only promotes structural polarization but also drives the formation of a strongly coupled heteroatomic coordination environment, enabling shortened electron migration distance and accelerated interfacial charge transport. The optimized Ni-Sn/e-NH 2 -UiO-66 catalyst exhibits a H 2 production rate of 293.6 mmolg Cat −1 h −1 , 13 times higher than that of the thermocatalytic counterpart, with an apparent quantum efficiency of 56.7% at 380 nm. Benefiting from synergistic photothermal activation and enhanced LMCT efficiency, methanol reforming is initiated at a low temperature of 120 °C with suppressed CO formation. This work highlights microwave-assisted LMCT cascade engineering as a versatile strategy for programming directional charge-transfer pathways in MOF-based photothermal catalytic systems. Download: Download high-res image (260KB) Download: Download full-size image Microwave irradiation is employed as a coordination-engineering tool rather than a conventional heating source, enabling the formation of a heteroatomic Ni–O–Sn–N coordination motif through stepwise installation of high-density Ni single sites and Sn relay nodes in etched NH 2 -UiO-66 framework. The resulting resulting electronically coupled architecture promotes a short-range N→Sn→O→Ni electron-relay pathway, facilitating ligand-to-metal charge transfer and electronic utilization for efficient photothermal methanol reforming.
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高影响因子
Catalysis Science & Technology
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2020
·Vol. 10
·期 6
·1699-1707
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IF 5.721
Yu-Ping Xu,Zhi-Qiao Wang,Hong-Zi Tan,Kai-Qiang Jing,Zhong-Ning Xu,Guo-Cong Guo
CO esterification to dimethyl carbonate (DMC) is an attractive route, although the catalyst is the main problem restricting the industrialization of this route. Supported palladium catalysts have been often used for this route. However, the effect of the support is not always clear. In this work, we firstly introduced three metal–organic frameworks (MOFs) materials as catalyst supports, namely UiO-66, MIL-101 and MOF-5, and studied the effect of Lewis acid sites in the MOFs supports on the catalytic activity and selectivity for CO esterification to DMC. Interestingly, the Pd(II)/UiO-66 catalyst exhibits superior catalytic performance to the other catalysts, with 87.9% CO conversion and 98.5% DMC selectivity due to the abundant Lewis acid sites in UiO-66. It was proven that UiO-66 with more defects would have a large number of Lewis acid sites, and the catalytic performance was positively correlated with the number of Lewis acid sites in MOFs supports, which can be demonstrated by characterization by NH3-TPD, pyridine-IR, XPS and in situ DRIRS. The current work not only revealed the relationship between the Lewis acidity of the support and catalytic performance, but also promotes the development of practical catalysts for CO esterification to DMC.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
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2022
·
IF 4.598
Qi Zhang,Tao Wei,Jiahao Lu,Cheng Sun,Yanyan Zhou,Mengting Wang,Ye Liu,Beibei Xiao,Xiangyun Qiu,Shoudong Xu
All solid-state lithium-ion batteries (ASSLBs) are thought to benefit from using solid composite electrolytes (SCEs) to increase their energy density and safety. In this study, we firstly introduce the PVB additives to SCEs and prepared a SCE composed of a mixture of nanostructured MOFs (UiO-67), PVDF-HFP, PVB, and LiTFSI. Electrochemical characterizations of the SCEs (EIS, LSV, CV and battery test) were also conducted. The SCE UBP-2 (PVB:PVDF-HFP = 1:10) shows a high lithium-ion transference number (t Li + =0.72) and good ionic conductivity (3.27×10 −4 S cm −1 at 60 °C). A symmetric Li cell with SCE UBP-2 can be continuously cycled at 0.1 mA cm −2 for more than 2500 h without experiencing a short circuit. The full cell (LiFePO 4 /UBP-2/Li) also maintained a high reversible discharge capacity of 154.9 mAh g −1 at 0.1C after 200 cycles at 60 °C. At 3C, a capacity of around 100 mAh g −1 was also achieved. This work might help to enhance the development of the forthcoming all solid-state batteries.
研究领域:
材料科学
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能源存储
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产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
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2023
·
IF 8.4
Yi Yang,Licheng Yu,Xiaowen Jiang,Yijun Li,Xiwen He,Langxing Chen,Yukui Zhang
A dual-modality enzyme assay combining the fluorescence and colorimetry merits based on nanoscale metal-organic frameworks (nMOFs) was established for the analysis of glutathione S-transferase (GST). In this design, HKUST-1 with Cu II metal nodes, was chosen as nMOFs and encapsulated with rhodamine 6 G (Rho 6 G) in one-step reaction to fabricate the functional nMOFs (Rho 6 G@Cu-MOFs). As a proof of concept , as a GST binding substrate, reductive glutathione (GSH) invokes competitive coordination with Cu nodes through sulfur atom as well as the valence transformation, of which the process results in coordination bond leakage and even framework collapse, leading to the releasing of internal Rho 6 G dyes for fluorescence-modality analysis. In addition, reductive GSH can interact with Cu nodes in the nMOFs and modulate Cu II to Cu I , along with a color change for colorimetry analysis. The dual-modality assay shows high analytical performance for GST quantification in a linear range of 0.25–100 nM with a detection limit down to 0.13 nM for fluorescence modality, and a linear range of 1–100 nM with a detection limit of 0.64 nM for colorimetry modality. In addition, the precision of the dual-modality assay shows good agreements with commercial GST activity assay kit.
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高影响因子
INORGANIC CHEMISTRY
·
2026
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IF 4.6
Peng Hu,Lvming Jin,Long Li,Xianlv Pan,Jialang Hu,Gui Shi,Mingyuan Jiang,Jun Wu,Chao Xiong,Shenwei Chen,Hongbing Ji
The removal of trace alkane impurities remains challenging due to their similar molecular properties. Here we propose a self-boosting kinetic separation process enabled by a “molecular lubrication” strategy, in which trace propane acts as a dynamic lubricant within a tailored Fe-based MOF featuring a bottleneck pore structure. Using in situ synchrotron XRD, DFT, and molecular simulations, we show that propane preferentially occupies the wide cavities rather than the narrow pore necks, smoothing the diffusion pathway and lowering the energy barrier. This leads to a volcano-shaped pressure dependence of diffusivity with an optimum at ∼5 kPa. Breakthrough experiments with a natural-gas mixture (CH4/C2H6/C3H8 = 85/10/5, v/v/v) yield methane purity ≥99.99%. Six-bed vacuum pressure-swing adsorption simulations further demonstrate a high CH4 recovery (80.4%), purity (≥99.95%), and productivity (4.04 mol kg–1 h–1). This work illustrates how trace-impurity-induced lubrication can be harnessed to design MOFs with enhanced diffusion kinetics for gas separation.
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DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
·
IF 9
Zhanqin Wang,Fei Shao,Mingzhe Dong,Xingwu Zou,Bo Li,Yan Jing,Shuxuan Wang,Yongzhong Jia
The rational design of high-performance adsorbents for lithium recovery from aqueous resources depends critically on understanding how metal doping modulates the structure and properties of metal-organic frameworks (MOFs). In this work, we systematically investigate the effects of Fe doping on the lithium adsorption and isotope separation performance of Al-MOFs through controlled synthesis of bimetallic Al/Fe-MOFs with varying metal ratios (1:4 to 4:1). The materials were characterized by XRD, XPS, TGA, and adsorption experiments, complemented by density functional theory calculations. Results show that optimal Fe incorporation (Al/Fe = 2:1) significantly improves Li + adsorption capacity (24.07 mg g −1 ) and isotopic selectivity ( α = 1.033) compared to the undoped MOFs ( Q = 12.97 mg g −1 , α = 1.027). Structural analyses reveal Al/Fe-MOFs contraction (Δ d (002) = 0.36 Å) and surface charge modification (pH ZPC shift from 10.26 to 8.73), while electronic structure studies demonstrate Fe 3+ /Fe 2+ redox activity promotes electron transfer. DFT calculations identify greatly increased adsorption energetics (−3.96 eV) through synergistic Al O/Fe O interactions, where the rigid Al O framework ensures structural stability and flexible Fe O sites support dynamic adsorption. The material exhibits excellent cycling stability (92 % capacity retention) due to dual stabilization mechanisms. These findings confirm that balanced bimetallic coordination in MOFs can enhance adsorption capacity and selectivity through geometric and electronic effects, providing valuable insights for designing advanced adsorbents for lithium recovery.
研究领域:
材料化学
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无机化学
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环境科学
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能源化学
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分离科学
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计算化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
·
IF 13.2
Cao Yang,Shanshan Shang,Yixuan Wang,Pei Wang,Lianpeng Sun,Xiao-yan Li
Single-atom catalysts (SACs) have garnered significant attention owing to their high reactivity; however, precise control of their electronic structure for Fenton-like process remains a challenge. In this study, we develop a novel technique for regulating the electronic environment of Cu-SACs to activate peroxymonosulfate (PMS) for highly effective degradation of emerging organic pollutants in water. By in-situ axial modification of Cu-SACs with Cu 2 O nanoclusters within a porphyrin metal–organic framework (Cu 2 O clu -Cu SA /PMOF), we finely tuned the electronic structure of Cu-SACs, leading to the selective generation of singlet oxygen ( 1 O 2 ) as the predominant reactive species in a nonradical Fenton-like process. The rate constant of the Cu 2 O clu -Cu SA /PMOF catalyst for PMS oxidation of sulfamethoxazole (SMX) surpassed that of Cu 2 O and Cu SA /PMOF by 12.9 and 3.7 times, respectively, outperforming most state-of-the-art heterogeneous catalysts for PMS activation. Density functional theory calculations elucidated that the modulation of electronic structure of the Cu sites in Cu 2 O clu -Cu SA /PMOF led to the preferred adsorption of PMS in the terminal-O mode and altered the electron transfer from PMS to the Cu sites for 1 O 2 generation through the self-reaction of SO 5 •− intermediates. This work presents a new material strategy by modulating the functionality of single-atoms via axial incorporation of nanoclusters in MOFs, realizing a highly efficient and selective Fenton-like oxidation process for sustainable water purification.
研究领域:
环境科学
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材料科学
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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
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2023
·
IF 15.1
Zhiyuan Liu,Linmeng Wang,Changan Wang,Rushuo Li,Peiyun Zhou,Hongyi Gao,Ge Wang
Strong metal-support interaction (SMSI) plays an important role in heterogeneous catalysis, but the influence of the chemical microenvironment of metal on it is often neglected. In this study, a mesoporous Ce-MOFs with pyridine N sites and open metal sites (OMS) were constructed, and highly dispersed Pt nanoclusters (NCs) and Pt-N x interface were subsequently introduced and constructed via SMSI effect for hydrogenation of dicyclopentadiene (DCPD). The spectroscopic results and density functional theory (DFT) computations demonstrate that pyridine N and OMS can regulate the SMSI effect between Ce-PyDC and Pt through Pt-N x interface and electronic interaction between Pt and OMS, which increase electron cloud density of Pt nanoclusters, promote DCPD adsorption, H 2 activation. The optimal Pt NCs@Ce-PyDC-3 can efficiently convert DCPD to tetrahydrodicyclopentadiene (THDCPD) at 50 °C, giving a 100 % DCPD conversion and 99 % THDCPD selectivity. This work provides an in-depth understanding of the correlation between the metal nanoparticle microenvironment and SISM effect.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2020
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IF 9.038
Yu Zhang,Hong Zheng,Pengyi Zhang,Xianming Zheng,Qi Zuo
Heavy metals are seriously hazardous contaminants and drinking water has been identified as an important route of human exposure to them. Herein, to efficiently and selectively remove trace heavy metal ions , a facile method was reported to achieve the slow polymerization of dopamine in the cages of MIL-100 (Fe) via ultrasonic treatment followed by the hydrolysis of the urea. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Brunner-Emmet-Teller (BET) and pore size distribution determination confirmed the formation of the polydopamine (PDA) and binding with the unsaturated Fe 3+ site in MIL-100 (Fe) pores. The composite not only retained pore structure of MOFs but also contained abundant reactive functional groups. When initial lead concentration was 150 ppb and 20 ppm calcium coexisted at pH of 6.5 ± 0.25, the effluent lead concentration met the safe drinking water standard in several tens of seconds, and decreased to 1.13 ppb in 10 min. The adsorption rate reached 99.35%. The synthetic strategy effectively overcomes mass transfer resistance of trace heavy metal ions and provides a facile approach to prepare adsorption materials for efficient and selective removal of trace heavy metal ions from drinking water.
研究领域:
环境科学
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材料科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Chao Feng,Yuehong Xie,Shanshan Qiao,Yuan Guo,Shiang Li,Li Zhang,Wei Wang,Jide Wang
We used a simple MOFs-assisted synthesis strategy based on the encapsulation and in-situ carburizing reaction of Cu-based metallic organic frameworks (NENU-5) to synthesize porous nano-octahedral materials, MoWN/MoWC@N C Ts (T = 700, 800, and 900). Together with the vapor deposition strategy, the volatile nitrogen species from the pyrolysis of dicyandiamide were captured by the nano-octahedral materials, and formed tungsten-molybdenum-based carbonitride nanocrystals encapsulated in nitrogen-doped carbon. The porous nano-octahedron has a unique heterostructure composed of Mo 2 N/MoC/W 2 N/WC. The representative MoWN/MoWC@N C 800 showed trifunctional electrocatalytic activity in oxygen reduction reaction/oxygen evolution reaction/hydrogen evolution reaction (ORR/OER/HER) in an alkaline medium (0.1 M KOH). The total oxygen electrode activity index ΔE = 0.795 V (vs. RHE) was found in OER/ORR, and the material also exhibits excellent HER performance. The minimum potential of −0.17 V (vs. RHE) was provided at a current density of −10 mA cm −2 . MoWN/MoWC@N C 800 showed excellent cycle stability and durability in ORR/OER/HER with the same electrolyte (0.1 M KOH). More importantly, MoWN/MoWC@N C 800 could be used to construct high-performance zinc-air batteries and sued for driving electrocatalytic water splitting in a self-powered manner. The successful preparation of the materials indicate that the synthetic strategy provides new reference ideas for developing functional materials with high catalytic properties for various applications.
研究领域:
材料科学
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电化学
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催化科学
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DOI
高影响因子
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