ACS Applied Materials & Interfaces
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2023
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IF 9.5
Xiaoyu Hu,Fengyun Ding,Renjin Xiong,Yongtao An,Xingwen Feng,Jiangfeng Song,Linsen Zhou,Peilong Li,Changlun Chen
Realizing ideal deuterium separation from isotopic mixtures remains a daunting challenge because of their almost identical sizes, shapes, and physicochemical properties. Using the quantum sieving effect in porous materials with suitable pore size and open metal sites (OMSs) enables efficient hydrogen isotope separation. Herein, synthetic HKUST-1-derived microporous mixed-valence Cu(I)Cu(II)-BTC (BTC = benzene-1,3,5-tricarboxylate), featuring a unique network of distinct Cu(I) and Cu(II) coordination sites, can remarkably boost the D2/H2 isotope separation, which has a high selectivity (SD2/H2) of 37.9 at 30 K, in comparison with HKUST-1 and other porous materials. Density functional theory (DFT) calculations indicate that the introduction of Cu(I) macrocycles in the framework decreases the pore size and further leads to relatively enhanced interaction of H2/D2 molecules on Cu(II) sites. The significantly enhanced selectivity of Cu(I)Cu(II)-BTC at 30 K can be mainly attributed to the synergistic effect of kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS). The results reveal that Cu(I) OMSs exhibit counterintuitive behaviors and play a crucial role in tuning quantum sieving without a complex structural design, which provides a deeper insight into quantum sieving mechanisms and a new strategy for the intelligent design of highly efficient isotope systems.
研究领域:
材料科学
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物理化学
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产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Xiaolong Fu,Yu Gong,Jiamao Li,Jingwei Hou,Junyan Wang,Wenjie Ding,Chengjian Xiao,Hongwen Huang,Heyi Wang
The separation of hydrogen isotopes is crucial in nuclear energy and biomedicine, but current techniques have limited separation coefficients. Utilizing flexible metal-organic frameworks (MOFs) with quantum sieving capabilities offers a promising solution. However, achieving high hydrogen isotope adsorption capacity while maintaining a high separation factor remains a challenge. This study presents a novel approach for the quantum sieving of hydrogen isotopes using MOFs with mobile ligands. The stable crystal structure of the microporous MOFs enables large hydrogen isotope adsorption capacity. The presence of mobile ligands acts as the gate in the dynamic adsorption and separation process, enhancing the performance of hydrogen isotope separation. The smaller quantum radius and larger molecular weight of deuterium facilitate its easier entry into the micropores, resulting in a maximum selectivity for D 2 over H 2 of 36.7 and a D 2 uptake of 17.3 mmol g −1 . Furthermore, the kinetic quantum sieving of hydrogen isotopes necessitates MOFs with mobile ligands that maintain their flexibility from 20 K to 70 K, as demonstrated by ultralow-frequency Raman spectra.
研究领域:
材料科学
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核能
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生物医药
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Rui Jiao,Yiwan Si,Wenjie Fan,Hanxue Sun,Jiyan Li,Zhaoqi Zhu,An Li
Considering the dangers of radioactive elements to the human body and the environment, the efficient and rapid removal of radioactive ions in water is an urgent matter. In this paper, an efficient adsorption material based on kinetic quantum sieving (KQS) effect through skillfully molecular design with specific space structure conjugated microporous polymer hollow spheres (CMPs-1) for disposal of radioactive iodide/cesium ions is reported. The adsorption properties of iodide/cesium ions at different concentrations at 10℃ were investigated. Moreover, the test results show that the iodide ions adsorption capacity of the CMPs-1 will increase with the increase of iodine ions concentration when the temperature, volume, and other conditions are fixed. The CMPs-1 exhibited up to the highest 16.93 mg g −1 iodide adsorption capacity for the solution containing 0.10 mmol L -1 iodide ions within 6 h under static adsorption experiments at a low temperature of 10℃, and the adsorption rate fitted by the pseudo-second-order kinetic model was 0.11 g mg -1 h −1 . Besides, the CMPs-1 maintained an effective adsorption capacity of 16.93, 7.51 and 5.92 mg g -1 at pH = 7, 10 and 13, respectively. Furthermore, unexpectedly, the constructed CMPs-1 showed superior heat resistance with higher adsorption capacity (26.32 mg g -1 , 1.6 times) at 30℃ compared to 10℃. The improvement reason is that the expansion of pores (significantly increased at 4–20 nm), and the developed porosity can provide enough space to accelerate the diffusion rate of reactants and intermediates, exposing more active sites. And the π-conjugated system and hollow structure of CMPs materials can effectively solve the problem of low diffusion rate caused by low temperature and microporous structure in the transfer of iodide/cesium ions. Therefore, this work demonstrates the customizable potential of materials in the field of molecular adsorption applications and also provides a new idea for the design of unique hollow structure adsorption materials.
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
高影响因子
INORGANIC CHEMISTRY
·
2023
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IF 4.6
Enming Ping,Xiaoxiao Chen,Yunshan Zhou,Lijuan Zhang,Lingyun Kong,Nan Chen
In this work, CAU-10-H@γ-AlOOH is prepared, and then UTSA-16 is loaded on CAU-10-H@γ-AlOOH to obtain UTSA-16@CAU-10-H@γ-AlOOH. Using the as-prepared composites as stationary materials by cryogenic gas chromatography at 77 K, while CAU-10-H@γ-AlOOH achieves the complete separation of ortho-H2 (o-H2) and D2 with a resolution R of 1.66 and a separation time t of 9.52 min, UTSA-16@CAU-10-H@γ-AlOOH achieves higher efficiency separation of hydrogen isotopes in a shorter separation time (4.56 min) with R = 1.7. Molecular simulation results show that CAU-10-H has both chemical affinity quantum sieving and kinetic sieving effects for H2/D2 at 77 K, and UTSA-16 can only exert the kinetic sieving effect. UTSA-16’s load on CAU-10-H@γ-AlOOH weakens the adsorption of hydrogen isotopes, and the presence of Co2+ in UTSA-16 promotes the conversion of para-H2 to ortho-H2. In gas chromatography, H2 was preferentially desorbed from the system due to strong D2 adsorption caused by the chemical affinity quantum sieving effect and faster H2 diffusion caused by the kinetic sieving effect. These additive effects achieved efficient hydrogen isotope separation at 77 K.
研究领域:
化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
Science China-Chemistry
·
2024
·Vol. 67
·期 4
·1242-1249
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IF 10.4
Zhang Jingjing,Deng Yongyan,Gai Dongxu,Shi Yang,Feng Xingwen,Li Peilong,An Yongtao,Zou Xiaoqin
Isotopic separation is of paramount importance for producing high-purity heavy hydrogen, yet the process remains hugely challenging. Here, we report on an Fe/ZSM-5 zeolite that was able to efficiently separate deuterium from protium via chemical quantum sieving. Structural data showed that four types of Fe species were present in Fe/ZSM-5 and oligomeric Fe–O clusters in the zeolite pores were correlated directly with gas selectivity. Gas adsorption revealed that Fe–O species served as the main adsorption sites and interacted with D 2 more strongly than with H 2 . D 2 /H 2 separation was exemplified using thermal desorption spectroscopy. D 2 /H 2 selectivity increased with Fe loading in Fe/ZSM-5 and a selectivity of 32.1 was obtained with an optimal loading of 7 wt%. The shift of desorption temperature supports the chemical affinity-based quantum sieving of D 2 over H 2 . This study demonstrates an effective strategy for enhancing D 2 /H 2 separation and the high selectivity means that Fe/ZSM-5 has strong potential in hydrogen isotope separation.
研究领域:
材料科学
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物理化学
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分离科学
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催化化学
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纳米材料
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DOI
高影响因子
DALTON TRANSACTIONS
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2022
·Vol. 52
·期 2
·376-383
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IF 4.569
Enming Ping,Lingyun Kong,Mengyao Liu,Yunshan Zhou,Lijuan Zhang,Nan Chen
The reaction of porous γ-Al2O3 particles acting as both a sacrificial template and an aluminum source with 1,4-naphthalene diacid (H2NDC) resulted in the formation of γ-AlOOH@Al(OH)(1,4-NDC) composites, in which ZIF-67 was then loaded by the in situ crystallization method, leading to the formation of γ-AlOOH@Al(OH)(1,4-NDC)@ZIF-67 composites. The deliberately designed composite was used to separate H2/D2 at 77 K in a 1 m chromatographic column. The results demonstrated that the optimized composite can achieve the effective separation of H2/D2 in gas chromatography due to the additive effects of kinetic sieving and chemical affinity quantum sieving of Al(OH)(1,4-NDC) and ZIF-67. By optimizing chromatographic separation conditions, the resolution R reached 2.02 with the separation time t = 7.72 min. The composite also showed satisfactory repeatability and reproducibility.
研究领域:
材料科学
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分离科学
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物理化学
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纳米材料
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能源化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）