MOLECULES
·
2024
·Vol. 29
·期 8
·1721
·
IF 4.2
Shoudong Wang,Lei Zhou,Hongyun Qin,Zixu Dong,Haoyuan Li,Bo Liu,Zhilu Wang,Lina Zhang,Qiang Fu,Xia Chen
Hydrofluorocarbons (HFCs) have important applications in different industries; however, they are environmentally unfriendly due to their high global warming potential (GWP). Hence, reclamation of used hydrofluorocarbons via energy-efficient adsorption-based separation will greatly contribute to reducing their impact on the environment. In particular, the separation of azeotropic refrigerants remains challenging, such as typical mixtures of CH2F2(HFC-23) and CHF3(HFC-32), due to a lack of adsorptive mechanisms. Metal–organic frameworks (MOFs) can provide a promising solution for the separation of CHF3–CH2F2mixtures. In this study, the adsorption mechanism of CHF3–CH2F2mixtures in TIFSIX-2-Cu-i was revealed at the microscopic level by combining static pure-component adsorption experiments, molecular simulations, and density-functional theory (DFT) calculations. The adsorption separation selectivity of CH2F2/CHF3in TIFSIX-2-Cu-i is 3.17 at 3 bar under 308 K. The existence of similar TiF62−binding sites for CH2F2or CHF3was revealed in TIFSIX-2-Cu-i. Interactions between the fluorine atom of the framework and the hydrogen atom of the guest molecule were found to be responsible for determining the high adsorption separation selectivity of CH2F2/CHF3. This exploration is important for the design of highly selective adsorbents for the separation of azeotropic refrigerants.
研究领域:
材料科学
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环境科学
·
化学工程
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
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
·
物理化学
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DOI
PubMed
高影响因子
RSC Advances
·
2017
·Vol. 7
·期 11
·6605-6614
·
IF 3.108
Ce Gao,Qingda An,Zuoyi Xiao,Shangru Zhai
Nowadays, processing of ultra-low sulfur fuel oil has been a hot topic of research all over the world; hence, an efficient adsorption process to tackle this issue is eliciting increasing attention. However, the preparation of high-performance adsorbents is still a challenge. Herein, zirconium-substituted mesoporous SBA-15 with highly dispersed active Cu(I) species has been successfully synthesized by our group at 493 K via a mild vapor-reduction method. The as-prepared material was characterized by powder X-ray diffraction (XRD), nitrogen adsorption and desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-vis diffuse reflectance (DRUV) spectroscopy. All characterization methods demonstrated that the Cu(I) species were highly dispersed in an ordered mesoporous framework with short channels rather than piled on the surface. The as-prepared materials also exhibited an excellent adsorption capacity for thiophene (up to 29.86 mg g−1 at 323 K). Pseudo-second-order kinetics model and Freundlich isotherm can well describe the adsorption kinetics and isotherm data, respectively. More remarkably, an ultrasound-assisted treatment can be effectively employed to regenerate adsorbent, with only a slight reduction in the adsorption capacity after five cycles.
研究领域:
材料科学
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能源化学
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环境工程
✓ 已验证
DOI
高影响因子
Small
·
2023
·Vol. 19
·期 49
·2304644
·
IF 13.3
Ping Lu,Zhaoyang Qi,Jie Chen,Changshen Ye,Ting Qiu
High-efficiency adsorption of aromatic sulfur-containing compounds from liquid hydrocarbon fuels over metal-organic frameworks (MOFs) is challenging because of inert metal sites. A new method, the Ce-enhanced modulation of MOFs’ microenvironment, is proposed to modulate the –COO···Cu(II)– coordination microenvironment of Hong Kong University of Science and Technology (HKUST-1) using Ce(III) as a molecular scalpel for fabricating abundant high-efficiency Cu(I) and Cu-coordination-unsaturated sites and improving the pore structures around adsorptive sites. The optimal CH-250 thus exhibits adsorptive capacities for 20.2, 28.0, and 58.3 mg S g –1 of thiophene, benzo-thiophene, and dibenzothiophene, respectively, which are superior to most reported MOFs, zeolites, and nanoporous carbons. The constructed Cu(I) sites show stronger affinity for dibenzothiophene (−0.86 eV) than the initial Cu(II) (−0.74 eV) for out-of-plane adsorption. Further, they are far stronger in-plane adsorption interactions in DBT/CH-250 (−0.90 eV) than those in DBT/HKUST-1 (−0.37 eV). Thus, molecular engineering for modulating the coordination microenvironment of MOFs shows great potential for adsorption desulfurization.
研究领域:
材料科学
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能源化学
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产品关联
DOI
PubMed
高影响因子
SEPARATION SCIENCE AND TECHNOLOGY
·
2013
·
IF 1.164
Xiaochun Chen,Shuimin Ming,Xinying Wu,Chang Chen,Charles Asumana,Guangren Yu
The absorption of propylene and propane in Cu(I)-based ionic liquids, i.e., 1-butyl-3-methylimidazolium chloride/CuCl ([Bmim][Cl]/CuCl), N-Methyl pyrrolidone chloride/CuCl ([HNMP][Cl]/CuCl), and tricaprylmethylammonium thiocyanate/CuSCN ([A336][SCN]/CuSCN), are investigated in this work. It is observed that such Cu(I)-based ionic liquids, especially Bmim-based ionic liquids, present good absorption capability for propylene and good selectivity over propane, e.g., 1.0 kilogram [Bmim][Cl]/CuCl is able to absorb 0.08 mol propylene while only 0.006 mol propane at 25°C and 1.3 bar with the selectivity of 13. The effects of pressure, Cu+ concentration, and temperature on the absorption are investigated; in addition, the absorption kinetics of propylene by [Bmim][Cl]/CuCl is obtained. The much higher absorption capability for propylene than propane is ascribed to the π-complexation between propylene and Cu+. This work shows that the absorption by Cu(I)-based ionic liquids is an potential alternative method for traditional cryogenic distillation with high energy cost to separate propylene and propane.
研究领域:
化学工程
·
材料科学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Mingxian Duan,Yeshuang Wang,Huiling Fan,Zhelin Su,Chao Yang,Jiawei Kou,Ju Shangguan
Thiophene (C 4 H 4 S) removal from coke oven gas is critical to its subsequent high valuable utilization but remains a challenge. MOF-199 was considered as a promising candidate for C 4 H 4 S adsorption removal owing to its nature of enriched opened Cu sites. However, the presence of mixed valence of Cu(II) and Cu(I) in MOF-199 makes it puzzling to their respective contribution to the removal of C 4 H 4 S. Herein, a series of MOF-199 with different Cu(I) contents were synthesized using different methods, including hydrothermal, solution diffusion, and ultrasonic, and their C 4 H 4 S adsorption performance were investigated. The respective contributions of Cu(II) and Cu(I) to the C 4 H 4 S removal was systematically discussed. The collected results indicated that although the samples prepared with different methods present a remarkable difference in textural characters, the latter was found to have a negligible influence on the C 4 H 4 S removal owing to MOF-199(H) affording an inferior surface area and pore volumes but performing the best C 4 H 4 S removal capacity of 53.7 mg S/g. The co-adsorption results of CH 3 SCH 3 and C 4 H 4 S indicated that the excellent performance of MOF-199(H) mainly attributed to the presence of Cu(I), which provides active sites for C 4 H 4 S adsorption through π complex coordination. Cu(II) species was also found to the C 4 H 4 S adsorption via soft-acid-base coordinated interaction, but its contribution is 8.3 mg S/g, only accounting for 15.5 %. Additionally, the adsorption of C 4 H 4 S on MOF-199(H) was found to follow the intra-particle diffusion model and the Langmuir models. Moreover, MOF-199(H) also exhibited an excellent regeneration performance due to the weak interaction between C 4 H 4 S and their opened Cu sites, the C 4 H 4 S adsorption capacity still reaches 50.6 mg S/g after three regeneration cycles, about 94 % of its initial value. The results collected in this study will provide new insights for the manipulation of performance of C 4 H 4 S adsorption on the MOF-199.
研究领域:
材料科学
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环境科学
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产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Songhao Yu,Guifen Tian,Liduan Li,Fei Wang,Kefeng Wang,Junyu Lei,Haijun Hao,Qinghong Xu
TpFO-PA, a novel spherical hollow mesoporous polyamide, was firstly synthesized by the reaction among 1,3,5-tris(4-aminophenyl)benzene (TAPB), furylamine and oxalyl chloride in using silica-gel nanoparticle as hard template, and the composite Cu(I)@TpFO-PA with high catalytic activities in C-N coupling reactions between (hetero)aryl bromide and (hetero)aryl amines under mild conditions was prepared basing on presence of N in the framework. A maximum activity of the catalyst with yield of C-N coupling product were about 311.9 g (product) /mol Cu(I) ·h and 95 % respectively, and the activity could be maintained at least 5 times after the catalyst was reused. The composite Cu(I)@TpFO-PA is a few heterogeneous catalysts reported in catalyzing coupling reaction between aromatic amines and brominated aromatic compounds.
研究领域:
化学
·
材料科学
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产品关联
DOI
高影响因子
CHEMICAL PAPERS
·
2017
·Vol. 72
·期 1
·51-56
·
IF 1.258
Wei Mengyi,Qian Chao,Chen Xinzhi
Based on the recycling of NO
x
, the Cu(I)- and HNO 3 -catalyzed oxidation of 2-chloro-4-(methylsulfonyl)toluene to 2-chloro-4-(methylsulfonyl)benzoic acid has been developed with an excellent yield of 84.2% and a purity of 99.7%. The optimized reaction conditions (160 °C, oxygen pressure 1.5 MPa, HNO 3 concentration 25 wt%, HNO 3 : substrate 0.5:1) use 1.0 mol% CuI as catalyst. The dosage of HNO 3 in the new process is only 25% of the stoichiometric amount and 12.5% of the amount of the traditional process. The NO
x
emission is 5% amount of the traditional process. The oxidation of several additional toluene derivatives with comparable yields demonstrates the generality to these reaction conditions.
研究领域:
化学
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环境科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Shuaiqi Zhao,Peng Wu,Jiajin Lin,Yifei Li,Anqi Li,Xiaojing Jin,Yu Chen,Bote Zhao,Yun Zhao,Guangxu Chen,Yongcai Qiu,Daiqi Ye,Shihe Yang
The development of low-temperature and water-resistant heterogeneous catalysts without noble metals is vital in the effective treatment of atmospheric pollutants in practical application. Herein, we report that Cu(I)-O-Co interfaces of ultrafine CuO x on Co 3 O 4 prepared by co-precipitation exhibit promising low-temperature activity and good water resistance. Experiment results together with density functional theory (DFT) calculations not only verify that Cu + species are stabilized over Cu(I)-O-Co interfaces because of the strong interaction between Cu 2 O 1 and Co 3 O 4 , but also demonstrate that the Cu(I)-O-Co interface facilitates oxygen species activation for promoting catalytic oxidation and reduces the accumulation of hydroxyl and bicarbonate species on the surface of CuO x /Co 3 O 4 . DFT calculations also reveal that the CO oxidation rate-limiting step via the dissociation pathway under dry conditions is the Co-OO-Cu species dissociation while the CO coupling with the adsorbed O 2 becomes the rate determining step for CO oxidation through the direct pathway over Cu(I)-O-Co interface under humid conditions. Further, the CuO x /Co 3 O 4 catalyst also exhibits superior and stable catalytic activity for toluene oxidation, comparable with partial supported noble metal catalysts (T 90 = 190 °C). The present work gives a useful strategy for the rational design of low-temperature and water-resistant non-precious-based catalysts to be applicable in CO and toluene removal in practical applications.
研究领域:
环境科学
·
材料科学
·
催化化学
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产品关联
DOI
高影响因子
Science Bulletin
·
2025
·
IF 21.1
Wanguo Gao,Zhe Lu,Yecheng Leng,Chengyang Wu,Yingfang Yao,Xi Zhu,Junchuan Sun,Xiwen Yu,Cheng Wang,Congping Wu,Wenlei Wu,Bing Wang,Lu Wang,Zhigang Zou
Cu-based catalysts attract considerable attention because of their exceptional CO 2 photo-/electro-/thermo-reduction capacities, where Cu(I) is generally treated as the active species. However, a significant problem hindering the large-scale applications of Cu-based catalysts is the inactivation of Cu(I) via irreversible redox to Cu(II)/Cu(0). This study proposes a Cu(I) valence pinning method based on hydroxyapatite (HAP). Experimental and theoretical studies demonstrate that the phonon resonance among the Cu(I) ions, their adjacent heteroatoms, and the intermediates adsorbed at the Cu(I) sites yields Cu(I) valence electrons in their lowest energy states. Thus, Cu(I) is stabilized, stable, and efficient photothermal CO 2 hydrogenation is promoted. However, because of the change of Cu(I) coordination environment during the CO 2 hydrogenation reaction, Cu(I) ions migrate into the bulk phase, leading to activity attenuation. Nevertheless, Cu(I) ions can be pulled out to the surface of HAP under the oxidative humid air condition, and the catalytic activity can be easily recovered. Thus, we propose a simple cyclic reaction/regeneration process. This enables the Ca 5 (FeCuCe) 5 -HAP catalyst to achieve the CO yield of 402.8 mmol g −1 h −1 and a CO 2 conversion rate of 27.7%, which is close to the thermodynamic equilibrium. This catalyst also displays a selectivity of approximately 100% and cycle stability of 156 h at 500 °C under a pressure of 1 atmospheric. Our study provides a viable method for the scale applications of Cu(I) based catalysts in the “negative carbon” industries.
研究领域:
材料科学
·
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Chem
·
2023
·
IF 23.5
Rongming Cai,Mingzi Sun,Fei Yang,Min Ju,Yanpeng Chen,M. Danny Gu,Bolong Huang,Shihe Yang
Summary By leveraging a Cu(OH)F precursor, we construct a disk-like Cu(I)/Cu(0) interface model (P-Cu x /Cu 2 OF) composed of F-stabilized Cu(I) shell and Cu(0) core by one-step pulsed potential conversion. The interfacial region is shown to facilitate ethanol formation, guaranteeing a high FE(C 2+ ) of up to 80.2%. Tuning the Cu(I)/Cu(0) ratio enhances the ethanol yield by 18.5-fold over pure P-Cu, with the corresponding partial current density (j ethanol ) reaching up to 128 mA/cm 2 . This is enabled by a 3.6-fold boost in selectivity for the ethanol product (35.4%) and an overall 7.8-fold boost in activity ( j C 2 + up to 288 mA/cm 2 ). The interactions between P-Cu and Cu 2 OF upshift the d-band center of Cu sites on the interface region, which is critical to asymmetrical C-C coupling to form OCCOH∗, concurrent with a lowered energy barrier for ethanol formation. On the other hand, the ethylene-forming symmetrical C-C coupling occurs primarily on P-Cu away from the Cu(I)/Cu(0) interface.
研究领域:
材料科学
·
电化学
·
催化
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Yiping Guo,Wei Xie,He Li,Jianping Li,Jun Hu,Honglai Liu
The adsorption desulfurization (ADS) is a promising technology for deep removing thiophene-type sulfurs, yet it remains challenges in maintaining good performance for real applications in the presence of water. Guided by theoretical calculations, we constructed hydrophobic selective channels by crosslinking porous aromatic framework (PAF) of PAF-56 on the surface of adsorbent MOF-199 with Cu nodes reduced. The optimized Cu(I)-BTC@PAF30 shows a high saturated dibenzothiophenes (DBT) adsorption capacity of 61.7 mgS g −1 from the dehydrated model oil. Attributed to the good DBT-affinity (with binding energy (BE) of −90.52 KJ mol −1 ) and water-repulsion (with BE of −14.72 KJ mol −1 ), PAF-56 coating layer significantly improves the hydrophobicity , and keeps the DBT adsorption capacity as high as 50.8 mgS g −1 in the presence of 0.5% (v/v) water, the decline of 17.6% was much smaller than the dramatical 70.9% decrease in pristine Cu(I)-BTC. More importantly, it effectively prevents Cu(I) nodes from the oxidation , and exhibits a superior stable cyclic performance with the removal efficiency above 91% after 20 cycles. Therefore, Cu(I)-BTC@PAF30 can be a good representative of this surface modification strategy to achieve promising application in industrial ADS.
研究领域:
材料科学
·
化学工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）