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FUEL · 2015 · IF 3.52

Thiophene adsorption onto metal–organic framework HKUST-1 in the presence of toluene and cyclohexene

Fuping Tian,Zhikai Fu,Huan Zhang,Jianjun Zhang,Yongying Chen,Cuiying Jia

Adsorption desulfurization is one of the most promising ways to reduce the sulfur content of gasoline at deeper level. In this work, thiophene (TP) adsorption capacity in cyclohexane onto [Cu 3 (BTC) 2 (H 2 O) 3 ] (HKUST-1) was measured by batch method, and the effect of cyclohexene and toluene on sulfur capacity was investigated. Adsorption isotherms of TP, cyclohexene, and toluene in cyclohexane onto HKUST-1 were conducted at 298.15–313.15   K to explicate the different extent of influence by cyclohexene or toluene addition. The results showed that, compared with cyclohexene, the addition of toluene in model gasoline led to a moderate decline in sulfur capacity of HKUST-1. The isotherm data of TP adsorption were well-correlated using Langmuir equation, while those of cyclohexene or toluene adsorption fitted Freundlich model, indicating different adsorption mechanisms between TP and competitors. The adsorption capacities followed the order of toluene   <   cyclohexene ≪TP at the same equilibrium concentrations, implying the order of the adsorption affinities, which is in good agreement with the different extent of influence by cyclohexene and toluene. The excellent regeneration performance of HKUST-1 in TP adsorption benefits from the physical adsorption mechanism, which was hinted by the enthalpy of TP adsorption (−37.31   ±   2.04   kJ   mol −1 ) and no detection of new sulfur species.

CAS / MDL: 554-95-0
研究领域: 化学工程 · 材料科学
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Journal of Energy Chemistry · 2018 · IF 3.886

Adsorption desulfurization of model gasoline by metal–organic framework Ni3(BTC)2

Fuping Tian,Qiaofeng Ru,Chenxia Qiao,Xin Sun,Cuiying Jia,Yu Wang,Yifu Zhang

This work presented the synthesis of Ni-based metal-organic framework material with a paddle-wheel structure Ni 3 (BTC) 2 (Ni-BTC) and its application in thiophene (TP) adsorption from gasoline distillate by batch method. Adsorption isotherms of TP, cyclohexene , and toluene in cyclohexane onto Ni-BTC were conducted at 298–308 K to interpret the different effect of cyclohexene and toluene on TP adsorption. The results showed that, compared with cyclohexene, toluene addition in model gasoline led to a more evident decline in sulfur capacity of Ni-BTC, which is opposite to isostructural HKUST-1. The adsorption isotherms of TP, cyclohexene and toluene fit Langmuir model, S-type model and Temkin model well, respectively, indicating that the adsorption mechanisms of TP and the two competitors are different from one another. The adsorption capacities on Ni-BTC followed the order of cyclohexene < toluene < TP at the same equilibrium concentrations , implying the order of the adsorption affinities, which is in good agreement with the different extent of influence by the two competitors. The enthalpy of TP adsorption on Ni-BTC was estimated to be −80.01 kJ/mol, almost twice that on HKUST-1. The poor reusability of Ni-BTC in batch experiment, which is owing to its sensitivity to the air, can be prevented from regenerating used Ni-BTC in fixed-bed reactor by N 2 flow. The difference between Ni-BTC and HKUST-1 in maximum adsorption capacity ( q 0 ), Δ H of TP adsorption, and stability demonstrates that the central metal in isostructural MOFs plays a key role in adjusting the desulfurization performance, which may open up a potential avenue for the development of MOF-based adsorbents with superior desulfurization performance.

CAS / MDL: 59-67-6 554-95-0
研究领域: 化学工程 · 材料科学
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RSC Advances · 2019 ·Vol. 9 ·期 27 ·15642-15647 · IF 3.049

Synthesis of bimetallic–organic framework Cu/Co-BTC and the improved performance of thiophene adsorption

Fuping Tian,Chenxia Qiao,Renyu Zheng,Qiaofeng Ru,Xin Sun,Yifu Zhang,Changgong Meng

A bimetallic–organic porous material (Cu/Co-BTC) with a paddle-wheel structure has been successfully synthesized by a solvothermal approach. The as-synthesized materials were characterized by XRD, SEM, ICP-AES, UV-Vis, TGA and N2 adsorption at 77 K. The prepared Cu/Co-BTC samples were investigated in thiophene (TP) adsorption from model gasolines by the fixed bed adsorption method at 298 K. The results showed that only a small amount of Co could be successfully introduced into the framework of HKUST-1, and the introduction of Co had little effect on the crystalline structure, morphology, porosity, and thermal stability. The bimetallic Cu/Co-BTC with a Cu/Co ratio of 174 displayed significantly improved adsorption desulfurization performance, showing an increase in breakthrough volume by 30% compared with HKUST-1, implying that the central metal in the MOF plays an important role in adsorption desulfurization. The addition of toluene or cyclohexene (3.20–3.30 vol%) as a competitor in the model gasoline led to a decline in desulfurization performance, especially when cyclohexene was added. The bimetallic Cu/Co-BTC showed a slight loss in breakthrough volume by only 5% after regenerating 7 times, displaying an excellent regeneration property.

CAS / MDL: 554-95-0
研究领域: 材料科学 · 化学工程
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Green Energy & Environment · 2024 · IF 10.7

Solvent-free Synthesis of Highly Dispersed Zinc-doped Porous Carbons as Efficient Dibenzothiophene Adsorbents

Ping Lu,Zhenhua Sun,Xinrong Ke,Changshen Ye,Zhixian Huang,Ting Qiu

Designing efficient adsorbents for the deep removal of refractory dibenzothiophene (DBT) from fuel oil is vital for addressing environmental issues such as acid rain. Herein, zinc gluconate and urea-derived porous carbons SF-ZnNC- T ( T represents the carbonization temperature) were synthesized without solvents. Through a temperature-controlled process of “melting the zinc gluconate and urea mixture, forming H-bonded polymers, and carbonizing the polymers,” the optimal carbon, SF-ZnNC-900, was obtained with a large surface area (2280 m 2 /g), highly dispersed Zn sites, and hierarchical pore structures. Consequently, SF-ZnNC-900 demonstrated significantly higher DBT adsorption capacity of 43.2 mg S/g, compared to just 4.3 mg S/g for the precursor. It also demonstrated good reusability, a fast adsorption rate, and the ability for ultra-deep desulfurization. The superior DBT adsorption performance resulted from the evaporation of residual zinc species, which generated abundant mesopores that facilitated DBT transformation, as well as the formation of Zn-N x sites that strengthened the host-guest interaction (Δ E = -1.466 eV). The solvent-free synthesized highly dispersed Zn-doped carbon shows great potential for producing sulfur-free fuel oil and for designing metal-loaded carbon adsorbents.

研究领域: 材料科学 · 环境科学
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MATERIALS CHEMISTRY AND PHYSICS · 2023 · IF 4.6

Facile fabrication of superior Pd and Ce containing SiO2 aerogel composite adsorbents for deep desulfurization of model fuels and aromatics

Xiao Teng,Bo Zhang,Luxia Yin,Wanyi Tao,Zhang Wen,Zekai Zhang,Wensheng Ning

A series of PdO/CeO 2 /SiO 2 -z aerogel composites with different molar ratio of Si/Ce were facilely fabricated via sol-gel method combined with atmospheric drying technology, where a major of Ce 3+ species could be oxidized to Ce 4+ species by adding hydrogen peroxide. They were used to remove thiophenics from model fuels and aromatics, compared with PdO/SiO 2 and CeO 2 /SiO 2 aerogel composites. Adding Ce and Pd led to an appearance of weak Lewis acid centers on the surface of adsorbents. Compared with PdO/SiO 2 and CeO 2 /SiO 2 , the adsorption capacity of PdO/CeO 2 /SiO 2 -z significantly increased, in which PdO/CeO 2 /SiO 2 -100 performed best and the adsorption capacity for thiophene was 15.0 mg-S/g ads , which was about the sum of PdO/SiO 2 -636 and CeO 2 /SiO 2 -100. The case was attributed to π-complexation of Pd 2+ and S-M (Pd, Ce, acted as Lewis acid centers) bond (σ) with thiophenics, where the adsorption process was dominated by S–Ce bond. Combined with the same chemical state of Pd and Ce in single metal and bimetal adsorbents verified by XPS , it can be deduced that no synergistic interaction between Pd and Ce species was formed in the adsorption process. PdO/CeO 2 /SiO 2 -100 exhibited a higher resistance for competitive adsorption of aromatics and a good solvent washing regeneration performance. The adsorption process of PdO/CeO 2 /SiO 2 -100 for thiophene was well fitted by Langmuir isothermal and pseudo-secound-order model and were spontaneous and endothermic. The solvents (n-heptane, benzene and p-xylene) have no obvious effect on the adsorption thermodynamics and kinetics of PdO/CeO 2 /SiO 2 -100.

研究领域: 材料科学 · 环境科学
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SURFACE SCIENCE · 2023 · IF 1.9

Metal-Organic frameworks with two different metal centers for thiophene adsorption: Synthesis, characterization and mechanism analysis

Yatao Wang,Peng Zhang,Hongjuan Li,Qiuju Xu,Shujun Liu,Xiaopeng Liu,Xuehua Guo,Yitao Li,Jinzhang Liu,Sen Dong,Zhi Wei Seh,Qianfan Zhang

Thiophene, widely found in fossil fuels, not only corrodes equipment but also causes great harm to the environment after combustion. Adsorptive desulfurization can deeply desulfurize fuels with low sulfur content and shows great development prospect. We experimentally studied the adsorption of thiophene and benzene in Cu-BTC and two types of IZE metal-organic frameworks (MOFs). By changing the temperature and concentration conditions, we compared the separation performance of MOFs with different metal centers. We found IZE-1 to have excellent s high thiophene adsorption capacity selectivity for thiophene adsorption at low thiophene concentration and (-up to 9.3 mg S/g MOF at 70 °C), superior to that of Cu-BTC. We performed first-principles calculations and elucidated the mechanism of thiophene adsorption by analyzing the electronic structure of MOFs. The molecular dynamics simulation further explains the high selectivity of thiophene adsorption and the adsorption process. This study demonstrates the potential for MOFs to be used in thiophene adsorption, particularly at high thiophene concentrations.

CAS / MDL: 10031-43-3 7697-37-2
研究领域: 材料科学 · 环境科学 · 化学工程
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