Catalysis Science & Technology
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2023
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IF 5
Jean Damascene Ndayambaje,Irfan Shabbir,Qianmeng Zhao,Li Dong,Qian Su,Weiguo Cheng
To address the ongoing rise in carbon dioxide (CO2) emissions, CO2 utilization presents a promising approach due to its ability to convert CO2 into valuable industrial products and enable carbon recycling. For this reason, a high-quality catalyst is required to ensure the effective activation and conversion of CO2. In this study, a series of dicationic pyrazolium ionic liquids (DPzILs) were first synthesized via a one-step process and employed as catalysts in the cycloaddition reaction of CO2 and epoxides, yielding cyclic carbonates. Among the synthesized DPzILs, [DMPz-6]I2 exhibited outstanding catalytic performance on diluted CO2 from simulated flue gas (60% CO2 in N2), achieving 94.1% PC yield and 100% selectivity under reaction conditions (100 °C and 10 bar CO2 pressure) without metal, co-catalyst, or solvent. The study investigated the effects of DPzILs structures, catalyst dosage, CO2 pressure, reaction temperature, and reaction time on the production of cyclic carbonates. Furthermore, [DMPz-6]I2 could be efficiently recovered and reused seven times without significant degradation of catalytic activity. It demonstrated significant adaptability to various epoxides. Structure–activity studies indicated that PO activation is synergistically facilitated by the presence of C3/C5 hydrogen from dual-pyrazolium cation rings tethered by alkyl chain lengths and a paired halide anion (I−/Br−/Cl−) in DPzILs. Finally, the reaction mechanism was investigated using FT-IR, 1H NMR, and DFT calculations.
研究领域:
化学
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环境科学
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材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2024
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IF 2
Yong Zheng,Jiahuan Luo,Ling Li,Qian Wang,Huichao Lv,Kai Wang,Changwei Lai
In this study, six pure 1-alkyl-2-methylpyrazolium-based ionic liquids (ILs) with methyl sulfate and bis(trifluoromethylsulfonyl)imide anions ([Cnmpz][MeSO4] and [Cnmpz][NTf2], n = 2, 3, and 4) were prepared and characterized. The density, viscosity, and refractive index of these pure ILs were measured from 298.15 to 353.15 K at 101.3 kPa, which fitted well with the corresponding empirical equations. Moreover, the values of the isobaric thermal expansion coefficient were also obtained. The results of experiments and density functional theory calculations indicate that the adjacent positions of two nitrogen atoms in pyrazolium cations lead to the close packing of ions, strong cation–anion interaction, and high molar polarizability per unit volume. The effects of temperature and N-alkyl chain length on the density, viscosity, and refractive index of these ILs are similar to those for imidazolium-based salts. Compared with [Cnmpz][MeSO4], [Cnmpz][NTf2] exhibits a higher density, lower viscosity, and lower refractive index under the same conditions. Moreover, the correlation between density and refractive index was studied, and a new empirical equation was proposed to express this correlation at different temperatures. It is expected that this work will enable deeper insights into the properties, structure, and structure–property relationship of pure pyrazolium-based ILs.
研究领域:
化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 19
·11448-11462
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IF 10.7
Jean Damascene Ndayambaje,Irfan Shabbir,Li Dong,Qian Su,Weiguo Cheng
The conversion of carbon dioxide (CO2) into valuable industrial materials effectively combats rising emissions and facilitates carbon recycling, which requires a top-tier catalyst. In this study, a series of dicationic pyrazolium ionic liquids were grafted onto pre-functionalized MCM-41, and the resulting CnPz–APTES/MCM-41 (n = 3–6), which integrate hydrogen bond donors, Lewis basic tertiary amines (dual N+ sites), nucleophilic ionic sites, high surface areas, and mesoporous structures, were employed as catalysts in the cycloaddition of CO2 and epoxides to yield cyclic carbonates. Among them, C6Pz–APTES/MCM-41 exhibited excellent catalytic performance achieving 98.2% PC yield and 100% selectivity under mild reaction conditions (70 °C and 0.5 MPa CO2 pressure) without a metal, co-catalyst, or solvent. The effect of reaction parameters on the production of cyclic carbonates was thoroughly investigated. Furthermore, C6Pz–APTES/MCM-41 could be efficiently recovered and reused six times without loss of its catalytic activity. It also showed significant adaptability to different epoxides. Structure–activity studies indicated that PO activation was synergistically promoted by the presence of C3/C5 hydrogens from dicationic pyrazolium rings bound by alkyl linkers and dibromide ions in CnPz–APTES/MCM-41. Finally, the reaction mechanism was further investigated using X-ray photoelectron spectroscopy (XPS), proton nuclear magnetic resonance (1H NMR), and density functional theory (DFT) computations.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
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2022
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IF 5.876
Yi Liu,Yuhang Hu,Jiarong Zhang,Jingsheng Zhou,Zhengkun Zhang,Li Wang,Jinglai Zhang
Immobilized ionic liquids are one of the most popular catalysts for the cycloaddition of carbon dioxide (CO 2 ) and epoxides with some distinguished advantages. However, the harsh reaction condition, especially for the high reaction pressure, is still the obstacle for its large-scale application. A series of amino-functionalized pyrazolium ionic liquids are grafted on SBA-15 in this work. Among them, SBA-15-APMPzBr(20) exhibits the best catalytic activity achieving 97.6% product yield under 0.5 MPa CO 2 pressure at 100 °C by using 100 mg SBA-15-APMPzBr(20) for 10 h. No solvent is added in the catalytic system. Moreover, SBA-15-APMPzBr(20) exhibits the good recyclability and generality. Its excellent catalytic performance is attributed to the contribution from both immobilized ionic liquids and the SBA-15 supporter. Besides the mesoporous feature, the hydroxyl groups in SBA-15 promote the ring-opening of substrate, which is testified by the experimental measurements and density functional theory calculations.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2017
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IF 5.951
Tengfei Wang,Danning Zheng,Jingshun Zhang,Baowan Fan,Yuan Ma,Tiegang Ren,Li Wang,Jinglai Zhang
A series of novel protic pyrazolium ionic liquids are first synthesized and utilized as catalysts for cycloaddition of carbon dioxide and epoxides to form cyclic carbonates under metal- and solvent-free conditions. The new developed protic pyrazolium ionic liquids present excellent catalytic activity toward the fixation of carbon dioxide. More importantly, they would be prepared by a facile two-step reaction from cheap raw starting materials with a yield more than 90%. The influence of catalyst dosage, reaction temperature, carbon dioxide pressure, and reaction time on the synthesis of cyclic carbonates is investigated to identify the optimal reaction conditions. Under the optimum conditions, the catalyst suitability is studied. Additionally, the possible reaction mechanism is investigated by the double-IL model to elucidate the synergistic effects of electrostatic and weak interaction in the catalytic process.
研究领域:
化学
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催化科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry C
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2016
·Vol. 4
·期 35
·8235-8244
·
IF 5.066
Tong He,Ye Feng Wang,Jing Hui Zeng
Further development of solid-state dye-sensitized solar cells (ssDSSCs) requires good fill factor as well as high photon to electron conversion efficiency. We synthesized a pyrazolium-based dication organic ionic conductor with good thermal stability and high ionic diffusion coefficient, Py2C6. This pyrazolium-based electrolyte for ssDSSC achieves an efficiency of 7.30% with a fill factor of up to 79.6% and an open-circuit voltage of 779 mV, which are superior to the respective parameters reported in the previous literature. The obtained cell was characterized by electrochemical impedance spectra (EIS), cyclic voltammetry (CV) and Tafel plot. The results show 24.43 Ω series resistance and 3.31 kΩ shunt resistance, very close to the values for the device with a frequently used liquid-state electrolyte, and these are the major contributors to the high fill factor. The back reaction of photoelectrons at the TiO2/electrolyte interface can also be markedly restrained as a result of the large recombination resistance, thus prolonging the electron lifetime. These factors, together with the remarkable catalytic activity of the counter electrode, lead to good photovoltaic parameters of the cell containing Py2C6. In stability tests, this device shows excellent long-term stability, maintaining 92% of the initial efficiency after 1000 h.
研究领域:
材料科学
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能源科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2021
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IF 6.165
Xinrui Zhu,Jingshun Zhang,Zhengkun Zhang,Fang Liu,Yuhang Hu,Yi Liu,Tiegang Ren,Li Wang,Jinglai Zhang
Amino-specified pyrazolium ionic liquid (APEPzBr) is synthesized by two steps. It is interesting that the product of the first step ([EPzPNH 3 ]Br 2 ) could also catalyze the coupling reaction of carbon dioxide (CO 2 ) and epoxides under 70 °C along with 0.5 MPa CO 2 pressure, which is even more benign than APEPzBr. It is attributed to the strong ability of [EPzPNH 3 ]Br 2 to absorb CO 2 along with robust electrophilic activation, which is testified by density functional theory and 13 C NMR measurement. The difference between [EPzPNH 3 ]Br 2 and APEPzBr is further elucidated by electron localization function (ELF) and atoms in molecules (AIM).
研究领域:
化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2022
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IF 10.53
Tao Jiang,Chenxi Wang,Tao Wang,Xuechao Wang,Xiaojuan Wang,Xueliang Li,Yunsheng Ding,Haibing Wei
Anion exchange membranes (AEMs) are a core component for energy conversion technologies such as fuel cells and water electrolyzers. Unfortunately, the functional cations in AEM often suffer from inferior durability in caustic media, especially at elevated temperatures or highly concentrated alkaline solutions. Therefore, the exploitation of novel cations that can endure highly alkaline environments while with synthetic feasibility and good ion conducting property is desired. Herein, a simple and easily available pyrazolium cation was evaluated and was alkaline stable in 5 M NaOH (aq) at 80 °C for at least 240 h, which is substantially stable than its structural isomer, imidazolium. The alkaline stability of pyrazolium was rationalized through analyses of the degradation energy barriers calculated by density functional theory. The excellent alkaline stability of pyrazolium cation encouraged the fabrication of AEMs functionalizing with pyrazolium head group anchored to poly(arylene alkylene) architecture. In contrast to imidazolium-based counterpart, pyrazolium cation enable the AEM with higher base stability, retaining ～80% of its initial conductivity after a 1000-h treatment in 1 M NaOH (aq) at 80 °C. Moreover, the AEM based on pyrazolium showed a high hydroxide ion conductivity up to 120 mS cm −1 at 80 °C and a high peak power density of 502 mW cm −2 after assembled into a H 2 –O 2 fuel cell device.
研究领域:
材料科学
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能源转换技术
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电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2019
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IF 4.561
Tengfei Wang,Yuan Ma,Jiamin Jiang,Xinrui Zhu,Baowan Fan,Guanyao Yu,Ningning Li,Shasha Wang,Tiegang Ren,Li Wang,Jinglai Zhang
Lots of ionic liquids have been utilized as catalyst for the coupling reaction of carbon dioxide with epoxides , however, catalyzed conditions could not be regarded as benign, especially when no co-catalyst and/or organic solvent is involved. A series of hydroxyl-functionalized pyrazolium ionic liquids are firstly synthesized. They would efficiently catalyze the cycloaddition of carbon dioxide and propylene oxide under 110 °C and 1.0 MPa carbon dioxide initial pressure with 1 mol% catalyst during 4 h resulting in the product yield of 91.2%. The catalytic condition is greatly refined as compared with other single-component ionic liquids with simple anion. Simultaneously, the effect of reaction temperature, amount of catalyst, carbon dioxide initial pressure, and reaction time is explored along with the reusability of catalyst. For most of epoxides with terminal substituted group, HEEPzBr presents acceptable catalytic activity. The difference of HEMPzBr, HEEPzBr, and HPEPzBr is also explored by the density functional theory calculations.
研究领域:
化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Jingshun Zhang,Xinrui Zhu,Baowan Fan,Jia Guo,Pan Ning,Tiegang Ren,Li Wang,Jinglai Zhang
Numerous ionic liquids have been developed to catalyze the coupling reaction of carbon dioxide with epoxides without co-catalyst and organic solvent. Although the catalytic activity is satisfied with cyclic carbonate yield over 90%, the reaction condition is still not regarded as benign enough, especially for reaction temperature and carbon dioxide initial pressure. Four new amino-functionalized pyrazolium ionic liquids, AEMPzBr, APMPzBr, AEEPzBr, and APEPzBr, have been firstly synthesized in simple reaction steps with cheap raw materials. Moreover, they would catalyze the coupling reaction of carbon dioxide with propyleneoxide under the optimal reaction conditions, 110 °C, 1.5 MPa carbon dioxide initial pressure as well as 1.0 mol% catalyst amount for 4.0 h, with propylene carbonate yield over 94%. The reaction temperature is decreased by 10–20 °C as compared with other single-component ionic liquids. At the same time, the carbon dioxide initial pressure is not increased to keep 1.5 MPa, which is also superior to lots of other ionic liquids, such as imidazolium, pyrazolium, and guanidinium ionic liquids. The recyclability and suitability of amino-functionalized pyrazolium ionic liquids are also explored. Finally, the catalytic mechanism is investigated by the density functional theory. Moreover, the influence of weak interactions on the reaction is analyzed by atoms in molecules and non-covalent interactions. As compared with other reported ionic liquids, the reaction condition catalyzed by APEPzBr is more benign with comparable product yield. More importantly, there is good balance among various reaction conditions without sacrificing one to ensure others. Amino-functionalized pyrazolium ionic liquids would be a new kind of powerful catalysts for the carbon dioxide fixation.
研究领域:
化学工程
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催化
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绿色化学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2017
·Vol. 7
·期 38
·23272-23278
·
IF 3.108
Peicheng Wang,Yang Zhao,Hongbin Zhang,Tao Yu,Yahong Zhang,Yi Tang
A series of diquaternary pyrazolium-derived organic templates (N,N′-dimethyl-N,N′-1,6-dihexylidenedipyrazolium, N,N′-diethyl-N,N′-1,6-dihexylidenedipyrazolium, N,N′-dipropyl-N,N′-1,6-dihexylidenedipyrazolium, denoted as 6C-DMP, 6C-DEP, 6C-DPP, respectively) with methyl, ethyl and propyl groups substituted on the N atom of pyrazole ring at both terminals have been used in the synthesis of high silica MTW and MFI zeolites. Through combining the characterization results, including XRD, NMR, elemental analysis, TG, XRF, FE-SEM, N2 sorption and FE-TEM, with molecular mechanics simulations to explore the location, orientation and the interaction energies of the three templates, we confirmed the state of templates in zeolite framework, carefully characterized their morphology/structure properties, and finally investigated their different spatial effects for the zeolite formation. The study found that 6C-DMP and 6C-DEP are able to produce MTW, while 6C-DPP is able to produce MFI. 6C-DMP, owing to a good match with the MTW framework and can be used to synthesize regular MTW zeolite with few defects. The MTW zeolite prepared by using 6C-DEP as a template presents more defects and irregular macromorphology due to a relatively poor match to the MTW framework. 6C-DPP can get MFI other than MTW due to a larger spatial hindrance, and it is located in the MFI framework with a special spatial orientation.
研究领域:
化学
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材料科学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）