111835-62-2Relevant articles and documents
Highly Efficient Fixation of Carbon Dioxide at RT and Atmospheric Pressure Conditions: Influence of Polar Functionality on Selective Capture and Conversion of CO2
Das, Rajesh,Nagaraja, C. M.
, (2020)
The rapid increase in the concentration of atmospheric carbon dioxide (CO2) has resulted in undesirable environmental issues. Hence, selective CO2 capture and utilization as C1 feedstock for the preparation of high-value chemicals and fuels has been considered as a promising step toward mitigating the growing concentration of atmospheric CO2. In this direction, herein we report rational construction of a Ag(I)-anchored sulfonate-functionalized UiO-66 MOF named as MOF-SO3Ag composed of CO2-philic sulfonate functionality and catalytically active alkynophilic Ag(I) sites for chemical fixation of carbon dioxide. The MOF-SO3Ag exhibits selective as well as recyclable adsorption of CO2 with a high heat of adsorption energy (Qst) of 37.8 kJ/mol. On the other hand, the analogous MOF, UiO-66 doped with Ag(I), showed a lower Qst value of 30 kJ/mol, highlighting the importance of the sulfonate group for stronger interaction with CO2. Furthermore, the MOF-SO3Ag acts as an efficient heterogeneous catalyst for cyclic carboxylation of propargylic alcohols to generate α-alkylidene cyclic carbonates in >99percent yield at mild conditions of RT and 1 bar CO2. More importantly, one-pot synthesis of oxazolidinones by a three-component reaction between CO2, propargylic alcohol, and primary amine has also been achieved using MOF-SO3Ag catalyst under the mild conditions. The MOF is highly recyclable and retains its superior catalytic activity even after several cycles. To the best of our knowledge, MOF-SO3Ag is the first example of MOF reported for RT chemical fixation of CO2 to oxazolidinones by aminolysis of α-alkylidene cyclic carbonates under the environment-friendly mild conditions.
Copper(i) iodide cluster-based lanthanide organic frameworks: Synthesis and application as efficient catalysts for carboxylative cyclization of propargyl alcohols with CO2 under mild conditions
Bai, Guoyi,Lan, Xingwang,Li, Meng,Wu, Zhilei,Zhang, Yaxin
, p. 11063 - 11069 (2019)
Two metal-organic frameworks (MOFs), namely, [Dy2Cu4I4(NA)6(DMF)2]n (1) and [Gd2Cu2I2(IN)6(DMF)4]·5DMF (2) (HNA = nicotinic acid, HIN = isonicotinic acid), constructed based on lanthanide ions and copper iodide clusters ([Cu4I4] and [Cu2I2]) were successfully synthesized and characterized. Compound 1 has a three-dimensional framework and compound 2 displays a two-dimensional plane with sql topology, respectively. Both of them exhibit high thermostability and solvent stabilities. Additionally, catalytic explorations reveal that 1 displays higher catalytic activity than 2 for the carboxylic cyclization of propargyl alcohols. More importantly, 1 also exhibits excellent catalytic performance in the carboxylation reactions of CO2 and terminal propargylic alcohols with various substituents. To the best of our knowledge, this is the first example of non-noble metal based MOF catalysts for the carboxylative cyclization of propargyl alcohols with CO2 under atmospheric pressure and at room temperature, which provides a highly promising approach for MOFs in the catalytic conversion of CO2 to valuable chemicals.
A simple and robust AgI/KOAc catalytic system for the carboxylative assembly of propargyl alcohols and carbon dioxide at atmospheric pressure
Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
, p. 2933 - 2939 (2017)
A simple and robust AgI/KOAc system was developed for the cyclization of propargyl alcohols and carbon dioxide under mild conditions, and was identified to have excellent activities for numerous substrates, especially sterically hindered terminal alkynes and internal alkynes. Notably, the Ag loading involved was an unprecedentedly low level of 0.05 mol%.
A rose bengal-functionalized porous organic polymer for carboxylative cyclization of propargyl alcohols with CO2
Yu, Xiaoxiao,Yang, Zhenzhen,Zhang, Fengtao,Liu, Zhenghui,Yang, Peng,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
, p. 12475 - 12478 (2019)
A Rose bengal-functionalized porous organic polymer (RB-POP) was prepared with a specific surface area of up to 562 m2 g-1. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, RB-POP supported Ag(0) nanoparticles exhibited excellent performance for catalyzing cyclization of propargyl alcohols with CO2 at 30 °C, achieving a TOF of 5000 h-1, the highest value among the reported ones.
A recyclable AgI/OAc- catalytic system for the efficient synthesis of α-alkylidene cyclic carbonates: Carbon dioxide conversion at atmospheric pressure
Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
, p. 2936 - 2940 (2017)
The cyclization of carbon dioxide and propargylic alcohols, especially challenging substrates, were efficiently catalyzed by a green and recyclable AgI/OAc- system under atmospheric pressure, which is shown to be the most recyclable system with 20 recycle rounds and has the lowest loading among all the reported recyclable systems that work under atmospheric pressure.
Synthesizing Ag Nanoparticles of Small Size on a Hierarchical Porosity Support for the Carboxylative Cyclization of Propargyl Alcohols with CO2 under Ambient Conditions
Cui, Meng,Qian, Qingli,He, Zhenhong,Ma, Jun,Kang, Xinchen,Hu, Jiayin,Liu, Zhimin,Han, Buxing
, p. 15924 - 15928 (2015)
Both immobilization of Ag nanoparticles (AgNPs) of very small size on hierarchical porosity supports and carboxylative cyclization of propargyl alcohols with CO2 under ambient conditions are very interesting. In this work, we synthesized AgNPs supported on sulfonated macroreticular resin (SMR) with hierarchical pores in water/alcohol solutions. It was shown that the size of the AgNPs on the SMR could be tailored easily by altering the synthetic solutions, and very small AgNPs with narrow size distribution (1-3 nm) could be obtained in water/methanol solution. It was found that the AgNPs/SMR with small AgNPs was highly efficient and an easily recyclable catalyst for the synthesis of α-alkylidene cyclic carbonates by carboxylative cyclization of propargyl alcohols with CO2 at ambient pressure and temperature, which was the first work to use metal nanoparticles as the catalysts for the reaction.
A dual-functional urea-linked conjugated porous polymer anchoring silver nanoparticles for highly efficient CO2conversion under mild conditions
Li, Lin,Li, Wang,Li, Yuting,Liu, Xiaozhen,Wang, Jianxin,Wang, Liping,Wang, Xiaoji,Zhu, Jie
, p. 13052 - 13059 (2020)
A dual-functional urea-linked conjugated porous polymer (UCPP) assembled by enol-imine with ordered unit arrays that act as potential anchoring sites in the networks was fabricated, and was further applied as a support for Ag nanoparticles by the coordinate interaction between them. The UCPP not only can well confine the Ag particle size and facilitate high dispersion, but also can afford special CO2-philic moieties to enhance the adsorption properties. The resulting Ag?UCPP as a heterogeneous catalyst exhibited excellent activity for the carboxylative cyclization of propargyl alcohols with CO2 under mild conditions, together with good recyclability, which is probably attributed to the synergistic effect of the UCPP on the adsorption and activation of CO2 and the immobilization of Ag nanoparticles. This work affords possible opportunities for the design and synthesis of a heterogeneous catalyst toward CO2 conversion.
Unusual Missing Linkers in an Organosulfonate-Based Primitive-Cubic (pcu)-Type Metal-Organic Framework for CO2 Capture and Conversion under Ambient Conditions
Zhang, Guiyang,Yang, Huimin,Fei, Honghan
, p. 2519 - 2525 (2018)
A noninterpenetrated organosulfonate-based metal-organic framework (MOF) with a defective primitive-cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (～43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.
Tetrabutylphosphonium-Based Ionic Liquid Catalyzed CO2 Transformation at Ambient Conditions: A Case of Synthesis of α-Alkylidene Cyclic Carbonates
Wu, Yunyan,Zhao, Yanfei,Li, Ruipeng,Yu, Bo,Chen, Yu,Liu, Xinwei,Wu, Cailing,Luo, Xiaoying,Liu, Zhimin
, p. 6251 - 6255 (2017)
A series of tetrabutylphosphonium ([Bu4P]+)-based ionic liquids (ILs) with multiple-site for CO2 capture and activation in their anions, which could efficiently catalyze the cyclization reaction of propargylic alcohols with CO2 at ambient conditions, are reported. Especially, the IL, [Bu4P]3[2,4-OPym-5-Ac], which has three interaction sites for attracting CO2 together with a pKa1 value of 9.13, exhibited the best performance, affording a series of α-alkylidene cyclic carbonates in moderate to good yields. The mechanism exploration demonstrated that IL served as a bifunctional catalyst with anion simultaneously activating CO2 via multiple-site cooperative interactions and the C≡C triple bond in propargylic alcohol via inductive effect, thus resulting in the production of α-alkylidene cyclic carbonates. (Chemical Equation Presented).
Solvent-Dependent Assembly and Magnetic Relaxation Behaviors of [Cu4I3] Cluster-Based Lanthanide MOFs: Acting as Efficient Catalysts for Carbon Dioxide Conversion with Propargylic Alcohols
Wu, Zhi-Lei,Gu, Ai-Ling,Gao, Ning,Cui, Hui-Ya,Wang, Wen-Min,Cui, Jian-Zhong
, p. 15111 - 15119 (2020)
Two structurally similar metal-organic frameworks (MOFs) [Dy2Cu4I3(IN)7(DMF)2]·DMF (1) and [Dy2Cu4I3(IN)7(DMA)2]·DMA (2) (HIN = isonicotinic acid) feathering different coordinated solvent molecules were successfully isolated by tuning the types of solvents in the reaction system. Structural tests indicate that 1 and 2 are both built from 1D Dy(III) chains and copper iodide clusters [Cu4I3], generating into three-dimensional frameworks with an open 1D channel along the a axis. 1 and 2 display extensive and excellent solvent stability. Magnetic studies of 1 and 2 indicate that they exhibit interesting solvent-dependent magnetization dynamics. Importantly, 1 and 2 can act as highly effective catalysts for the carboxylic cyclization of propargyl alcohols with carbon dioxide (CO2) under ambient operating conditions. Additionally, the substrate scope was further explored over compound 1 based on the optimal conditions, and it exhibits efficient cyclic carboxylation of various terminal propargylic alcohols with CO2. This research offers an effective approach for the solvent-guided synthesis of MOFs materials and also presents the great application value of MOFs in CO2 chemical conversion.
