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.
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 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.
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.
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).
A Noble-Metal-Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols
Hou, Sheng-Li,Dong, Jie,Jiang, Xiao-Lei,Jiao, Zhuo-Hao,Zhao, Bin
, p. 577 - 581 (2019)
Cyclization of propargylic alcohols with CO2 is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO2 without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between CuI and InIII plays a key role in the conversion of CO2.
Synthesis of α-alkylidene cyclic carbonatesviaCO2fixation under ambient conditions promoted by an easily available silver carbamate
Bresciani, Giulio,Bortoluzzi, Marco,Ghelarducci, Claudia,Marchetti, Fabio,Pampaloni, Guido
, p. 4340 - 4346 (2021)
The simple and cost-effective compound [Ag(O2CNEt2)], in combination with PPh3, works as an effective catalytic precursor in the carboxylation of propargyl alcohols at ambient temperature and atmospheric CO2pressure, and in most cases under solventless conditions. The silver carbamate revealed a better performance than commercial silver oxide, Ag2O, and allowed to obtain a series of α-alkylidene cyclic carbonates in high yields.
One-pot carboxylative cyclization of propargylic alcohols and CO2 catalysed by N-heterocyclic carbene/Ag systems
Yuan, Ye,Xie, Yu,Song, Dandan,Zeng, Cheng,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
, (2017)
A series of N-heterocyclic carbene (NHC)/Ag systems were developed for the carboxylative assembly of propargylic alcohols and carbon dioxide (CO2). With the catalysis of these catalytic systems, a variety of target α-alkylidene cyclic carbonates could be obtained smoothly under atmospheric CO2 pressure in straightforward one-pot processes. Particularly, these reactions could be performed without any stoichiometric addition of bases or additives. Further mechanistic investigation reveals that the excellent activities are attributed to the effective activations of CO2 accomplished by the NHCs via the formation of the NHC-CO2 adducts.
Noble metal-free Cu(i)-anchored NHC-based MOF for highly recyclable fixation of CO2under RT and atmospheric pressure conditions
Das, Rajesh,Nagaraja, C. M.
supporting information, p. 5195 - 5204 (2021/07/29)
The utilization of CO2as a C1 feedstock for the synthesis of high-value chemicals and fuels is an important step towards mitigating the increasing concentration of atmospheric carbon dioxide as well as the production of value-added chemicals. Herein, we demonstrate the development of an efficient recyclable catalyst for the conversion of CO2into oxazolidinones, which are important commodity chemicals for antibiotics, by utilizing an N-heterocyclic carbene (NHC)-based metal-organic framework (MOF). The NHC-centers lined in the pore walls of the MOF were utilized to anchor catalytically active Cu(i) ions by post-synthetic modification (PSM). The Cu(i)-embedded MOF showed highly recyclable and selective CO2uptake properties with a high heat of interaction energy of 43 kJ mol?1. The presence of a high density of CO2-philic NHC and catalytic Cu(i) sites in the 1D channels of the MOF render highly efficient catalytic activity for fixation of CO2into α-alkylidene cyclic carbonates and oxazolidinones at RT and atmospheric pressure conditions. Notably, Cu(i)@NHC-MOF showed excellent recyclability for up to 10 cycles of regeneration with retention of catalytic activity as well as chemical stability. To the best of our knowledge, Cu(i)@NHC-MOF is the first example of a noble metal-free MOF-based heterogeneous catalyst for the utilization of CO2to synthesize important value-added chemicals under mild conditions.
