scholarly journals Understanding the Photo- and Electro-Carboxylation of o-Methylbenzophenone with Carbon Dioxide

Catalysts ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 664
Author(s):  
Keyi Tian ◽  
Ruonan Chen ◽  
Jiafang Xu ◽  
Ge Yang ◽  
Xintong Xu ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Density Functional ◽  
Radical Reaction ◽  
Diels Alder ◽  
Synthesis Methods ◽  
One Pot ◽  
Polycarboxylic Acids ◽  
Electro Catalysis ◽  
Electron Reduction ◽  
Carbon Dioxide Co2

The lack of understanding of the radical reaction mechanism of Carbon dioxide (CO2) in photo- and electro-catalysis results in the development of such applications far behind the traditional synthesis methods. Using methylbenzophenone as the model, we clarify and compare the photo-enolization/Diels−Alder (PEDA) mechanism for photo-carboxylation and the two-step single-electron reduction pathway for electro-carboxylation with CO2 through careful control experiments. The regioselective carboxylation products, o-acylphenylacetic acid and α-hydroxycarboxylic acid are obtained, respectively, in photo- and electro-chemistry systems. On the basis of understanding the mechanism, a one-pot step-by-step dicarboxylation of o-methylbenzophenone is designed and conducted. Both the experimental results and related density functional theory (DFT) calculation verify the feasibility of the possible pathway in which electro-carboxylation is conducted right after photo-carboxylation in one vessel. This synthesis approach may provide a mild, eco-friendly strategy for the production of polycarboxylic acids in industry.

scholarly journals Cu(I)/Ionic Liquids Promote the Conversion of Carbon Dioxide into Oxazolidinones at Room Temperature

Molecules ◽  
2019 ◽  
Vol 24 (7) ◽  
pp. 1241 ◽  
Author(s):  
Jikuan Qiu ◽  
Yue Zhao ◽  
Yuling Zhao ◽  
Huiyong Wang ◽  
Zhiyong Li ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Noble Metal ◽  
Room Temperature ◽  
Ambient Pressure ◽  
Sustainable Chemistry ◽  
One Pot ◽  
Propargylic Alcohols ◽  
Noble Metal Catalysts ◽  
Three Component Reaction ◽  
Carbon Dioxide Co2

Recently, the efficient chemical fixation of carbon dioxide (CO2) into high value chemicals without using noble metal catalysts has become extremely appealing from the viewpoint of sustainable chemistry. In this work, a one-pot three component reaction of propargylic alcohols, anines and CO2 that can proceed in an atom economy and environmentally benign manner by combination of CuI and tetrabutylphosphonium imidazol ([P4444][Im]) as a catalyst was described. Catalysis studies indicate that this catalytic system is an effective catalyst for the conversion of CO2 into oxazolidinones at room temperature and ambient pressure without any solvent. The results provide a useful way to design novel noble metal-free catalyst systems for the transformation of CO2 into other valuable compounds.

Photochemical hydrogen production based on HCOOH/CO2 cycle promoted by pentanuclear cobalt complex

2022 ◽  
Author(s):  
Takuya Akai ◽  
Mio Kondo ◽  
Yutaka Saga ◽  
Shigeyuki Masaoka
Keyword(s):  
Carbon Dioxide ◽  
Hydrogen Production ◽  
Formic Acid ◽  
Ambient Temperature ◽  
Cobalt Complex ◽  
Catalytic Cycle ◽  
Electron Reduction ◽  
Carbon Dioxide Co2

The first catalytic cycle for hydrogen production based on the photochemical two-electron reduction of carbon dioxide (CO2) and the dehydrogenation of formic acid at ambient temperature was demonstrated using a...

scholarly journals Diatomite-Metal-Organic Framework Composite with Hierarchical Pore Structures for Adsorption/Desorption of Hydrogen, Carbon Dioxide and Water Vapor

Materials ◽  
2020 ◽  
Vol 13 (21) ◽  
pp. 4700
Author(s):  
Gaofeng Wang ◽  
Elizabeth Graham ◽  
Shuilin Zheng ◽  
Jianxi Zhu ◽  
Runliang Zhu ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Water Vapor ◽  
Metal Organic Framework ◽  
Hydrolytic Stability ◽  
One Pot ◽  
Pore Networks ◽  
Pore Structures ◽  
Metal Organic ◽  
Hierarchical Pore ◽  
Carbon Dioxide Co2

Distinctive Cr-MOF@Da composites have been constructed using chromium-based metal-organic frameworks (MOFs) and diatomite (Da). The new materials have hierarchical pore structures containing micropores, mesopores and macropores. We have synthesized various morphologies of the MOF compound Cr-MIL-101 to combine with Da in a one-pot reaction step. These distinctive hierarchical pore networks within Cr-MIL-101@Da enable exceptional adsorptive performance for a range of molecules, including hydrogen (H2), carbon dioxide (CO2) and water (H2O) vapor. Selectivity for H2 or CO2 can be moderated by the morphology and composition of the Cr-MIL-101 included in the Cr-MOF@Da composite. The encapsulation and growth of Cr-MIL-101 within and on Da have resulted in excellent water retention as well as high thermal and hydrolytic stability. In some cases, Cr-MIL-101@Da composite materials have demonstrated increased thermal stability compared with that of Cr-MIL-101; for example, decomposition temperatures >340 ℃ can be achieved. Furthermore, these Cr-MIL-101@Da composites retain structural and morphological integrity after 60 cycles of repeated hydration/dehydration, and after storage for more than one year. These characteristics are difficult to achieve with many MOF materials, and thus suggest that MOF–mineral composites show high potential for practical gas storage and water vapor capture.

Janus silver/ternary silver halide nanostructures as plasmonic photocatalysts boost the conversion of CO2 to acetaldehyde

Nanoscale ◽  
2021 ◽  
Author(s):  
Henglei Jia ◽  
Yanrong Dou ◽  
Yuanyuan Yang ◽  
Fan Li ◽  
Chun-Yang Zhang
Keyword(s):  
Carbon Dioxide ◽  
Silver Halide ◽  
Liquid Product ◽  
Reduction Process ◽  
Coupling Reaction ◽  
Electron Reduction ◽  
Carbon Dioxide Co2

Photocatalytic conversion of carbon dioxide (CO2) to liquid product acetaldehyde (CH3CHO) remains a great challenge due to the involvement of complex 10-electron reduction process and sluggish C–C coupling reaction. Herein,...

scholarly journals A Binuclear Cobalt Complex for Molecular CO2 Electrocatalysis

2021 ◽  
Author(s):  
Antoine Bohn ◽  
Juan José Moreno ◽  
Pierre Thuéry ◽  
Marc Robert ◽  
Orestes Rivada Wheelaghan
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Saturated Calomel Electrode ◽  
Cobalt Complex ◽  
Reduction Process ◽  
Inert Atmosphere ◽  
Electrochemical Studies ◽  
Electron Reduction ◽  
Carbon Dioxide Co2 ◽  
Reduction Of Co2

A pyrazole–based ligand substituted with terpyridine groups at the 3 and 5positions has been synthesized to form the dinuclear cobalt complex 1, that electrocatalytically reduces carbon dioxide (CO2) to carbon monoxide (CO) in the presence of Brønsted acids in DMF. Chemical, electrochemical and UV–vis spectro–electrochemical studies under inert atmosphere indicate a single 2 electron reduction process of complex 1 at first, followed by a 1 electron reduction at the ligand. Infrared spectro–electrochemical studies under CO2 and CO atmosphere allowed us to identify a reduced CO–containing dicobalt complex which results from the electroreduction of CO2. In the presence of trifluoroethanol (TFE), electrocatalytic studies revealed single–site mechanism with up to 94 % selectivity towards CO formation when 1.47 M TFE were present, at –1.35 V vs Saturated Calomel Electrode in DMF (0.39 V overpotential). The low faradaic efficiencies obtained (<50%) are attributed to the generation of CO–containing species formed during the electrocatalytic process, which inhibit the reduction of CO2.

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

Communication: Photoinduced Carbon Dioxide Binding with Surface-Functionalized Silicon Quantum Dots

2018 ◽  
Author(s):  
Oscar A. Douglas-Gallardo ◽  
Cristián Gabriel Sánchez ◽  
Esteban Vöhringer-Martinez
Keyword(s):  
Carbon Dioxide ◽  
Quantum Dots ◽  
Atmospheric Carbon Dioxide ◽  
Density Functional ◽  
Tight Binding ◽  
Carbon Dioxide Concentration ◽  
Research Area ◽  
Silicon Quantum Dots ◽  
Dependent Model ◽  
Photoinduced Charge

<div> <div> <div> <p>Nowadays, the search of efficient methods able to reduce the high atmospheric carbon dioxide concentration has turned into a very dynamic research area. Several environmental problems have been closely associated with the high atmospheric level of this greenhouse gas. Here, a novel system based on the use of surface-functionalized silicon quantum dots (sf -SiQDs) is theoretically proposed as a versatile device to bind carbon dioxide. Within this approach, carbon dioxide trapping is modulated by a photoinduced charge redistribution between the capping molecule and the silicon quantum dots (SiQDs). Chemical and electronic properties of the proposed SiQDs have been studied with Density Functional Theory (DFT) and Density Functional Tight-Binding (DFTB) approach along with a Time-Dependent model based on the DFTB (TD-DFTB) framework. To the best of our knowledge, this is the first report that proposes and explores the potential application of a versatile and friendly device based on the use of sf -SiQDs for photochemically activated carbon dioxide fixation. </p> </div> </div> </div>

Influence of intramolecular interactions on carbon dioxide gas adsorption capacity in Mesoporous Imine polymers

2018 ◽  
Author(s):  
Jaya Prakash Madda ◽  
Pilli Govindaiah ◽  
Sushant Kumar Jena ◽  
Sabbhavat Krishna ◽  
Rupak Kishor
Keyword(s):  
Carbon Dioxide ◽  
Adsorption Capacity ◽  
Density Functional ◽  
Gas Adsorption ◽  
Ambient Pressure ◽  
Condensation Reaction ◽  
Intramolecular Interactions ◽  
Carbon Dioxide Adsorption ◽  
Nitrogen Gas ◽  
Adsorption Characteristic

<p>Covalent organic Imine polymers with intrinsic meso-porosity were synthesized by condensation reaction between 4,4-diamino diphenyl methane and (para/meta/ortho)-phthaladehyde. Even though these polymers were synthesized from precursors of bis-bis covalent link mode, the bulk materials were micrometer size particles with intrinsic mesoporous enables nitrogen as well as carbon dioxide adsorption in the void spaces. These polymers were showed stability up to 260<sup>o</sup> centigrade. Nitrogen gas adsorption capacity up to 250 cc/g in the ambient pressure was observed with type III adsorption characteristic nature. Carbon dioxide adsorption experiments reveal the possible terminal amine functional group to carbamate with CO<sub>2</sub> gas molecule to the polymers. One of the imine polymers, COP-3 showed more carbon dioxide sorption capacity and isosteric heat of adsorption (Q<sub>st</sub>) than COP-1 and COP-2 at 273 K even though COP-3 had lower porosity for nitrogen gas than COP-1 and COP-2. We explained the trends in gas adsorption capacities and Qst values as a consequence of the intra molecular interactions confirmed by Density Functional Theory computational experiments on small molecular fragments.</p>

Electronic Structure Benchmark Calculations of Inorganic and Biochemical Carboxylation Reactions

2018 ◽  
Author(s):  
Oscar A. Douglas-Gallardo ◽  
David A. Sáez ◽  
Stefan Vogt-Geisse ◽  
Esteban Vöhringer-Martinez
Keyword(s):  
Electronic Structure ◽  
Chemical Reactions ◽  
Density Functional ◽  
Correlation Energy ◽  
Electronic Energy ◽  
Basis Sets ◽  
Electronic Correlation ◽  
Correct Description ◽  
Carbon Dioxide Co2 ◽  
High Level

<div><div><div><p>Carboxylation reactions represent a very special class of chemical reactions that is characterized by the presence of a carbon dioxide (CO2) molecule as reactive species within its global chemical equation. These reactions work as fundamental gear to accomplish the CO2 fixation and thus to build up more complex molecules through different technological and biochemical processes. In this context, a correct description of the CO2 electronic structure turns out to be crucial to study the chemical and electronic properties associated with this kind of reactions. Here, a sys- tematic study of CO2 electronic structure and its contribution to different carboxylation reaction electronic energies has been carried out by means of several high-level ab-initio post-Hartree Fock (post-HF) and Density Functional Theory (DFT) calculations for a set of biochemistry and inorganic systems. We have found that for a correct description of the CO2 electronic correlation energy it is necessary to include post-CCSD(T) contributions (beyond the gold standard). These high-order excitations are required to properly describe the interactions of the four π-electrons as- sociated with the two degenerated π-molecular orbitals of the CO2 molecule. Likewise, our results show that in some reactions it is possible to obtain accurate reaction electronic energy values with computationally less demanding methods when the error in the electronic correlation energy com- pensates between reactants and products. Furthermore, the provided post-HF reference values allowed to validate different DFT exchange-correlation functionals combined with different basis sets for chemical reactions that are relevant in biochemical CO2 fixing enzymes.</p></div></div></div>

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