The chlorine evolution reaction promoted by organocatalysts with amide functional groups

Since the nineteenth century, the chlor-alkali process entails the electrochemical oxidation of sodium chloride solutions to Cl_(2) by the chlorine evolution reaction(CER) and the simultaneous production of sodium hydroxide and H_(2) at the cathode, of which sodium hydroxide and Cl_(2) are widely used as important chemicals [1].

Photochemical and Electrochemical Carbon Dioxide Utilization with Organic Compounds

In the last few years, photochemical and electrochemical CO2 transformations have attracted increasing attention in response to topical interest in renewable energy and green chemistry. The present minireview offers an overview about the current approaches for the photochemical and electrochemical carbon dioxide fixation with organic compounds. Valuable products, including carboxylic acids and heterocyclic compounds, are accessible through carboxylation and carboxylative cyclization, respectively. In photochemical and electrochemical processes, photo- or electro-induced radical ions or other high-energy organic compounds are considered as key intermediates to react with CO2. Besides, activation of CO2 to produce radical anion has also been reported.

Protic ionic liquid-promoted synthesis of dimethyl carbonate from ethylene carbonate and methanol

In this work,the protic ionic liquid[DBUH][Im](1,8-diazabicyclo[5.4.0]-7-undeceniumimidazolide)was developed as an efficient catalyst for the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate.At 70℃,up to 97%conversion of ethylene carbonate and 91%yield of dimethyl ca rbonate were obtained with 1 mol%[DBUH][Im](relative to ethylene carbonate)as catalyst in 2 h.Even at room temperature,the conversion of ethylene carbonate can reach 94%and the yield of dimethyl carbonate can approach 81%for 6 h.Catalytic mechanism investigation showed the high catalytic efficiency of this ionic liquid results from the synergistic activation effect,wherein the cation can activate ethylene carbonate and the anion can activate methanol through hydrogen bond formatio n.Although the reusability of the ionic liquid need to be further improved,high efficiency and comme rcial availability of[DBUH][Im]render it a promising catalyst for the preparation of dimethyl carbonate.

Upgrading CO2 by Incorporation into Urethanes through Silver-Catalyzed One-Pot Stepwise Amidation Reaction

One-pot two-step stepwise reaction of terminal propargylic alcohols, carbon dioxide, and primary/secondary amines for the effective synthesis of various urethanes through robust silver-catalysed C-O/C-N bond formation is reported, Catalytic activities were investigated by controlling catalyst loading, reaction pressure and time, and very high turnover number （turnover frequency） was obtained： 3350 （35 h-1） with 0.01 mol% silver catalyst under 0.1 MPa, and up to 13360 （139 h-1） with 0.005 mol% silver catalyst under 2.0 MPa at room temperature. The strategy was ingeniously regulated, and synchronously afforded a wide range of β-oxopropylcarbamate and 1,3-oxazolidin-2-one motifs in excellent yields and selectivity together with unprecedented high turnover number （TON） and turnover frequency （TOF） value.

Polyoxometalate-based ionic liquids-promoted CO_2 conversion

Polyoxometalates(POMs) are a class of molecular metal oxides, showing numerous applications in various chemical processes due to their unique acid/base and redox features. By adjusting the tunable molecular structures of the anions and counter cations, plenty of POM-based ionic liquids(POM-based ILs) have been fabricated to be used in various fields, such as catalysis, structural chemistry and material science. As a class of excellent catalysts, POM-based ILs have shown advantages in the emerging field of CO_2 utilization such as CO_2 capture, cycloaddition of CO_2 to epoxides, and reduction of CO_2, owing to the efficient activation of CO_2 by POM anions. This review summarizes recent advances in the catalysis of POM-based ILs, and particularly highlights the areas that are related to CO_2 conversion.

Efficient and Recyclable Cobalt(Ⅱ)/Ionic Liquid Catalytic System for CO2 Conversion to Prepare 2-Oxazolinones at Atmospheric Pressure

Summary of main observation and conclusion Converting CO2 into value-added chemicals represents a promising way to alleviate the CO2 derived environmental issues,for which the development of catalysts with high efficiency and recyclability is very desirable.Herein,the catalytic system by combining cobalt source and ionic liquid(IL)has been developed as the efficacious and recyclable catalyst for the carboxylative cyclization of propargylic amine and CO2 to prepare 2-oxazolinones.In this protocol,various propargylic amines were successfully transformed into the corresponding 2-oxazolinones with CoBr2 and diethylimidazolium acetate([EEIM][OAc])as the catalyst under atmospheric CO2 pressure.It is worth noting that the turnover number(TON)of this transformation can be up to 1740,presumably being attributed to the cooperative effect of the cobalt and IL.Furthermore,the existence of IL enables the catalytic system to be easily recycled to 10 times without losing its activity.

CO_(2) capture and utilization with solid waste

Nowadays,the massive consumption of fossil fuels and the resulting excessive emission of carbon dioxide(CO_(2))have broken the original carbon balance of nature,resulting in global warming and the consequent detrimental environmental impacts.To address these issues,various initiatives have been proposed,among which CO_(2) cap-ture and utilization(CCU)is considered as the direct way to mitigate the accumulation of CO_(2) in the atmosphere.Although a plethora of CO_(2) capture reagents and utilization routes have been developed,the cost of CO_(2) capture reagents as well as the amount of CO_(2) utilization still encounters limitations.Recently,CCU with solid wastes have attracted sustained attention due to its ability to synchronize CO_(2) fixation with solid wastes utilization.Especially,the huge amount and low cost of the solid wastes can promote the economic fixation of CO_(2) and thus contribute significantly to the carbon sink.Given the tremendous utility of this strategy,this review article summarizes the state-of-the-art of CO_(2) capture and utilization with solid wastes such as steel slag,concrete waste,fly ash,red mud,calcium carbide residue,and biomass etc.And three parts including CO_(2) mineralization,solid waste-based catalyst promoted CO_(2) transformation,and collaborative transformation of CO_(2) and solid waste are introduced according to the roles of solid waste in CO_(2) utilization.We hope this review can arouse broad concern and spur further development in this field.

Ionic Liquid-Modified Porous Organometallic Polymers as Efficient and Selective Photocatalysts for Visible-Light-Driven CO_(2) Reduction

In the photoreduction of CO_(2) to CO,the competitive H2 evolution is always inevitable due to the approximate reduction potentials of H+/H2 and CO_(2)/CO,which results in poor selectivity for CO production.Herein,imidazolium-type ionic liquid-(IL-)modified rhenium bipyridine-based porous organometallic polymers(Re-POMP-IL)were designed as efficient and selective photocatalysts for visible-light CO_(2) photoreduction to CO based on the affinity of IL with CO_(2).Photoreduction studies demonstrated that CO_(2) photoreduction promoted by Re-POMP-IL functioning as the catalyst exhibits excellent CO selectivity up to 95.5%and generate 40.1 mmol CO/g of Re-POMP-IL1.0(obtained by providing equivalent[(5,5′-divinyl-2,2′-bipyridine)Re(CO)_(3)Cl]and 3-ethyl-1-vinyl-1H-imidazol-3-ium bromide)at 12 h,outperforming that attained with the corresponding Re-POMP analogue without IL,which highlights the crucial role of IL.Notably,CO_(2) adsorption,light harvesting,and transfer of photogenerated charges as key steps for CO_(2)RR were studied by employing POMPs modified with different amounts of IL as photocatalysts,among which the CO_(2) affinity as an important factor for POMPs catalyzed CO_(2) reduction is revealed.Overall,this work provides a practical pathway to improve the CO_(2) photoreduction efficiency and CO selectivity by employing IL as a regulator.

Carbon dioxide chemistry towards carbon-neutrality

Startling rise of carbon dioxide concentration in the atmosphere has become a serious concern to scientists and others.Obviously,reduction of CO_(2) will be ideal to save the future world but increasing number of pop-ulation and theirbelongings is the major drawback to imply this.Whilethe Covid-19 pandemic reduced the CO_(2) concentration temporarily in the last two years,but still carbon dioxide concentrations are ata recordhigh.

Ruthenium-promoted reductive transformation of CO2

The reductive transformation of CO_2 to energy related products including formic acid, CO, formamide, methanol and methylamine could be a promising option to supply renewable energy. In this aspect, ruthenium has found wide application in hydrogenation of various carbonyl groups, and has successfully been applied to reductive transformation of CO_2 with high catalytic efficiency and excellent selectivity. In addition, ruthenium complexes have also served as effective photosensitizers for CO_2 photoreduction.Classified by reductive products, this review summarizes and updates advances in the Ru-catalyzed reduction of CO_2 along with catalyst development on the basis of mechanistic understanding at a molecular level.

Fe(NO_3)_3-9H_2O-catalyzed aerobic oxidation of sulfides to sulfoxides under mild conditions with the aid of trifluoroethanol

Selective oxidation of sulfides to sulfoxides was successfully performed by employing readily available Fe（NO3）3-9H2O as the active catalyst with oxygen as the oxidant in 2,2,2-trifluoroethanol （TFE） without the formation of sulfones. Nitrate anion could play a crucial role in promoting the reaction due to the oxidation capacity under acidic media. High yields of sulfoxides were exclusively obtained from the corresponding sulfides. Furthermore, both aromatic and aliphatic sulfides gave moderate to high yields of sulfoxides with this protocol.

Green process for hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate over diatomite supported Cu/Ni bimetallic catalyst

A series of diatomite supported Cu/Ni bimetallic catalysts were prepared using the co-impregnation method to improve the efficiency and selectivity toward methyl 12-hydroxystearate in the hydrogenation of methyl ricinoleate.The catalysts were characterized using X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy and energy dispersive X-ray spectroscopy(SEM-EDS),X-ray photoelectron spectroscopy(XPS)and temperature programmed reduction(H2-TPR).All the characterization results verified the formation of highly dispersed Cu/Ni alloy on support.Moreover,by subtly regulating the Ni/Cu molar ratio as well as the reaction parameters,the hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate proceeded efficiently and selectively,affording 97%yield of methyl 12-hydroxystearate and nearly equivalent conversion of methyl ricinoleate under 2 MPa H2 pressure and at 130 C in 4 h with only 1 wt%of the catalyst Ni7Cu1/diatomite(based on methyl ricinoleate).Besides,the supported Cu–Ni bimetallic catalyst is stable during recycle and reuse.After five cycles of reuse,much catalytic activity is still preserved.Therefore,this low-cost and stable bimetallic catalyst would be promising for the hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate,representing an example of green catalysis for efficiently conversion of biomass to value-added chemicals and materials.