The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving c...The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.展开更多
Due to its properties of mutagenic,teratogenic,and carcinogenic,the detection of furazolidone(FZD)in aquaculture is of great importance for food safety and human health.In this study,molecularly imprinted fi lms modif...Due to its properties of mutagenic,teratogenic,and carcinogenic,the detection of furazolidone(FZD)in aquaculture is of great importance for food safety and human health.In this study,molecularly imprinted fi lms modifi ed with carboxylated multi-walled carbon nanotube-phosphomolybdic acid composite were used to fabricate an electrochemical sensor for the determination of FZD.The nanocomposites were characterized using infrared spectroscopy,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and X-ray diff raction.The electrochemical characteristics of the modifi ed electrodes were examined using electrochemical impedance spectroscopy,cyclic voltammetry,and diff erential pulse voltammetry.The sensor exhibited exceptional catalytic performance.The calibration curves were acquired in the concentration range of 6 nmol·L^(−1)to 0.6μmol·L^(−1),with a limit of detection of 3.38 nmol·L^(−1).Additionally,the sensor proved successful in recognizing FZD in shrimp samples with satisfactory recoveries and precision.The method provides a strategy to construct a molecularly imprinted electrochemical sensing platform using nanomaterials,which has great promise in the field of food safety.展开更多
Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via...Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.展开更多
An ultrasensitive electrochemical sensor based on polydopamine/carboxylic multi-walled carbon nanotubes(MWCNTs à COOH) nanocomposites modified glassy carbon electrode(GCE) was presented in this work, which has be...An ultrasensitive electrochemical sensor based on polydopamine/carboxylic multi-walled carbon nanotubes(MWCNTs à COOH) nanocomposites modified glassy carbon electrode(GCE) was presented in this work, which has been developed for highly selective and highly sensitive determination of an antimicrobial drug, metronidazole. The preparation of polydopamine/MWCNTs–COOH nanocomposites/GCE sensor is simple and possesses high reproducible, where polydopamine can be coated on the surface of MWCNTs–COOH via a simple electropolymerization process. Under optimized conditions, the proposed sensor showed ultrasensitive determination for metronidazole with a wide linear detection range from5 to 5000 mmol/dm^3 and a low detection limit of 0.25 mmol/dm^3(S/N=3). Moreover, the proposed sensor has been successfully applied for the quantitative determination of metronidazole in real drug samples. This work may provide a novel and effective analytical platform for determination of metronidazole in application of real pharmaceutical and biological samples analysis.展开更多
Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, elect...Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide （scCO2） has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.展开更多
The electrochemical behavior of a carboxyl-modified carbon nanotube films was investigated to explore its possibility in electroanalytical applicaton. Cyclic voltammetry of quinone was conducted in 1mol/L Na2SO4, whic...The electrochemical behavior of a carboxyl-modified carbon nanotube films was investigated to explore its possibility in electroanalytical applicaton. Cyclic voltammetry of quinone was conducted in 1mol/L Na2SO4, which showed a stable, quasi-reversible voltammetric response for quinone / hydroquinone, and the anodic and the cathodic peak potentials were 0.657V and -0.029V (vs. SCE) at a scan rate of 0.1V.s-1, respectively. Both anodic and cathodic peak currents depended linearly on the square root of the scan rate over the range of 0.01-0.5V.s-1, which suggested that the process of the electrode reactions was diffusion-controlled. Carboxyl-modified carbon nanotube electrodes made it possible to determine low level of dopamine selectively in the presence of a large excess of ascorbic acid in acidic media using derivative voltammetry. The results obtained were discussed in details. This work demonstrates the potential of carboxyl-modified carbon nanotube electrodes for electroanalytical applications.展开更多
The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative...The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.展开更多
Electrocarboxylation of carbon dioxide(CO_(2))using organic substrates has emerged as a promising method for the sustainable synthesis of value-added carboxylic acids due to its renewable energy source and mild reacti...Electrocarboxylation of carbon dioxide(CO_(2))using organic substrates has emerged as a promising method for the sustainable synthesis of value-added carboxylic acids due to its renewable energy source and mild reaction conditions.The reactivity and product selectivity of electrocarboxylation are highly dependent on the cathodic behavior,involving a sequence of electron transfers and chemical reactions.Hence,it is necessary to understand the cathodic reaction mechanisms for optimizing reaction performance and product distribution.In this work,a review of recent advancements in the electrocarboxylation of CO_(2)with organic substrates based on different cathodic reaction pathways is presented to provide a reference for the development of novel methodologies of CO_(2)electrocarboxylation.Herein,cathodic reactions are particularly classified into two categories based on the initial electron carriers(i.e.,CO_(2)radical anion and substrate radical anion).Furthermore,three cathodic pathways(ENE(N),ENED,and EDEN)of substrate radical anion-induced electrocarboxylation are discussed,which differ in their electron transfer sequence,substrate dissociation,and nucleophilic reaction,to highlight their implications on reactivity and product selectivity.展开更多
A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild rea...A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild reaction conditions.This reaction provides a facile and sustainable method for the synthesis of tricarboxylates by using CO_(2) as the carboxylic source.展开更多
Dearomative carboxylation of aromatic compounds with carbon dioxide(CO_(2))could be utilized for the synthesis of cyclic carboxylative frameworks.The dearomative carboxylation exhibits advantages such as reconstitutio...Dearomative carboxylation of aromatic compounds with carbon dioxide(CO_(2))could be utilized for the synthesis of cyclic carboxylative frameworks.The dearomative carboxylation exhibits advantages such as reconstitution molecular spatial structure,environmental friendliness,mild conditions,high yield,and high selectivity,and is of significant importance in pharmaceutical synthesis and natural product chemistry.The recent advancements in the dearomative carboxylation of aromatics with CO_(2) are summarized,including elucidation of the reaction characteristics and the scope of substrates via transition-metal catalysis,photoredox catalysis,and electropromoted chemistry.展开更多
基金financial support from the King Abdullah University of Science and Technology(KAUST).
文摘The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.
基金Supported by the National Natural Science Foundation of China(Grant No.22271119).
文摘Due to its properties of mutagenic,teratogenic,and carcinogenic,the detection of furazolidone(FZD)in aquaculture is of great importance for food safety and human health.In this study,molecularly imprinted fi lms modifi ed with carboxylated multi-walled carbon nanotube-phosphomolybdic acid composite were used to fabricate an electrochemical sensor for the determination of FZD.The nanocomposites were characterized using infrared spectroscopy,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and X-ray diff raction.The electrochemical characteristics of the modifi ed electrodes were examined using electrochemical impedance spectroscopy,cyclic voltammetry,and diff erential pulse voltammetry.The sensor exhibited exceptional catalytic performance.The calibration curves were acquired in the concentration range of 6 nmol·L^(−1)to 0.6μmol·L^(−1),with a limit of detection of 3.38 nmol·L^(−1).Additionally,the sensor proved successful in recognizing FZD in shrimp samples with satisfactory recoveries and precision.The method provides a strategy to construct a molecularly imprinted electrochemical sensing platform using nanomaterials,which has great promise in the field of food safety.
基金supported by the National Nature Science Foundation of China (J1210060, 21143002)
文摘Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21475046,21427809)
文摘An ultrasensitive electrochemical sensor based on polydopamine/carboxylic multi-walled carbon nanotubes(MWCNTs à COOH) nanocomposites modified glassy carbon electrode(GCE) was presented in this work, which has been developed for highly selective and highly sensitive determination of an antimicrobial drug, metronidazole. The preparation of polydopamine/MWCNTs–COOH nanocomposites/GCE sensor is simple and possesses high reproducible, where polydopamine can be coated on the surface of MWCNTs–COOH via a simple electropolymerization process. Under optimized conditions, the proposed sensor showed ultrasensitive determination for metronidazole with a wide linear detection range from5 to 5000 mmol/dm^3 and a low detection limit of 0.25 mmol/dm^3(S/N=3). Moreover, the proposed sensor has been successfully applied for the quantitative determination of metronidazole in real drug samples. This work may provide a novel and effective analytical platform for determination of metronidazole in application of real pharmaceutical and biological samples analysis.
文摘Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide （scCO2） has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.
文摘The electrochemical behavior of a carboxyl-modified carbon nanotube films was investigated to explore its possibility in electroanalytical applicaton. Cyclic voltammetry of quinone was conducted in 1mol/L Na2SO4, which showed a stable, quasi-reversible voltammetric response for quinone / hydroquinone, and the anodic and the cathodic peak potentials were 0.657V and -0.029V (vs. SCE) at a scan rate of 0.1V.s-1, respectively. Both anodic and cathodic peak currents depended linearly on the square root of the scan rate over the range of 0.01-0.5V.s-1, which suggested that the process of the electrode reactions was diffusion-controlled. Carboxyl-modified carbon nanotube electrodes made it possible to determine low level of dopamine selectively in the presence of a large excess of ascorbic acid in acidic media using derivative voltammetry. The results obtained were discussed in details. This work demonstrates the potential of carboxyl-modified carbon nanotube electrodes for electroanalytical applications.
基金supported by the National Natural Science Foundation of China(21878038)the Natural Science Foundation of Liaoning Province(20170540156)the Program for Changjiang Scholars and Innovative Research Team in University(IRT-17R14)~~
文摘The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.
基金received from the National Natural Science Foundation of China(No.22278305)National Key R&D Program of China(2022YFB4101900)。
文摘Electrocarboxylation of carbon dioxide(CO_(2))using organic substrates has emerged as a promising method for the sustainable synthesis of value-added carboxylic acids due to its renewable energy source and mild reaction conditions.The reactivity and product selectivity of electrocarboxylation are highly dependent on the cathodic behavior,involving a sequence of electron transfers and chemical reactions.Hence,it is necessary to understand the cathodic reaction mechanisms for optimizing reaction performance and product distribution.In this work,a review of recent advancements in the electrocarboxylation of CO_(2)with organic substrates based on different cathodic reaction pathways is presented to provide a reference for the development of novel methodologies of CO_(2)electrocarboxylation.Herein,cathodic reactions are particularly classified into two categories based on the initial electron carriers(i.e.,CO_(2)radical anion and substrate radical anion).Furthermore,three cathodic pathways(ENE(N),ENED,and EDEN)of substrate radical anion-induced electrocarboxylation are discussed,which differ in their electron transfer sequence,substrate dissociation,and nucleophilic reaction,to highlight their implications on reactivity and product selectivity.
文摘A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild reaction conditions.This reaction provides a facile and sustainable method for the synthesis of tricarboxylates by using CO_(2) as the carboxylic source.
文摘Dearomative carboxylation of aromatic compounds with carbon dioxide(CO_(2))could be utilized for the synthesis of cyclic carboxylative frameworks.The dearomative carboxylation exhibits advantages such as reconstitution molecular spatial structure,environmental friendliness,mild conditions,high yield,and high selectivity,and is of significant importance in pharmaceutical synthesis and natural product chemistry.The recent advancements in the dearomative carboxylation of aromatics with CO_(2) are summarized,including elucidation of the reaction characteristics and the scope of substrates via transition-metal catalysis,photoredox catalysis,and electropromoted chemistry.
