The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added valu...The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.展开更多
Utilizing CO_(2)for bio-succinic acid production is an attractive approach to achieve carbon capture and recycling(CCR)with simultaneous production of a useful platform chemical.Actinobacillus succinogenes and Basfia ...Utilizing CO_(2)for bio-succinic acid production is an attractive approach to achieve carbon capture and recycling(CCR)with simultaneous production of a useful platform chemical.Actinobacillus succinogenes and Basfia succiniciproducens were selected and investigated as microbial catalysts.Firstly,the type and concentration of inorganic carbon concentration and glucose concentration were evaluated.6 g C/L MgCO_(3)and 24 g C/L glucose were found to be the optimal basic operational conditions,with succinic acid production and carbon yield of over 30 g/L and over 40%,respectively.Then,for maximum gaseous CO_(2)fixation,carbonate was replaced with CO_(2)at different ratios.The“less carbonate more CO_(2)”condition of the inorganic carbon source was set as carbonate:CO_(2)=1:9(based on the mass of carbon).This condition presented the highest availability of CO_(2)by well-balanced chemical reaction equilibrium and phase equilibrium,showing the best performance with regarding CO_(2)fixation(about 15 mg C/(L·hr)),with suppressed lactic acid accumulation.According to key enzymes analysis,the ratio of phosphoenolpyruvate carboxykinase to lactic dehydrogenase was enhanced at high ratios of gaseous CO_(2),which could promote glucose conversion through the succinic acid path.To further increase gaseous CO_(2)fixation and succinic acid production and selectivity,stepwise CO_(2)addition was evaluated.50%-65%increase in inorganic carbon utilization was obtained coupled with 20%-30%increase in succinic acid selectivity.This was due to the promotion of the succinic acid branch of the glucose metabolism,while suppressing the pyruvate branch,along with the inhibition on the conversion from glucose to lactic acid.展开更多
Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an eff...Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.展开更多
Carbon dioxide(CO_(2))is an important and valuable C1 resource for the synthesis of numerous of value-added products. However, efficient fixation and conversion of CO_(2) into organic carbonates under mild conditions ...Carbon dioxide(CO_(2))is an important and valuable C1 resource for the synthesis of numerous of value-added products. However, efficient fixation and conversion of CO_(2) into organic carbonates under mild conditions remain great challenges. Herein, graphdiyne(GDY)-based nickel atomic catalysts(Ni0/GDYs) were synthesized through a facile in-situ reduction method. Experimental results showed that the obtained Ni0/GDY had outstanding catalytic performances for converting CO_(2) into cyclic carbonates with a high reaction conversion(99%) and reaction selectivity(ca. 100%) at 80℃ and under 1 atm(1 atm=101325 Pa). Specially, the activation energy (Ea) value for the Ni0/GDY is 37.05 kJ/mol, lower than those of reported catalysts. The reaction mechanism was next carefully analyzed by using density functional theory(DFT) calculations. Such an excellent catalytic property could be mainly attributed to the high dispersion of active sites on the Ni0/GDY, and the unique incomplete charge transfer properties of GDY-based zero-valent metallic catalysts.展开更多
Carbon dioxide(CO_(2))is an attractive C1 building block in chemical synthesis due to its abundance,availability and sustainability.However,the low reactivity and high stability generally limits its transformations un...Carbon dioxide(CO_(2))is an attractive C1 building block in chemical synthesis due to its abundance,availability and sustainability.However,the low reactivity and high stability generally limits its transformations under mild conditions to value added chemicals.Recent advances in flow chemistry provide effective means for the chemical transformation of CO_(2),and many new methods and techniques that fully utilized the advantages of continuous flow platforms for the chemical fixation of CO_(2)have been realized.In view of the rapid development and the urgent need for continuous transformation of CO_(2),herein we wish to present an update of the recent advances in this research area.展开更多
Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented ...Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal conditions.Among them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions.Two main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium clusters.Given the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these compounds.Remarkably,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic activity.Also,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room temperature.Moreover,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.展开更多
By taking the functional adva ntages of both pyrazolate and carboxylate ligands,a unique dual-functional pyrazolate-carboxylate ligand acid,4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid(H3PCBA) was designed and...By taking the functional adva ntages of both pyrazolate and carboxylate ligands,a unique dual-functional pyrazolate-carboxylate ligand acid,4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid(H3PCBA) was designed and synthesized.Using it,a new Co(Ⅱ)-based metal-organic framework(MOF),Co_(3)(PCBA)_(2)(H_(2)O)_(2)(BUT-75) has been constructed.It revealed a(3,6)-connected net based on the 6-connected linear trinuclear metal node,and showed good chemical stability in a wide pH range from 3 to 12 at room temperature,as well as in boiling water.Due to the presence of rich exposed Co(Ⅱ) sites in pores,BUT-75 presented high selective CO_(2) adsorption capacity over N2 at 298 K.Simultaneously,it demonstrated fine catalytic performance for the cycloaddition of CO_(2) with epoxides into cyclic carbonates under ambient conditions.This work has not only enriched the MOF community through integrating diverse functio nalities into one ligand but also contributed a versatile platform for CO_(2) fixation,thereby pushing MOF chemistry forward by stability enhancement and application expansion.展开更多
The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel ...The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel strategy for the synthesis of hierarchically porous MOFs(e.g., MIL-101)-encapsulated N-doped nanocarbon(CN@MIL) by controlled pyrolysis of ionic liquids@MIL-101 precursors(ILs@MIL). The obtained CN@MIL composites not only possess abundant enlarged mesopores,but also show multi-active sites without the sacrifice of their structure stability. The CN@MIL can efficiently facilitate the mass transfer of substrates, exhibiting excellent catalytic performance in the synthesis of cyclic carbonates from epoxides and CO_(2) under mild and co-catalyst-free conditions(i.e., 90 ℃ and ambient pressure of CO_(2)). Furthermore, the multi-active Lewis acid sites and nucleophilic sites(Br ions) as well as the strong affinity of catalysts toward CO_(2)also contribute to the excellent catalytic activity of the CN@MIL. This study might open a new avenue for the rational design of MOF-based composites by employing ILs@MOF as precursors for advanced heterogeneous catalysis.展开更多
基金supported by the National Key R&D Program of China (2018YFA0901700)National Natural Science Foundation of China (22278241)+1 种基金a grant from the Institute Guo Qiang, Tsinghua University (2021GQG1016)Department of Chemical Engineering-iBHE Joint Cooperation Fund。
文摘The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.
基金supported by the Beijing Nova Program(No.Z201100006820022)the National Natural Science Foundation of China(Nos.52100023,U20B2022)+2 种基金the China Postdoctoral Science Foundation(No.2020M680314)the Key Science and Technology Development Program of Xinjiang Corps(No.2021DB006)the EU ACT Coo CE ERA-NET program cofunded with EUDP-2021-Ⅱ(No.64021-2006)。
文摘Utilizing CO_(2)for bio-succinic acid production is an attractive approach to achieve carbon capture and recycling(CCR)with simultaneous production of a useful platform chemical.Actinobacillus succinogenes and Basfia succiniciproducens were selected and investigated as microbial catalysts.Firstly,the type and concentration of inorganic carbon concentration and glucose concentration were evaluated.6 g C/L MgCO_(3)and 24 g C/L glucose were found to be the optimal basic operational conditions,with succinic acid production and carbon yield of over 30 g/L and over 40%,respectively.Then,for maximum gaseous CO_(2)fixation,carbonate was replaced with CO_(2)at different ratios.The“less carbonate more CO_(2)”condition of the inorganic carbon source was set as carbonate:CO_(2)=1:9(based on the mass of carbon).This condition presented the highest availability of CO_(2)by well-balanced chemical reaction equilibrium and phase equilibrium,showing the best performance with regarding CO_(2)fixation(about 15 mg C/(L·hr)),with suppressed lactic acid accumulation.According to key enzymes analysis,the ratio of phosphoenolpyruvate carboxykinase to lactic dehydrogenase was enhanced at high ratios of gaseous CO_(2),which could promote glucose conversion through the succinic acid path.To further increase gaseous CO_(2)fixation and succinic acid production and selectivity,stepwise CO_(2)addition was evaluated.50%-65%increase in inorganic carbon utilization was obtained coupled with 20%-30%increase in succinic acid selectivity.This was due to the promotion of the succinic acid branch of the glucose metabolism,while suppressing the pyruvate branch,along with the inhibition on the conversion from glucose to lactic acid.
基金the National Natural Science Foundation of China(No.U1808210)the Natural Science Foundation of Liaoning province(No.2019-MS-046).
文摘Development of new metal-free heterogeneous catalysts has long been the focus of intense research interest.The integration of multifunctional monomers into the skeletons of porous organic polymers(POPs)provides an efficient pathway to achieve this goal.Herein,we rationally designed and successfully prepared a new Troger’s base(TB)-derived POPs by insertion of pillar[5]arene macrocycle as a positively auxiliary group.Combined the both merits of pillar[5]arene macrocycle and TB moiety,the as-prepared polymer was further explored as an effective metal-free heterogeneous catalyst and exhibited promoted catalytic performance in Knoevenagel condensation and CO_(2)conversion.This work provides a new strategy to fabricate metal-free heterogeneous catalysts based on macrocyclic POPs.
基金This work was supported by the National Key Research and Development Project of China(No.2018YFA0703501)the National Natural Science Foundation of China(Nos.21790050,21790051,22021002)the Key Program of the Chinese Academy of Sciences(No.QYZDY-SSW-SLH015).
文摘Carbon dioxide(CO_(2))is an important and valuable C1 resource for the synthesis of numerous of value-added products. However, efficient fixation and conversion of CO_(2) into organic carbonates under mild conditions remain great challenges. Herein, graphdiyne(GDY)-based nickel atomic catalysts(Ni0/GDYs) were synthesized through a facile in-situ reduction method. Experimental results showed that the obtained Ni0/GDY had outstanding catalytic performances for converting CO_(2) into cyclic carbonates with a high reaction conversion(99%) and reaction selectivity(ca. 100%) at 80℃ and under 1 atm(1 atm=101325 Pa). Specially, the activation energy (Ea) value for the Ni0/GDY is 37.05 kJ/mol, lower than those of reported catalysts. The reaction mechanism was next carefully analyzed by using density functional theory(DFT) calculations. Such an excellent catalytic property could be mainly attributed to the high dispersion of active sites on the Ni0/GDY, and the unique incomplete charge transfer properties of GDY-based zero-valent metallic catalysts.
基金The financial support from the National Key Research and Development Program of China(No.2020YFA0710200)National Natural Science Foundation of China(No.22171090)+1 种基金the Shanghai Science and Technology Innovation Action Plan(No.20JC1416900)the Fundamental Research Funds for the Central Universities is highly appreciated。
文摘Carbon dioxide(CO_(2))is an attractive C1 building block in chemical synthesis due to its abundance,availability and sustainability.However,the low reactivity and high stability generally limits its transformations under mild conditions to value added chemicals.Recent advances in flow chemistry provide effective means for the chemical transformation of CO_(2),and many new methods and techniques that fully utilized the advantages of continuous flow platforms for the chemical fixation of CO_(2)have been realized.In view of the rapid development and the urgent need for continuous transformation of CO_(2),herein we wish to present an update of the recent advances in this research area.
基金supported by the Natural Science Foundation of Jiangsu(BK20191359)the National Natural Science Foundation of China(92161109)+1 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_1343)the Social Science Foundation of Jiangsu(19TQB002)。
文摘Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal conditions.Among them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions.Two main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium clusters.Given the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these compounds.Remarkably,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic activity.Also,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room temperature.Moreover,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.
基金financially supported by the National Natural Science Foundation of China (Nos.21771012,21601008,51621003)the Science & Technology Project of Beijing Municipal Education Committee (No.KZ201810005004)。
文摘By taking the functional adva ntages of both pyrazolate and carboxylate ligands,a unique dual-functional pyrazolate-carboxylate ligand acid,4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid(H3PCBA) was designed and synthesized.Using it,a new Co(Ⅱ)-based metal-organic framework(MOF),Co_(3)(PCBA)_(2)(H_(2)O)_(2)(BUT-75) has been constructed.It revealed a(3,6)-connected net based on the 6-connected linear trinuclear metal node,and showed good chemical stability in a wide pH range from 3 to 12 at room temperature,as well as in boiling water.Due to the presence of rich exposed Co(Ⅱ) sites in pores,BUT-75 presented high selective CO_(2) adsorption capacity over N2 at 298 K.Simultaneously,it demonstrated fine catalytic performance for the cycloaddition of CO_(2) with epoxides into cyclic carbonates under ambient conditions.This work has not only enriched the MOF community through integrating diverse functio nalities into one ligand but also contributed a versatile platform for CO_(2) fixation,thereby pushing MOF chemistry forward by stability enhancement and application expansion.
基金financially supported by the National Natural Science Foundation of China (21825802, 22138003)the Natural Science Foundation of Guangdong Province (2017A030312005)+1 种基金the Guangdong Natural Science Funds for Distinguished Young Scholar (2018B030306050)the Science and Technology Program of Qingyuan City (2021YFJH01002)。
文摘The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel strategy for the synthesis of hierarchically porous MOFs(e.g., MIL-101)-encapsulated N-doped nanocarbon(CN@MIL) by controlled pyrolysis of ionic liquids@MIL-101 precursors(ILs@MIL). The obtained CN@MIL composites not only possess abundant enlarged mesopores,but also show multi-active sites without the sacrifice of their structure stability. The CN@MIL can efficiently facilitate the mass transfer of substrates, exhibiting excellent catalytic performance in the synthesis of cyclic carbonates from epoxides and CO_(2) under mild and co-catalyst-free conditions(i.e., 90 ℃ and ambient pressure of CO_(2)). Furthermore, the multi-active Lewis acid sites and nucleophilic sites(Br ions) as well as the strong affinity of catalysts toward CO_(2)also contribute to the excellent catalytic activity of the CN@MIL. This study might open a new avenue for the rational design of MOF-based composites by employing ILs@MOF as precursors for advanced heterogeneous catalysis.
