The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging....The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging.Herein,strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer(PML-Cu)and Bi_(12)O_(17)Br_(2)(BOB),which triggers the surface interface dual polarization of PML-Cu/BOB(PBOB).In this multi-step polarization,the built-in electric field formed between the interfaces induces the electron transfer from con-duction band(CB)of BOB to CB of PML-Cu and suppresses its reverse migration.Moreover,the surface polarization of PML-Cu further promotes the electron converge in Cu atoms.The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB,significantly promoting the adsorption and activation of CO_(2) and CO desorption.The conversion rate of CO_(2) photoreduction to CO for PBOB can reach 584.3μmol g-1,which is 7.83 times higher than BOB and 20.01 times than PML-Cu.This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.展开更多
The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic acti...The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).展开更多
Herein we report CO_(2) electrochemical reduction reaction(CO_(2) ERR)on the cobalt tetraphenylporphyrin(Co TPP)modified TiO_(2) nanotube(TNT)electrode.It was found the axial coordination of drop-casting solvent to Co...Herein we report CO_(2) electrochemical reduction reaction(CO_(2) ERR)on the cobalt tetraphenylporphyrin(Co TPP)modified TiO_(2) nanotube(TNT)electrode.It was found the axial coordination of drop-casting solvent to Co TPP and the porphyrin structure are the major factors that have significant effects on the catalytic performance of the electrode.As confirmed by spectrophotometric titration,pyridine has a stronger coordination bond to Co TPP than DMF and THF thus leading to the highest efficiency among the dropcasting solvents tested in the study.Based on the spectrophotometric analysis,possible coordination mechanism between drop-casting solvents and Co TPP is put forward.On the other hand,introduction of-COOMe substituents in phenyl rings of Co TPP weakens the coordination bond between pyridine and Co TPP as clearly evidenced by deuterium NMR spectra,resulting in a detrimental effect on CO_(2) ERR.Therefore,the manipulation of the coordination environment around the metal center of immobilized catalyst is crucial in designing an efficient electrocatalytic system.展开更多
The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali...The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.展开更多
Coronavirus disease 2019 is a serious disease that causes acute respiratory syndrome and negatively affects the central nervous system.Severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)crosses the blood-brain...Coronavirus disease 2019 is a serious disease that causes acute respiratory syndrome and negatively affects the central nervous system.Severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)crosses the blood-brain barrier due to the spike(S) protein on the surface of the viral particles.Thus,it is important to develop compounds that not only have an inhibitory effect but are also capable of completely deactivating the S protein function.This study describes the purposeful modification of porphyrins and proposes compounds,asymmetrically hetaryl-substituted porphyrins with benzothiazole,benzoxazole,and N-methylbenzimidazole residues,to deactivate the S protein functions.Molecular docking of SARS-CoV-2 proteins with hetaryl-substituted porphyrins showed that the viral S protein,nucleocapsid(N) protein,and non-structural protein 13(nsp13) exhibited the highest binding affinity.Hetaryl-substituted porphyrins form strong complexes(13-14 kcal/mol) with the receptor-binding domain of the S protein,while the distance from the porphyrins to the receptor-binding motif(RBM)does not exceed 20 ?;therefore,RBM can be oxidized by ^(1)O_(2),which is generated by porphyrin.Hetarylsubstituted porphyrins interact with the N protein in the serine/arginine-rich region,and a number of vulnerable amino acid residues are located in the photooxidation zone.This damage complicates the packaging of viral RNA into new virions.High-energy binding of hetaryl-substituted porphyrins with the N-and C-terminal domains of nsp13 was observed.This binding blocks the action of nsp13 as an enzyme of exoribonuclease and methyltransferase,thereby preventing RNA replication and processing.A procedure for the synthesis of hetaryl-substituted porphyrins was developed,new compounds were obtained,their structures were identified,and their photocatalytic properties were studied.展开更多
In this work, metal free and zinc tetraphenylporphyrin films were employed as nitrogen dioxide (NO2) gas sensors. The films were vacuum evaporated and the sensor response was evaluated as changes in the optical absorp...In this work, metal free and zinc tetraphenylporphyrin films were employed as nitrogen dioxide (NO2) gas sensors. The films were vacuum evaporated and the sensor response was evaluated as changes in the optical absorption spectra, hydrophobic properties and conductivity at different gas concentrations. From UV-Vis results, important changes in the absorption peaks were observed after gas exposure. The morphology of the films before and after gas interaction was obtained by using scanning electron and atomic force microscopy. The films morphology showed a degradation after gas adsorption for the metal free system but gas entrapment for the zinc porphyrin film. In order to elucidate the gas adsorption phenomena, density functional theory calculations were also performed. Here, it was observed that the porphyrin chemical structure not only affects the gas coordination sites which affect the porphyrin electronic distribution and packing arrangement, but also, determines the gas detection mechanism for sensing applications.展开更多
在采用区域选择性硝化方法合成β-硝基-5,10,15,20-四芳基卟啉铜、镍配合物的过程中,发现并通过核磁等方法分析了5,10,15,20-四(2-甲氧基苯基)卟啉及其相应β-硝基取代物的阻旋异构现象。图谱分析表明,与其结构类似的5,10,15,20-四(2-...在采用区域选择性硝化方法合成β-硝基-5,10,15,20-四芳基卟啉铜、镍配合物的过程中,发现并通过核磁等方法分析了5,10,15,20-四(2-甲氧基苯基)卟啉及其相应β-硝基取代物的阻旋异构现象。图谱分析表明,与其结构类似的5,10,15,20-四(2-羟基苯基)卟啉及5,10,15,20-四(4-甲氧基苯基)卟啉系列化合物没有该阻旋异构现象,说明邻位甲氧基阻碍了苯环与芳环之间C-C单键的旋转。进一步通过Chemdraw 3D Ultra软件能量最小化计算,讨论了阻转异构体可能的方式。展开更多
Mercury is the most toxic and harmful heavy metal pollutant, and it is essential to detect and remove mercury from beverages. Inducing the porphyrin molecules into the chitosan structure, a novel membrane sensor tetra...Mercury is the most toxic and harmful heavy metal pollutant, and it is essential to detect and remove mercury from beverages. Inducing the porphyrin molecules into the chitosan structure, a novel membrane sensor tetrakis(4-carboxyphenyl)porphyrin-grafted chitosan fiber membrane (TCPP-CS) was prepared by electrospinning method and applied to recognize Hg^(2+) contaminant selectively. Compared with other common metal ions (Pb^(2+), Cu^(2+), Fe^(3+), Cr^(3+), Mg^(2+), and Zn^(2+)), the colorimetric sensor has specific color development and sensitivity to Hg^(2+) and the detection limit of the sensor reaches 1 × 10^(−5) mol·L^(−1). The response time of the membrane is 5 s, and it can be specifically colored in various pH environments convenient for practical application. Hg^(2+) resulted in a visual color change of the fiber membrane from brown to yellow-green, indicating a potential interaction between the porphyrin-functionalized chitosan fiber membrane and Hg^(2+) ions, and the wavelength shift of the UV–visible spectrum can be observed. It has the advantages of simplicity, rapidity, high selectivity, and high sensitivity, providing a new method for removing and detecting heavy metals in traditional Chinese medicine and drinks.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.22138011,22205108,22378206)Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials and Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces(KLMEACM 202201),Zhejiang Normal University.
文摘The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging.Herein,strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer(PML-Cu)and Bi_(12)O_(17)Br_(2)(BOB),which triggers the surface interface dual polarization of PML-Cu/BOB(PBOB).In this multi-step polarization,the built-in electric field formed between the interfaces induces the electron transfer from con-duction band(CB)of BOB to CB of PML-Cu and suppresses its reverse migration.Moreover,the surface polarization of PML-Cu further promotes the electron converge in Cu atoms.The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB,significantly promoting the adsorption and activation of CO_(2) and CO desorption.The conversion rate of CO_(2) photoreduction to CO for PBOB can reach 584.3μmol g-1,which is 7.83 times higher than BOB and 20.01 times than PML-Cu.This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.
基金supported by NSERC DG 2016-06122 and 201606589 through Discovery Grants to HBK and X.A.Z.,respectivelyby the Canada Foundation for Innovation,Canada Research Chair,and the Ontario Research Fund。
文摘The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).
基金Financial support from the ARC Discovery Project(DP1901013720)。
文摘Herein we report CO_(2) electrochemical reduction reaction(CO_(2) ERR)on the cobalt tetraphenylporphyrin(Co TPP)modified TiO_(2) nanotube(TNT)electrode.It was found the axial coordination of drop-casting solvent to Co TPP and the porphyrin structure are the major factors that have significant effects on the catalytic performance of the electrode.As confirmed by spectrophotometric titration,pyridine has a stronger coordination bond to Co TPP than DMF and THF thus leading to the highest efficiency among the dropcasting solvents tested in the study.Based on the spectrophotometric analysis,possible coordination mechanism between drop-casting solvents and Co TPP is put forward.On the other hand,introduction of-COOMe substituents in phenyl rings of Co TPP weakens the coordination bond between pyridine and Co TPP as clearly evidenced by deuterium NMR spectra,resulting in a detrimental effect on CO_(2) ERR.Therefore,the manipulation of the coordination environment around the metal center of immobilized catalyst is crucial in designing an efficient electrocatalytic system.
文摘The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.
文摘Coronavirus disease 2019 is a serious disease that causes acute respiratory syndrome and negatively affects the central nervous system.Severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)crosses the blood-brain barrier due to the spike(S) protein on the surface of the viral particles.Thus,it is important to develop compounds that not only have an inhibitory effect but are also capable of completely deactivating the S protein function.This study describes the purposeful modification of porphyrins and proposes compounds,asymmetrically hetaryl-substituted porphyrins with benzothiazole,benzoxazole,and N-methylbenzimidazole residues,to deactivate the S protein functions.Molecular docking of SARS-CoV-2 proteins with hetaryl-substituted porphyrins showed that the viral S protein,nucleocapsid(N) protein,and non-structural protein 13(nsp13) exhibited the highest binding affinity.Hetaryl-substituted porphyrins form strong complexes(13-14 kcal/mol) with the receptor-binding domain of the S protein,while the distance from the porphyrins to the receptor-binding motif(RBM)does not exceed 20 ?;therefore,RBM can be oxidized by ^(1)O_(2),which is generated by porphyrin.Hetarylsubstituted porphyrins interact with the N protein in the serine/arginine-rich region,and a number of vulnerable amino acid residues are located in the photooxidation zone.This damage complicates the packaging of viral RNA into new virions.High-energy binding of hetaryl-substituted porphyrins with the N-and C-terminal domains of nsp13 was observed.This binding blocks the action of nsp13 as an enzyme of exoribonuclease and methyltransferase,thereby preventing RNA replication and processing.A procedure for the synthesis of hetaryl-substituted porphyrins was developed,new compounds were obtained,their structures were identified,and their photocatalytic properties were studied.
文摘In this work, metal free and zinc tetraphenylporphyrin films were employed as nitrogen dioxide (NO2) gas sensors. The films were vacuum evaporated and the sensor response was evaluated as changes in the optical absorption spectra, hydrophobic properties and conductivity at different gas concentrations. From UV-Vis results, important changes in the absorption peaks were observed after gas exposure. The morphology of the films before and after gas interaction was obtained by using scanning electron and atomic force microscopy. The films morphology showed a degradation after gas adsorption for the metal free system but gas entrapment for the zinc porphyrin film. In order to elucidate the gas adsorption phenomena, density functional theory calculations were also performed. Here, it was observed that the porphyrin chemical structure not only affects the gas coordination sites which affect the porphyrin electronic distribution and packing arrangement, but also, determines the gas detection mechanism for sensing applications.
文摘在采用区域选择性硝化方法合成β-硝基-5,10,15,20-四芳基卟啉铜、镍配合物的过程中,发现并通过核磁等方法分析了5,10,15,20-四(2-甲氧基苯基)卟啉及其相应β-硝基取代物的阻旋异构现象。图谱分析表明,与其结构类似的5,10,15,20-四(2-羟基苯基)卟啉及5,10,15,20-四(4-甲氧基苯基)卟啉系列化合物没有该阻旋异构现象,说明邻位甲氧基阻碍了苯环与芳环之间C-C单键的旋转。进一步通过Chemdraw 3D Ultra软件能量最小化计算,讨论了阻转异构体可能的方式。
基金supported by Natural Science Foundation-Steel and Iron Foundation of Hebei Province of China(No.B2020209022)PhD Startup Program of North China University of Science and Technology(No.BS2017031)Tianjin Science and Technology plan project(No.24ZYCGSN01250).
文摘Mercury is the most toxic and harmful heavy metal pollutant, and it is essential to detect and remove mercury from beverages. Inducing the porphyrin molecules into the chitosan structure, a novel membrane sensor tetrakis(4-carboxyphenyl)porphyrin-grafted chitosan fiber membrane (TCPP-CS) was prepared by electrospinning method and applied to recognize Hg^(2+) contaminant selectively. Compared with other common metal ions (Pb^(2+), Cu^(2+), Fe^(3+), Cr^(3+), Mg^(2+), and Zn^(2+)), the colorimetric sensor has specific color development and sensitivity to Hg^(2+) and the detection limit of the sensor reaches 1 × 10^(−5) mol·L^(−1). The response time of the membrane is 5 s, and it can be specifically colored in various pH environments convenient for practical application. Hg^(2+) resulted in a visual color change of the fiber membrane from brown to yellow-green, indicating a potential interaction between the porphyrin-functionalized chitosan fiber membrane and Hg^(2+) ions, and the wavelength shift of the UV–visible spectrum can be observed. It has the advantages of simplicity, rapidity, high selectivity, and high sensitivity, providing a new method for removing and detecting heavy metals in traditional Chinese medicine and drinks.
