The orientation is the key factor to determine the physicochemical properties of the metal-organic framework(MOF)films.New strategies for oriented MOF films are of fundamental importance in the advancement of science ...The orientation is the key factor to determine the physicochemical properties of the metal-organic framework(MOF)films.New strategies for oriented MOF films are of fundamental importance in the advancement of science and technology.Here we report a unified approach to the synthesis of a large variety of porphyrin-based MOF films with different directions,chemistries and properties.This strategy is based on a general electrochemical regulation of coordination process of different metal cation(M_(1)=Zn,Co,Ni,Ce)and tetra(4-carboxyphenyl)porphyrin(M_(2)TCPP,M_(2)=H,Cu,Pt,Pd)on various conductive substrates.The cathode strategy relies on the reduction of M_(2)TCPP ligands and follows the electrochemical reaction mechanism to achieve effective control over crystallizing M_(1)-M_(2)TCPP MOF films oriented in the(110)direction.The highly oriented M_(1)-M_(2)TCPP MOF films are endowed with excellent crystalline,spatial network structure and hierarchical three-dimensional pore structure,which is conducive to charge transfer and material transmission and suitable for use as an electrochemical catalyst.The Zn-TCPP MOF films on conductive substrate could be used directly as an electrochemical sensor for electrocatalytic oxidation of NaNO2,and showed wide linear range,low limit of detection(0.24μM),high sensitivity(285.8 mA/(mM·cm2))and good anti-interference performance.We believe our methodology provides a simple and convenient route to a variety of oriented porphyrin-based MOF films for nanodevices with novel structure and function in nanotechnology.展开更多
In order to broaden the absorption range of graphitic carbon nitride,one of the common methods is to couple the well-known photosensitizer porphyrin with graphitic carbon nitride through van der Waals weak in teractio...In order to broaden the absorption range of graphitic carbon nitride,one of the common methods is to couple the well-known photosensitizer porphyrin with graphitic carbon nitride through van der Waals weak in teractions.To date,to combine porphyrin with graphitic carbon nitridethrough covalent in teractions has not been settled.In this work,through rational molecular design,we successfully in corporated porphyrininto the matrixes of graphitic carbon nitride by covale nt bonding via on expot thermal copolymerization.The resulta nt material not only can wide nthe absorption range but also possess the enlarged specific surface area and construction intramolecular heterojunctions which can contributeto improve electron-holes separation efficiency.The resultant photocatalyst exhibited enhanced H2 production rate(7.6 mmol·g^-1·h^-1)and withthe apparent quantum efficiency(AQE)of 13.3%at 450 nm.At the same time,this method opens a way to fabricate graphitic carb on nitridenano sheets via bottom-up strategy.展开更多
Molecular self-assembly is a natured-inspired strategy to integrate individual functional molecules into supramolecular nanostructured materials through noncovalent bond interactions for solar to fuel conversion.Howev...Molecular self-assembly is a natured-inspired strategy to integrate individual functional molecules into supramolecular nanostructured materials through noncovalent bond interactions for solar to fuel conversion.However,the design and engineering of the morphology,size,and orderly stacking of supramolecular nanostructures remain a great challenge.In this study,regular porphyrin nanocrystals with different orderly stacked structures are synthesized through noncovalent self-assembly of Pt(II)meso-tetra(4-carboxyphenyl)porphine(PtTCPP),using surfactants with different electronegativity.The synergy of noncovalent bond interactions between porphyrin molecules,and between porphyrin molecules and surfactants resulted in different molecular packing patterns.Due to the spatial ordering of PtTCPP molecules,the different nanocrystals exhibit both collective optical properties and morphology-dependent activities in photocatalytic hydrogen production.The measurements of the photodeposition of dual cocatalysts showed that the photogenerated electrons and holes selectively aggregated at different active sites,revealing separation pathways and directional transfer of photogenerated electrons and holes in the assemblies.This study provides a new strategy to exert rational control over porphyrin self-assembly nanocrystals for highly efficient water splitting.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21422102,21171049,21501045,21403054,and 22405072)Postdoctoral Fellowship Program of CPSF(No.GZC20230673)+3 种基金Program for Science&Technology Innovation Talents in Universities of Henan Province(No.13HASTIT009)Program for Changjiang Scholars and Innovative Research Team in University(No.PCS IRT1126)China Postdoctoral Science Foundation(No.2024M760782)Key Research Projects of Higher Education Institutions in Henan Province(No.24A150003).
文摘The orientation is the key factor to determine the physicochemical properties of the metal-organic framework(MOF)films.New strategies for oriented MOF films are of fundamental importance in the advancement of science and technology.Here we report a unified approach to the synthesis of a large variety of porphyrin-based MOF films with different directions,chemistries and properties.This strategy is based on a general electrochemical regulation of coordination process of different metal cation(M_(1)=Zn,Co,Ni,Ce)and tetra(4-carboxyphenyl)porphyrin(M_(2)TCPP,M_(2)=H,Cu,Pt,Pd)on various conductive substrates.The cathode strategy relies on the reduction of M_(2)TCPP ligands and follows the electrochemical reaction mechanism to achieve effective control over crystallizing M_(1)-M_(2)TCPP MOF films oriented in the(110)direction.The highly oriented M_(1)-M_(2)TCPP MOF films are endowed with excellent crystalline,spatial network structure and hierarchical three-dimensional pore structure,which is conducive to charge transfer and material transmission and suitable for use as an electrochemical catalyst.The Zn-TCPP MOF films on conductive substrate could be used directly as an electrochemical sensor for electrocatalytic oxidation of NaNO2,and showed wide linear range,low limit of detection(0.24μM),high sensitivity(285.8 mA/(mM·cm2))and good anti-interference performance.We believe our methodology provides a simple and convenient route to a variety of oriented porphyrin-based MOF films for nanodevices with novel structure and function in nanotechnology.
文摘In order to broaden the absorption range of graphitic carbon nitride,one of the common methods is to couple the well-known photosensitizer porphyrin with graphitic carbon nitride through van der Waals weak in teractions.To date,to combine porphyrin with graphitic carbon nitridethrough covalent in teractions has not been settled.In this work,through rational molecular design,we successfully in corporated porphyrininto the matrixes of graphitic carbon nitride by covale nt bonding via on expot thermal copolymerization.The resulta nt material not only can wide nthe absorption range but also possess the enlarged specific surface area and construction intramolecular heterojunctions which can contributeto improve electron-holes separation efficiency.The resultant photocatalyst exhibited enhanced H2 production rate(7.6 mmol·g^-1·h^-1)and withthe apparent quantum efficiency(AQE)of 13.3%at 450 nm.At the same time,this method opens a way to fabricate graphitic carb on nitridenano sheets via bottom-up strategy.
基金supported by the National Natural Science Foundation of China(Nos.21771055,U21A2085,and U1604139)the Zhongyuan High Level Talents Special Support Plan(No.204200510010)+1 种基金the Scientific and Technological Innovation Team in University of Henan Province(No.20IRTSTHN001)Science and Technique Foundation of Henan Province(No.222102310544).
文摘Molecular self-assembly is a natured-inspired strategy to integrate individual functional molecules into supramolecular nanostructured materials through noncovalent bond interactions for solar to fuel conversion.However,the design and engineering of the morphology,size,and orderly stacking of supramolecular nanostructures remain a great challenge.In this study,regular porphyrin nanocrystals with different orderly stacked structures are synthesized through noncovalent self-assembly of Pt(II)meso-tetra(4-carboxyphenyl)porphine(PtTCPP),using surfactants with different electronegativity.The synergy of noncovalent bond interactions between porphyrin molecules,and between porphyrin molecules and surfactants resulted in different molecular packing patterns.Due to the spatial ordering of PtTCPP molecules,the different nanocrystals exhibit both collective optical properties and morphology-dependent activities in photocatalytic hydrogen production.The measurements of the photodeposition of dual cocatalysts showed that the photogenerated electrons and holes selectively aggregated at different active sites,revealing separation pathways and directional transfer of photogenerated electrons and holes in the assemblies.This study provides a new strategy to exert rational control over porphyrin self-assembly nanocrystals for highly efficient water splitting.
