Porous organic frameworks(POFs)have become a highly sought-after research domain that offers a promising avenue for developing cutting-edge nanostructured materials,both in their pristine state and when subjected to v...Porous organic frameworks(POFs)have become a highly sought-after research domain that offers a promising avenue for developing cutting-edge nanostructured materials,both in their pristine state and when subjected to various chemical and structural modifications.Metal–organic frameworks,covalent organic frameworks,and hydrogen-bonded organic frameworks are examples of these emerging materials that have gained significant attention due to their unique properties,such as high crystallinity,intrinsic porosity,unique structural regularity,diverse functionality,design flexibility,and outstanding stability.This review provides an overview of the state-of-the-art research on base-stable POFs,emphasizing the distinct pros and cons of reticular framework nanoparticles compared to other types of nanocluster materials.Thereafter,the review highlights the unique opportunity to produce multifunctional tailoring nanoparticles to meet specific application requirements.It is recommended that this potential for creating customized nanoparticles should be the driving force behind future synthesis efforts to tap the full potential of this multifaceted material category.展开更多
Despite the engineering potential by the co-existence of inorganic and organic substances to protect vulnerable metallic materials from corrosive environments,both their interaction and in-situ formation mechanism to ...Despite the engineering potential by the co-existence of inorganic and organic substances to protect vulnerable metallic materials from corrosive environments,both their interaction and in-situ formation mechanism to induce the nature-inspired composite remained less understood.The present work used three distinctive mercaptobenzazole(MB)compounds working as corrosion inhibitors,such as 2-mercaptobenzoxazole(MBO),2-mercaptobenzothiazole(MBT),and 2-mercaptobenzimidazole(MBI)in a bid to understand how the geometrical structure arising from O,S,and N atoms affected the interaction toward inorganic layer.MB compounds that were used here to control the corrosion kinetics would be interacted readily with the pre-existing MgO layer fabricated by plasma electrolysis.This phenomenon triggered the nucleation of the root network since MB compounds were seen to be adsorbed actively on the defective surface through the active sites in MB compound.Then,the molecule with twin donor atoms adjacent to the mercapto-sites affected the facile growth of the grass-like structures with‘uniform’distribution via molecular self-assembly,which showed better corrosion performance than those with having dissimilar donor atoms with the inhibition efficiency(η)of 97%approximately.The formation mechanism underlying nucleation and growth behavior of MB molecule was discussed concerning the theoretical calculation of density functional theory.展开更多
Heterocyclic compounds are the promising biological compounds as nature-friendly for the corrosion protection of metallic surface.In this work,three heterocyclic compounds such as 1-azanaphthalene-8-ol(8-AN),2-methylq...Heterocyclic compounds are the promising biological compounds as nature-friendly for the corrosion protection of metallic surface.In this work,three heterocyclic compounds such as 1-azanaphthalene-8-ol(8-AN),2-methylquinoline-8-ol(8-MQ),and 8-quinolinol-5-sulfonic acid(8-QSA)were used as green compounds,and their anti-corrosion performance for AZ31 Mg in saline water was discussed on the basis of impedance interpretation and surface analysis.Findings found that the electrochemical performance was improved in the order of 8-AN>8-MQ>8-QSA,demonstrating the electron donor effect of N-heterocycles to form coordination complexes on the magnesium surface.From the electrochemical performance,the protective layer constructed at the optimal concentration reinforces the barrier against aggressive environments,with potential inhibition efficiency of 87.4%,99.0%,and 99.9%for 8-QSA,8-MQ,and 8-AN,respectively.Quantum chemical parameters and electron density distribution for free organic species in the absence and presence of Mg^(2+)cation were evaluated using density functional theory(DFT).Upon the formation of coordination complexes between organic compound and Mg^(2+),energy gap underwent change about ΔE=5.7 eV in the 8-AN/Mg^(2+)system.Furthermore,the adsorption of heterocyclic compounds on Mg surface reveals the formation of strong covalent bonds with Mg atoms,which further confirmed by the electron density difference and projected density of states analyses.Based on theoretical calculations,three inhibitors can adsorb on the metal surface in both parallel and perpendicular orientations via C,O and N atoms.In the parallel configuration,the C-Mg,N-Mg and O-Mg bond distances are between 2.11 and 2.25˚A,whereas the distances in the case of perpendicular adsorption are between 2.20 and 2.40˚A(covalent bonds via O and N atoms).The results indicated that parallel configurations are energetically more stable,in which the adsorption energies are-4.48 eV(8-AN),-4.28 eV(8-MQ)and-3.82 eV(8-QSA)compared to that of perpendicular adsorption(-3.65,-3.40,and-2.63 eV).As a result,experimental and theoretical studies were in well agreement and confirm that the nitrogen and oxygen atoms will be the main adsorption sites.展开更多
This work looked into the influence of the sealing treatment on the structural feature and electrochemical response of AZ31 Mg alloy coated via plasma electrolytic oxidation(PEO).Here,the inorganic layers produced by ...This work looked into the influence of the sealing treatment on the structural feature and electrochemical response of AZ31 Mg alloy coated via plasma electrolytic oxidation(PEO).Here,the inorganic layers produced by PEO in an alkaline-phosphate electrolyte were subsequently immersed for different periods in cold(60°C)and hot(100°C)aqueous solutions containing either 1 or 3 gr of cobalt nitrate hexahydrate in the presence of hydrogen peroxide as an initiator.The results showed that the sealing treatments in the hot solutions could trigger the hydration reactions of PEO coating which would largely assist the surface incorporation of Co_(3)O_(4)into the coating.In contrast,the sealing in cold solutions led to less compact coatings,which was attributed to the fact the hydration reactions would be restricted at 60°C.A nearly fully sealed coating with a porosity of~0.5%was successfully formed on the sample immersed in the hot solution containing 1 gr of cobalt nitrate hexahydrate.Thus,the electrochemical stability of this fully sealed coating was superior to the other samples as it had the lowest corrosion current density(4.71×10^(-10)A·cm^(-2))and the highest outer layer resistance(3.81×10^(7)Ω·cm^(2)).The composite coatings developed in this study are ideal for applications requiring high electrochemical stability.展开更多
Plasma electrolytic oxidation(PEO)is a promising surface treatment to generate adherent and thick anti-corrosive coating on light-weight metals(Al,Mg,Ti,etc.)using an eco-friendly alkaline electrolyte.High energy plas...Plasma electrolytic oxidation(PEO)is a promising surface treatment to generate adherent and thick anti-corrosive coating on light-weight metals(Al,Mg,Ti,etc.)using an eco-friendly alkaline electrolyte.High energy plasma,however,inevitably generates porous structures that limit their practical performance.The present study proposes a straight-forward simple method by utilizing sub-zero electrolyte(268 K)to alter the plasma characteristics during formation of the protective coating on AZ31 Mg alloy via PEO with a comparison to the electrolyte at room temperature(298 K).In refrigerated electrolyte,the formation of micro-defects is suppressed relatively at the expense of low coating growth,which is measured to be twice lower than that at 298 K due to the temperature-dependent soft plasma discharges contributing to the development of the present coating.As a consequence,corrosion resistance of the sample processed at 268 K is superior to that of 298K,implying that the effect of coating thickness is less dominant than that of compactness.This phenomenon is interpreted in relation to the ionic movement and oxide solidification controlled by soft plasma discharges arising from the temperature gradient between electrolyte and surface of the substrate during PEO.展开更多
This work was made to investigate how nucleation and growth behavior of the coating film were affected by surface topographies of Mg–Al–Zn alloy substrate during the initial stage of plasma electrolytic oxidation(PE...This work was made to investigate how nucleation and growth behavior of the coating film were affected by surface topographies of Mg–Al–Zn alloy substrate during the initial stage of plasma electrolytic oxidation(PEO).To satisfy this end,a single substrate was prepared by mechanical treatment exhibiting rough and smooth regions with an equal area on the surface.The rough region with prominent hills and grooves induced the breakdown of passive film,which was indicated by an early appearance of plasma discharge on the rough region since nucleation of coating film occurred preferentially around the hills.However,the coating film grown on the grooves was somewhat thicker and more porous than the film grown on the hills and smooth regions.This was due to the fact that the growth of the coating film was found to be localized in the presence of rough region,which was in line with the discharge activities.Herein,the nucleation and growth behavior during the initial stage of PEO will be discussed schematically on the basis of microstructural interpretation.展开更多
The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemic...The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemical stability in a 3.5 wt.%Na Cl solution.Herein,the inorganic layer(IL)obtained by plasma electrolytic oxidation of AZ31 Mg alloy in an alkaline-phosphate-WO_(3)electrolyte was soaked in an organic solution composed of ALB and HA for 10 and 24 h at 60℃.Although albumin and HA may coexist on the same surface of IL,the higher reactivity of ALB molecules would prevent the formation of a thick layer of HA.The donor-acceptor complexes formed due to the unique interactions between ALB and/or HA and IL surface would reduce the area exposed to the corrosive species which in turn would efficiently protect the substrate from corrosion.The porous structure of the IL would provide preferable sites for the physical and chemical locking triggered by charge-transfer phenomena,leading to the inhomogeneous nucleation and crystal growth of a flowery flakes-like organic layer.DFT calculations were performed to reveal the primary bonding modes between the ALB,HA,and IL and to assess the mechanistic insights into the formation of such novel hybrid composites.展开更多
基金supported by the Fundamental-Core National Project of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(2022R1F1A1072739).
文摘Porous organic frameworks(POFs)have become a highly sought-after research domain that offers a promising avenue for developing cutting-edge nanostructured materials,both in their pristine state and when subjected to various chemical and structural modifications.Metal–organic frameworks,covalent organic frameworks,and hydrogen-bonded organic frameworks are examples of these emerging materials that have gained significant attention due to their unique properties,such as high crystallinity,intrinsic porosity,unique structural regularity,diverse functionality,design flexibility,and outstanding stability.This review provides an overview of the state-of-the-art research on base-stable POFs,emphasizing the distinct pros and cons of reticular framework nanoparticles compared to other types of nanocluster materials.Thereafter,the review highlights the unique opportunity to produce multifunctional tailoring nanoparticles to meet specific application requirements.It is recommended that this potential for creating customized nanoparticles should be the driving force behind future synthesis efforts to tap the full potential of this multifaceted material category.
基金supported by the Fundamental-Core National Project of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea with the grant number 2022R1F1A1072739.
文摘Despite the engineering potential by the co-existence of inorganic and organic substances to protect vulnerable metallic materials from corrosive environments,both their interaction and in-situ formation mechanism to induce the nature-inspired composite remained less understood.The present work used three distinctive mercaptobenzazole(MB)compounds working as corrosion inhibitors,such as 2-mercaptobenzoxazole(MBO),2-mercaptobenzothiazole(MBT),and 2-mercaptobenzimidazole(MBI)in a bid to understand how the geometrical structure arising from O,S,and N atoms affected the interaction toward inorganic layer.MB compounds that were used here to control the corrosion kinetics would be interacted readily with the pre-existing MgO layer fabricated by plasma electrolysis.This phenomenon triggered the nucleation of the root network since MB compounds were seen to be adsorbed actively on the defective surface through the active sites in MB compound.Then,the molecule with twin donor atoms adjacent to the mercapto-sites affected the facile growth of the grass-like structures with‘uniform’distribution via molecular self-assembly,which showed better corrosion performance than those with having dissimilar donor atoms with the inhibition efficiency(η)of 97%approximately.The formation mechanism underlying nucleation and growth behavior of MB molecule was discussed concerning the theoretical calculation of density functional theory.
基金financially supported by the National Research Laboratory Project of the National Research Foundation funded by the Ministry of Science and ICT,Republic of Korea(NRF-2020R1A2C2004192)G.Y.H.for research support via the YGY Project(YGY20150627000)supported by National Research Foundation(NRF)of South Korea(2022R1A2C1004392)。
文摘Heterocyclic compounds are the promising biological compounds as nature-friendly for the corrosion protection of metallic surface.In this work,three heterocyclic compounds such as 1-azanaphthalene-8-ol(8-AN),2-methylquinoline-8-ol(8-MQ),and 8-quinolinol-5-sulfonic acid(8-QSA)were used as green compounds,and their anti-corrosion performance for AZ31 Mg in saline water was discussed on the basis of impedance interpretation and surface analysis.Findings found that the electrochemical performance was improved in the order of 8-AN>8-MQ>8-QSA,demonstrating the electron donor effect of N-heterocycles to form coordination complexes on the magnesium surface.From the electrochemical performance,the protective layer constructed at the optimal concentration reinforces the barrier against aggressive environments,with potential inhibition efficiency of 87.4%,99.0%,and 99.9%for 8-QSA,8-MQ,and 8-AN,respectively.Quantum chemical parameters and electron density distribution for free organic species in the absence and presence of Mg^(2+)cation were evaluated using density functional theory(DFT).Upon the formation of coordination complexes between organic compound and Mg^(2+),energy gap underwent change about ΔE=5.7 eV in the 8-AN/Mg^(2+)system.Furthermore,the adsorption of heterocyclic compounds on Mg surface reveals the formation of strong covalent bonds with Mg atoms,which further confirmed by the electron density difference and projected density of states analyses.Based on theoretical calculations,three inhibitors can adsorb on the metal surface in both parallel and perpendicular orientations via C,O and N atoms.In the parallel configuration,the C-Mg,N-Mg and O-Mg bond distances are between 2.11 and 2.25˚A,whereas the distances in the case of perpendicular adsorption are between 2.20 and 2.40˚A(covalent bonds via O and N atoms).The results indicated that parallel configurations are energetically more stable,in which the adsorption energies are-4.48 eV(8-AN),-4.28 eV(8-MQ)and-3.82 eV(8-QSA)compared to that of perpendicular adsorption(-3.65,-3.40,and-2.63 eV).As a result,experimental and theoretical studies were in well agreement and confirm that the nitrogen and oxygen atoms will be the main adsorption sites.
基金supported by the National Research Foundation of Korea(NRF)funded by the Korean government(MSIT)(No.2022R1A2C1006743)
文摘This work looked into the influence of the sealing treatment on the structural feature and electrochemical response of AZ31 Mg alloy coated via plasma electrolytic oxidation(PEO).Here,the inorganic layers produced by PEO in an alkaline-phosphate electrolyte were subsequently immersed for different periods in cold(60°C)and hot(100°C)aqueous solutions containing either 1 or 3 gr of cobalt nitrate hexahydrate in the presence of hydrogen peroxide as an initiator.The results showed that the sealing treatments in the hot solutions could trigger the hydration reactions of PEO coating which would largely assist the surface incorporation of Co_(3)O_(4)into the coating.In contrast,the sealing in cold solutions led to less compact coatings,which was attributed to the fact the hydration reactions would be restricted at 60°C.A nearly fully sealed coating with a porosity of~0.5%was successfully formed on the sample immersed in the hot solution containing 1 gr of cobalt nitrate hexahydrate.Thus,the electrochemical stability of this fully sealed coating was superior to the other samples as it had the lowest corrosion current density(4.71×10^(-10)A·cm^(-2))and the highest outer layer resistance(3.81×10^(7)Ω·cm^(2)).The composite coatings developed in this study are ideal for applications requiring high electrochemical stability.
基金the Mid-Level Researcher National Project of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(NRF-2020R1A2C2004192)supported partly by the Competency Development Program for Industry Specialist of the Korea Institute for Advancement of Technology(KIAT)funded by the Ministry of Trade,Industry,and Energy,Republic of Korea(P0002019)。
文摘Plasma electrolytic oxidation(PEO)is a promising surface treatment to generate adherent and thick anti-corrosive coating on light-weight metals(Al,Mg,Ti,etc.)using an eco-friendly alkaline electrolyte.High energy plasma,however,inevitably generates porous structures that limit their practical performance.The present study proposes a straight-forward simple method by utilizing sub-zero electrolyte(268 K)to alter the plasma characteristics during formation of the protective coating on AZ31 Mg alloy via PEO with a comparison to the electrolyte at room temperature(298 K).In refrigerated electrolyte,the formation of micro-defects is suppressed relatively at the expense of low coating growth,which is measured to be twice lower than that at 298 K due to the temperature-dependent soft plasma discharges contributing to the development of the present coating.As a consequence,corrosion resistance of the sample processed at 268 K is superior to that of 298K,implying that the effect of coating thickness is less dominant than that of compactness.This phenomenon is interpreted in relation to the ionic movement and oxide solidification controlled by soft plasma discharges arising from the temperature gradient between electrolyte and surface of the substrate during PEO.
基金supported by the Mid-Level Researcher National Project of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(NRF-2020R1A2C2004192)supported partly by the Competency Development Program for Industry Specialist of the Korea Institute for Advancement of Technology(KIAT)funded by the Ministry of Trade,Industry,and Energy,Republic of Korea(P0002019)。
文摘This work was made to investigate how nucleation and growth behavior of the coating film were affected by surface topographies of Mg–Al–Zn alloy substrate during the initial stage of plasma electrolytic oxidation(PEO).To satisfy this end,a single substrate was prepared by mechanical treatment exhibiting rough and smooth regions with an equal area on the surface.The rough region with prominent hills and grooves induced the breakdown of passive film,which was indicated by an early appearance of plasma discharge on the rough region since nucleation of coating film occurred preferentially around the hills.However,the coating film grown on the grooves was somewhat thicker and more porous than the film grown on the hills and smooth regions.This was due to the fact that the growth of the coating film was found to be localized in the presence of rough region,which was in line with the discharge activities.Herein,the nucleation and growth behavior during the initial stage of PEO will be discussed schematically on the basis of microstructural interpretation.
基金the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.NRF-2019R1G1A1099335)supported also by the Mid-Level Researcher National Project of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(NRF-2020R1A2C2004192)supported partly by Basic Research Program through the National Research Foundation,Republic of Korea(NRF-2019R1FA1062702)。
文摘The unique interactions between hexadecanoic acid(HA)and albumin(ALB)molecules on the surface of the porous layer of AZ31 Mg alloy were exploited to fabricate a novel hybrid composite film with excellent electrochemical stability in a 3.5 wt.%Na Cl solution.Herein,the inorganic layer(IL)obtained by plasma electrolytic oxidation of AZ31 Mg alloy in an alkaline-phosphate-WO_(3)electrolyte was soaked in an organic solution composed of ALB and HA for 10 and 24 h at 60℃.Although albumin and HA may coexist on the same surface of IL,the higher reactivity of ALB molecules would prevent the formation of a thick layer of HA.The donor-acceptor complexes formed due to the unique interactions between ALB and/or HA and IL surface would reduce the area exposed to the corrosive species which in turn would efficiently protect the substrate from corrosion.The porous structure of the IL would provide preferable sites for the physical and chemical locking triggered by charge-transfer phenomena,leading to the inhomogeneous nucleation and crystal growth of a flowery flakes-like organic layer.DFT calculations were performed to reveal the primary bonding modes between the ALB,HA,and IL and to assess the mechanistic insights into the formation of such novel hybrid composites.
