Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenge...Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.展开更多
A highly efficient photoelectrochemical(PEC)biosensor for glutathione(GSH)assay was constructed based on the targettriggered etching of CdS@MnO_(2)nanocomposites(NCs).The core-shell CdS@MnO_(2)NCs were prepared by a h...A highly efficient photoelectrochemical(PEC)biosensor for glutathione(GSH)assay was constructed based on the targettriggered etching of CdS@MnO_(2)nanocomposites(NCs).The core-shell CdS@MnO_(2)NCs were prepared by a hydrothermal method and coated on the indium tin oxide(ITO)electrode as a PEC sensing platform.The PEC sensing platform gave a near-zero PEC signal due to the excellent light absorption ability of MnO_(2)nanosheet coating on the CdS nanoparticles.In the presence of GSH,the etching of MnO_(2)on the CdS@MnO_(2)NCs was triggered because of the unique etching reaction between MnO_(2)and GSH,leading to the exposure of inner photoactive nanomaterials,i.e.,CdS in this system.This inevitably causes an obvious increase in the photocurrent response,which is related to the GSH concentration.Thanks to the excellent quenching effect of MnO_(2)on the PEC signal of CdS,acceptable PEC performance of CdS,and the specific interaction between GSH and MnO_(2),the targets-triggered etching strategy exhibited excellent analytical performance for GSH detection with a detection limit of 0.05μmol/L and a linear range from 0.2 to 100μmol/L.The PEC biosensor has advantages such as good selectivity,excellent stability,and low background.This work contributed a fresh idea to detect GSH sensitively through the PEC sensing method.展开更多
Covalent organic frameworks(COFs),characterized by their reticular chemistry with covalent bonds between organic building blocks,have emerged as the state-of-the-art membrane materials in numerous applications.Compare...Covalent organic frameworks(COFs),characterized by their reticular chemistry with covalent bonds between organic building blocks,have emerged as the state-of-the-art membrane materials in numerous applications.Compared to conventional polymer membranes,COF membranes hold superior capacities in pushing the boundary of separation performance with high permeability and selectivity,due to their merits of highly tunable and ordered crystalline pore structure,programmable chemistry,high porosity,and excellent stability.Over the past decade,substantial advances in material design and application exploration of COF membranes have sparked ever-increasing research attention.To offer insightful implication for researchers from different fields,it is highly valuable to systematically summarize the recent advancements of COF membranes from the perspective of nanochannel structure and chemical property,two of the most important indicators to dictate their separation performance.In this review,we discuss recent progress in the mainstream fabrication methods of COF membranes,mainly including interfacial polymerization,in-situ growth,and nanosheets assembly and stacking.Then,we emphasize how to engineering nanochannel structure and chemical property of COF membranes in these three kinds of fabrication methods,as well as highlight their potential application in many areas such as ion/molecule sieving,gas separation and osmatic energy harvesting.Finally,some unsolved challenges and future perspectives in this field will be discussed,inspiring for the design and synthesis of advanced COF membranes.展开更多
基金support from the National Natural Science Foundation of China(Grant No.22102140the Natural Science Foundation of Jiangsu Province(Grant No.BK20211602)+1 种基金the Qing Lan Project of Yangzhou Universitythe Postgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University,Grant No.SJCX23_1911).
文摘Electrocatalytic valorization of disused poly(ethylene terephthalate)(PET)plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading,but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol(EG)electrooxidation.Herein,we proposed pyramid arrays on sheet Fe-doped NiO/FeNi_(3)(SPA-NiFeO_(x)/FeNi_(3))heterostructure,which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots(GQDs).Such SPA-NiFeO_(x)/FeNi_(3)exhibits superior catalytic performance on the electrooxidation of EG(EGOR)from PET hydrolysate,with a formic acid(FA)selectivity of 91.5%and a Faradaic efficiency of 92%.The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations,which revealed that such spatially separated NiFeO_(x)and FeNi_(3)components by GQDs possess more active sites to anticipate in electrocatalytic EGOR,and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe,resulting in high-valenced Ni^(δ+)/Fe^(δ+)in FeNi_(3)and Ni(2+δ)in NiO,respectively.Furthermore,the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs.Therefore,the adsorption of EG on Ni^(δ+)for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption,which was promoted by the enrichment of OH−on nearby Ni^((2+δ))sites,along with optimized Gibbs free energy change in the multistep reaction pathway.This work provides an efficient multi-active-site catalyst for disused PET plastics valorization,thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.
基金support from the National Natural Science Foundation of China(22304146,21874115,and 21675136)Program for Innovative Research Team in Science and Technology in University of Henan Province(24IRTSTHN004)+3 种基金the Natural Science Foundation of Henan Province(232300420389)Key Scientific Research Project of Higher Education Institutions in Henan Province(24A150037,22A150022)Shandong Key Laboratory of Biochemical Analysis(SKLBA2205)the Nanhu Young Scholar Supporting Program of XYNU。
文摘A highly efficient photoelectrochemical(PEC)biosensor for glutathione(GSH)assay was constructed based on the targettriggered etching of CdS@MnO_(2)nanocomposites(NCs).The core-shell CdS@MnO_(2)NCs were prepared by a hydrothermal method and coated on the indium tin oxide(ITO)electrode as a PEC sensing platform.The PEC sensing platform gave a near-zero PEC signal due to the excellent light absorption ability of MnO_(2)nanosheet coating on the CdS nanoparticles.In the presence of GSH,the etching of MnO_(2)on the CdS@MnO_(2)NCs was triggered because of the unique etching reaction between MnO_(2)and GSH,leading to the exposure of inner photoactive nanomaterials,i.e.,CdS in this system.This inevitably causes an obvious increase in the photocurrent response,which is related to the GSH concentration.Thanks to the excellent quenching effect of MnO_(2)on the PEC signal of CdS,acceptable PEC performance of CdS,and the specific interaction between GSH and MnO_(2),the targets-triggered etching strategy exhibited excellent analytical performance for GSH detection with a detection limit of 0.05μmol/L and a linear range from 0.2 to 100μmol/L.The PEC biosensor has advantages such as good selectivity,excellent stability,and low background.This work contributed a fresh idea to detect GSH sensitively through the PEC sensing method.
基金supported by the Natural Science Foundation of Zhejiang Province(Grant no.LZ24E030001)the National Natural Science Foundation of China(Grant no.22375174)the Fundamental Research Funds for the Central Universities(Grant no.226-2024-00027).
文摘Covalent organic frameworks(COFs),characterized by their reticular chemistry with covalent bonds between organic building blocks,have emerged as the state-of-the-art membrane materials in numerous applications.Compared to conventional polymer membranes,COF membranes hold superior capacities in pushing the boundary of separation performance with high permeability and selectivity,due to their merits of highly tunable and ordered crystalline pore structure,programmable chemistry,high porosity,and excellent stability.Over the past decade,substantial advances in material design and application exploration of COF membranes have sparked ever-increasing research attention.To offer insightful implication for researchers from different fields,it is highly valuable to systematically summarize the recent advancements of COF membranes from the perspective of nanochannel structure and chemical property,two of the most important indicators to dictate their separation performance.In this review,we discuss recent progress in the mainstream fabrication methods of COF membranes,mainly including interfacial polymerization,in-situ growth,and nanosheets assembly and stacking.Then,we emphasize how to engineering nanochannel structure and chemical property of COF membranes in these three kinds of fabrication methods,as well as highlight their potential application in many areas such as ion/molecule sieving,gas separation and osmatic energy harvesting.Finally,some unsolved challenges and future perspectives in this field will be discussed,inspiring for the design and synthesis of advanced COF membranes.
