The oxygen evolution reaction(OER) is the cornerstone for many important energy conversion devices, including metal–air battery and water splitting.Herein, an optimized NiFe-based metal–organic framework is develope...The oxygen evolution reaction(OER) is the cornerstone for many important energy conversion devices, including metal–air battery and water splitting.Herein, an optimized NiFe-based metal–organic framework is developed as highly efficient active material for OER. It just needs a low overpotential of 0.31 V to deliver a current density of 10 mA cm-2 with a favorable Tafel slope of 43.7 mV dec-1 in 0.1 M KOH electrolyte for the as-prepared Ni0.75Fe0.25 BDC, which is superior to RuO2. This efficient catalytic performance is due to the introduction of Fe in Ni-based MOFs could benefit the kinetics and charge transfer efficiency, resulting in the optimal activity toward OER. Besides, the obtained active material demonstrates good stability, suggesting the great potential value in sustainable electrochemical energy storage and conversion devices.展开更多
The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-...The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-based metal-organic cages(MOCs)depending on different anions.Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF_(4)^(–)or NO_(3)^(–),respectively.MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating,accelerated by excess BF_(4)^(–)to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation.The vip encapsulation behaviors of MOC-35 and MOC-36 have also been tested.These results manifest a significance of host-anion dynamics beyond complementary anion template,shedding light on the understanding of intricate anion recognition in nature.展开更多
Simultaneous ethane and acetylene removal from a C_(2)-gases mixture(C_(2)H_(6),C_(2)H_(4),and C_(2)H_(2))through a one-step separation process for ethylene purification is of great importance yet challenging in petro...Simultaneous ethane and acetylene removal from a C_(2)-gases mixture(C_(2)H_(6),C_(2)H_(4),and C_(2)H_(2))through a one-step separation process for ethylene purification is of great importance yet challenging in petrochemical industry,owing to their similar molecule sizes and physical properties.Herein,a series of multifunctionalized metal–organic frameworks(MOFs),LIFM-XYY-1∼8(LIFM stands for Lehn Institute of Functional Materials,and XYY are the initials of the first author),are constructed via a dynamic spacer installation(DSI)approach to optimize the pore-nanospaces for efficient C_(2)H_(4) isolation from the ternary C_(2)-gases mixture.Installation of variable organic-spacers into the prototypical MOFs,LIFM-28 or PCN-700,results in dramatically improved pore volume/surface area,contracted pore size,and functionalized pore surface,which in turn bring out high C_(2)-gases uptake capacities,enhanced C_(2)H_(6) and C_(2)H_(2) adsorption selectivities over C_(2)H_(4),and fast adsorption kinetics,providing an effective strategy to achieve delicate trade-off among these indexes for adequate separation performance.Specifically,optimized LIFM-XYY-7 presents four-times C_(2)H_(6) and C_(2)H_(2) adsorption capacities than proto-PCN-700.Dynamic breakthrough experiments reveal that poly-grade C_(2)H_(4)(>99.9%)can be obtained from binary or ternary C_(2)-hydrocarbon mixtures through a single separation process.Combined with themolecular simulations,this work demonstrates a promising protocol of porenanospace engineering via multi-functional optimization by the DSI approach to screen out MOFs for a formidable task.展开更多
Using halide perovskite nanomaterials for solarto-fuel conversion has recently attracted a lot of attention due to their excellent photoelectric properties.However,severe photogenerated charge carrier recombinations a...Using halide perovskite nanomaterials for solarto-fuel conversion has recently attracted a lot of attention due to their excellent photoelectric properties.However,severe photogenerated charge carrier recombinations and poor reaction kinetics greatly restrict their photocatalytic performance.In this study,a ternary WO_(3)/CsPbBr_(3)/ZIF-67 heterostructure was designed for efficient CO_(2) photoreduction.The results indicate that the Z-scheme charge transfer pathway constructed between WO_(3)and CsPbBr_(3)ensures the effective transfer and separation of photogenerated charge carriers.Meanwhile,the subsequent surface modification of zeolitic imidazolate frameworks(ZIF-67)with active Co centers further benefits CO_(2)adsorption and activation.Accordingly,the synergistic effects of charge separation and CO_(2)uptake greatly promote the photocatalytic activity.The optimal WO_(3)/CsPbBr_(3)/ZIF-67 heterostructure yields a CO production of 99.38μmol g^(−1)in 3 h,which is 6.8 times of that produced by CsPbBr_(3).This work will inspire new insights in developing efficient photocatalysts for CO_(2)reduction and even more challenging photocatalytic reactions by elaborately regulating the functional ingredient.展开更多
Photocatalytic dual-functional reaction under visible light irradiation represents a sustainable development strategy.In detail,H2production coupled with benzylamine oxidation can remarkably lower the cost by replacin...Photocatalytic dual-functional reaction under visible light irradiation represents a sustainable development strategy.In detail,H2production coupled with benzylamine oxidation can remarkably lower the cost by replacing sacrificial agents.In this work,Cd S quantum dots(Cd S QDs)were successfully loaded onto the surface of a porphyrinic metal-organic framework(Pd-PCN-222)by the electrostatic selfassembly at room temperature.The consequent Pd-PCN-222/CdS heterojunction composites displayed superb photocatalytic activity under visible light irradiation,achieving a H2production and benzylamine oxidation rate of 5069 and 3717μmol g^(-1)h^(-1)with>99%selectivity in 3 h.There is no noticeable loss of catalytic capability during three successive runs.Mechanistic studies by in situ electron spin resonance and X-ray photoelectron spectroscopy disclosed that CdS QDs injected photoexcited electrons to Pd-PCN-222 and then Zr6clusters under visible-light irradiation,and thus Cd S QDs and Zr6clusters behave as the photocatalytic oxidation and reduction centers,respectively.展开更多
A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4（pbeddb）4（H2O）2（DMAC）2] （MOC-18; pbeddb2- = 3,3＇-（1,3-phenylenebis（ethyne-2,1-diyl））dibenzoate） was applied to the N-- H insertion reactions wit...A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4（pbeddb）4（H2O）2（DMAC）2] （MOC-18; pbeddb2- = 3,3＇-（1,3-phenylenebis（ethyne-2,1-diyl））dibenzoate） was applied to the N-- H insertion reactions with diazo compounds. This method offered an environmentally friendly and highly efficient approach for C--N bond formation.展开更多
Fluorinated organic compounds are of great importance to modern industries,while their release to the environment is inevitable,causing extreme environmental pollution and the subsequent hazardous effect on ecosystems...Fluorinated organic compounds are of great importance to modern industries,while their release to the environment is inevitable,causing extreme environmental pollution and the subsequent hazardous effect on ecosystems.This is because the degradation of fluorinated compounds under mild conditions remains a challenging task due to the strong C-F bond strength.In this study,we report preparation of PdRu@MIL-101 through immobilizing ultrafine PdRu alloy nanoparticles with a mean diameter of∼2 nminto the metal-organic framework(MOF),MIL-101(Cr),which was highly active and stable in the hydrodefluorination of 4-fluorophenol(4-FP)under mild aqueous conditions.The optimized catalyst Pd0.5Ru0.5@MIL-101 achieved impressive hydrogenation performance with a 98.5% conversion of 4-FP and a 97.7% selectivity of cyclohexanol,much better than the single metal-doped Pd@MIL-101 and Ru@MIL-101 catalysts.The excellent catalytic behavior contributed to the synergistic effect of combining the PdRu alloying effect and the MOF nanospace confinement effect,providing a promising strategy to develop highly efficient hydrodefluorination catalysts to assist environmental restoration and green ecology.展开更多
In molecular level lanthanide complexes,it is still challenging to achieve near-infrared(NIR)down-conversion luminescence(DCL)and visible up-conversion luminescence(UCL)efficiently under ambient conditions.By delicate...In molecular level lanthanide complexes,it is still challenging to achieve near-infrared(NIR)down-conversion luminescence(DCL)and visible up-conversion luminescence(UCL)efficiently under ambient conditions.By delicate design of hybridized iridium−europium−ytterbium(Ir–Eu–Yb)trimetallic complexes from an Ir-metalloligand,DCL and UCL emissions with opposite photon conversion pathways were achieved simultaneously in one integrated system.In detail,three different types of energy transfer(ET)and photoluminescence(PL)were detected,as follows:(1)Highly sensitized NIR-DCL from Yb(III)center via ETIr→Eu→Yb,which gave the longest decay lifetime(553μs)at room temperature ever reported in solid-state Yb-complexes.(2)Unprecedented UCL red emission from Eu(III)center via ETYb→Eu using 980 nm continuous wavelength(CW)laser excitation,which required ultralow energy threshold(0.616W/cm2).(3)Two-photon excited fluorescence(TPEF)via ETIr→Eu using femtosecond pulsed laser excitation.This exquisite module of“one stone,three birds”provides a new stimulus in the design and application of multifunctional UCL/DCL/TPEF optical materials under ambient conditions.展开更多
基金supported by The Thousand Talents Plan Foundation of China and Guangdong ProvinceThe 100 Talents Plan Foundation of Sun Yat-sen University (31000-18821107)+2 种基金the Program for Guangdong Introducing Innovative and Enterpreneurial Teams (2017ZT07C069)the NSFC Projects (21573291, 21720102007)the STP Project of Guangzhou (201504010031)
文摘The oxygen evolution reaction(OER) is the cornerstone for many important energy conversion devices, including metal–air battery and water splitting.Herein, an optimized NiFe-based metal–organic framework is developed as highly efficient active material for OER. It just needs a low overpotential of 0.31 V to deliver a current density of 10 mA cm-2 with a favorable Tafel slope of 43.7 mV dec-1 in 0.1 M KOH electrolyte for the as-prepared Ni0.75Fe0.25 BDC, which is superior to RuO2. This efficient catalytic performance is due to the introduction of Fe in Ni-based MOFs could benefit the kinetics and charge transfer efficiency, resulting in the optimal activity toward OER. Besides, the obtained active material demonstrates good stability, suggesting the great potential value in sustainable electrochemical energy storage and conversion devices.
基金supported by the NKRD Program of China(No.2021YFA1500401)the National Natural Science Foundation of China(Nos.21821003,21890380)the LIRTP of Guangdong Pearl River Talents Program(No.2017BT01C161)。
文摘The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-based metal-organic cages(MOCs)depending on different anions.Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF_(4)^(–)or NO_(3)^(–),respectively.MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating,accelerated by excess BF_(4)^(–)to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation.The vip encapsulation behaviors of MOC-35 and MOC-36 have also been tested.These results manifest a significance of host-anion dynamics beyond complementary anion template,shedding light on the understanding of intricate anion recognition in nature.
基金supported by the NKRD Program of China(grant no.2021YFA1500401)NSFC Projects(grant nos.21890380,21821003,22001271,22090061,and 21801252)+1 种基金the LIRT Project of Guangdong PRTP(grant no.2017BT01C161)FRF for the Central Universities(grant no.20lgpy79).
文摘Simultaneous ethane and acetylene removal from a C_(2)-gases mixture(C_(2)H_(6),C_(2)H_(4),and C_(2)H_(2))through a one-step separation process for ethylene purification is of great importance yet challenging in petrochemical industry,owing to their similar molecule sizes and physical properties.Herein,a series of multifunctionalized metal–organic frameworks(MOFs),LIFM-XYY-1∼8(LIFM stands for Lehn Institute of Functional Materials,and XYY are the initials of the first author),are constructed via a dynamic spacer installation(DSI)approach to optimize the pore-nanospaces for efficient C_(2)H_(4) isolation from the ternary C_(2)-gases mixture.Installation of variable organic-spacers into the prototypical MOFs,LIFM-28 or PCN-700,results in dramatically improved pore volume/surface area,contracted pore size,and functionalized pore surface,which in turn bring out high C_(2)-gases uptake capacities,enhanced C_(2)H_(6) and C_(2)H_(2) adsorption selectivities over C_(2)H_(4),and fast adsorption kinetics,providing an effective strategy to achieve delicate trade-off among these indexes for adequate separation performance.Specifically,optimized LIFM-XYY-7 presents four-times C_(2)H_(6) and C_(2)H_(2) adsorption capacities than proto-PCN-700.Dynamic breakthrough experiments reveal that poly-grade C_(2)H_(4)(>99.9%)can be obtained from binary or ternary C_(2)-hydrocarbon mixtures through a single separation process.Combined with themolecular simulations,this work demonstrates a promising protocol of porenanospace engineering via multi-functional optimization by the DSI approach to screen out MOFs for a formidable task.
基金financially supported by the National Natural Science Foundation of China(21890382)the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01C161)+1 种基金Guangdong Basic and Applied Basic Research Foundation(2020A1515110937)the Fundamental Research Funds for the Central Universities(19lgzd24 and 20lgpy80)。
文摘Using halide perovskite nanomaterials for solarto-fuel conversion has recently attracted a lot of attention due to their excellent photoelectric properties.However,severe photogenerated charge carrier recombinations and poor reaction kinetics greatly restrict their photocatalytic performance.In this study,a ternary WO_(3)/CsPbBr_(3)/ZIF-67 heterostructure was designed for efficient CO_(2) photoreduction.The results indicate that the Z-scheme charge transfer pathway constructed between WO_(3)and CsPbBr_(3)ensures the effective transfer and separation of photogenerated charge carriers.Meanwhile,the subsequent surface modification of zeolitic imidazolate frameworks(ZIF-67)with active Co centers further benefits CO_(2)adsorption and activation.Accordingly,the synergistic effects of charge separation and CO_(2)uptake greatly promote the photocatalytic activity.The optimal WO_(3)/CsPbBr_(3)/ZIF-67 heterostructure yields a CO production of 99.38μmol g^(−1)in 3 h,which is 6.8 times of that produced by CsPbBr_(3).This work will inspire new insights in developing efficient photocatalysts for CO_(2)reduction and even more challenging photocatalytic reactions by elaborately regulating the functional ingredient.
基金support from the National Natural Science Foundation of China(Nos.21773314,21821003 and 21890382)the Guangdong Natural Science Funds for Distinguished Young Scholar(No.2019B151502017)。
文摘Photocatalytic dual-functional reaction under visible light irradiation represents a sustainable development strategy.In detail,H2production coupled with benzylamine oxidation can remarkably lower the cost by replacing sacrificial agents.In this work,Cd S quantum dots(Cd S QDs)were successfully loaded onto the surface of a porphyrinic metal-organic framework(Pd-PCN-222)by the electrostatic selfassembly at room temperature.The consequent Pd-PCN-222/CdS heterojunction composites displayed superb photocatalytic activity under visible light irradiation,achieving a H2production and benzylamine oxidation rate of 5069 and 3717μmol g^(-1)h^(-1)with>99%selectivity in 3 h.There is no noticeable loss of catalytic capability during three successive runs.Mechanistic studies by in situ electron spin resonance and X-ray photoelectron spectroscopy disclosed that CdS QDs injected photoexcited electrons to Pd-PCN-222 and then Zr6clusters under visible-light irradiation,and thus Cd S QDs and Zr6clusters behave as the photocatalytic oxidation and reduction centers,respectively.
文摘A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4（pbeddb）4（H2O）2（DMAC）2] （MOC-18; pbeddb2- = 3,3＇-（1,3-phenylenebis（ethyne-2,1-diyl））dibenzoate） was applied to the N-- H insertion reactions with diazo compounds. This method offered an environmentally friendly and highly efficient approach for C--N bond formation.
基金supported by the National Key R&D Program of China(no.2018YFA0108300)the Overseas High-level Talents Plan of China and Guangdong Province,the Fundamental Research Funds for the Central Universities+2 种基金the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(no.2017Z T07C069)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(no.2017BT01C161)the NSFC Projects(nos.22075321,21821003,21890380,and 21905315).
文摘Fluorinated organic compounds are of great importance to modern industries,while their release to the environment is inevitable,causing extreme environmental pollution and the subsequent hazardous effect on ecosystems.This is because the degradation of fluorinated compounds under mild conditions remains a challenging task due to the strong C-F bond strength.In this study,we report preparation of PdRu@MIL-101 through immobilizing ultrafine PdRu alloy nanoparticles with a mean diameter of∼2 nminto the metal-organic framework(MOF),MIL-101(Cr),which was highly active and stable in the hydrodefluorination of 4-fluorophenol(4-FP)under mild aqueous conditions.The optimized catalyst Pd0.5Ru0.5@MIL-101 achieved impressive hydrogenation performance with a 98.5% conversion of 4-FP and a 97.7% selectivity of cyclohexanol,much better than the single metal-doped Pd@MIL-101 and Ru@MIL-101 catalysts.The excellent catalytic behavior contributed to the synergistic effect of combining the PdRu alloying effect and the MOF nanospace confinement effect,providing a promising strategy to develop highly efficient hydrodefluorination catalysts to assist environmental restoration and green ecology.
基金supported by NSFC(21771197,21821003,21720102007,and 21890380)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01C161),and FRF for the Central Universities.
文摘In molecular level lanthanide complexes,it is still challenging to achieve near-infrared(NIR)down-conversion luminescence(DCL)and visible up-conversion luminescence(UCL)efficiently under ambient conditions.By delicate design of hybridized iridium−europium−ytterbium(Ir–Eu–Yb)trimetallic complexes from an Ir-metalloligand,DCL and UCL emissions with opposite photon conversion pathways were achieved simultaneously in one integrated system.In detail,three different types of energy transfer(ET)and photoluminescence(PL)were detected,as follows:(1)Highly sensitized NIR-DCL from Yb(III)center via ETIr→Eu→Yb,which gave the longest decay lifetime(553μs)at room temperature ever reported in solid-state Yb-complexes.(2)Unprecedented UCL red emission from Eu(III)center via ETYb→Eu using 980 nm continuous wavelength(CW)laser excitation,which required ultralow energy threshold(0.616W/cm2).(3)Two-photon excited fluorescence(TPEF)via ETIr→Eu using femtosecond pulsed laser excitation.This exquisite module of“one stone,three birds”provides a new stimulus in the design and application of multifunctional UCL/DCL/TPEF optical materials under ambient conditions.
