A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temp...A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.展开更多
Even though titanium-based metal-organic frameworks(Ti-MOFs)are promising as efficient photocata-lysts,the high reactivity of titanium ions makes the synthesis and structure determination of new Ti-MOFs quite challeng...Even though titanium-based metal-organic frameworks(Ti-MOFs)are promising as efficient photocata-lysts,the high reactivity of titanium ions makes the synthesis and structure determination of new Ti-MOFs quite challenging.In this study,we propose a chelating coordination modulation(CCM)method for the synthesis of Ti-MOF single crystals by using molecules with chelating coordination groups as the modu-lator.Thanks to this method,three Ti-MOFs(FIR-117-119)have been obtained and their structures were determined by single crystal X-ray diffraction(SCXRD),validating the universality of this approach.By cap-turing the intermediate and determining its single crystal structure,the role of the modulator in the growth of Ti-MOF single crystals is clarified:the use of a chelating coordination molecule as the modu-lator and a competitive ligand slows down the reaction rate by forming Ti-modulator key intermediates,which balance the formation of Ti-MOFs and growth of single crystals.Furthermore,FIR-119 exhibits excellent photocatalytic performance under visible light due to its good light absorption ability with a narrow bandgap.These results highlight the potential of the chelating coordination modulation method in the synthesis of new photoactive Ti-MOFs and their single crystals.展开更多
Rational design of highly active and durable oxygen reduction reaction(ORR)electrocatalysts to replace expensive platinum-based catalysts and significantly improve the electrocatalytic performance of rechargeable zinc...Rational design of highly active and durable oxygen reduction reaction(ORR)electrocatalysts to replace expensive platinum-based catalysts and significantly improve the electrocatalytic performance of rechargeable zinc-air batteries(ZABs)has become a key goal in the field of energy storage technology.Here,we modulate the coordination structure of single-atom Zn sites on an N-doped graphene matrix using a rapid heating method to enhance the ORR performance.In 0.1 M KOH solution,the half-wave potential(E_(1/2))of Zn-NG-800 is 0.84 V,and it exhibits good anti-Fenton reaction performance.The zincair battery assembled with Zn-NG-800 as the cathode material has an open-circuit voltage(OCV)of up to 1.50 V and exhibits a maximum power density of 158 mW cm^(−2) and excellent output stability for over 200 h.Theoretical calculations show that the Zn-N_(4)G configuration exhibits a lower ORR barrier than Zn-N_(2)G and Zn-N_(3)G structures.The rate-determining step on Zn-N_(2)G and Zn-N_(3)G is ^(*)O→^(*)OH,and both show a reaction barrier significantly greater than 1.00 eV.In contrast,the rate-determining step on Zn-N_(4)G is ^(*)OH→^(*)+H_(2)O,and the energy barrier is only 0.68 eV,thus exhibiting better catalytic performance.展开更多
Realizing Sb^(3+)-activated efficient broadband near-infrared(NIR)emission under blue light excitation remains a significant challenge in lead-free metal halides.To overcome the above difficulties,a coordination struc...Realizing Sb^(3+)-activated efficient broadband near-infrared(NIR)emission under blue light excitation remains a significant challenge in lead-free metal halides.To overcome the above difficulties,a coordination structure modulation strategy was adopted,and the broadband NIR emission under blue light excitation was achieved in Sb^(3+)-doped zero-dimensional(0D)organic tin(Ⅳ)bromide.展开更多
The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in orde...The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.展开更多
Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among va...Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among various catalysts,single atom catalysts(SACs)have attracted much attention due to their high atom utilization efficiency and expressive catalytic performances.Additionally,SACs serve as an ideal platform for the investigation of complex reaction pathways and mechanisms thanks to their explicit active sites.In this review,the possible re-action pathways for the generation of various products(mainly C1 products for SACs)were firstly summarized.Then,recent progress of SACs for electrochemical reduction of CO_(2)was discussed in aspect of different central metal sites.As the most popular and efficient coordination modulation strategy,introducing heteroatom was then reviewed.Moreover,as an extension of SACs,the development of dual atom catalysts was also briefly discussed.At last,some issues and challenges regarding the SACs for CO_(2)reduction reaction(CO_(2)RR)were listed,followed by corresponding suggestions.展开更多
Optimizing the adsorption energy of intermediates by precisely modulating the coordination structure of single-atom M–N_(x)–C electrocatalysts to significantly improve the oxygen reduction reaction(ORR)performance s...Optimizing the adsorption energy of intermediates by precisely modulating the coordination structure of single-atom M–N_(x)–C electrocatalysts to significantly improve the oxygen reduction reaction(ORR)performance still remains a great challenge.In this work,guided by density functional theory(DFT)calculations,an axial coordination FeN_(5) single-atom catalyst was constructed by way of an FeN_(4) species anchored with the N atom from nitrogen-doped graphene to promote the ORR catalytic performance.The special coordination structure of FeN_(5) can significantly optimize the adsorption of the reaction intermediate and reduce the overpotential of the ORR process compared to that of the FeN_(4) planar structure,which is commonly used.Hence,the constructed axial coordination FeN_(5) single-atom catalyst shows extraordinary ORR catalytic performance(E_(onset)/E_(half-wave)=0.992/0.916 V vs.reversible hydrogen electrode(RHE),J_(L)=6.06 mA cm^(−2) and a 93.9%current retention after 15 h)and a maximum power density of 141 mW cm^(−2) in a zinc–air battery,which is superior to those of commercial Pt/C.These findings provide new insights into the construction of high-efficiency ORR catalysts from the design of a single atom coordination environment.展开更多
Rationalizing the use of depleted uranium resources has always been of great interest.Herein,we have obtained two actinide compounds by regulating the ratio of each component in the crystal growth process.By modulatin...Rationalizing the use of depleted uranium resources has always been of great interest.Herein,we have obtained two actinide compounds by regulating the ratio of each component in the crystal growth process.By modulating the coordination microenvironment of uranyl,the actinide compounds exhibited significant differences in photocatalytic CO_(2)reduction performance.The photocatalytic CO_(2)reduction by UCu2 exhibited excellent reactivity,and the CO generation rate reached 481.6μmol g^(−1)h^(−1).This study provides a reference and support for the rational application of depleted uranium resources and the application of coordinated polymers in the field of photocatalytic CO_(2)reduction.展开更多
The electrosynthesis of hydrogen peroxide is limited by the competitive four-electron oxygen reduction reaction(ORR)pathway.The modulation for the adsorption of OOH^(*)intermediate on active sites is considered as the...The electrosynthesis of hydrogen peroxide is limited by the competitive four-electron oxygen reduction reaction(ORR)pathway.The modulation for the adsorption of OOH^(*)intermediate on active sites is considered as the effective approach to tune the ORR selectivity,but it remains challenging.Herein,we report the neighboring phosphorus atom in the second coordination shell to regulate the electronic structure of the isolated Ni-N_(4) sites,leading to the favored OOH^(*)adsorption and thus boosting the electrocatalytic ORR to hydrogen peroxide through the two-electron pathway.Spectroscopy characterizations and density functional theory calculations indicate the neighboring phosphorus atom in the second coordination shell triggers the electron transfer to central Ni atom,strengthening the adsorption of OOH^(*)on Ni sites and thus increasing the catalytic performance for two-electron ORR,delivering a selectivity above 90%for production of hydrogen peroxide under the current density of 150 mA·cm^(−2).This work reveals tailoring second coordination shell of isolated metal sites could be as a precise and efficient way to engineer the catalytic performance,which thus provides a promising approach to the design of advanced catalysts.展开更多
Heterogeneous metal atom doping is considered as an effective strategy to boost catalytic activity through the coordinated modulation of metal active sites and the electronic structure,which is also beneficial for est...Heterogeneous metal atom doping is considered as an effective strategy to boost catalytic activity through the coordinated modulation of metal active sites and the electronic structure,which is also beneficial for establishing the relationship between structure and performance in energy conversion devices.Herein,we developed Mo-doped NiSe hierarchical microspheres with different Mo doping amounts by a simple solvothermal method.DFT calculation results including the more appropriate adsorption energy for adsorption of I_(3)^(-),the further elongated I_(1)-I_(2)bond length of I_(3)^(-),and efficient interaction between metal 3d and I 5p states collectively indicated that the catalytic activity for the IRR can be significantly enhanced by doping molybdenum in NiSe.Subsequently,dye-sensitized solar cells(DSSCs)fabricated with the optimized Mo_(0.10)-NiSe display a remarkable power conversion efficiency of 8.92%,superior to that of the Mo_(0.05)-NiSe(8.40%),Mo_(0.15)-NiSe(8.62%),NiSe(7.51%),and Pt-based devices(7.74%)in comparison.The impressive performance endows Mo_(0.10)-NiSe with a new opportunity to achieve the substitution of noble Pt in low-cost DSSCs.展开更多
Efficient activation of dioxygen (O₂) under mild and environmentally friendly conditions remains a challenging yet crucial area of research in chemistry.In this study,we present a simple yet effective approach for O₂ ...Efficient activation of dioxygen (O₂) under mild and environmentally friendly conditions remains a challenging yet crucial area of research in chemistry.In this study,we present a simple yet effective approach for O₂ activation under 450 nm light irradiation by rationally modulating the coordination environment of Cu(Ⅰ) ions and incorporating a photoactive Ir(Ⅲ) module into a supramolecular system,leading to efficient C(sp³)−H photo-oxidation of N-aryl tetrahydroisoquinolines.The hexaformyl end-capped fac-Ir(ppy)₃ module (1),the Ir(Ⅲ)-based twin-cavity cage (2),and the supramolecular Cu₂@2 entity—where two Cu(Ⅰ) ions are coordinated within cage 2—were comprehensively characterized using NMR,HR-MS,and X-ray crystallography.The confined cavities of 2 effectively trap Cu(Ⅰ) ions,protecting them from oxidation by O₂.Mechanistic studies reveal that photoinduced singlet oxygen (¹O₂),generated by the fac-Ir(ppy)₃ module,activates Cu(Ⅰ) to generate superoxide radical (O₂•⁻) species.Importantly,the Cu(Ⅰ) redox-active state is regenerated through electron transfer from the photoexcited *Ir(Ⅲ) state to the resulting Cu(Ⅱ) ions.This study introduces a gradual and controlled energy/electron delivery mechanism from Ir(Ⅲ) module to O₂ and the Cu centres,offering an advanced supramolecular strategy for photo-induced O₂ activation in oxidation reactions.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.21173034,20907006)
文摘A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.
基金supported by the National Natural Science Foundation of China(21935010)the Natural Science Foundation of Fujian Province(2022J01505).
文摘Even though titanium-based metal-organic frameworks(Ti-MOFs)are promising as efficient photocata-lysts,the high reactivity of titanium ions makes the synthesis and structure determination of new Ti-MOFs quite challenging.In this study,we propose a chelating coordination modulation(CCM)method for the synthesis of Ti-MOF single crystals by using molecules with chelating coordination groups as the modu-lator.Thanks to this method,three Ti-MOFs(FIR-117-119)have been obtained and their structures were determined by single crystal X-ray diffraction(SCXRD),validating the universality of this approach.By cap-turing the intermediate and determining its single crystal structure,the role of the modulator in the growth of Ti-MOF single crystals is clarified:the use of a chelating coordination molecule as the modu-lator and a competitive ligand slows down the reaction rate by forming Ti-modulator key intermediates,which balance the formation of Ti-MOFs and growth of single crystals.Furthermore,FIR-119 exhibits excellent photocatalytic performance under visible light due to its good light absorption ability with a narrow bandgap.These results highlight the potential of the chelating coordination modulation method in the synthesis of new photoactive Ti-MOFs and their single crystals.
基金supported by the Natural Science Foundation of Jilin Province(No.20220101051JC)the National Natural Science Foundation of China(No.22075099)。
文摘Rational design of highly active and durable oxygen reduction reaction(ORR)electrocatalysts to replace expensive platinum-based catalysts and significantly improve the electrocatalytic performance of rechargeable zinc-air batteries(ZABs)has become a key goal in the field of energy storage technology.Here,we modulate the coordination structure of single-atom Zn sites on an N-doped graphene matrix using a rapid heating method to enhance the ORR performance.In 0.1 M KOH solution,the half-wave potential(E_(1/2))of Zn-NG-800 is 0.84 V,and it exhibits good anti-Fenton reaction performance.The zincair battery assembled with Zn-NG-800 as the cathode material has an open-circuit voltage(OCV)of up to 1.50 V and exhibits a maximum power density of 158 mW cm^(−2) and excellent output stability for over 200 h.Theoretical calculations show that the Zn-N_(4)G configuration exhibits a lower ORR barrier than Zn-N_(2)G and Zn-N_(3)G structures.The rate-determining step on Zn-N_(2)G and Zn-N_(3)G is ^(*)O→^(*)OH,and both show a reaction barrier significantly greater than 1.00 eV.In contrast,the rate-determining step on Zn-N_(4)G is ^(*)OH→^(*)+H_(2)O,and the energy barrier is only 0.68 eV,thus exhibiting better catalytic performance.
基金supported by the Guangxi NSF project(no.2020GXNSFDA238004)the“Guangxi Bagui Scholars”fund,the Guangxi Science and Technology Major Project(AA23073018)+1 种基金the Scientific and Technological Bases and Talents of Guangxi(Guike AD21238027 and AD23026119)for financial supportThe calculation was supported by the highperformance computing platform of Guangxi University。
文摘Realizing Sb^(3+)-activated efficient broadband near-infrared(NIR)emission under blue light excitation remains a significant challenge in lead-free metal halides.To overcome the above difficulties,a coordination structure modulation strategy was adopted,and the broadband NIR emission under blue light excitation was achieved in Sb^(3+)-doped zero-dimensional(0D)organic tin(Ⅳ)bromide.
基金supported by the National Natural Science Foundation of China (Nos. 22072101, 22075193, 51911540473)the Natural Science Research Project of Jiangsu Higher Education Institutions of China (18KJA480004)+2 种基金the Key Technology Initiative of Suzhou Municipal Science and Technology Bureau (SYG201934) Six Talent Peaks Project in Jiangsu Province (TD-XCL-006)the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutionsthe support from the Honorary Professor Program of Jiangsu Province。
文摘The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.
文摘Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among various catalysts,single atom catalysts(SACs)have attracted much attention due to their high atom utilization efficiency and expressive catalytic performances.Additionally,SACs serve as an ideal platform for the investigation of complex reaction pathways and mechanisms thanks to their explicit active sites.In this review,the possible re-action pathways for the generation of various products(mainly C1 products for SACs)were firstly summarized.Then,recent progress of SACs for electrochemical reduction of CO_(2)was discussed in aspect of different central metal sites.As the most popular and efficient coordination modulation strategy,introducing heteroatom was then reviewed.Moreover,as an extension of SACs,the development of dual atom catalysts was also briefly discussed.At last,some issues and challenges regarding the SACs for CO_(2)reduction reaction(CO_(2)RR)were listed,followed by corresponding suggestions.
基金financially supported by the National Natural Science Foundation of China(Grant No.52072114)the Natural Science Foundation of Henan Province(Grant No.222300420206)+3 种基金China Postdoctoral Science Foundation(Grant No.2022M721049)the 111 Project(Grant No.D17007)Henan Center for Outstanding Overseas Scientists(Grant No.GZS2022017)Key Specialized Research and Development-International Science and Technology Coorporation Program in Henan Province(Grant No.231111520500).
文摘Optimizing the adsorption energy of intermediates by precisely modulating the coordination structure of single-atom M–N_(x)–C electrocatalysts to significantly improve the oxygen reduction reaction(ORR)performance still remains a great challenge.In this work,guided by density functional theory(DFT)calculations,an axial coordination FeN_(5) single-atom catalyst was constructed by way of an FeN_(4) species anchored with the N atom from nitrogen-doped graphene to promote the ORR catalytic performance.The special coordination structure of FeN_(5) can significantly optimize the adsorption of the reaction intermediate and reduce the overpotential of the ORR process compared to that of the FeN_(4) planar structure,which is commonly used.Hence,the constructed axial coordination FeN_(5) single-atom catalyst shows extraordinary ORR catalytic performance(E_(onset)/E_(half-wave)=0.992/0.916 V vs.reversible hydrogen electrode(RHE),J_(L)=6.06 mA cm^(−2) and a 93.9%current retention after 15 h)and a maximum power density of 141 mW cm^(−2) in a zinc–air battery,which is superior to those of commercial Pt/C.These findings provide new insights into the construction of high-efficiency ORR catalysts from the design of a single atom coordination environment.
基金the National Natural Science Foundation of China(No.22076187,22076186,and 11875138)the National Science Fund for Distinguished Young Scholars(21925603).
文摘Rationalizing the use of depleted uranium resources has always been of great interest.Herein,we have obtained two actinide compounds by regulating the ratio of each component in the crystal growth process.By modulating the coordination microenvironment of uranyl,the actinide compounds exhibited significant differences in photocatalytic CO_(2)reduction performance.The photocatalytic CO_(2)reduction by UCu2 exhibited excellent reactivity,and the CO generation rate reached 481.6μmol g^(−1)h^(−1).This study provides a reference and support for the rational application of depleted uranium resources and the application of coordinated polymers in the field of photocatalytic CO_(2)reduction.
基金financially supported by the Taishan Scholar Project Foundation of Shandong Province(Nos.tsqn202211028 and tsqn202306080)the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ08 and 2023HWYQ-028)the Instrument Improvement Founds of Shandong University Public Technology Platform(No.ts20230209).
文摘The electrosynthesis of hydrogen peroxide is limited by the competitive four-electron oxygen reduction reaction(ORR)pathway.The modulation for the adsorption of OOH^(*)intermediate on active sites is considered as the effective approach to tune the ORR selectivity,but it remains challenging.Herein,we report the neighboring phosphorus atom in the second coordination shell to regulate the electronic structure of the isolated Ni-N_(4) sites,leading to the favored OOH^(*)adsorption and thus boosting the electrocatalytic ORR to hydrogen peroxide through the two-electron pathway.Spectroscopy characterizations and density functional theory calculations indicate the neighboring phosphorus atom in the second coordination shell triggers the electron transfer to central Ni atom,strengthening the adsorption of OOH^(*)on Ni sites and thus increasing the catalytic performance for two-electron ORR,delivering a selectivity above 90%for production of hydrogen peroxide under the current density of 150 mA·cm^(−2).This work reveals tailoring second coordination shell of isolated metal sites could be as a precise and efficient way to engineer the catalytic performance,which thus provides a promising approach to the design of advanced catalysts.
基金support of the National Natural Science Foundation of China(22005161)the Fundamental Research Funds in Heilongjiang Provincial Universities of China(145109209)the Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary(BMHXJKF006).
文摘Heterogeneous metal atom doping is considered as an effective strategy to boost catalytic activity through the coordinated modulation of metal active sites and the electronic structure,which is also beneficial for establishing the relationship between structure and performance in energy conversion devices.Herein,we developed Mo-doped NiSe hierarchical microspheres with different Mo doping amounts by a simple solvothermal method.DFT calculation results including the more appropriate adsorption energy for adsorption of I_(3)^(-),the further elongated I_(1)-I_(2)bond length of I_(3)^(-),and efficient interaction between metal 3d and I 5p states collectively indicated that the catalytic activity for the IRR can be significantly enhanced by doping molybdenum in NiSe.Subsequently,dye-sensitized solar cells(DSSCs)fabricated with the optimized Mo_(0.10)-NiSe display a remarkable power conversion efficiency of 8.92%,superior to that of the Mo_(0.05)-NiSe(8.40%),Mo_(0.15)-NiSe(8.62%),NiSe(7.51%),and Pt-based devices(7.74%)in comparison.The impressive performance endows Mo_(0.10)-NiSe with a new opportunity to achieve the substitution of noble Pt in low-cost DSSCs.
基金support from the National Natural Science Foundation of China(22171033 and 22477014).
文摘Efficient activation of dioxygen (O₂) under mild and environmentally friendly conditions remains a challenging yet crucial area of research in chemistry.In this study,we present a simple yet effective approach for O₂ activation under 450 nm light irradiation by rationally modulating the coordination environment of Cu(Ⅰ) ions and incorporating a photoactive Ir(Ⅲ) module into a supramolecular system,leading to efficient C(sp³)−H photo-oxidation of N-aryl tetrahydroisoquinolines.The hexaformyl end-capped fac-Ir(ppy)₃ module (1),the Ir(Ⅲ)-based twin-cavity cage (2),and the supramolecular Cu₂@2 entity—where two Cu(Ⅰ) ions are coordinated within cage 2—were comprehensively characterized using NMR,HR-MS,and X-ray crystallography.The confined cavities of 2 effectively trap Cu(Ⅰ) ions,protecting them from oxidation by O₂.Mechanistic studies reveal that photoinduced singlet oxygen (¹O₂),generated by the fac-Ir(ppy)₃ module,activates Cu(Ⅰ) to generate superoxide radical (O₂•⁻) species.Importantly,the Cu(Ⅰ) redox-active state is regenerated through electron transfer from the photoexcited *Ir(Ⅲ) state to the resulting Cu(Ⅱ) ions.This study introduces a gradual and controlled energy/electron delivery mechanism from Ir(Ⅲ) module to O₂ and the Cu centres,offering an advanced supramolecular strategy for photo-induced O₂ activation in oxidation reactions.
