Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and...Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and polymers,yet the use of organic metal complexes in PSCs applications remains less explored.To date,most of reported HTMs require additional chemical additives(e.g.Li-TFSI,t-TBP)towards high performance,however,the introduction of additives decrease the PSCs device stability.Herein,an organic metal complex(Ni-TPA)is first developed as a dopant-free HTM applied in PSCs for its facile synthesis and efficient hole extract/transfer ability.Consequently,the dopant-free Ni-TPAbased device achieves a champion efficiency of 17.89%,which is superior to that of pristine Spiro-OMeTAD(14.25%).Furthermore,we introduce a double HTM layer with a graded energy bandgap containing a Ni-TPA layer and a CuSCN layer into PSCs,the non-encapsulated PSCs based on the Ni-TPA/CuSCN layers affords impressive efficiency up to 20.39%and maintains 96%of the initial PCE after 1000 h at a relative humidity around 40%.The results have demonstrated that metal organic complexes represent a great promise for designing new dopant-free HTMs towards highly stable PSCs.展开更多
Sn-based metal organic complexes with coordination bonds,multi-active sites,and high theoretical capacity have attracted much attention as promising anodes for lithium ion batteries.However,the low electrical conducti...Sn-based metal organic complexes with coordination bonds,multi-active sites,and high theoretical capacity have attracted much attention as promising anodes for lithium ion batteries.However,the low electrical conductivity and huge volume changes restricted their electrochemical stability and practical utilization.Herein,Snbased anode with superior electrochemical performance,including a high reversible capacity of 1050.1 mAh·g^(-1)at 2 A·g^(-1)and a stable capacity of 1105.5 mAh·g^(-1)after 500 cycles at 1 A·g^(-1),was fabricated via a low-temperature calcination strategy from Sn metal organic complexes.The low-temperature calcination process regulates Sn-O bond and prevents the agglomeration of SnO_(2),generating highly dispersed SnO_(2) decorated metal organic complexes and providing sufficient active sites for ion storage.Ex situ characterizations expound that the undecomposed Sn-based metal organic complexes could be transformed into SnO_(2) during lithiation and delithiation,which enhances the electrical conductivity and induces a strong pseudo-capacitive behavior,accelerating the electrochemical kinetics;the multiple solid electrolyte interface with inflexible LiF and flexible ROCO_(2)Li buffers the volume variation of the electrode,resulting in its high electrochemical stability.This work provides a simple strategy for preparing excellent Sn-based anodes from metal organic complexes and reveals the lithium storage mechanism of the prepared Snbased anode.展开更多
[Pb(HL)(phen)]n (1) and [Cd3L2(phen)]n (2), where phen = 1,10-phenanthroline and L = 4,4'-(2-carboxylatopropane-1,3-diyl)dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-cr...[Pb(HL)(phen)]n (1) and [Cd3L2(phen)]n (2), where phen = 1,10-phenanthroline and L = 4,4'-(2-carboxylatopropane-1,3-diyl)dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-crystal diffraction, infrared spectroscopy and thermogravimetric analyses. The decomposition temperature of 1 and 2 was measured to be ca. 304 and 416 ℃, respectively. The charge transfer transition based absorption of 1 and 2 was also verified by the powder scattering spectra and theoretical analyses.展开更多
Terephthalic acid reformed Al/Zn metal organic nanoflake was prepared and functionalized with trie-thylamine(T-AlZn).Without adding terephthalic acid,there was no product of metal organic nanoflake.T-AlZn has a remark...Terephthalic acid reformed Al/Zn metal organic nanoflake was prepared and functionalized with trie-thylamine(T-AlZn).Without adding terephthalic acid,there was no product of metal organic nanoflake.T-AlZn has a remarkable performance in removing trace lead(Ⅱ)ions(Pb^(2+)).The adsorption equipoise with the removal rate≥97%was reached within 35 min.The removal rates of T-AlZn for Pb^(2+)declined by only 16.73%after four regenerations.The adsorption of T-AlZn for Pb^(2+)follows the Langmuir isotherms model and pseudo-second-order dynamics model.The utmost adsorption competence was calculated as 215.27 mg g^(-1).The T-AlZn adsorbent exhibits a bright prospect in the adsorption for Pb^(2+)and is a considerable candidate in the disposal of industrial sewage.展开更多
In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(1...In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(12)O_(40))(H_(2)O)_(2)]·2H_(2)O(1),H[Cu(4-bpmah)_(2)(PMo_(12)O_(4)0)(H_(2)O)_(2)]·2H_(2)O(2)and[Cu(4-bpmah)(H_(2)O)_(2)]·[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]·4H_(2)O(3)were synthesized by hydrothermal method.Single crystal X-ray analyses showed that complexes 1 and 2 were isostructural,in which the isolated Keggin-type[SiMo1_(2)O_(40)]^(4–)/[PMo_(12)O_(40)]^(3–)anions and[Cu(4-bpmah)_(2)(H_(2)O)2]^(2n+)units were expanded into 3D supramolecular structures through hydrogen bond interactions.In complex 3,the 1D[Cu(4-bpmah)(H_(2)O)_(2)]^(2n+)metal–organic chains and isolated[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]^(2n–)units were expanded into a 3D supramolecular framework by the hydrogen bond interactions.In this paper,carbon cloth working electrodes composited by the title complexes(1/CC,2/CC and 3/CC)were prepared and used as electrodes for supercapacitors.The performance of supercapacitors as well as the influence of electrolyte solution and title complexes quality load on the performance of supercapacitors were studied.Furthermore,the electrochemistry and electrocatalytic behaviors of complexes 1–3 bulk-modified carbon paste electrodes(1-CPE,2-CPE and 3-CPE)toward the reduction of KBrO_(3),KNO_(2),Cr(Ⅵ),as well as their sensing behaviors on Cr(Ⅵ)were investigated.展开更多
A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueou...A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueous solutions.The removal rates were higher than 95%and the adsorption was equilibrated in 15 min.The isotherms and kinetics for the adsorption Pb^(2+)by the FeCo@BDC adsorbents followed Langmuir model and pseudo-second-order model,respectively.The maximum adsorption capacity was 220.48 mg g^(-1).The FeCo@BDC adsorbents also own a prominent regeneration performance.The prominent performance of in the removal of trace Pb^(2+)makes FeCo@BDC an ideal candidate as commercial adsorbent materials.展开更多
The development of alternative low-cost and high-performing hole-transporting materials(HTMs) is of great significance for the potential large-scale application of perovskite solar cells(PSCs) in the future.Here,a fac...The development of alternative low-cost and high-performing hole-transporting materials(HTMs) is of great significance for the potential large-scale application of perovskite solar cells(PSCs) in the future.Here,a facilely synthesized solution-processable copper tetra-(2,4-dimethyl-3-pentoxy) phthalocyanine(CuPc-DMP) via only two simple steps,has been incorporated as a hole-transporting material(HTM) in mesoscopic perovskite solar cells(PSCs).The optimized devices based on such a HTM afford a very competitive power conversion efficiency(PCE) of up to 17.1%measured at 100 mW cm^(-2) AM 1.5G irradiation,which is on par with that of the well-known 2,2',7,7'-tetrakis(N'N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene(spiro-OMeTAD)(16.7%) under equivalent conditions.This is,to the best of our knowledge,the highest value reported so far for metal organic complex-based HTMs in PSCs.The advantages of this HTM observed,such as facile synthetic procedure,superior hole transport characteristic,high photovoltaic performance together with the feasibility of tailoring the molecular structure would make solution-processable copper phthalocyanines as a class of promising HTM that can be further explored in PSCs.The present finding highlights the potential application of solution processed metal organic complexes as HTMs for cost-effective and high-performing PSCs.展开更多
基金the National Natural Science Foundation of China(22065038)the Key Project of Natural Science Foundation of Yunnan(KC10110419)+4 种基金the High-Level Talents Introduction in Yunnan Province(C619300A010)the Fund for Excellent Young Scholars of Yunnan(K264202006820)the Program for Excellent Young Talents of Yunnan University and Major Science(C176220200)the International Joint Research Center for Advanced Energy Materials of Yunnan Province(202003AE140001)the Technology Project of Precious Metal Materials Genetic Engineering in Yunnan Province(No.2019Z E001-1202002AB080001)for financial support。
文摘Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and polymers,yet the use of organic metal complexes in PSCs applications remains less explored.To date,most of reported HTMs require additional chemical additives(e.g.Li-TFSI,t-TBP)towards high performance,however,the introduction of additives decrease the PSCs device stability.Herein,an organic metal complex(Ni-TPA)is first developed as a dopant-free HTM applied in PSCs for its facile synthesis and efficient hole extract/transfer ability.Consequently,the dopant-free Ni-TPAbased device achieves a champion efficiency of 17.89%,which is superior to that of pristine Spiro-OMeTAD(14.25%).Furthermore,we introduce a double HTM layer with a graded energy bandgap containing a Ni-TPA layer and a CuSCN layer into PSCs,the non-encapsulated PSCs based on the Ni-TPA/CuSCN layers affords impressive efficiency up to 20.39%and maintains 96%of the initial PCE after 1000 h at a relative humidity around 40%.The results have demonstrated that metal organic complexes represent a great promise for designing new dopant-free HTMs towards highly stable PSCs.
基金financially supported by the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.24HASTIT006)the Natural Science Foundations of China(No.42002040)+2 种基金Natural Science Foundations of Henan Province(No.222300420502)Key Science and Technology Program of Henan Province(No.222102240044)Key Scientific Research Projects in Colleges and Universities of Henan Province(No.21B610010)。
文摘Sn-based metal organic complexes with coordination bonds,multi-active sites,and high theoretical capacity have attracted much attention as promising anodes for lithium ion batteries.However,the low electrical conductivity and huge volume changes restricted their electrochemical stability and practical utilization.Herein,Snbased anode with superior electrochemical performance,including a high reversible capacity of 1050.1 mAh·g^(-1)at 2 A·g^(-1)and a stable capacity of 1105.5 mAh·g^(-1)after 500 cycles at 1 A·g^(-1),was fabricated via a low-temperature calcination strategy from Sn metal organic complexes.The low-temperature calcination process regulates Sn-O bond and prevents the agglomeration of SnO_(2),generating highly dispersed SnO_(2) decorated metal organic complexes and providing sufficient active sites for ion storage.Ex situ characterizations expound that the undecomposed Sn-based metal organic complexes could be transformed into SnO_(2) during lithiation and delithiation,which enhances the electrical conductivity and induces a strong pseudo-capacitive behavior,accelerating the electrochemical kinetics;the multiple solid electrolyte interface with inflexible LiF and flexible ROCO_(2)Li buffers the volume variation of the electrode,resulting in its high electrochemical stability.This work provides a simple strategy for preparing excellent Sn-based anodes from metal organic complexes and reveals the lithium storage mechanism of the prepared Snbased anode.
基金supported by the National Natural Science Foundation of China(No.21271033)
文摘[Pb(HL)(phen)]n (1) and [Cd3L2(phen)]n (2), where phen = 1,10-phenanthroline and L = 4,4'-(2-carboxylatopropane-1,3-diyl)dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-crystal diffraction, infrared spectroscopy and thermogravimetric analyses. The decomposition temperature of 1 and 2 was measured to be ca. 304 and 416 ℃, respectively. The charge transfer transition based absorption of 1 and 2 was also verified by the powder scattering spectra and theoretical analyses.
基金The supports from Shenzhen Science&Technology Project(grant No.KCXFZ20201221173612033)School level technical research project of Shenzhen University(grant No.SZIIT2022KJ081)arehighl yappreciated.
文摘Terephthalic acid reformed Al/Zn metal organic nanoflake was prepared and functionalized with trie-thylamine(T-AlZn).Without adding terephthalic acid,there was no product of metal organic nanoflake.T-AlZn has a remarkable performance in removing trace lead(Ⅱ)ions(Pb^(2+)).The adsorption equipoise with the removal rate≥97%was reached within 35 min.The removal rates of T-AlZn for Pb^(2+)declined by only 16.73%after four regenerations.The adsorption of T-AlZn for Pb^(2+)follows the Langmuir isotherms model and pseudo-second-order dynamics model.The utmost adsorption competence was calculated as 215.27 mg g^(-1).The T-AlZn adsorbent exhibits a bright prospect in the adsorption for Pb^(2+)and is a considerable candidate in the disposal of industrial sewage.
基金financially supported by the National Natural Science Foundation of China (Nos. 21971024, 21671025)Liaoning Revitalization Talents Program (No. XLYC1902011)
文摘In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(12)O_(40))(H_(2)O)_(2)]·2H_(2)O(1),H[Cu(4-bpmah)_(2)(PMo_(12)O_(4)0)(H_(2)O)_(2)]·2H_(2)O(2)and[Cu(4-bpmah)(H_(2)O)_(2)]·[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]·4H_(2)O(3)were synthesized by hydrothermal method.Single crystal X-ray analyses showed that complexes 1 and 2 were isostructural,in which the isolated Keggin-type[SiMo1_(2)O_(40)]^(4–)/[PMo_(12)O_(40)]^(3–)anions and[Cu(4-bpmah)_(2)(H_(2)O)2]^(2n+)units were expanded into 3D supramolecular structures through hydrogen bond interactions.In complex 3,the 1D[Cu(4-bpmah)(H_(2)O)_(2)]^(2n+)metal–organic chains and isolated[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]^(2n–)units were expanded into a 3D supramolecular framework by the hydrogen bond interactions.In this paper,carbon cloth working electrodes composited by the title complexes(1/CC,2/CC and 3/CC)were prepared and used as electrodes for supercapacitors.The performance of supercapacitors as well as the influence of electrolyte solution and title complexes quality load on the performance of supercapacitors were studied.Furthermore,the electrochemistry and electrocatalytic behaviors of complexes 1–3 bulk-modified carbon paste electrodes(1-CPE,2-CPE and 3-CPE)toward the reduction of KBrO_(3),KNO_(2),Cr(Ⅵ),as well as their sensing behaviors on Cr(Ⅵ)were investigated.
文摘A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueous solutions.The removal rates were higher than 95%and the adsorption was equilibrated in 15 min.The isotherms and kinetics for the adsorption Pb^(2+)by the FeCo@BDC adsorbents followed Langmuir model and pseudo-second-order model,respectively.The maximum adsorption capacity was 220.48 mg g^(-1).The FeCo@BDC adsorbents also own a prominent regeneration performance.The prominent performance of in the removal of trace Pb^(2+)makes FeCo@BDC an ideal candidate as commercial adsorbent materials.
基金supported by the National Natural Science Foundation of China(21606039,21120102036,91233201)the National Basic Research Program of China(2014CB239402)+2 种基金the Swedish Energy Agencythe KnutAlice Wallenberg Foundatioa
文摘The development of alternative low-cost and high-performing hole-transporting materials(HTMs) is of great significance for the potential large-scale application of perovskite solar cells(PSCs) in the future.Here,a facilely synthesized solution-processable copper tetra-(2,4-dimethyl-3-pentoxy) phthalocyanine(CuPc-DMP) via only two simple steps,has been incorporated as a hole-transporting material(HTM) in mesoscopic perovskite solar cells(PSCs).The optimized devices based on such a HTM afford a very competitive power conversion efficiency(PCE) of up to 17.1%measured at 100 mW cm^(-2) AM 1.5G irradiation,which is on par with that of the well-known 2,2',7,7'-tetrakis(N'N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene(spiro-OMeTAD)(16.7%) under equivalent conditions.This is,to the best of our knowledge,the highest value reported so far for metal organic complex-based HTMs in PSCs.The advantages of this HTM observed,such as facile synthetic procedure,superior hole transport characteristic,high photovoltaic performance together with the feasibility of tailoring the molecular structure would make solution-processable copper phthalocyanines as a class of promising HTM that can be further explored in PSCs.The present finding highlights the potential application of solution processed metal organic complexes as HTMs for cost-effective and high-performing PSCs.