A new benzothiadiazole-based D-A-D hole transport material(DTBT)has been designed and synthesized with a more planar structure by introducing of thiophene bridges.The results indicate a lower band gap and quite higher...A new benzothiadiazole-based D-A-D hole transport material(DTBT)has been designed and synthesized with a more planar structure by introducing of thiophene bridges.The results indicate a lower band gap and quite higher hole mobility for the DTBT.Furthermore,the enhancement in molecular planarity with simple thiophene unit increases the hole mobility of DTBT(8.77×10^-4cm^2 V^-1s^-1)by about 40%.And when DTBT is used as hole transport material in perovskite solar cells,the photoelectric conversion efficiency of the corresponding dopant-free devices is also significantly improved compared with that of the conventional BT model molecule without thiophene.In terms of device stability,DTBT-based devices show a favorable long-term stability,which keep 83%initial efficiency after 15 days.Therefore,the introducing of thiophene bridges in D-A-D typed HTMs can improve the molecular planarity effectively,thereby increasing the hole mobility and improving device performance.展开更多
A series of spiro-type hole transporting materials, spiro-OMe TAD, spiro-SMe TAD and spiro-OSMe TAD,with methoxy, methylsulfanyl or half methoxy and half methylsulfanyl terminal groups are designed and prepared. The i...A series of spiro-type hole transporting materials, spiro-OMe TAD, spiro-SMe TAD and spiro-OSMe TAD,with methoxy, methylsulfanyl or half methoxy and half methylsulfanyl terminal groups are designed and prepared. The impact of varied terminal groups on bulk properties, such as photophysical, electrochemical, thermal, hole extraction, and photovoltaic performance in perovskite solar cells is investigated.It is noted that the terminal groups of the hole transporting material with half methoxy and half methylsulfanyl exhibit a better device performance and decreased hysteresis compared with all methoxy or methylsulfanyl counterparts due to better film-forming ability and improved hole extraction capability.Promisingly, the spiro-OSMe TAD also shows comparable performance than high-purity commercial spiro-OMe TAD. Moreover, the highest power conversion efficiency of the optimized device employing spiro-OSMe TAD exceeding 20% has been achieved.展开更多
Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been pro...Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been proved as efficient HTMs.Herein,a series of novel C≡N functionalized carbazole-arylamine derivatives with variable C≡N substitution positions(para,meta,and ortho)on benzene-carbazole skeleton(on the adjacent benzene of carbazole)were synthesized(p-HTM,m-HTM and o-HTM).The experimental results exhibit that the substitution positions of the Ctriple bondN unit on HTMs have minor difference on the HOMO energy level and hydrophobicity.m-HTM has a relatively lower glass transition temperature compared with that of p-HTM and o-HTM.The functional theory calculations show that the C≡N located on meta position exposed very well,and the exposure direction is also the same with the methoxy.Upon applying these molecules as HTMs in PSCs,their device performance is found to sensitively depend on the substitution position of the C≡N unit on the molecule skeleton.The devices using m-HTM and o-HTM exhibit better performance than that of p-HTM.Moreover,m-HTM-based devices exhibit better light-soaking performance and long-term stability,which could be resulted from better interaction with the perovskite according to DFT results.Moreover,we further prepared a HTM with two C≡N units on the symmetrical meta position of molecular skeleton(2m-HTM).Interestingly,2m-HTM-based devices exhibit relatively inferior performance compared with that of the m-HTM,which could be resulted from weak negative electrical character of C≡N unit on 2m-HTM.The results give some new insights for designing ideal HTM for efficient and stable PSCs.展开更多
In the light of superior interaction between pyridine unit and perovskite,a facile star-shaped triphenylamine-based hole transport material(HTM)incorporating pyridine core(coded as H-Pyr)is designed and synthesized.A ...In the light of superior interaction between pyridine unit and perovskite,a facile star-shaped triphenylamine-based hole transport material(HTM)incorporating pyridine core(coded as H-Pyr)is designed and synthesized.A reference HTM with benzene core,coded as H-Ben,is also prepared for a comparative study.The effects of varying core on HTMs are investigated by comparing the photophysical,electrochemical and hole mobility properties.It is found that pyridine core exhibits better conjunction and decreased dihedral angles with triphenylamine side arms than that of benzene,leading to obviously better hole mobility and well-matched work function.The perovskite film prepared on H-Pyr also shows improved crystallization than on H-Ben.Photoluminescence and electrochemical impedance studies indicate improved charge extraction and reduced recombination in the H-Pyr-based perovskite solar cells.Consequently,H-Pyr-based device exhibits higher efficiency than H-Ben-based one.After doping with a Lewis acid,tris(pentafluorophenyl)borane,H-Pyr-based device delivers a champion efficiency of 17.09%,which is much higher compared with 12.14% of the device employing conventional poly(3,4-ethy lenedioxythiophene)polystyrene sulfonate(PEDOT:PSS)as HTM.Moreover,the H-Pyr-based device displays good long-term stability that the power conversion efficiency remains over 80% of the initial value after storage in ambient(relative humidity=50±5%)for 20 days.展开更多
The computational modelling supported by experimental results can explain the molecular structure, vibrational assignments, reactive sites and several structural properties. In this context, the spectroscopic (FT-IR, ...The computational modelling supported by experimental results can explain the molecular structure, vibrational assignments, reactive sites and several structural properties. In this context, the spectroscopic (FT-IR, FT-Raman and NMR) analysis, electronic properties (HOMO and LUMO energies) and molecular structure of pyrimethamine (Pyr) were investigated by density functional theory (DFT) method associated with three levels of theory viz., B3LYP, MN15 and wB97XD with 6-311++G(d,p) and def2TZVPP as basis sets, respectively in the Gaussian 16 programs. The <sup>1</sup>H and <sup>13</sup>C NMR chemical shifts were calculated with a gauge-independent atomic orbital (GIAO) approach by also applying the same levels of theory and basis sets. All experimental results were compared with theoretical data. Although the results revealed high degrees of correlation between the theoretical and experimental values for spectroscopic properties using the three methods. Furthermore, the atomic and natural charges, energy band gap and chemical reactivity were determined, while the frontier molecular orbital (FMO) and molecular electrostatic potential (MEP) surfaces were plotted to explain the reactive nature of the title molecule.展开更多
We reported a quantum mechanical study of the complexes formed between Sm3＋ and the bisphosphonate ligand pamidronate in aqueous solution. According to available experimental p K a values pamidronate was expected to ...We reported a quantum mechanical study of the complexes formed between Sm3＋ and the bisphosphonate ligand pamidronate in aqueous solution. According to available experimental p K a values pamidronate was expected to exist in aqueous solution, at physiologically relevant p H, in its di- and tri-protonated forms（denoted by H3 L and H2L）. The most stable structures of the ligands and Sm3＋ complexes were found by using a detailed analysis of the conformational space with semiempirical and DFT methods. The results showed that both H2 L and H3 L bisphosphonates acted as a tridentate ligands in their complexes with Sm3＋. The addition of explicit water molecules to the coordination sphere of the metal not only gave different coordination numbers for H2 L and H3 L complexes（CN=9 and 10）, but also provided different trends in stabilization energies. The results highlighted the importance of considering not only an explicit first coordination shell, but also a second hydration shell, for an adequate description of this type of complexes in aqueous solution.展开更多
Aqueous Zn-based batteries are promising energy storage technology due to their low cost and high safety.However, the solvation structure of electrolyte leads to dendrite growth, parasitic reactions, and poor low-temp...Aqueous Zn-based batteries are promising energy storage technology due to their low cost and high safety.However, the solvation structure of electrolyte leads to dendrite growth, parasitic reactions, and poor low-temperature properties, limiting their practical application. Here, we report 1,2-propanediol(PG) electrolyte with a modulated solvation structure, which can suppress Zn dendrite growth and parasitic reactions. PG can break the interaction between H_(2)O molecules and the interaction between H_(2)O and Zn^(2+) due to the higher electron density of O and higher Gutmann donor number of PG than those of H_(2)O, which increase the H–O covalent bond strength, decrease the water activity and freezing point, and change the solvation structure of Zn^(2+). As a result, the battery exhibits high cycling stability(Zn//Zn battery cycle over 1000 h), high reversibility(Coulombic efficiency of 98.9%), high capacity properties(specific capacity of225 m A h g^(-1)at 5 A g^(-1), and capacity retention of 92.6% for5000 cycles), and excellent anti-freezing properties(specific capacity of 190 m A h g^(-1) at-20℃ over 500 cycles). This work provides a promising strategy for the development of highperformance aqueous zinc-ion batteries.展开更多
Proton transfer in carbonic anhydrase II has been studied at the B3LYP/6-31G(D) level. The active site model consists of the zinc ion, four histidine residues, two threonine residues, and three water molecules. Our ca...Proton transfer in carbonic anhydrase II has been studied at the B3LYP/6-31G(D) level. The active site model consists of the zinc ion, four histidine residues, two threonine residues, and three water molecules. Our calcula- tions showed that the proton of the zinc-bound water mole- cule could be transferred to the nearest water molecule and an intermediate containing H3O+ is then formed. The inter- mediate is only 1.3 kJ·mol-1 above the reactant complex, whereas the barrier height for the proton transfer is about 8.1 kJ·mol?1.展开更多
基金the National Key R&D Program of China(2018YFB1500101)National Basic Research Program of China(No.2015CB932200)CAS-Iranian Vice Presidency for Science and Technology Joint Research Project(No.116134KYSB20160130).
文摘A new benzothiadiazole-based D-A-D hole transport material(DTBT)has been designed and synthesized with a more planar structure by introducing of thiophene bridges.The results indicate a lower band gap and quite higher hole mobility for the DTBT.Furthermore,the enhancement in molecular planarity with simple thiophene unit increases the hole mobility of DTBT(8.77×10^-4cm^2 V^-1s^-1)by about 40%.And when DTBT is used as hole transport material in perovskite solar cells,the photoelectric conversion efficiency of the corresponding dopant-free devices is also significantly improved compared with that of the conventional BT model molecule without thiophene.In terms of device stability,DTBT-based devices show a favorable long-term stability,which keep 83%initial efficiency after 15 days.Therefore,the introducing of thiophene bridges in D-A-D typed HTMs can improve the molecular planarity effectively,thereby increasing the hole mobility and improving device performance.
基金supported by the National Key Research and Development Program of China(Grant No.2020YFB1506400)the National Natural Science Foundation of China(Grant Nos.61904053,51702096,U1705256,51961165106)the Fundamental Research Funds for the Central Universities(Grant Nos.2019MS026,2019MS027,2020MS080)。
文摘A series of spiro-type hole transporting materials, spiro-OMe TAD, spiro-SMe TAD and spiro-OSMe TAD,with methoxy, methylsulfanyl or half methoxy and half methylsulfanyl terminal groups are designed and prepared. The impact of varied terminal groups on bulk properties, such as photophysical, electrochemical, thermal, hole extraction, and photovoltaic performance in perovskite solar cells is investigated.It is noted that the terminal groups of the hole transporting material with half methoxy and half methylsulfanyl exhibit a better device performance and decreased hysteresis compared with all methoxy or methylsulfanyl counterparts due to better film-forming ability and improved hole extraction capability.Promisingly, the spiro-OSMe TAD also shows comparable performance than high-purity commercial spiro-OMe TAD. Moreover, the highest power conversion efficiency of the optimized device employing spiro-OSMe TAD exceeding 20% has been achieved.
基金Zi'an Zhou and Xianfu Zhang contributed equally to this work.This work was supported by the National Key R&D Program ofChina(2018YFB1500101)the 111 Project(No.B16016)+1 种基金the National Natural Science Foundation of China(No.61904053,51702096,U1705256 and 51961165106)the FundamentalResearch Funds for the Central Universities(No.2019MSO_(2)6.2019MS027,and 2020MS080)。
文摘Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been proved as efficient HTMs.Herein,a series of novel C≡N functionalized carbazole-arylamine derivatives with variable C≡N substitution positions(para,meta,and ortho)on benzene-carbazole skeleton(on the adjacent benzene of carbazole)were synthesized(p-HTM,m-HTM and o-HTM).The experimental results exhibit that the substitution positions of the Ctriple bondN unit on HTMs have minor difference on the HOMO energy level and hydrophobicity.m-HTM has a relatively lower glass transition temperature compared with that of p-HTM and o-HTM.The functional theory calculations show that the C≡N located on meta position exposed very well,and the exposure direction is also the same with the methoxy.Upon applying these molecules as HTMs in PSCs,their device performance is found to sensitively depend on the substitution position of the C≡N unit on the molecule skeleton.The devices using m-HTM and o-HTM exhibit better performance than that of p-HTM.Moreover,m-HTM-based devices exhibit better light-soaking performance and long-term stability,which could be resulted from better interaction with the perovskite according to DFT results.Moreover,we further prepared a HTM with two C≡N units on the symmetrical meta position of molecular skeleton(2m-HTM).Interestingly,2m-HTM-based devices exhibit relatively inferior performance compared with that of the m-HTM,which could be resulted from weak negative electrical character of C≡N unit on 2m-HTM.The results give some new insights for designing ideal HTM for efficient and stable PSCs.
基金supported by the National Key R&D Program of China(2019YFB1503202)the 111 Project(B16016)+1 种基金the National Natural Science Foundation of China(61904053,51702096,U1705256 and 51572080)the Fundamental Research Funds for the Central Universities(2019MS026,2019MS027 and 2020MS080)。
文摘In the light of superior interaction between pyridine unit and perovskite,a facile star-shaped triphenylamine-based hole transport material(HTM)incorporating pyridine core(coded as H-Pyr)is designed and synthesized.A reference HTM with benzene core,coded as H-Ben,is also prepared for a comparative study.The effects of varying core on HTMs are investigated by comparing the photophysical,electrochemical and hole mobility properties.It is found that pyridine core exhibits better conjunction and decreased dihedral angles with triphenylamine side arms than that of benzene,leading to obviously better hole mobility and well-matched work function.The perovskite film prepared on H-Pyr also shows improved crystallization than on H-Ben.Photoluminescence and electrochemical impedance studies indicate improved charge extraction and reduced recombination in the H-Pyr-based perovskite solar cells.Consequently,H-Pyr-based device exhibits higher efficiency than H-Ben-based one.After doping with a Lewis acid,tris(pentafluorophenyl)borane,H-Pyr-based device delivers a champion efficiency of 17.09%,which is much higher compared with 12.14% of the device employing conventional poly(3,4-ethy lenedioxythiophene)polystyrene sulfonate(PEDOT:PSS)as HTM.Moreover,the H-Pyr-based device displays good long-term stability that the power conversion efficiency remains over 80% of the initial value after storage in ambient(relative humidity=50±5%)for 20 days.
文摘The computational modelling supported by experimental results can explain the molecular structure, vibrational assignments, reactive sites and several structural properties. In this context, the spectroscopic (FT-IR, FT-Raman and NMR) analysis, electronic properties (HOMO and LUMO energies) and molecular structure of pyrimethamine (Pyr) were investigated by density functional theory (DFT) method associated with three levels of theory viz., B3LYP, MN15 and wB97XD with 6-311++G(d,p) and def2TZVPP as basis sets, respectively in the Gaussian 16 programs. The <sup>1</sup>H and <sup>13</sup>C NMR chemical shifts were calculated with a gauge-independent atomic orbital (GIAO) approach by also applying the same levels of theory and basis sets. All experimental results were compared with theoretical data. Although the results revealed high degrees of correlation between the theoretical and experimental values for spectroscopic properties using the three methods. Furthermore, the atomic and natural charges, energy band gap and chemical reactivity were determined, while the frontier molecular orbital (FMO) and molecular electrostatic potential (MEP) surfaces were plotted to explain the reactive nature of the title molecule.
文摘We reported a quantum mechanical study of the complexes formed between Sm3＋ and the bisphosphonate ligand pamidronate in aqueous solution. According to available experimental p K a values pamidronate was expected to exist in aqueous solution, at physiologically relevant p H, in its di- and tri-protonated forms（denoted by H3 L and H2L）. The most stable structures of the ligands and Sm3＋ complexes were found by using a detailed analysis of the conformational space with semiempirical and DFT methods. The results showed that both H2 L and H3 L bisphosphonates acted as a tridentate ligands in their complexes with Sm3＋. The addition of explicit water molecules to the coordination sphere of the metal not only gave different coordination numbers for H2 L and H3 L complexes（CN=9 and 10）, but also provided different trends in stabilization energies. The results highlighted the importance of considering not only an explicit first coordination shell, but also a second hydration shell, for an adequate description of this type of complexes in aqueous solution.
基金supported by the National Key R&D Program of China (2017YFE0133800)the CASHIPS Director’s Fund (YZJJ201902 and YZJJZX202018)Anhui Provincial Natural Science Foundation (1908085QB52 and 2008085ME135)。
文摘Aqueous Zn-based batteries are promising energy storage technology due to their low cost and high safety.However, the solvation structure of electrolyte leads to dendrite growth, parasitic reactions, and poor low-temperature properties, limiting their practical application. Here, we report 1,2-propanediol(PG) electrolyte with a modulated solvation structure, which can suppress Zn dendrite growth and parasitic reactions. PG can break the interaction between H_(2)O molecules and the interaction between H_(2)O and Zn^(2+) due to the higher electron density of O and higher Gutmann donor number of PG than those of H_(2)O, which increase the H–O covalent bond strength, decrease the water activity and freezing point, and change the solvation structure of Zn^(2+). As a result, the battery exhibits high cycling stability(Zn//Zn battery cycle over 1000 h), high reversibility(Coulombic efficiency of 98.9%), high capacity properties(specific capacity of225 m A h g^(-1)at 5 A g^(-1), and capacity retention of 92.6% for5000 cycles), and excellent anti-freezing properties(specific capacity of 190 m A h g^(-1) at-20℃ over 500 cycles). This work provides a promising strategy for the development of highperformance aqueous zinc-ion batteries.
基金supported by the National Natural Science Foundation of China(Grant No.30370337)
文摘Proton transfer in carbonic anhydrase II has been studied at the B3LYP/6-31G(D) level. The active site model consists of the zinc ion, four histidine residues, two threonine residues, and three water molecules. Our calcula- tions showed that the proton of the zinc-bound water mole- cule could be transferred to the nearest water molecule and an intermediate containing H3O+ is then formed. The inter- mediate is only 1.3 kJ·mol-1 above the reactant complex, whereas the barrier height for the proton transfer is about 8.1 kJ·mol?1.
