A new glass system (Bi2O3)50(Fe2O3)10(Li2O)x(K2O)40-x, where x changes in steps of 5 mole fraction between 0 and 40, was selected to study the electrical relaxation and the mixed alkali effect (MAE) phenomen...A new glass system (Bi2O3)50(Fe2O3)10(Li2O)x(K2O)40-x, where x changes in steps of 5 mole fraction between 0 and 40, was selected to study the electrical relaxation and the mixed alkali effect (MAE) phenomena. Measurements of ac conductivity σac, dielectric permittivity ε′ and loss factor tanδ in the frequency range of 0.12~10^2 kHz and in the temperature range of 300~650 K were carried out. The temperature dependence of the ac conductivity shows a slow increasing rate at low temperature and high frequency and a rapid increase at high temperature and low frequency. At constant temperature, the ac conductivity is found to be proportional to ω^8, where s is the frequency exponent, which is less than 1. Analysis of the conductivity data and the frequency exponent shows that the overlapping large polaron tunnelling (OLPT) model of ions is the most favorable mechanism for the ac conduction in the present glass system. The ac response, the dc conductivity and dielectric relaxation have the same activation energy and they originate from the same basic transport mechanism. The results of the dielectric permittivity show no maximum peak in the temperature and frequency range studied. This absence of maximum peak is an indication of non-ferroelectric behavior of all the studied samples. The MAE has been detected in the ac conductivity, which is the same as the classical MAE in the dc conductivity. The electrical parameters such as dielectric permittivity ε′ and real dielectric modulus M′ show a typical minimum deviation from linearity by about two orders of magnitude. The loss factor tanδ and the imaginary dielectric modulus M″ are insignificantly dependent on composition even at the same transition temperature Tg.展开更多
The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali...The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.展开更多
The mixed alkali effect was investigated in the glass system 0.75B2O3-0.25[xNa2O-(1 -x)K20] through thermodynamic properties. The calorimetric measurements were performed in HF solution calorimetry at 298 K. The mix...The mixed alkali effect was investigated in the glass system 0.75B2O3-0.25[xNa2O-(1 -x)K20] through thermodynamic properties. The calorimetric measurements were performed in HF solution calorimetry at 298 K. The mixing enthalpy values show non-linear behaviour upon substitution of one alkali ion by another. This thermodynamic non-ideality is caused by the slight variations of distance between metallic cations, the macromolecular structure being unchanged. It can be explained, at least qualitatively, using electrolyte theory based on the Coulombic interactions of charged species originally developed by Debye and Hückel.展开更多
A set of borophosphate glasses doped with alkali and transition metal (TM) ions have been synthesized. The glasses were carried through;annealing, XRD, density, DC conductivity studies. Molar volume and density varied...A set of borophosphate glasses doped with alkali and transition metal (TM) ions have been synthesized. The glasses were carried through;annealing, XRD, density, DC conductivity studies. Molar volume and density varied nonlinearly. High temperature activation energy is analysed taking into consideration of Mott’s SPH model. The low temperature electrical conductivity was analysed by Mott and Greaves VRH. Several polaron hopping related parameters at high temperature region and density of states at low temperature region were computed. The high temperature DC activation energy measured by conductivity, calculated numerous pertained parameters varied nonlinearly with mole fraction of vanadium content. The Study exhibits DC electrical conduction is due to both alkali and transition metal ions and thus confirms the mixed conductivity. A crossover conduction mechanism from the ionic dominant region to polaronic predominant region has been also observed. Studies revealed the single transition effect at 0.4 mol fraction of V<sub>2</sub>O<sub>5</sub> content.展开更多
In order to understand the effect of powders ground from reactive sandstone replacing cement on reducing or suppressing alkali-silica reaction(ASR), and to identify the mechanism of suppressing ASR by this powders, ...In order to understand the effect of powders ground from reactive sandstone replacing cement on reducing or suppressing alkali-silica reaction(ASR), and to identify the mechanism of suppressing ASR by this powders, mortar and paste containing reactive sandstone powders of four replacement levels ranging from 10wt% to 40wt% and four specific surfaces areas ranging from 210 m^2/kg to 860 m^2/kg were studied. The experimental results showed that incorporation of 40wt% reactive sandstone powders could suppress ASR effectively except for mortar containing reactive sandstone powders with specific surface area of 610 m^2/kg, which disagreed with the most results reported that the higher reactive powder specific surface area, the smaller ASR expansion. By means of fl ame photometry, Fourier transform infrared spectroscopy(FT-IR) and thermo gravimetric analysis(TG), the mechanism of reactive sandstone powders on reducing or suppressing ASR was soluble alkalis type of reactive sandstone powders and the competition of liberating and bonding alkali of cement paste containing reactive sandstone powders,when the ability of alkali bonding was greater than the ability of alkali liberation, ASR caused by reactive sandstone was supressed effectively.展开更多
Cu(In,Ga)Se_(2)(CIGS)is a promising candidate to replace crystalline silicon solar cells and dominate the photovoltaic market in the future.Alkali elements such as sodium(Na),potassium(K),rubidium(Rb),and Cesium(Cs)ar...Cu(In,Ga)Se_(2)(CIGS)is a promising candidate to replace crystalline silicon solar cells and dominate the photovoltaic market in the future.Alkali elements such as sodium(Na),potassium(K),rubidium(Rb),and Cesium(Cs)are commonly accepted as indispensable parts to boost cell efficiencies of CIGS thin-film solar cells.Therefore,a comprehensive understanding of alkali effects on the electronic and chemical properties of the CIGS layer as well as the underlying mechanisms is of paramount importance for achieving high-performance solar cells.This paper reviews the development process and incorporation pathways of alkalis and then overviews the roles of different alkali elements and their effects on CIGS cells in detail.Furthermore,the unsolved problems and future development prospects are also proposed.Overall,the understanding and development of widely adopted alkali-fluoride post-deposition treatments(PDTs)are still underway,and together with newly updated research,it will likely enable the CIGS technology to make the conversion efficiency closer to its theoretical limit.展开更多
文摘A new glass system (Bi2O3)50(Fe2O3)10(Li2O)x(K2O)40-x, where x changes in steps of 5 mole fraction between 0 and 40, was selected to study the electrical relaxation and the mixed alkali effect (MAE) phenomena. Measurements of ac conductivity σac, dielectric permittivity ε′ and loss factor tanδ in the frequency range of 0.12~10^2 kHz and in the temperature range of 300~650 K were carried out. The temperature dependence of the ac conductivity shows a slow increasing rate at low temperature and high frequency and a rapid increase at high temperature and low frequency. At constant temperature, the ac conductivity is found to be proportional to ω^8, where s is the frequency exponent, which is less than 1. Analysis of the conductivity data and the frequency exponent shows that the overlapping large polaron tunnelling (OLPT) model of ions is the most favorable mechanism for the ac conduction in the present glass system. The ac response, the dc conductivity and dielectric relaxation have the same activation energy and they originate from the same basic transport mechanism. The results of the dielectric permittivity show no maximum peak in the temperature and frequency range studied. This absence of maximum peak is an indication of non-ferroelectric behavior of all the studied samples. The MAE has been detected in the ac conductivity, which is the same as the classical MAE in the dc conductivity. The electrical parameters such as dielectric permittivity ε′ and real dielectric modulus M′ show a typical minimum deviation from linearity by about two orders of magnitude. The loss factor tanδ and the imaginary dielectric modulus M″ are insignificantly dependent on composition even at the same transition temperature Tg.
文摘The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.
文摘The mixed alkali effect was investigated in the glass system 0.75B2O3-0.25[xNa2O-(1 -x)K20] through thermodynamic properties. The calorimetric measurements were performed in HF solution calorimetry at 298 K. The mixing enthalpy values show non-linear behaviour upon substitution of one alkali ion by another. This thermodynamic non-ideality is caused by the slight variations of distance between metallic cations, the macromolecular structure being unchanged. It can be explained, at least qualitatively, using electrolyte theory based on the Coulombic interactions of charged species originally developed by Debye and Hückel.
文摘A set of borophosphate glasses doped with alkali and transition metal (TM) ions have been synthesized. The glasses were carried through;annealing, XRD, density, DC conductivity studies. Molar volume and density varied nonlinearly. High temperature activation energy is analysed taking into consideration of Mott’s SPH model. The low temperature electrical conductivity was analysed by Mott and Greaves VRH. Several polaron hopping related parameters at high temperature region and density of states at low temperature region were computed. The high temperature DC activation energy measured by conductivity, calculated numerous pertained parameters varied nonlinearly with mole fraction of vanadium content. The Study exhibits DC electrical conduction is due to both alkali and transition metal ions and thus confirms the mixed conductivity. A crossover conduction mechanism from the ionic dominant region to polaronic predominant region has been also observed. Studies revealed the single transition effect at 0.4 mol fraction of V<sub>2</sub>O<sub>5</sub> content.
基金Funded partly by the the National 973 Program of China(No.2013CB035901)the National Natural Science Foundation of China(No.51379163)
文摘In order to understand the effect of powders ground from reactive sandstone replacing cement on reducing or suppressing alkali-silica reaction(ASR), and to identify the mechanism of suppressing ASR by this powders, mortar and paste containing reactive sandstone powders of four replacement levels ranging from 10wt% to 40wt% and four specific surfaces areas ranging from 210 m^2/kg to 860 m^2/kg were studied. The experimental results showed that incorporation of 40wt% reactive sandstone powders could suppress ASR effectively except for mortar containing reactive sandstone powders with specific surface area of 610 m^2/kg, which disagreed with the most results reported that the higher reactive powder specific surface area, the smaller ASR expansion. By means of fl ame photometry, Fourier transform infrared spectroscopy(FT-IR) and thermo gravimetric analysis(TG), the mechanism of reactive sandstone powders on reducing or suppressing ASR was soluble alkalis type of reactive sandstone powders and the competition of liberating and bonding alkali of cement paste containing reactive sandstone powders,when the ability of alkali bonding was greater than the ability of alkali liberation, ASR caused by reactive sandstone was supressed effectively.
基金supported by the National Natural Science Foundation of China(Nos.11975135 and 61176003)financial support of Special Funds for Fundamental Research Funds for Central Universities(No.2018 NTST29)the Chinese Postdoctoral Science Foundation(No.2019M650524)。
文摘Cu(In,Ga)Se_(2)(CIGS)is a promising candidate to replace crystalline silicon solar cells and dominate the photovoltaic market in the future.Alkali elements such as sodium(Na),potassium(K),rubidium(Rb),and Cesium(Cs)are commonly accepted as indispensable parts to boost cell efficiencies of CIGS thin-film solar cells.Therefore,a comprehensive understanding of alkali effects on the electronic and chemical properties of the CIGS layer as well as the underlying mechanisms is of paramount importance for achieving high-performance solar cells.This paper reviews the development process and incorporation pathways of alkalis and then overviews the roles of different alkali elements and their effects on CIGS cells in detail.Furthermore,the unsolved problems and future development prospects are also proposed.Overall,the understanding and development of widely adopted alkali-fluoride post-deposition treatments(PDTs)are still underway,and together with newly updated research,it will likely enable the CIGS technology to make the conversion efficiency closer to its theoretical limit.