Reported here are several new calculation methods for the inner-sphere reorganization energy of hydrated metal ions involved in electron transfer processes.It is based on the self-exchange model of reorganization and ...Reported here are several new calculation methods for the inner-sphere reorganization energy of hydrated metal ions involved in electron transfer processes.It is based on the self-exchange model of reorganization and utilizes the more exact potential functions between central metal ion and the inner-sphere ligands.The parameters involved are determined via the spectroscopic and thermodynamic data.The predictions of the inner-sphere reorganization energies from those models agree well with the photoemission experimental results.展开更多
Based on the capture force field potential model and the adiabatic invariant proposed by Bates, adopting improved average dipole orientation (IADO) theory, the force constants between transition metal ions and benzene...Based on the capture force field potential model and the adiabatic invariant proposed by Bates, adopting improved average dipole orientation (IADO) theory, the force constants between transition metal ions and benzene (bz) and also a series of inner-sphere reoganization energy (REin) were calculated. The reasons for the differences between theoretical predictions and experimental results were discussed.展开更多
On the basis of the-improved self-exchange model of reorganization phenomenon and accurate potential functions from ab initio calculation at HFSCF 6-31G* and DZP levels a new calculation method was,presented for the i...On the basis of the-improved self-exchange model of reorganization phenomenon and accurate potential functions from ab initio calculation at HFSCF 6-31G* and DZP levels a new calculation method was,presented for the inner-sphere reorganization energy, values for diatomic molecular redox couples in gas phase electron transfer process have been calculated. Results agree well with the experimental data, and the effectiveness and importance of this method have been demonstrated for calculation of inner-sphere reorganization energy in gas phase electron transfer process.展开更多
Traditional lanthanum-based powdered adsorbents for phosphate recovery often face challenges such as powder loss,low stability,and high material costs,while lacking agricultural applicability.To address these limitati...Traditional lanthanum-based powdered adsorbents for phosphate recovery often face challenges such as powder loss,low stability,and high material costs,while lacking agricultural applicability.To address these limitations and bridge water treatment with agricultural reuse,we developed a novel composite adsorbent,PFS-PVA-La,by incorporating La(OH)_(3) nanoparticles onto a polyvinyl alcohol(PVA)-coated polyurethane foam sponge(PFS)matrix.The designed material serves dual functions:efficient phosphorus capture from water and subsequent utilization as a hydroponic growth substrate.The results demonstrate that the PFS-PVA-La configuration effectively mitigates the issue of powder loss typically associated with traditional lanthanum-based adsorbents,retaining 94%of the original adsorption capacity of La(OH)_(3) nanoparticles.Moreover,the PFS-PVA-La exhibits a high phosphorus adsorption capacity of 39.66 mgP/g,surpassing the performance of most existing composite adsorbents.La(OH)3 nanoparticles are physically encapsulated within cross-linked PVA layers on the hydrophilic,three-dimensional pore structure of the PFS.The mechanism for phosphate recovery by PFS-PVA-La is attributed to inner-sphere complexation,pore filling,and electrostatic interactions,all of which are significantly enhanced by the incorporation of PVA and La(OH)3 nanoparticles.Importantly,hydroponic experiments demonstrate the prepared adsorbent’s agricultural value:When used as growth substrate for lettuce,PFS-PVA-La increases fresh weight by 23%compared to control groups while maintaining optimal leaf chlorophyll and vitamin C levels.This work offers a stable,cost-effective material for phosphorus management while creating new value in hydroponic food production.展开更多
Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and trans...Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and transforming into toxic Cr(VI)due to the presence of manganese oxides in sediments.In this study,Citric Acid(CA)was selected as a representative organic ligand to prepare and characterize Cr(III)-CA complexes.The characteristics,mechanisms and environmental factors influencing the adsorption of Cr(Ⅲ)-CA on porous media(silts and fine sands)were investigated in the study.The results show that Cr(Ⅲ)coordinates with CA at a 1:1 molar ratio,forming stable and soluble Cr(Ⅲ)-CA complexes.Compared to Cr(III)ions,the equilibrium adsorption capacity of Cr(Ⅲ)-CA is an order of magnitude lower in silts and fine sands.The adsorption of Cr(Ⅲ)-CA in silts and fine sands is dominated by chemical adsorption of monolayers,following the pseudo-second-order kinetic equation and the Langmuir isotherm adsorption model.Varying contents of clay minerals and iron-aluminum oxides prove to be the main causes of differences in adsorption capacity of Cr(Ⅲ)-CA in silts and fine sands.Changes in solution pH affect the adsorption rate and capacity of Cr(Ⅲ)-CA by altering its ionic form.The adsorption process is irreversible and only minimally influenced by ionic strength,suggesting that inner-sphere complexation serves as the dominant Cr(Ⅲ)-CA adsorption mechanism.展开更多
基金Supported by the Natural Science Foundation of Shandong Province
文摘Reported here are several new calculation methods for the inner-sphere reorganization energy of hydrated metal ions involved in electron transfer processes.It is based on the self-exchange model of reorganization and utilizes the more exact potential functions between central metal ion and the inner-sphere ligands.The parameters involved are determined via the spectroscopic and thermodynamic data.The predictions of the inner-sphere reorganization energies from those models agree well with the photoemission experimental results.
文摘Based on the capture force field potential model and the adiabatic invariant proposed by Bates, adopting improved average dipole orientation (IADO) theory, the force constants between transition metal ions and benzene (bz) and also a series of inner-sphere reoganization energy (REin) were calculated. The reasons for the differences between theoretical predictions and experimental results were discussed.
文摘On the basis of the-improved self-exchange model of reorganization phenomenon and accurate potential functions from ab initio calculation at HFSCF 6-31G* and DZP levels a new calculation method was,presented for the inner-sphere reorganization energy, values for diatomic molecular redox couples in gas phase electron transfer process have been calculated. Results agree well with the experimental data, and the effectiveness and importance of this method have been demonstrated for calculation of inner-sphere reorganization energy in gas phase electron transfer process.
基金supported by the National Key Research and Development Program of China(No.2022YFE0127800)the Key Research and Development Project of Science and Technology Department of Zhejiang Province(Nos.2023C02019 and 2025C02096)+3 种基金the Zhejiang Province’s“Three Rural and Nine Directions”Science and Technology Collaboration Plan(No.2024SNJF065)Zhejiang University Student Science and Technology Innovation Activity Plan(New Seedling talent Plan subsidy project(No.2023R412005))the talent starting-up project of research development fund of Zhejiang A&F University(Nos.2024LFR042 and 2034020103)the Overseas Expertise Introduction Project for Discipline Innovation(111 Project D18008).
文摘Traditional lanthanum-based powdered adsorbents for phosphate recovery often face challenges such as powder loss,low stability,and high material costs,while lacking agricultural applicability.To address these limitations and bridge water treatment with agricultural reuse,we developed a novel composite adsorbent,PFS-PVA-La,by incorporating La(OH)_(3) nanoparticles onto a polyvinyl alcohol(PVA)-coated polyurethane foam sponge(PFS)matrix.The designed material serves dual functions:efficient phosphorus capture from water and subsequent utilization as a hydroponic growth substrate.The results demonstrate that the PFS-PVA-La configuration effectively mitigates the issue of powder loss typically associated with traditional lanthanum-based adsorbents,retaining 94%of the original adsorption capacity of La(OH)_(3) nanoparticles.Moreover,the PFS-PVA-La exhibits a high phosphorus adsorption capacity of 39.66 mgP/g,surpassing the performance of most existing composite adsorbents.La(OH)3 nanoparticles are physically encapsulated within cross-linked PVA layers on the hydrophilic,three-dimensional pore structure of the PFS.The mechanism for phosphate recovery by PFS-PVA-La is attributed to inner-sphere complexation,pore filling,and electrostatic interactions,all of which are significantly enhanced by the incorporation of PVA and La(OH)3 nanoparticles.Importantly,hydroponic experiments demonstrate the prepared adsorbent’s agricultural value:When used as growth substrate for lettuce,PFS-PVA-La increases fresh weight by 23%compared to control groups while maintaining optimal leaf chlorophyll and vitamin C levels.This work offers a stable,cost-effective material for phosphorus management while creating new value in hydroponic food production.
基金financially supported jointly by Natural Science Foundation of Fujian Province of China(NO.2023J01227)Natural Science Foundation of Hebei Province(NO.D2020504003)Key Laboratory of Groundwater Remediation of Hebei Province and China Geological Survey(NO.SK202303).
文摘Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and transforming into toxic Cr(VI)due to the presence of manganese oxides in sediments.In this study,Citric Acid(CA)was selected as a representative organic ligand to prepare and characterize Cr(III)-CA complexes.The characteristics,mechanisms and environmental factors influencing the adsorption of Cr(Ⅲ)-CA on porous media(silts and fine sands)were investigated in the study.The results show that Cr(Ⅲ)coordinates with CA at a 1:1 molar ratio,forming stable and soluble Cr(Ⅲ)-CA complexes.Compared to Cr(III)ions,the equilibrium adsorption capacity of Cr(Ⅲ)-CA is an order of magnitude lower in silts and fine sands.The adsorption of Cr(Ⅲ)-CA in silts and fine sands is dominated by chemical adsorption of monolayers,following the pseudo-second-order kinetic equation and the Langmuir isotherm adsorption model.Varying contents of clay minerals and iron-aluminum oxides prove to be the main causes of differences in adsorption capacity of Cr(Ⅲ)-CA in silts and fine sands.Changes in solution pH affect the adsorption rate and capacity of Cr(Ⅲ)-CA by altering its ionic form.The adsorption process is irreversible and only minimally influenced by ionic strength,suggesting that inner-sphere complexation serves as the dominant Cr(Ⅲ)-CA adsorption mechanism.
基金the financial support from the National Natural Science Foundation of China(51878332,21976084,and 21925602)the Fundamental Research Funds for the Central Universities.
