The stability and safety of aqueous aluminum metal batteries(AAMBs)have garnered an enormous amount of attention.However,severe corrosion during cycling and inefficient deposition behavior at the Al anode hinder their...The stability and safety of aqueous aluminum metal batteries(AAMBs)have garnered an enormous amount of attention.However,severe corrosion during cycling and inefficient deposition behavior at the Al anode hinder their application.In this paper,CeCl_(3)was selected as a water inhibition additive to achieve active water confinement,which dramatically improved the corrosion behavior and prolonged the cycle life of the Al electrode.A combination of spectroscopic characterization and computational analysis showed that Cl^(-)breaks hydrogen bonds in the electrolyte and has higher adsorption energy on Al,thus inhibiting water-induced corrosion.Meanwhile,Ce^(3+)has a stronger affinity for Al than H_(2)O,thus promoting the formation of the surface protective layer.Cl^(-)in the modified electrolyte results in less hydration around Al^(3+).Due to the excellent water inhibition effect of CeCl_(3),the corrosion phenomenon of Al electrodes was significantly improved,and the dominant growth of the Al(111)crystal plane was achieved.Al//Prussian blue analogue(PBA)full cells with CeCl_(3)exhibit significantly improved voltage polarization(0.342 V),cycle life(550 cycles),discharge specific capacity(112 mAh g^(-1)),and selfdischarge behavior(87.97%).The Ce^(3+)in the additive is also able to be co-intercalated into the PBA with Al^(3+),improving the stability of the PBA.However,the conductivity reduction of this strategy at higher concentrations needs to be further addressed.Compared with organic electrolyte and molten salt systems,the cycle life of the aqueous electrolyte in this work still falls short.This modification method paves the way for further development of efficient AAMBs.展开更多
It remains challenging to achievevaluableplatformchemicals from lignin because of itscomplicated polymeric structure and inherent inert chemical activities.So far,only a fewexamples have been reported for the selectiv...It remains challenging to achievevaluableplatformchemicals from lignin because of itscomplicated polymeric structure and inherent inert chemical activities.So far,only a fewexamples have been reported for the selective cleavage of C–C bonds in lignin due to their intrinsic inertness and ubiquity.Here,we present a simple and commercially available cerium(Ⅲ)chloride(CeCl_(3))-promoted photocatalytic depolymerization strategy to realize the simultaneous cleavage and amination ofC_(α)–C_(β)bond in a variety of lignin model compounds at room temperature.This procedure does not require any pretreatments and breakdown of C–O bonds or loss ofγ-CH_(2)OHgroup to generate aldehydes(up to 97%)and N-containing products(up to 95%)in good to excellent yields.Additionally,this CeCl_(3)-based photocatalyst system could maintain excellent catalytic performance even after 10 sequential cycles with newstarting materials.Moreover,this approach realizes the precise control over the reaction via switching the external light stimuli on/off.Further,this method is effective for the depolymerization of real lignin,thus affording the corresponding cleavage and amination products of C_(α)–C_(β)bonds.展开更多
The thermal decomposition of CeCl3·7 H2O was studied from room temperature to 800 ℃. Analysis was performed by applying TG-DTA, XRD, FESEM, EDXS, and TG-MS technologies to investigate the thermal decomposition m...The thermal decomposition of CeCl3·7 H2O was studied from room temperature to 800 ℃. Analysis was performed by applying TG-DTA, XRD, FESEM, EDXS, and TG-MS technologies to investigate the thermal decomposition mechanism of CeCl3·7 H2O in air atmosphere. Multiple forms of hydrated cerium chloride compound were observed in the dehydration products. The CeCl3hydrolysis product was separated by a continuous centrifugation method and the phase composition was identified as CeO2,Ce(OH)3,and CeCl3·4 H2O by XRD analysis. The evolved gas composition was identified as CI2and HCI by TG-MS system. Based on the analysis of the experimental results, the mechanism of thermal decomposition of CeCl3·7 H2O was proposed with completion of the dehydration reaction at 224 ℃,the hydrolysis reaction at 170-480 ℃,and the oxidation reaction of CeCl3above 480 ℃.展开更多
基金financial support from the following sources:the National Natural Science Foundation of China(NSFC)(grants 52171206,52271209)the Key Project of Hebei Natural Science Foundation(F2024201031,E2020201030)+1 种基金the Science Research Project of Hebei Education Department(JCZX2025019)the Interdisciplinary Research Program of Hebei University(DXK202401)。
文摘The stability and safety of aqueous aluminum metal batteries(AAMBs)have garnered an enormous amount of attention.However,severe corrosion during cycling and inefficient deposition behavior at the Al anode hinder their application.In this paper,CeCl_(3)was selected as a water inhibition additive to achieve active water confinement,which dramatically improved the corrosion behavior and prolonged the cycle life of the Al electrode.A combination of spectroscopic characterization and computational analysis showed that Cl^(-)breaks hydrogen bonds in the electrolyte and has higher adsorption energy on Al,thus inhibiting water-induced corrosion.Meanwhile,Ce^(3+)has a stronger affinity for Al than H_(2)O,thus promoting the formation of the surface protective layer.Cl^(-)in the modified electrolyte results in less hydration around Al^(3+).Due to the excellent water inhibition effect of CeCl_(3),the corrosion phenomenon of Al electrodes was significantly improved,and the dominant growth of the Al(111)crystal plane was achieved.Al//Prussian blue analogue(PBA)full cells with CeCl_(3)exhibit significantly improved voltage polarization(0.342 V),cycle life(550 cycles),discharge specific capacity(112 mAh g^(-1)),and selfdischarge behavior(87.97%).The Ce^(3+)in the additive is also able to be co-intercalated into the PBA with Al^(3+),improving the stability of the PBA.However,the conductivity reduction of this strategy at higher concentrations needs to be further addressed.Compared with organic electrolyte and molten salt systems,the cycle life of the aqueous electrolyte in this work still falls short.This modification method paves the way for further development of efficient AAMBs.
基金supported by the National Natural Science Foundation of China(grant nos.21975102,21871107,and 21774042).
文摘It remains challenging to achievevaluableplatformchemicals from lignin because of itscomplicated polymeric structure and inherent inert chemical activities.So far,only a fewexamples have been reported for the selective cleavage of C–C bonds in lignin due to their intrinsic inertness and ubiquity.Here,we present a simple and commercially available cerium(Ⅲ)chloride(CeCl_(3))-promoted photocatalytic depolymerization strategy to realize the simultaneous cleavage and amination ofC_(α)–C_(β)bond in a variety of lignin model compounds at room temperature.This procedure does not require any pretreatments and breakdown of C–O bonds or loss ofγ-CH_(2)OHgroup to generate aldehydes(up to 97%)and N-containing products(up to 95%)in good to excellent yields.Additionally,this CeCl_(3)-based photocatalyst system could maintain excellent catalytic performance even after 10 sequential cycles with newstarting materials.Moreover,this approach realizes the precise control over the reaction via switching the external light stimuli on/off.Further,this method is effective for the depolymerization of real lignin,thus affording the corresponding cleavage and amination products of C_(α)–C_(β)bonds.
基金Project supported by the National Natural Science Foundation of China(51274060)National Sci-Tech Support Plan(2012BAE01B02)Basic scientific research business expenses(N150204019)
文摘The thermal decomposition of CeCl3·7 H2O was studied from room temperature to 800 ℃. Analysis was performed by applying TG-DTA, XRD, FESEM, EDXS, and TG-MS technologies to investigate the thermal decomposition mechanism of CeCl3·7 H2O in air atmosphere. Multiple forms of hydrated cerium chloride compound were observed in the dehydration products. The CeCl3hydrolysis product was separated by a continuous centrifugation method and the phase composition was identified as CeO2,Ce(OH)3,and CeCl3·4 H2O by XRD analysis. The evolved gas composition was identified as CI2and HCI by TG-MS system. Based on the analysis of the experimental results, the mechanism of thermal decomposition of CeCl3·7 H2O was proposed with completion of the dehydration reaction at 224 ℃,the hydrolysis reaction at 170-480 ℃,and the oxidation reaction of CeCl3above 480 ℃.
