Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox ...Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox activity,which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns.Herein,a flake-like LLO is prepared and aberration-corrected scanning transmission electron microscopy(STEM),in situ high-temperature X-ray diffraction(HT-XRD),and soft X-ray absorption spectrum(sXAS)are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes.Void-induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage.Particle degradation originates from side facets,such as the(010)facet,while the close(003)facet is stable.These results are further understood through ab initio molecular dynamics calculations,which show that oxygen atoms are lost from the{010}facets.Therefore,the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating,which result in crevice-voids in the ab plane facets.The study reveals important aspects of the mechanism responsible for oxygen-anionic activity-based degradation of LLO cathode materials used in lithium-ion batteries.In particular,this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO.展开更多
Electrochemical degradation of sulfamethoxazole(SMX)and its metabolite acetyl-sulfamethoxazole(AcSMX)by Ti/SnO_(2)-Sb/Er-PbO_(2) were investigated.Results indicated that the electrochemical degradation of SMX and Ac-S...Electrochemical degradation of sulfamethoxazole(SMX)and its metabolite acetyl-sulfamethoxazole(AcSMX)by Ti/SnO_(2)-Sb/Er-PbO_(2) were investigated.Results indicated that the electrochemical degradation of SMX and Ac-SMX followed pseudo-first-order kinetics.The rate constants of SMX and Ac-SMX were 0.268 and 0.072 min-1 at optimal curre nt density of 10 and 14 mA/cm^(2),respectively.Transformation products of SMX and Ac-SMX were identified and the possible degradation pathways,including the cleavage of S-N bond,opening ring of isoxazole and nitration of amino group,were proposed.Total organic carbon removal of SMX was nearly 63.2%after 3 h electrochemical degradation.22.4%nitrogen of SMX was trans formed to NO_(3)-,and 98.8%sulfur of SMX was released as SO_(4)2-.According to quantitative structureactivity relationship model,toxicities of SMX and Ac-SMX to aquatic organisms significantly decreased after electrochemical degradation.Electric energy consumption for 90%SMX and Ac-SMX degradation was determined to be 0.58-8.97 and 6.88-44.19 Wh/L at different experimental conditions,respectively.Compared with parent compound SMX,the metabolite Ac-SMX is more refractory and toxic,which emphasizes the importance of taking its metabolites into account when investigating the disposal of pharmaceuticals from wastewater.展开更多
Prazosin(PRZ) and levonorgestrel(LNG) are widely used as an anti-disease drugs due to their biological activity in the human body. The frequent detection of these compounds in water samples requires alternative te...Prazosin(PRZ) and levonorgestrel(LNG) are widely used as an anti-disease drugs due to their biological activity in the human body. The frequent detection of these compounds in water samples requires alternative technologies for the removal of both compounds. After electrochemical degradation of PRZ and LNG, the parent compounds could be completely removed after treatment, but the identification and characterization of by-products are necessary as well. In this study, the effects of NaCl concentration and applied voltage were investigated during the electrochemical degradation process. The results revealed that the increase of NaCl concentration and applied voltage could promote the generation of hypochlorite OCl-and then enhance the degradation of PRZ and LNG. After initial study, 6 V and 0.2 g NaCl were selected for further experiments(96% and 99% removal of PRZ and LNG after 40 min, respectively). Energy consumption was also evaluated and calculated for PRZ and LNG at 3, 6 and 8 V. Solid phase extraction(SPE) method plays an important role in enhancing the detection limit of by-products. Furthermore, characterization and identification of chlorinated and non-chlorinated by-products were conducted using an accurate liquid chromatography-time of flight/mass spectrometry LC-TOF/MS instrument. The monitoring of products during the electrochemical degradation process was performed at6 V and 0.2 g NaCl in a 50 m L solution. The results indicated that two chlorinated products were formed during the electrochemical process. The toxicity of by-products toward E. coli bacteria was investigated at 37°C and 20 hr incubation time.展开更多
To avoid environmental pollution due to organic dye solutions,the electrophoresis and degradation of dye in organic solvents such as alcohol were investigated.Many dyes were tested in the Indium tin oxide(ITO)electrod...To avoid environmental pollution due to organic dye solutions,the electrophoresis and degradation of dye in organic solvents such as alcohol were investigated.Many dyes were tested in the Indium tin oxide(ITO)electrode driving cell,and about 15 dyes moved under voltage driving.Both the curves of ultraviolet-visible(UV-Vis)and infrared(IR)spectra of the electrophoresis samples showed that the metal complexes Red 04 and Acid Black 1 were degradable in alcohol solution by electrochemical reaction.The cyclic volt-ampere curves of the samples from the electrochemi-cal working station proved that electrochemical reactions took place.Based on the analysis of UV-Vis and IR spectra,the electrochemical degradation products of azo and metal complex azo dyes at lower voltage driving(1–5 V)in organic solvents are oxidized azobenzene,not hydrazine,which was found in the electrochemical degradation of dye water solutions.When the ITO electrode is modified by a polyimide(PI)film to a thickness less than 4μm,the electrochemical degradation of the dye in alcohol solution will not appear in the cyclic volt-ampere curves.A dye electrophoresis in organic solution flexible prototype e-paper display was formed and the display picture is shown.展开更多
The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode active materials(CAMs)are considered a promising alternative to commercially available cathodes such as layered and polyanion oxide cathodes,primarily due to their notab...The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode active materials(CAMs)are considered a promising alternative to commercially available cathodes such as layered and polyanion oxide cathodes,primarily due to their notable safety and high energy density,particularly in their single-crystal type.Nevertheless,the industrial application of the LNMO CAMs is severely inhibited due to the interfacial deterioration and corrosion under proton-rich and high-voltage conditions.This study successfully designed and synthesized two typical types of crystal facets-exposed single-crystal LNMO CAMs.By tracking the electrochemical deterioration and chemical corrosion evolution,this study elucidates the surface degradation mechanisms and intrinsic instability of the LNMO,contingent upon their crystal facets.The(111)facet,due to its elevated surface energy,is found to be more susceptible to external attack compared to the(100)and(110)facets.Our study highlights the electrochemical corrosion stability of crystal plane engineering for spinel LNMO CAMs.展开更多
On the sand-blasting-treated titanium(Ti) substrate, the boron-doped diamond(BDD) electrodes with a wide potential window were prepared by microwave plasma chemical vapor deposition(MPCVD). The electrochemi- cal...On the sand-blasting-treated titanium(Ti) substrate, the boron-doped diamond(BDD) electrodes with a wide potential window were prepared by microwave plasma chemical vapor deposition(MPCVD). The electrochemi- cal oxidation ratios of phenol at BDD/Ti electrodes at elevated temperatures(from 20 ℃ to 80 ℃) were examined by the chemical oxygen demand(COD) of phenol electrolyte during electrolysis. The results show that the COD removal was increased at high temperatures and the optimized temperature for enhancing the electrochemical oxidation ratio of phenol is 60 ℃. The mechanism for the temperature-dependent electrochemical oxidation ratios of phenol at the electrodes was investigated. The study would be favorable for further improving the performance of BDD/Ti elec- trodes, especially working at high temperatures.展开更多
An ionic fluid based on aromatic heterocyclic family constituted by 1,3-diazole groups was investigated. The purpose is to describe their electrochemical characteristics in order to identify the strategy to avoid the ...An ionic fluid based on aromatic heterocyclic family constituted by 1,3-diazole groups was investigated. The purpose is to describe their electrochemical characteristics in order to identify the strategy to avoid the A36 carbon steel surface degradation by using electrochemical measurements. We found that the linear polarization resistance reveals an increasing value when the organic unsaturated cyclic ionic fluid was added to the corrosive electrolyte. The polarization curves and Tafel Extrapolation obtained to know the slopes tafel and the inhibitor efficiency from current density (i<sub>corr</sub>) shows a high efficiency inhibition value.展开更多
Electrochemical oxidation is an effective method to degrade persistent organic pollutants.However,due to the limited catalytic activity of traditional thin film electrodes,the anodic oxidation process is slow and usua...Electrochemical oxidation is an effective method to degrade persistent organic pollutants.However,due to the limited catalytic activity of traditional thin film electrodes,the anodic oxidation process is slow and usually requires high energy consumption.Herein,Ti/SnO_(2)-Sb electrode with regulated surface structure was reported to enhance the performance for electrochemical oxidation of persistent organic pollutants.The electrode deposited with SnO_(2)-Sb nanoneedles(Ti/N-SnO_(2)-Sb)showed higher oxidation activity.Its kinetic constant for perfluorooctanoic acid(PFOA)oxidation was 2.0 h^(-1)and the total organic carbon removal rate was 81.7%(4 h)at a relatively low current density of 6 mA/cm^2.Compared with Ti/SnO_(2)-Sb thin film and nanoparticles,Ti/N-SnO_(2)-Sb significantly improved the electrochemical active area and·OH yield,and simultaneously reduced the electron transfer resistance,which enabled it to oxidize PFOA more rapidly even at a lower potential.This work provides a new strategy for promoting the electrochemical oxidation performance.展开更多
Excessive consumption of electrical energy has hampered the widespread application of electrochemical technology for degradation of various contaminants. In this paper, a Fe-based metallic glass(MG) was demonstrated a...Excessive consumption of electrical energy has hampered the widespread application of electrochemical technology for degradation of various contaminants. In this paper, a Fe-based metallic glass(MG) was demonstrated as a new type of electrocatalyst to effectively and economically degrade an azo dye. In comparison to other typical electrodes, Fe-based MG electrodes exhibit a minimized degradation time, and the specific energy is 4-6 orders of magnitude lower than that of dimensionally stable anode(DSA), metal-like boron-doped diamond(BDD) and other electrodes. As sacrificial electrode materials, Fe-based MGs have less specific electrode mass consumption than iron electrodes. The use of Fe-based MGs will promote the practical application of electrochemical technology and the use of MGs as functional materials.展开更多
The degradation of acid orange II(AO II)by a nanoporous Fe-Si-B(NP-Fe Si B)electrode under the pulsed square-wave potential has been investigated in this research.Defect-enriched NP-Fe Si B electrode was fabricated th...The degradation of acid orange II(AO II)by a nanoporous Fe-Si-B(NP-Fe Si B)electrode under the pulsed square-wave potential has been investigated in this research.Defect-enriched NP-Fe Si B electrode was fabricated through dealloying of annealed Fe_(76)Si_(9)B_(15)amorphous ribbons.The results of UV-vis spectra and FTIR indicated that AO II solution was degraded efficiently into unharmful molecules H_(2)O and CO_(2)on NPFe Si B electrode within 5 mins under the square-wave potential of±1.5 V.The degradation efficiency of the NP-Fe Si B electrode remains 98.9%even after 5-time recycling.The large amount of active surface area of the nanoporous Fe Si B electrode with lattice disorders and stacking faults,and alternate electrochemical redox reactions were mainly responsible for the excellent degradation performance of the NP-Fe Si B electrode.The electrochemical pulsed square-wave process accelerated the redox of Fe element in Fe-based nanoporous electrode and promoted the generation of hydroxyl radicals(·OH)with strong oxidizability as predominant oxidants for the degradation of azo dye molecules,which was not only beneficial to improving the catalytic degradation activity,but also beneficial to enhancing the reusability of the nanoporous electrode.This work provides a highly possibility to efficiently degrade azo dyes and broadens the application fields of nanoporous metals.展开更多
基金supported by the Guangdong Provincial Science and Technology Commission,Guangdong Key Areas R&D Program(2020B0909030004)the Beijing Natural Science Foundation Committee,Haidian Original Innovation Joint Fund Project(L182023)Youth Fund Project of GRINM(Grant No.12620203129011).
文摘Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox activity,which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns.Herein,a flake-like LLO is prepared and aberration-corrected scanning transmission electron microscopy(STEM),in situ high-temperature X-ray diffraction(HT-XRD),and soft X-ray absorption spectrum(sXAS)are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes.Void-induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage.Particle degradation originates from side facets,such as the(010)facet,while the close(003)facet is stable.These results are further understood through ab initio molecular dynamics calculations,which show that oxygen atoms are lost from the{010}facets.Therefore,the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating,which result in crevice-voids in the ab plane facets.The study reveals important aspects of the mechanism responsible for oxygen-anionic activity-based degradation of LLO cathode materials used in lithium-ion batteries.In particular,this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO.
基金the National Science Fund for Distinguished Young Scholars(No.51625801)the Guangdong Innovation Team Project for Colleges and Universities(No.2016KCXTD023)+1 种基金Guangdong Province Universities andColleges Pearl River Scholar Funded Scheme(2017)the China Postdoctoral Science Foundation(No.2018M643671)。
文摘Electrochemical degradation of sulfamethoxazole(SMX)and its metabolite acetyl-sulfamethoxazole(AcSMX)by Ti/SnO_(2)-Sb/Er-PbO_(2) were investigated.Results indicated that the electrochemical degradation of SMX and Ac-SMX followed pseudo-first-order kinetics.The rate constants of SMX and Ac-SMX were 0.268 and 0.072 min-1 at optimal curre nt density of 10 and 14 mA/cm^(2),respectively.Transformation products of SMX and Ac-SMX were identified and the possible degradation pathways,including the cleavage of S-N bond,opening ring of isoxazole and nitration of amino group,were proposed.Total organic carbon removal of SMX was nearly 63.2%after 3 h electrochemical degradation.22.4%nitrogen of SMX was trans formed to NO_(3)-,and 98.8%sulfur of SMX was released as SO_(4)2-.According to quantitative structureactivity relationship model,toxicities of SMX and Ac-SMX to aquatic organisms significantly decreased after electrochemical degradation.Electric energy consumption for 90%SMX and Ac-SMX degradation was determined to be 0.58-8.97 and 6.88-44.19 Wh/L at different experimental conditions,respectively.Compared with parent compound SMX,the metabolite Ac-SMX is more refractory and toxic,which emphasizes the importance of taking its metabolites into account when investigating the disposal of pharmaceuticals from wastewater.
基金Universiti Kebangsaan Malaysia for the scholarship of Z. H. Mussa (matric No. p69014)
文摘Prazosin(PRZ) and levonorgestrel(LNG) are widely used as an anti-disease drugs due to their biological activity in the human body. The frequent detection of these compounds in water samples requires alternative technologies for the removal of both compounds. After electrochemical degradation of PRZ and LNG, the parent compounds could be completely removed after treatment, but the identification and characterization of by-products are necessary as well. In this study, the effects of NaCl concentration and applied voltage were investigated during the electrochemical degradation process. The results revealed that the increase of NaCl concentration and applied voltage could promote the generation of hypochlorite OCl-and then enhance the degradation of PRZ and LNG. After initial study, 6 V and 0.2 g NaCl were selected for further experiments(96% and 99% removal of PRZ and LNG after 40 min, respectively). Energy consumption was also evaluated and calculated for PRZ and LNG at 3, 6 and 8 V. Solid phase extraction(SPE) method plays an important role in enhancing the detection limit of by-products. Furthermore, characterization and identification of chlorinated and non-chlorinated by-products were conducted using an accurate liquid chromatography-time of flight/mass spectrometry LC-TOF/MS instrument. The monitoring of products during the electrochemical degradation process was performed at6 V and 0.2 g NaCl in a 50 m L solution. The results indicated that two chlorinated products were formed during the electrochemical process. The toxicity of by-products toward E. coli bacteria was investigated at 37°C and 20 hr incubation time.
基金The study was financially supported by a funding project for academic human resources development in the Institutions of Higher Learning under the jurisdiction of Beijing Municipality(PHR,IHLB).
文摘To avoid environmental pollution due to organic dye solutions,the electrophoresis and degradation of dye in organic solvents such as alcohol were investigated.Many dyes were tested in the Indium tin oxide(ITO)electrode driving cell,and about 15 dyes moved under voltage driving.Both the curves of ultraviolet-visible(UV-Vis)and infrared(IR)spectra of the electrophoresis samples showed that the metal complexes Red 04 and Acid Black 1 were degradable in alcohol solution by electrochemical reaction.The cyclic volt-ampere curves of the samples from the electrochemi-cal working station proved that electrochemical reactions took place.Based on the analysis of UV-Vis and IR spectra,the electrochemical degradation products of azo and metal complex azo dyes at lower voltage driving(1–5 V)in organic solvents are oxidized azobenzene,not hydrazine,which was found in the electrochemical degradation of dye water solutions.When the ITO electrode is modified by a polyimide(PI)film to a thickness less than 4μm,the electrochemical degradation of the dye in alcohol solution will not appear in the cyclic volt-ampere curves.A dye electrophoresis in organic solution flexible prototype e-paper display was formed and the display picture is shown.
基金supported by the National Natural Science Foundation of China (52374311)the National Natural Science Foundation of Shaanxi (2022KXJ-146)+3 种基金the Fundamental Research Funds for the Central Universities (D5000230091)Open project of Shaanxi Laboratory of Aerospace Power (2022ZY2-JCYJ-01-09)full-depth-sea battery project (No.2020-XXXX-XX-246-00)the Youth Innovation Team of Shaanxi Universities。
文摘The spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode active materials(CAMs)are considered a promising alternative to commercially available cathodes such as layered and polyanion oxide cathodes,primarily due to their notable safety and high energy density,particularly in their single-crystal type.Nevertheless,the industrial application of the LNMO CAMs is severely inhibited due to the interfacial deterioration and corrosion under proton-rich and high-voltage conditions.This study successfully designed and synthesized two typical types of crystal facets-exposed single-crystal LNMO CAMs.By tracking the electrochemical deterioration and chemical corrosion evolution,this study elucidates the surface degradation mechanisms and intrinsic instability of the LNMO,contingent upon their crystal facets.The(111)facet,due to its elevated surface energy,is found to be more susceptible to external attack compared to the(100)and(110)facets.Our study highlights the electrochemical corrosion stability of crystal plane engineering for spinel LNMO CAMs.
基金Supported by the Project of the Development and Reform Commission in Jilin Province,China(No.2009-633)the New Century Excellent Talents in Universities of China(No.NCET-06-0303)the National Natural Science Foundation of China(No.20873051)
文摘On the sand-blasting-treated titanium(Ti) substrate, the boron-doped diamond(BDD) electrodes with a wide potential window were prepared by microwave plasma chemical vapor deposition(MPCVD). The electrochemi- cal oxidation ratios of phenol at BDD/Ti electrodes at elevated temperatures(from 20 ℃ to 80 ℃) were examined by the chemical oxygen demand(COD) of phenol electrolyte during electrolysis. The results show that the COD removal was increased at high temperatures and the optimized temperature for enhancing the electrochemical oxidation ratio of phenol is 60 ℃. The mechanism for the temperature-dependent electrochemical oxidation ratios of phenol at the electrodes was investigated. The study would be favorable for further improving the performance of BDD/Ti elec- trodes, especially working at high temperatures.
文摘An ionic fluid based on aromatic heterocyclic family constituted by 1,3-diazole groups was investigated. The purpose is to describe their electrochemical characteristics in order to identify the strategy to avoid the A36 carbon steel surface degradation by using electrochemical measurements. We found that the linear polarization resistance reveals an increasing value when the organic unsaturated cyclic ionic fluid was added to the corrosive electrolyte. The polarization curves and Tafel Extrapolation obtained to know the slopes tafel and the inhibitor efficiency from current density (i<sub>corr</sub>) shows a high efficiency inhibition value.
基金supported by Liaoning Revitalization Talents Program(No.XLYC2007069)the National Natural Science Foundation of China(Nos.22076019 and 22222601)open project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.HC201705)。
文摘Electrochemical oxidation is an effective method to degrade persistent organic pollutants.However,due to the limited catalytic activity of traditional thin film electrodes,the anodic oxidation process is slow and usually requires high energy consumption.Herein,Ti/SnO_(2)-Sb electrode with regulated surface structure was reported to enhance the performance for electrochemical oxidation of persistent organic pollutants.The electrode deposited with SnO_(2)-Sb nanoneedles(Ti/N-SnO_(2)-Sb)showed higher oxidation activity.Its kinetic constant for perfluorooctanoic acid(PFOA)oxidation was 2.0 h^(-1)and the total organic carbon removal rate was 81.7%(4 h)at a relatively low current density of 6 mA/cm^2.Compared with Ti/SnO_(2)-Sb thin film and nanoparticles,Ti/N-SnO_(2)-Sb significantly improved the electrochemical active area and·OH yield,and simultaneously reduced the electron transfer resistance,which enabled it to oxidize PFOA more rapidly even at a lower potential.This work provides a new strategy for promoting the electrochemical oxidation performance.
基金supported financially by the National Natural Science Foundation of China(Nos.51790484,51434008(U1435204) and 51531005)the CAS Key Project(No.ZDRW-CN-2017-1)DongGuan Innovative Research Team Program(No.2014607134)
文摘Excessive consumption of electrical energy has hampered the widespread application of electrochemical technology for degradation of various contaminants. In this paper, a Fe-based metallic glass(MG) was demonstrated as a new type of electrocatalyst to effectively and economically degrade an azo dye. In comparison to other typical electrodes, Fe-based MG electrodes exhibit a minimized degradation time, and the specific energy is 4-6 orders of magnitude lower than that of dimensionally stable anode(DSA), metal-like boron-doped diamond(BDD) and other electrodes. As sacrificial electrode materials, Fe-based MGs have less specific electrode mass consumption than iron electrodes. The use of Fe-based MGs will promote the practical application of electrochemical technology and the use of MGs as functional materials.
基金financially supported by Shi-changxu Innovation Center for Advanced Materials,Institute of Metal Research,Chinese Academy of Sciences,the National Natural Science Foundation of China(51790484,51671106)Chinese Academy of Sciences(ZDBSLY-JSC023)Fundamental Research Funds for the Central Universities(30919011404)。
文摘The degradation of acid orange II(AO II)by a nanoporous Fe-Si-B(NP-Fe Si B)electrode under the pulsed square-wave potential has been investigated in this research.Defect-enriched NP-Fe Si B electrode was fabricated through dealloying of annealed Fe_(76)Si_(9)B_(15)amorphous ribbons.The results of UV-vis spectra and FTIR indicated that AO II solution was degraded efficiently into unharmful molecules H_(2)O and CO_(2)on NPFe Si B electrode within 5 mins under the square-wave potential of±1.5 V.The degradation efficiency of the NP-Fe Si B electrode remains 98.9%even after 5-time recycling.The large amount of active surface area of the nanoporous Fe Si B electrode with lattice disorders and stacking faults,and alternate electrochemical redox reactions were mainly responsible for the excellent degradation performance of the NP-Fe Si B electrode.The electrochemical pulsed square-wave process accelerated the redox of Fe element in Fe-based nanoporous electrode and promoted the generation of hydroxyl radicals(·OH)with strong oxidizability as predominant oxidants for the degradation of azo dye molecules,which was not only beneficial to improving the catalytic degradation activity,but also beneficial to enhancing the reusability of the nanoporous electrode.This work provides a highly possibility to efficiently degrade azo dyes and broadens the application fields of nanoporous metals.