Supercapacitors(SCs) are high-power energy storage devices with ultra-fast charge/discharge properties.SCs using concentrated aqueous-based electrolytes can work at low temperatures due to their intrinsic properties, ...Supercapacitors(SCs) are high-power energy storage devices with ultra-fast charge/discharge properties.SCs using concentrated aqueous-based electrolytes can work at low temperatures due to their intrinsic properties, such as higher freezing point depression(FPD) and robustness. Besides the traditional organic-and aqueous-based(salt-in-water) electrolytes used in SCs, water-in-salt(WISE) sodium perchlorate electrolytes offer high FPD, non-flammability, and low-toxicity conditions, allowing the fabrication of safer, environmentally friendly, and more robust devices. For the first time, this work reports a comprehensive study regarding WISE system’s charge-storage capabilities and physicochemical properties under low-temperature conditions(T < 0 ℃) using mesoporous carbon-based electrodes. The effect of temperature reduction on the electrolyte viscosity and electrical properties was investigated using different techniques and the in-situ(or operando) Raman spectroscopy under dynamic polarization conditions.The cell voltage, equivalent series resistance, and specific capacitance were investigated as a function of the temperature. The cell voltage(U) increased ~ 50%, while the specific capacitance decreased ~20%when the temperature was reduced from 25 ℃ to -10 ℃. As a result, the maximum specific energy(E = CU^(2)/2) increased ~ 100%. Therefore, low-temperature WISEs are promising candidates to improve the energy-storage characteristics in SCs.展开更多
A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.The...A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.展开更多
The chemical analysis of a complex sulphide concentrate by emission spectrometry and X-ray diffraction shows that it contains essentially copper, lead, zinc and iron in the form of chalcopyrite, sphalerite and galena....The chemical analysis of a complex sulphide concentrate by emission spectrometry and X-ray diffraction shows that it contains essentially copper, lead, zinc and iron in the form of chalcopyrite, sphalerite and galena. A small amount of pyrite is also present in the ore but does not be detected with X-ray diffraction. The cupric chloride leaching of the sulphide concentrate at various durations and solid/liquid ratios at 100 ℃ shows that the rate of dissolution of the ore is the fastest in the first several hours, and after 12 h it does not evolve significantly. If oxygen is excluded from the aqueous cupric chloride solution during the leaching experiment at 100 ℃, the pyrite in the ore will not be leached. The determination of principal dissolved metals in the leaching liquor by flame atomic absorption spectrometry, and the chemical analysis of solid residues by emission spectrometry and X-ray diffraction allow to conclude that the rate of dissolution of the minerals contained in the complex sulphide concentrate are in the order of galena >sphalerite>chalcopyrite.展开更多
Through targeted and reproducible electrochemical treatment of glassy carbon electrodes, investigations have been carried out on the electrochemical behaviour of the oxidation of V2＋, VO2＋ and the reductions of VO2...Through targeted and reproducible electrochemical treatment of glassy carbon electrodes, investigations have been carried out on the electrochemical behaviour of the oxidation of V2＋, VO2＋ and the reductions of VO2＋, VO2＋ and V3＋ in order to pretreat electrodes specifically for use in vanadium redox flow batter- ies and, if possible, to treat them in situ. For this purpose, a glassy carbon electrode was treated poten- tiostatically for a period of 30 s at different potentials in the range of 500 mV-2000 mV vs. Hg/Hg_2SO_4 in 2 M H_2SO_4 and then linear sweep voltammograms were performed in the different vanadium-containing solutions. With this method, it could be shown that all reactions are extremely surface sensitive and the reaction speeds changed by several decades. The reaction rates increased significantly in all reac- tions compared to polished electrodes and had an optimum treatment potential of approx. 1600 mV vs. Hg/Hg_2SO_4, although the oxidation reaction of V2＋ and the reduction reactions of V3＋ and VO2＋ had opposite tendencies to oxidation of VO2＋ and the reduction of VO2＋ in the area of low treatment po- tentials. In the former, the kinetics increased and in the latter, they decreased. In addition, causes were investigated using confocal microscopy and XPS. No correlation was found to the roughness or size of the stretched surfaces, although these changed significantly as a result of the treatment. XPS measure- ments gave indications of a dependence on hydroxyl groups for the oxidation of VO2＋ and the reduction of VO2＋, while for the reactions of oxygen-free cations and the reduction of VO2＋ weak indications of a dependence on carboxyl groups were obtained.展开更多
Artificial catalytic synthesis of ammonia has become a hot research frontier in recent years.It is regarded as a promising approach that may replace the Haber-Bosch process and reduce global carbon dioxide emission.Ho...Artificial catalytic synthesis of ammonia has become a hot research frontier in recent years.It is regarded as a promising approach that may replace the Haber-Bosch process and reduce global carbon dioxide emission.However,it is extremely difficult for the cleavage of nitrogen molecules under ambient conditions.Thus the ammonia yield rate is still low and the study is still limited in lab scale.If nitrites or nitrates are used as nitrogen sources,rather than nitrogen gas,the catalytic efficiency can be significantly improved,and the residual nitrate and nitrite contaminations in water systems can be efficiently eliminated and converted to energy sources at the same time.It is an emerging alternative for artificial ammonia synthesis,while there is not enough focus on the reduction of nitrate and nitrite.Herein,we systematically compared the differences between the reduction of nitrogen and nitrates,as well as listed the challenges in this area.The total conversion rate and energy efficiency of catalytic nitrate reduction are much higher than nitrogen gas reduction due to the much higher solubility and better converting pathway,which might be further enhanced by employing catalysts improvement strategies.Further,we also proposed suitable materials as well as a few future researches needs that may help boost the development of artificial ammonia synthesis using nitrate.展开更多
The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited o...The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited on Pt/C from Bi3＋ containing acidic solution from 0 to 90% coverage degree. The stability of the Bi layer in acid and alkaline corresponded to previous studies and started to dissolve at 0.7 V and 0.8 V versus re- versible hydrogen electrode （RIIE）, respectively. However, in neutral phosphate buffer the layer showed remarkable stability to at least 1.2V versus RHE. Bi modification at low （20%） and high （80%） coverage showed the highest increase in the activity of Pt/C toward GOR by a factor up to 7 due to the increased poisoning resistance of the modified catalyst. The effect of poisoning was especially reduced at high Bi coverage （80%）, which shows that adsorbate blocked by Bi through the third-body effect is effective. Finally, with or without Bi modification GOR on PtIC was most active in alkaline conditions.展开更多
We report here the activated carbon and cobalt hexacyanoferrate composite,which is applied as the electrode materials in symmetric supercapacitors containing a 1.0 M Na_(2)SO_(4) aqueous electrolyte.This novel materia...We report here the activated carbon and cobalt hexacyanoferrate composite,which is applied as the electrode materials in symmetric supercapacitors containing a 1.0 M Na_(2)SO_(4) aqueous electrolyte.This novel material combines high specific surface area and electrochemical stability of activated carbon with the redox properties of cobalt hexacyanoferrate,resulting in maximum specific capacitance of 329 F g^(-1) with large voltage working window of 2.0 V.Electrochemical studies indicated that cobalt hexacyanoferrate introduces important pseudocapacitive properties accounting for the overall charge-storage process,especially when I<0.5 A g^(-1).At lower gravimetric currents(e.g.,0.05 A g^(-1))and up to 1.0 V,the presence of cobalt hexacyanoferrate improves the specific energy for more than 300%.In addition,to better understanding the energy storage process we also provided a careful investigation of the electrode materials under dynamic polarization conditions using the in situ Raman spectroscopy and synchrotron light Xray diffraction techniques.Interesting complementary findings were obtained in these studies.We believe that this novel electrode material is promising for applications regarding the energy-storage process in pseudocapacitors with long lifespan properties.展开更多
We discuss here essential aspects of the experimental supercapacitors characterization by a series of well-known electrochemical methods.We are motivated by a considerable number of publications that misreport procedu...We discuss here essential aspects of the experimental supercapacitors characterization by a series of well-known electrochemical methods.We are motivated by a considerable number of publications that misreport procedures and results.Authors often conceal or neglect essential information about the electrochemical analytical apparatus used and its configuration.The lack of such information may lead researchers,especially inexperienced ones,to misunderstand the procedures and results.Eventually,the misled electrochemical equipment configuration favors misinterpretation of data and low reproducibility rates.This paper aims to highlight these issues and clarify them.We explain fundamental concepts of some electrochemical analytical methods,such as cyclic voltammetry,galvanostatic charge-discharge,single potential step chronoamperometry,and electrochemical impedance spectroscopy,focusing on the supercapacitor field.Distinct configurations of electrical parameters are presented and discussed to highlight the effects of incorrect setup and uncover misleading results.We discuss how the electrochemical setup and data analyses matter in reliable data results for the supercapacitor.展开更多
Compressing supercapacitor(SCs)electrode is essential for improving the energy storage characteristics and minimizing ions’distance travel,faradaic reactions,and overall ohmic resistance.Studies comprising the ion dy...Compressing supercapacitor(SCs)electrode is essential for improving the energy storage characteristics and minimizing ions’distance travel,faradaic reactions,and overall ohmic resistance.Studies comprising the ion dynamics in SC electrodes under compression are still rare.So,the ionic dynamics of five aqueous electrolytes in electrodes under compression were studied in this work for tracking electrochemical and structural changes under mechanical stress.A superionic state is formed when the electrode is compressed until the micropores match the dimensions with the electrolyte’s hydrated ion sizes,which increases the capacitance.If excessive compression is applied,the accessible pore regions decrease,and the capacitance drops.Hence,as the studied hydrated ions have different dimensions,the match between ion/pore sizes differs.To the LiOH and NaClO4electrolytes,increasing the pressure from 60 to 120 and 100 PSI raised the capacitance from 13.5 to 35.2 F g^(-1)and 30.9 to 39.0 F g^(-1),respectively.So,the KOH electrolyte with the lowest and LiCl with the biggest combination of hydrated ion size have their point of maximum capacitance(39.5 and 36.7F g^(-1))achieved at 140 and 80 PSI,respectively.To LiCl and KCl electrolytes,overcompression causes a drop in capacitance higher than 23%.展开更多
Cuprous chloride hydrochloric acid solutions were electrolysed in a two compartments cell without agitation for copper extraction. It is found that the current density affects the colour and the size of copper deposit...Cuprous chloride hydrochloric acid solutions were electrolysed in a two compartments cell without agitation for copper extraction. It is found that the current density affects the colour and the size of copper deposits. During electrodeposition of copper from cuprous solution in the presence of various concentrations of lead, zinc or iron ions at different current densities, it is observed that lead is codeposited with copper by increasing current density.In all experiments, the current efficiency for the copper deposition reaction fluctuates between 88.50% and 95.50%.展开更多
The paper presents the influence of relative electrode-electrolyte movement over productivity for silver ions recovery by electrodeposition from diluted solutions. Wasted photographic fixing agent solution in various ...The paper presents the influence of relative electrode-electrolyte movement over productivity for silver ions recovery by electrodeposition from diluted solutions. Wasted photographic fixing agent solution in various concentrations was used. For each concentration three regimes were studied： stationary, electrode rotation with 100 rpm and electrode rotation with 300 rpm. Polarization curves were drawn and working conditions from silver recovery point of view were discussed.展开更多
Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their o...Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.展开更多
Nanocomposites exhibiting high electric conductivity and high saturation magnetization were synthesized in bulk using a solvent-thermal route, which combined the hybridization growth of Fe3O4 nanoparticles, graphene o...Nanocomposites exhibiting high electric conductivity and high saturation magnetization were synthesized in bulk using a solvent-thermal route, which combined the hybridization growth of Fe3O4 nanoparticles, graphene oxide, and a conductive oligomer in one step. The hybrid spheres with diameters of 100–300 nm(mostly approximately 200 nm) consisted of a homogenous phase without obvious interfaces between the ternary components. The electric conductivity of the hybrid material was greatly improved after heat treatment at high temperature. Because of the interfacial polarization and good separation property due to its magnetism properties, the interpenetrating nature of the materials yielded good synergistic effects on the electromagnetic wave absorbing properties. The multi-frequency reflection band covering the C band and Ku band with a maximum reflection loss of-45 d B for a thickness of 5 mm is promising for lightweight and strong electromagnetic attenuation applications.展开更多
Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multi-electron(>2e–)products provides a green and sustainable route for producing fuels and chemicals.Introducing the second metal element is a feasible strategy fo...Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multi-electron(>2e–)products provides a green and sustainable route for producing fuels and chemicals.Introducing the second metal element is a feasible strategy for"managing"the key intermediate on Cu-based materials to further improve the CO_(2)RR catalytic performance.In this work,palladium,which promises the generation of CO,was introduced into the poly(ionic liquid)-based copper hybrid(Cu@PIL)to construct a novel Cu-Pd bimetallic electrocatalyst(Cu@PIL@Pd).Remarkably,with a small dosage of palladium(2.0 mol%compared with Cu),a high faradaic efficiency(FE)for C_(2+)products(68.7%)was achieved at–1.01 V(with respect to the reversible hydrogen electrode(RHE),the same below)with a high partial current density of 178.3 mA cm^(-2).Meanwhile,high selectivity towards CH4(FE=42.5%)and corresponding partial current density of 172.8 mA cm^(-2)were obtained on the same catalyst at–1.24 V,signifying a significant potential-dependent selectivity.Mechanistic studies reveal that both copper and palladium oxides are reduced to metallic states during the CO_(2)RR.The presence of the adjoint copper phase and the highly dispersed electrostatic layer promote the generation of CO on the palladium components(both the PdO_(2)phase and the Pd(II)site).Besides,the local CO^(*)was enriched by the significant diffusion resistance of CO in the PIL layer.The spillover of CO^(*)from Pd sites to the adjoint Cu sites,accompanied by the increased local concentration of CO^(*)around Cu sites,accounted for the observed good CO_(2)RR catalytic performance,especially the high C_(2+)product selectivity.展开更多
Predicting and monitoring battery life early and across chemistries is a significant challenge due to the plethora of degradation paths,form factors,and electrochemical testing protocols.Existing models typically tran...Predicting and monitoring battery life early and across chemistries is a significant challenge due to the plethora of degradation paths,form factors,and electrochemical testing protocols.Existing models typically translate poorly across different electrode,electrolyte,and additive materials,mostly require a fixed number of cycles,and are limited to a single discharge protocol.Here,an attention-based recurrent algorithm for neural analysis(ARCANA)architecture is developed and trained on an ultralarge,proprietary dataset from BASF and a large Li-ion dataset gathered from literature across the globe.ARCANA generalizes well across this diverse set of chemistries,electrolyte formulations,battery designs,and cycling protocols and thus allows for an extraction of data-driven knowledge of the degradation mechanisms.The model’s adaptability is further demonstrated through fine-tuning on Na-ion batteries.ARCANA advances the frontier of large-scale time series models in analytical chemistry beyond textual data and holds the potential to significantly accelerate discovery-oriented battery research endeavors.展开更多
基金the financial support from the Brazilian funding agencies CNPq(310544/2019-0),FAPESP(2014/02163-7&2017/11958-1)FAPEMIG(Financial support for the LMMA/UFVJM Laboratory)and CNPq(PQ-2 grant:Process 301095/2018-3)the support from Shell and the strategic importance of the support given by ANP(Brazil’s National Oil,Natural Gas,and Biofuels Agency)through the R&D levy regulation。
文摘Supercapacitors(SCs) are high-power energy storage devices with ultra-fast charge/discharge properties.SCs using concentrated aqueous-based electrolytes can work at low temperatures due to their intrinsic properties, such as higher freezing point depression(FPD) and robustness. Besides the traditional organic-and aqueous-based(salt-in-water) electrolytes used in SCs, water-in-salt(WISE) sodium perchlorate electrolytes offer high FPD, non-flammability, and low-toxicity conditions, allowing the fabrication of safer, environmentally friendly, and more robust devices. For the first time, this work reports a comprehensive study regarding WISE system’s charge-storage capabilities and physicochemical properties under low-temperature conditions(T < 0 ℃) using mesoporous carbon-based electrodes. The effect of temperature reduction on the electrolyte viscosity and electrical properties was investigated using different techniques and the in-situ(or operando) Raman spectroscopy under dynamic polarization conditions.The cell voltage, equivalent series resistance, and specific capacitance were investigated as a function of the temperature. The cell voltage(U) increased ~ 50%, while the specific capacitance decreased ~20%when the temperature was reduced from 25 ℃ to -10 ℃. As a result, the maximum specific energy(E = CU^(2)/2) increased ~ 100%. Therefore, low-temperature WISEs are promising candidates to improve the energy-storage characteristics in SCs.
基金support from National Science Foundation of China(No.22075012).
文摘A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.
文摘The chemical analysis of a complex sulphide concentrate by emission spectrometry and X-ray diffraction shows that it contains essentially copper, lead, zinc and iron in the form of chalcopyrite, sphalerite and galena. A small amount of pyrite is also present in the ore but does not be detected with X-ray diffraction. The cupric chloride leaching of the sulphide concentrate at various durations and solid/liquid ratios at 100 ℃ shows that the rate of dissolution of the ore is the fastest in the first several hours, and after 12 h it does not evolve significantly. If oxygen is excluded from the aqueous cupric chloride solution during the leaching experiment at 100 ℃, the pyrite in the ore will not be leached. The determination of principal dissolved metals in the leaching liquor by flame atomic absorption spectrometry, and the chemical analysis of solid residues by emission spectrometry and X-ray diffraction allow to conclude that the rate of dissolution of the minerals contained in the complex sulphide concentrate are in the order of galena >sphalerite>chalcopyrite.
基金the German Federal Ministry of Education and Research (BMBF) for funding the project under the number 01DR17027
文摘Through targeted and reproducible electrochemical treatment of glassy carbon electrodes, investigations have been carried out on the electrochemical behaviour of the oxidation of V2＋, VO2＋ and the reductions of VO2＋, VO2＋ and V3＋ in order to pretreat electrodes specifically for use in vanadium redox flow batter- ies and, if possible, to treat them in situ. For this purpose, a glassy carbon electrode was treated poten- tiostatically for a period of 30 s at different potentials in the range of 500 mV-2000 mV vs. Hg/Hg_2SO_4 in 2 M H_2SO_4 and then linear sweep voltammograms were performed in the different vanadium-containing solutions. With this method, it could be shown that all reactions are extremely surface sensitive and the reaction speeds changed by several decades. The reaction rates increased significantly in all reac- tions compared to polished electrodes and had an optimum treatment potential of approx. 1600 mV vs. Hg/Hg_2SO_4, although the oxidation reaction of V2＋ and the reduction reactions of V3＋ and VO2＋ had opposite tendencies to oxidation of VO2＋ and the reduction of VO2＋ in the area of low treatment po- tentials. In the former, the kinetics increased and in the latter, they decreased. In addition, causes were investigated using confocal microscopy and XPS. No correlation was found to the roughness or size of the stretched surfaces, although these changed significantly as a result of the treatment. XPS measure- ments gave indications of a dependence on hydroxyl groups for the oxidation of VO2＋ and the reduction of VO2＋, while for the reactions of oxygen-free cations and the reduction of VO2＋ weak indications of a dependence on carboxyl groups were obtained.
基金the Australian Research Council(ARC)Future Fellowship(No.FT160100195)the Polish National Agency for Academic Exchange(Narodowa Agencja Wymiany Akademickiej(NAWA))Project(No.POWR.03.03.00-00-PN13/18)Beijing NBET Technology Co.,Ltd.
文摘Artificial catalytic synthesis of ammonia has become a hot research frontier in recent years.It is regarded as a promising approach that may replace the Haber-Bosch process and reduce global carbon dioxide emission.However,it is extremely difficult for the cleavage of nitrogen molecules under ambient conditions.Thus the ammonia yield rate is still low and the study is still limited in lab scale.If nitrites or nitrates are used as nitrogen sources,rather than nitrogen gas,the catalytic efficiency can be significantly improved,and the residual nitrate and nitrite contaminations in water systems can be efficiently eliminated and converted to energy sources at the same time.It is an emerging alternative for artificial ammonia synthesis,while there is not enough focus on the reduction of nitrate and nitrite.Herein,we systematically compared the differences between the reduction of nitrogen and nitrates,as well as listed the challenges in this area.The total conversion rate and energy efficiency of catalytic nitrate reduction are much higher than nitrogen gas reduction due to the much higher solubility and better converting pathway,which might be further enhanced by employing catalysts improvement strategies.Further,we also proposed suitable materials as well as a few future researches needs that may help boost the development of artificial ammonia synthesis using nitrate.
基金Jane and Aatos Erkko FoundationJenny and Antti Wihuri Foundation for funding
文摘The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited on Pt/C from Bi3＋ containing acidic solution from 0 to 90% coverage degree. The stability of the Bi layer in acid and alkaline corresponded to previous studies and started to dissolve at 0.7 V and 0.8 V versus re- versible hydrogen electrode （RIIE）, respectively. However, in neutral phosphate buffer the layer showed remarkable stability to at least 1.2V versus RHE. Bi modification at low （20%） and high （80%） coverage showed the highest increase in the activity of Pt/C toward GOR by a factor up to 7 due to the increased poisoning resistance of the modified catalyst. The effect of poisoning was especially reduced at high Bi coverage （80%）, which shows that adsorbate blocked by Bi through the third-body effect is effective. Finally, with or without Bi modification GOR on PtIC was most active in alkaline conditions.
基金the financial support from the Brazilian funding agencies CNPq(301486/2016-6)FAPESP(2014/02163-7,2017/11958-1,2018/20756-6)+2 种基金FAPEMIG(Financial support for the LMMA/UFVJM Laboratory)CNPq(PQ-2 grant:Process 301095/2018-3)the support from Shell and the strategic importance of the support given by ANP(Brazil’s National Oil,Natural Gas and Biofuels Agency)through the R&D levy regulation。
文摘We report here the activated carbon and cobalt hexacyanoferrate composite,which is applied as the electrode materials in symmetric supercapacitors containing a 1.0 M Na_(2)SO_(4) aqueous electrolyte.This novel material combines high specific surface area and electrochemical stability of activated carbon with the redox properties of cobalt hexacyanoferrate,resulting in maximum specific capacitance of 329 F g^(-1) with large voltage working window of 2.0 V.Electrochemical studies indicated that cobalt hexacyanoferrate introduces important pseudocapacitive properties accounting for the overall charge-storage process,especially when I<0.5 A g^(-1).At lower gravimetric currents(e.g.,0.05 A g^(-1))and up to 1.0 V,the presence of cobalt hexacyanoferrate improves the specific energy for more than 300%.In addition,to better understanding the energy storage process we also provided a careful investigation of the electrode materials under dynamic polarization conditions using the in situ Raman spectroscopy and synchrotron light Xray diffraction techniques.Interesting complementary findings were obtained in these studies.We believe that this novel electrode material is promising for applications regarding the energy-storage process in pseudocapacitors with long lifespan properties.
基金the financial support from the Brazilian funding agencies CNPq(310544/2019-0)FAPESP(2014/02163-7,2017/11958-1&2016/08645-9)+2 种基金FAPEMIG(Financial support for the LMMA/UFVJM Laboratory)CNPq(PQ-2 grant:Process 301095/2018-3)the support from Shell。
文摘We discuss here essential aspects of the experimental supercapacitors characterization by a series of well-known electrochemical methods.We are motivated by a considerable number of publications that misreport procedures and results.Authors often conceal or neglect essential information about the electrochemical analytical apparatus used and its configuration.The lack of such information may lead researchers,especially inexperienced ones,to misunderstand the procedures and results.Eventually,the misled electrochemical equipment configuration favors misinterpretation of data and low reproducibility rates.This paper aims to highlight these issues and clarify them.We explain fundamental concepts of some electrochemical analytical methods,such as cyclic voltammetry,galvanostatic charge-discharge,single potential step chronoamperometry,and electrochemical impedance spectroscopy,focusing on the supercapacitor field.Distinct configurations of electrical parameters are presented and discussed to highlight the effects of incorrect setup and uncover misleading results.We discuss how the electrochemical setup and data analyses matter in reliable data results for the supercapacitor.
基金the financial support from the Brazilian funding agencies CNPq(301486/2016-6)FAPESP(2014/02163-7,2017/11958-1,2018/20756-6)the support from Shell。
文摘Compressing supercapacitor(SCs)electrode is essential for improving the energy storage characteristics and minimizing ions’distance travel,faradaic reactions,and overall ohmic resistance.Studies comprising the ion dynamics in SC electrodes under compression are still rare.So,the ionic dynamics of five aqueous electrolytes in electrodes under compression were studied in this work for tracking electrochemical and structural changes under mechanical stress.A superionic state is formed when the electrode is compressed until the micropores match the dimensions with the electrolyte’s hydrated ion sizes,which increases the capacitance.If excessive compression is applied,the accessible pore regions decrease,and the capacitance drops.Hence,as the studied hydrated ions have different dimensions,the match between ion/pore sizes differs.To the LiOH and NaClO4electrolytes,increasing the pressure from 60 to 120 and 100 PSI raised the capacitance from 13.5 to 35.2 F g^(-1)and 30.9 to 39.0 F g^(-1),respectively.So,the KOH electrolyte with the lowest and LiCl with the biggest combination of hydrated ion size have their point of maximum capacitance(39.5 and 36.7F g^(-1))achieved at 140 and 80 PSI,respectively.To LiCl and KCl electrolytes,overcompression causes a drop in capacitance higher than 23%.
文摘Cuprous chloride hydrochloric acid solutions were electrolysed in a two compartments cell without agitation for copper extraction. It is found that the current density affects the colour and the size of copper deposits. During electrodeposition of copper from cuprous solution in the presence of various concentrations of lead, zinc or iron ions at different current densities, it is observed that lead is codeposited with copper by increasing current density.In all experiments, the current efficiency for the copper deposition reaction fluctuates between 88.50% and 95.50%.
文摘The paper presents the influence of relative electrode-electrolyte movement over productivity for silver ions recovery by electrodeposition from diluted solutions. Wasted photographic fixing agent solution in various concentrations was used. For each concentration three regimes were studied： stationary, electrode rotation with 100 rpm and electrode rotation with 300 rpm. Polarization curves were drawn and working conditions from silver recovery point of view were discussed.
基金the financial support from the Brazilian funding agencies CNPq(301486/2016-6)FAEPEX(2426/17)+7 种基金FAPESP(2020/04431-0,2020/04281-8,2016/25082-8,2017/11986-5,2017/11958-1,2014/02163-7,2018/20756-6,2018/02713-8)CAPES(1740195)the financial support from CNPq(Processes 131234/2020-0 and 130741/2021-3)the Fundação ao AmparoàPesquisa do Estado de Minas Gerais(FAPEMIGCNPq for the PQ-2 grant(Process 310544/20190)the support of Shell,the strategic importance of the support given by Brazil’s National Oil,Natural Gas,and Biofuels Agency(ANP)through the R&D levy regulationthe Center for Innovation on New Energies(CINE)the LNLS/CNPEM。
文摘Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.
基金supported by the Fundamental Research Funds for the Central Universities, UESTC (ZYGX2013J034)
文摘Nanocomposites exhibiting high electric conductivity and high saturation magnetization were synthesized in bulk using a solvent-thermal route, which combined the hybridization growth of Fe3O4 nanoparticles, graphene oxide, and a conductive oligomer in one step. The hybrid spheres with diameters of 100–300 nm(mostly approximately 200 nm) consisted of a homogenous phase without obvious interfaces between the ternary components. The electric conductivity of the hybrid material was greatly improved after heat treatment at high temperature. Because of the interfacial polarization and good separation property due to its magnetism properties, the interpenetrating nature of the materials yielded good synergistic effects on the electromagnetic wave absorbing properties. The multi-frequency reflection band covering the C band and Ku band with a maximum reflection loss of-45 d B for a thickness of 5 mm is promising for lightweight and strong electromagnetic attenuation applications.
基金Key Research Program of Frontier Sciences,CAS(ZDBS-LY-JSC022)Excellent Young Scientists Fund(22022815)+1 种基金National Natural Science Foundation of China(U1704251 and 21776291)Zhengzhou High Level Talent Certificate(20180200052)is gratefully acknowledged.
文摘Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multi-electron(>2e–)products provides a green and sustainable route for producing fuels and chemicals.Introducing the second metal element is a feasible strategy for"managing"the key intermediate on Cu-based materials to further improve the CO_(2)RR catalytic performance.In this work,palladium,which promises the generation of CO,was introduced into the poly(ionic liquid)-based copper hybrid(Cu@PIL)to construct a novel Cu-Pd bimetallic electrocatalyst(Cu@PIL@Pd).Remarkably,with a small dosage of palladium(2.0 mol%compared with Cu),a high faradaic efficiency(FE)for C_(2+)products(68.7%)was achieved at–1.01 V(with respect to the reversible hydrogen electrode(RHE),the same below)with a high partial current density of 178.3 mA cm^(-2).Meanwhile,high selectivity towards CH4(FE=42.5%)and corresponding partial current density of 172.8 mA cm^(-2)were obtained on the same catalyst at–1.24 V,signifying a significant potential-dependent selectivity.Mechanistic studies reveal that both copper and palladium oxides are reduced to metallic states during the CO_(2)RR.The presence of the adjoint copper phase and the highly dispersed electrostatic layer promote the generation of CO on the palladium components(both the PdO_(2)phase and the Pd(II)site).Besides,the local CO^(*)was enriched by the significant diffusion resistance of CO in the PIL layer.The spillover of CO^(*)from Pd sites to the adjoint Cu sites,accompanied by the increased local concentration of CO^(*)around Cu sites,accounted for the observed good CO_(2)RR catalytic performance,especially the high C_(2+)product selectivity.
基金This work contributes to the research performed at CELEST(Center for Electrochemical Energy Storage Ulm-Karlsruhe)and was partly funded by the German Research Foundation(DFG)under Project ID 390874152(POLiS Cluster of Excellence)This project also received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No.957189(BIG-MAP)+1 种基金funded by the European Union’s Horizon 2020 research and innovation program under Grant Agreement No.957213HSS acknowledges funding from the German Research Foundation(DFG)under Project ID 390776260(eConversion Cluster of Excellence).
文摘Predicting and monitoring battery life early and across chemistries is a significant challenge due to the plethora of degradation paths,form factors,and electrochemical testing protocols.Existing models typically translate poorly across different electrode,electrolyte,and additive materials,mostly require a fixed number of cycles,and are limited to a single discharge protocol.Here,an attention-based recurrent algorithm for neural analysis(ARCANA)architecture is developed and trained on an ultralarge,proprietary dataset from BASF and a large Li-ion dataset gathered from literature across the globe.ARCANA generalizes well across this diverse set of chemistries,electrolyte formulations,battery designs,and cycling protocols and thus allows for an extraction of data-driven knowledge of the degradation mechanisms.The model’s adaptability is further demonstrated through fine-tuning on Na-ion batteries.ARCANA advances the frontier of large-scale time series models in analytical chemistry beyond textual data and holds the potential to significantly accelerate discovery-oriented battery research endeavors.
