In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl gro...In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.展开更多
As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batter...As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs.展开更多
The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)...The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.展开更多
The development of aqueous zinc ion battery cathode materials with high capacity and high magnification is still a challenge.Herein,porous vanadium oxide/carbon(p-VO_(x)@C,mainly VO_(2) with a small amount of V_(2)O_(...The development of aqueous zinc ion battery cathode materials with high capacity and high magnification is still a challenge.Herein,porous vanadium oxide/carbon(p-VO_(x)@C,mainly VO_(2) with a small amount of V_(2)O_(3)) core/shell microspheres with oxygen vacancies are facilely fabricated by using a vanadium-based metal-organic framework(MIL-100(V)) as a sacrificial template.This unique structure can improve the conductivity of the VO_(x),accelerate electrolyte diffusion,and suppress structural collapse during circulation.Subsequently,H_(2)O molecules are introduced into the interlayer of VO_(x) through a highly efficient in-situ electrochemical activation process,facilitating the intercalation and diffusion of zinc ions.After the activation,an optimal sample exhibits a high specific capacity of 464.3 mA h g^(-1) at0.2 A g^(-1) and 395.2 mA h g^(-1) at 10 A g^(-1),indicating excellent rate performance.Moreover,the optimal sample maintains a capacity retention of about 89.3% after 2500 cycles at 10 A g^(-1).Density functional theory calculation demonstrates that the presence of oxygen vacancies and intercalated water molecules can significantly reduce the diffusion barrier for zinc ions.In addition,it is proved that the storage of zinc ions in the cathode is achieved by reversible intercalation/extraction during the charge and discharge process through various ex-situ analysis technologies.This work demonstrates that the p-VO_(x)@C has great potential for applications in aqueous ZIBs after electrochemical activation.展开更多
Electronic waste(e-waste)and diabetes are global challenges to modern societies.However,solving these two challenges together has been challenging until now.Herein,we propose a laser-induced transfer method to fabrica...Electronic waste(e-waste)and diabetes are global challenges to modern societies.However,solving these two challenges together has been challenging until now.Herein,we propose a laser-induced transfer method to fabricate portable glucose sensors by recycling copper from e-waste.We bring up a laser-induced full-automatic fabrication method for synthesizing continuous heterogeneous Cu_(x)O(h-Cu_(x)O)nano-skeletons electrode for glucose sensing,offering rapid(<1 min),clean,air-compatible,and continuous fabrication,applicable to a wide range of Cu-containing substrates.Leveraging this approach,h-Cu_(x)O nanoskeletons,with an inner core predominantly composed of Cu_(2)O with lower oxygen content,juxtaposed with an outer layer rich in amorphous Cu_(x)O(a-Cu_(x)O)with higher oxygen content,are derived from discarded printed circuit boards.When employed in glucose detection,the h-Cu_(x)O nano-skeletons undergo a structural evolution process,transitioning into rigid Cu_(2)O@CuO nano-skeletons prompted by electrochemical activation.This transformation yields exceptional glucose-sensing performance(sensitivity:9.893 mA mM^(-1) cm^(-2);detection limit:0.34μM),outperforming most previously reported glucose sensors.Density functional theory analysis elucidates that the heterogeneous structure facilitates gluconolactone desorption.This glucose detection device has also been downsized to optimize its scalability and portability for convenient integration into people’s everyday lives.展开更多
Biphasic layered oxide cathodes,known for their superior electrochemical performance,are prime candidates for commercializing in Na-ion batteries.Herein,we unveil a series of P3/P2 monophasic and biphasic Al-substitut...Biphasic layered oxide cathodes,known for their superior electrochemical performance,are prime candidates for commercializing in Na-ion batteries.Herein,we unveil a series of P3/P2 monophasic and biphasic Al-substituted Na_(3/4)Mn_(5-x/8)Al_(2x/8)Ni_(3-x/8)O_(2)layered oxide cathodes that lie along the‘zero Mn^(3+)line’in the Na_(3/4)(Mn-Al-Ni)O_(2)pseudo-ternary system.The structural analysis showed a larger Na^(+)conduction bottleneck area in both P3 and P2 structures with a higher Al3+content,which enhanced their rate performance.In each composition,the P3/P2 biphasic compound with nearly equal fractions of P3 and P2 phases outperformed their monophasic counterparts in almost all electrochemical performance parameters.Operando synchrotron XRD measurements obtained for the monophasic P3 and biphasic P2/P3 samples revealed the absence of the O3 phase during cycling.The high structure stability and faster Na^(+)transport kinetics in the biphasic samples underpins the enhancement of electrochemical properties in the Al-substituted P3/P2 cathodes.These results highlight fixed oxidation state lines as a novel tool to identify and design layered oxide cathodes for Na-ion batteries in pseudo-ternary diagrams involving Jahn-Teller active cations.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(...Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.展开更多
Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of ...Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.展开更多
Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface mo...Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.展开更多
The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed...The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.展开更多
Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired ...Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.展开更多
The anodic surface oxidation of natural pyrrhotite in 0.3mol/L KCl and HCl solution (pH 4.0) and0.1mol/L Na2B4O7 solution (pH 9.18) respectively was investigated by using cyclic voltammetry, Tafel plot, and ch...The anodic surface oxidation of natural pyrrhotite in 0.3mol/L KCl and HCl solution (pH 4.0) and0.1mol/L Na2B4O7 solution (pH 9.18) respectively was investigated by using cyclic voltammetry, Tafel plot, and chronoamperometry. In 0.3mol/L KCl and HCl solution (pH 4.0), at potential less than 0.5V(vs SHE), the production of anodic oxidation on pyrrhotite surface can not maintain a stable phase to form a passive film. In 0.1mol/L Na2B4O7 solution (pH 9.18), when the electrode potential increases to more than 0.5V (vs SHE), part of S is oxidized to sulfate, making the passive film somewhat porous, but elemental S and metal oxidates Fe(OH)3 still remain on the electrode surface, and the passive film can not be broken down totally. According to PARCalc Tafel analysis, the corresponding corrosion current density (J0) is 5.34μA/cm2, which is also the exchange current density of the oxidation reaction on pyrrhotite electrode surface in 0.1mol/L Na2B4O7 solution (pH 9.18). The electrochemical dynamics equation of the oxidation was determined.展开更多
Electrochemical oxidation of aniline in aqueous solution was investigated over a novel Ti/TiOxHy/Sb-SnO2 electrode prepared by the electrodeposition method.Scanning electron microscopy,X-ray diffraction,and electroche...Electrochemical oxidation of aniline in aqueous solution was investigated over a novel Ti/TiOxHy/Sb-SnO2 electrode prepared by the electrodeposition method.Scanning electron microscopy,X-ray diffraction,and electrochemical measurements were used to characterize its morphology,crystal structure,and electrochemical properties.Removal of aniline by the Ti/TiOxHy/Sb-SnO2electrode was investigated by ultraviolet-Visible spectroscopy and chemical oxygen demand(COD)analysis under different conditions,including current densities,initial concentrations of aniline,pH values,concentrations of chloride ions,and types of reactor.It was found that a higher current density,a lower initial concentration of aniline,an acidic solution,the presence of chloride ions(0.2wt%NaCl),and a three-dimensional(3D) reactor promoted the removal efficiency of aniline.Electrochemical degradation of aniline followed pseudo-first-order kinetics.The aniline(200 mL of 100mg·L-(-1)) and COD removal efficiencies reached 100%and 73.5%,respectively,at a current density of 20 mA·cm-(-2),pH of 7.0,and supporting electrolyte of 0.5 wt%Na2SO4 after 2 h electrolysis in a 3D reactor.These results show that aniline can be significantly removed on the Ti/TiOxHy/Sb-SnO2electrode,which provides an efficient way for elimination of aniline from aqueous solution.展开更多
Methanol oxidation reaction (MOR) at Pt and Pt electrode surface deposited with various amounts of Ru (denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML) in 0.1 mol/L HClO4+0.5 mol/L MeOH has been ...Methanol oxidation reaction (MOR) at Pt and Pt electrode surface deposited with various amounts of Ru (denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML) in 0.1 mol/L HClO4+0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that (i) CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V (vs. RHE); (ii) at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; (iii) MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; (iv) at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/(site sec). Suggestions for further improving of PtRu catalysts for MOR are provided.展开更多
The treatment of biologically treated wastewater of coffee-curing industry by the electrochemical oxidation using steel anode was investigated. Bench-scale experiments were conducted for activated sludge process on ra...The treatment of biologically treated wastewater of coffee-curing industry by the electrochemical oxidation using steel anode was investigated. Bench-scale experiments were conducted for activated sludge process on raw wastewater and the treated effluents were further treated by electrochemical oxidation method for its colour and organic content removal. The efficiency of the process was determined in terms of removal percentage of COD, BOD and colour during the course of reaction. Several operating parameters like time, pH and current density were examined to ascertain their effects on the treatment efficiency. Steel anode was found to be effective for the COD and colour removal with anode efficiency of 0.118 kgCOD\5h -1\5A -1\5m -2 and energy consumption 20.61 kWh\5kg -1 of COD at pH 9. The decrease in pH from 9 to 3 found to increase the anode efficiency from 0.118 kgCOD\5h -1\5A -1\5m -2 to 0.144 kWh\5kg -1 of COD while decrease the energy consumption from 20.61 kWh\5kg -1 of COD to 12.86 kWh\5kg -1 of COD. The pH of 5 was considered an ideal from the present treatment process as it avoids the addition of chemicals for neutralization of treated effluents and also economical with respect to energy consumption. An empirical relation developed for relationship between applied current density and COD removal efficiency showed strong predictive capability with coefficient of determination of 96.5%.展开更多
基金The authors gratefully acknowledge the financial support of the Natural Science Foundation of China,China(Grant No.21975082 and 21736003)the Guangdong Basic and Applied Basic Research Foundation(Grant Number:2019A1515011472 and 2022A1515011341)the Science and Technology Program of Guangzhou(Grant Number:202102080479).
文摘In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.
基金supports from the National Natural Science Foundation of China(No.21805063)the Natural Science Foundation of Guangdong Province for Distinguished Young Scholars(No.2018B030306022)+2 种基金the Project of International Science and Technology Cooperation in Guangdong Province(No.2020A0505100016)the Shenzhen Sauvage Nobel Laureate Laboratory for Smart Materialsthe Shenzhen Science and Technology Program(Nos.KQTD20200820113045083,ZDSYS20190902093220279)。
文摘As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs.
基金supported by the National Projects of the National Research Foundation(NRF)funded by Republic of Korea(#2022R1F1A1072739 and#2022R1A2C1004392)Prof.Nashrah is also grateful for financial supports by the YU Infra-Project in conjunction with BK21 FOUR National Program(#222A251009)by the Nano-Fab-NRF grant funded by Republic of Korea(#2009-0082580).
文摘The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.
基金supported by the National Natural Science Foundation of China(Nos.92163118,51972234)。
文摘The development of aqueous zinc ion battery cathode materials with high capacity and high magnification is still a challenge.Herein,porous vanadium oxide/carbon(p-VO_(x)@C,mainly VO_(2) with a small amount of V_(2)O_(3)) core/shell microspheres with oxygen vacancies are facilely fabricated by using a vanadium-based metal-organic framework(MIL-100(V)) as a sacrificial template.This unique structure can improve the conductivity of the VO_(x),accelerate electrolyte diffusion,and suppress structural collapse during circulation.Subsequently,H_(2)O molecules are introduced into the interlayer of VO_(x) through a highly efficient in-situ electrochemical activation process,facilitating the intercalation and diffusion of zinc ions.After the activation,an optimal sample exhibits a high specific capacity of 464.3 mA h g^(-1) at0.2 A g^(-1) and 395.2 mA h g^(-1) at 10 A g^(-1),indicating excellent rate performance.Moreover,the optimal sample maintains a capacity retention of about 89.3% after 2500 cycles at 10 A g^(-1).Density functional theory calculation demonstrates that the presence of oxygen vacancies and intercalated water molecules can significantly reduce the diffusion barrier for zinc ions.In addition,it is proved that the storage of zinc ions in the cathode is achieved by reversible intercalation/extraction during the charge and discharge process through various ex-situ analysis technologies.This work demonstrates that the p-VO_(x)@C has great potential for applications in aqueous ZIBs after electrochemical activation.
基金The Key-Area Research and Development Program of Guangdong Province(2022B0111130004)National Natural Science Foundation of China(52272257)Innovation Team of Jiangsu Province(JSSCTD202241)。
基金funded by the Hong Kong Research Grants Council(25201620/C6001-22Y)the Hong Kong Innovation Technology Commission(ITC)under project No.MHP/060/21support of the State Key Laboratory of Advanced Displays and Optoelectronics Technologies at HKUST.
文摘Electronic waste(e-waste)and diabetes are global challenges to modern societies.However,solving these two challenges together has been challenging until now.Herein,we propose a laser-induced transfer method to fabricate portable glucose sensors by recycling copper from e-waste.We bring up a laser-induced full-automatic fabrication method for synthesizing continuous heterogeneous Cu_(x)O(h-Cu_(x)O)nano-skeletons electrode for glucose sensing,offering rapid(<1 min),clean,air-compatible,and continuous fabrication,applicable to a wide range of Cu-containing substrates.Leveraging this approach,h-Cu_(x)O nanoskeletons,with an inner core predominantly composed of Cu_(2)O with lower oxygen content,juxtaposed with an outer layer rich in amorphous Cu_(x)O(a-Cu_(x)O)with higher oxygen content,are derived from discarded printed circuit boards.When employed in glucose detection,the h-Cu_(x)O nano-skeletons undergo a structural evolution process,transitioning into rigid Cu_(2)O@CuO nano-skeletons prompted by electrochemical activation.This transformation yields exceptional glucose-sensing performance(sensitivity:9.893 mA mM^(-1) cm^(-2);detection limit:0.34μM),outperforming most previously reported glucose sensors.Density functional theory analysis elucidates that the heterogeneous structure facilitates gluconolactone desorption.This glucose detection device has also been downsized to optimize its scalability and portability for convenient integration into people’s everyday lives.
基金the Science and Engineering Research Board(SERB),Govt.of India,for the financial support(grant number:CRG/2021/005548).
文摘Biphasic layered oxide cathodes,known for their superior electrochemical performance,are prime candidates for commercializing in Na-ion batteries.Herein,we unveil a series of P3/P2 monophasic and biphasic Al-substituted Na_(3/4)Mn_(5-x/8)Al_(2x/8)Ni_(3-x/8)O_(2)layered oxide cathodes that lie along the‘zero Mn^(3+)line’in the Na_(3/4)(Mn-Al-Ni)O_(2)pseudo-ternary system.The structural analysis showed a larger Na^(+)conduction bottleneck area in both P3 and P2 structures with a higher Al3+content,which enhanced their rate performance.In each composition,the P3/P2 biphasic compound with nearly equal fractions of P3 and P2 phases outperformed their monophasic counterparts in almost all electrochemical performance parameters.Operando synchrotron XRD measurements obtained for the monophasic P3 and biphasic P2/P3 samples revealed the absence of the O3 phase during cycling.The high structure stability and faster Na^(+)transport kinetics in the biphasic samples underpins the enhancement of electrochemical properties in the Al-substituted P3/P2 cathodes.These results highlight fixed oxidation state lines as a novel tool to identify and design layered oxide cathodes for Na-ion batteries in pseudo-ternary diagrams involving Jahn-Teller active cations.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(No.22178197)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.
基金supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(KJQN202200550)the Natural Science Foundation Joint Fund for Innovation and Development of Chongqing Municipal Education Commission(CSTB2022NSCQ-LZX0077)+4 种基金the National Natural Science Foundation of China(No.52100065)the Science and Technology Research Program of Natural Science Foundation of Chongqing(cstc2021ycjh-bgzxm0037)the Science and Technology Research Program of Chongqing Municipal Education Commission(KJZD-M202200503)the Chongqing Innovation Research Group Project(No.CXQT21015)the Doctor Start/Talent Introduction Program of Chongqing Normal University(No.02060404/2020009000321)。
文摘Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.
基金Funded by the Key R&D Program of the Science and Technology Department of Hubei Province(No.2022BCE008)。
文摘Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.
文摘The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.
基金supported by Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(Nos.2019R1A6C1010042 and 2021R1A6C103A427)the financial support from National Research Foundation of Korea(NRF),(2022R1A2C2010686,2022R1A4A3033528,2019H1D3A1A01071209,and 2021R1I1A1A01060380)
文摘Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.
基金Project(50204013) supported by the National Natural Science Foundation of China
文摘The anodic surface oxidation of natural pyrrhotite in 0.3mol/L KCl and HCl solution (pH 4.0) and0.1mol/L Na2B4O7 solution (pH 9.18) respectively was investigated by using cyclic voltammetry, Tafel plot, and chronoamperometry. In 0.3mol/L KCl and HCl solution (pH 4.0), at potential less than 0.5V(vs SHE), the production of anodic oxidation on pyrrhotite surface can not maintain a stable phase to form a passive film. In 0.1mol/L Na2B4O7 solution (pH 9.18), when the electrode potential increases to more than 0.5V (vs SHE), part of S is oxidized to sulfate, making the passive film somewhat porous, but elemental S and metal oxidates Fe(OH)3 still remain on the electrode surface, and the passive film can not be broken down totally. According to PARCalc Tafel analysis, the corresponding corrosion current density (J0) is 5.34μA/cm2, which is also the exchange current density of the oxidation reaction on pyrrhotite electrode surface in 0.1mol/L Na2B4O7 solution (pH 9.18). The electrochemical dynamics equation of the oxidation was determined.
基金supported by the National Natural Science Foundation of China(21507104)the Fundamental Research Funds for the Central Universities of China
文摘Electrochemical oxidation of aniline in aqueous solution was investigated over a novel Ti/TiOxHy/Sb-SnO2 electrode prepared by the electrodeposition method.Scanning electron microscopy,X-ray diffraction,and electrochemical measurements were used to characterize its morphology,crystal structure,and electrochemical properties.Removal of aniline by the Ti/TiOxHy/Sb-SnO2electrode was investigated by ultraviolet-Visible spectroscopy and chemical oxygen demand(COD)analysis under different conditions,including current densities,initial concentrations of aniline,pH values,concentrations of chloride ions,and types of reactor.It was found that a higher current density,a lower initial concentration of aniline,an acidic solution,the presence of chloride ions(0.2wt%NaCl),and a three-dimensional(3D) reactor promoted the removal efficiency of aniline.Electrochemical degradation of aniline followed pseudo-first-order kinetics.The aniline(200 mL of 100mg·L-(-1)) and COD removal efficiencies reached 100%and 73.5%,respectively,at a current density of 20 mA·cm-(-2),pH of 7.0,and supporting electrolyte of 0.5 wt%Na2SO4 after 2 h electrolysis in a 3D reactor.These results show that aniline can be significantly removed on the Ti/TiOxHy/Sb-SnO2electrode,which provides an efficient way for elimination of aniline from aqueous solution.
文摘Methanol oxidation reaction (MOR) at Pt and Pt electrode surface deposited with various amounts of Ru (denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML) in 0.1 mol/L HClO4+0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that (i) CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V (vs. RHE); (ii) at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; (iii) MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; (iv) at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/(site sec). Suggestions for further improving of PtRu catalysts for MOR are provided.
文摘The treatment of biologically treated wastewater of coffee-curing industry by the electrochemical oxidation using steel anode was investigated. Bench-scale experiments were conducted for activated sludge process on raw wastewater and the treated effluents were further treated by electrochemical oxidation method for its colour and organic content removal. The efficiency of the process was determined in terms of removal percentage of COD, BOD and colour during the course of reaction. Several operating parameters like time, pH and current density were examined to ascertain their effects on the treatment efficiency. Steel anode was found to be effective for the COD and colour removal with anode efficiency of 0.118 kgCOD\5h -1\5A -1\5m -2 and energy consumption 20.61 kWh\5kg -1 of COD at pH 9. The decrease in pH from 9 to 3 found to increase the anode efficiency from 0.118 kgCOD\5h -1\5A -1\5m -2 to 0.144 kWh\5kg -1 of COD while decrease the energy consumption from 20.61 kWh\5kg -1 of COD to 12.86 kWh\5kg -1 of COD. The pH of 5 was considered an ideal from the present treatment process as it avoids the addition of chemicals for neutralization of treated effluents and also economical with respect to energy consumption. An empirical relation developed for relationship between applied current density and COD removal efficiency showed strong predictive capability with coefficient of determination of 96.5%.