PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula...PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula for Pr BSCF is AA'B_(2)O_(5+δ), with Pr(A-site) and Ba/Sr(A'-site) alternately stacked along the c-axis. Due to these structural features, the bulk oxygen ion diffusivity is significantly enhanced through the disorder-free channels in the PrO layer;thus, the A site cations(lanthanide ions) play a pivotal role in determining the overall electrochemical properties of layered perovskites. Consequently, previous research has predominantly focused on the electrical properties and oxygen bulk/surface kinetics of Ln cation effects,whereas the hydration properties for PCFC systems remain unidentified. Here, we thoroughly examined the proton uptake behavior and thermodynamic parameters for the hydration reaction to conclusively determine the changes in the electrochemical performances depending on LnBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(LnBSCF,Ln=Pr, Nd, and Gd) cathodes. At 500 ℃, the quantitative proton concentration of PrBSCF was 2.04 mol% and progressively decreased as the Ln cation size decreased. Similarly, the Gibbs free energy indicated that less energy was required for the formation of protonic defects in the order of Pr BSCF < Nd BSCF < Gd BSCF. To elucidate the close relationship between hydration properties and electrochemical performances in LnBSCF cathodes, PCFC single cell measurements and analysis of the distribution of relaxation time were further investigated.展开更多
Platinum-based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present,but an in-depth understanding of the relationship between their short-range structural information and ...Platinum-based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present,but an in-depth understanding of the relationship between their short-range structural information and catalytic performance is still lacking.Herein,we present a synthetic strategy that uses transition-metal oxide-assisted thermal diffusion.PtCo/C catalysts with localized tetragonal distortion were obtained by controlling the thermal diffusion process of transition-metal elements.This localized structural distortion induced a significant strain effect on the nanoparticle surface,which further shortened the length of the Pt-Pt bond,improved the electronic state of the Pt surface,and enhanced the performance of the catalyst.PtCo/C catalysts with special short-range structures achieved excellent mass activity(2.27 Amg_(Pt)^(-1))and specific activity(3.34 A cm^(-2)).In addition,the localized tetragonal distortion-induced surface compression of the Pt skin improved the stability of the catalyst.The mass activity decreased by only 13%after 30,000 cycles.Enhanced catalyst activity and excellent durability have also been demonstrated in the proton exchange membrane fuel cell configuration.This study provides valuable insights into the development of advanced Pt-based nanocatalysts and paves the way for reducing noble-metal loading and increasing the catalytic activity and catalyst stability.展开更多
A novel polybenzimidazole(PBI)-based trilayer membrane assembly is developed for application in vanadium redox flow battery(VRFB).The membrane comprises a 1μm thin cross-linked poly[2,2′-(p-oxydiphenylene)−5,5′-bib...A novel polybenzimidazole(PBI)-based trilayer membrane assembly is developed for application in vanadium redox flow battery(VRFB).The membrane comprises a 1μm thin cross-linked poly[2,2′-(p-oxydiphenylene)−5,5′-bibenzimidazole](OPBI)sandwiched between two 20μm thick porous OPBI membranes(p-OPBI)without further lamination steps.The trilayer membrane demonstrates exceptional properties,such as high conductivity and low area-specific resistance(ASR)of 51 mS cm−1 and 81mΩcm^(2),respectively.Contact with vanadium electrolyte increases the ASR of trilayer membrane only to 158mΩcm^(2),while that of Nafion is 193mΩcm^(2).VO^(2+)permeability is 2.73×10^(-9) cm^(2) min^(−1),about 150 times lower than that of Nafion NR212.In addition,the membrane has high mechanical strength and high chemical stability against VO^(2+).In VRFB,the combination of low resistance and low vanadium permeability results in excellent performance,revealing high Coulombic efficiency(>99%),high energy efficiency(EE;90.8%at current density of 80mA cm^(−2)),and long-term durability.The EE is one of the best reported to date.展开更多
In this perspective article,the synthesis and thermodynamic properties of aqueous solutions of formate salts(FS,HCO2-)are described in relationship to the concept of H2carriers.The physiochemical properties of solid F...In this perspective article,the synthesis and thermodynamic properties of aqueous solutions of formate salts(FS,HCO2-)are described in relationship to the concept of H2carriers.The physiochemical properties of solid FS,aqueous formate solutions,and aqueous bicarbonate solutions set the limitations for storage capacity,deliverable capacity,and usable H2capacity of these H2carriers,respectively.These parameters will help in the design of systems that use H2carriers for storage and transport of H2for fuel cell power applications.FS,as well as admixtures with formic acid(FA,H2CO2),have potential to address the goals outlined in the U.S.Department of Energy’s H2@scale initiative to store in chemical bonds a significant quantity of energy(hundreds of megawatts)obtained from large scale renewable resources.展开更多
The amalgamation of artificial intelligence(AI)with various areas has been in the picture for the past few years.AI has enhanced the functioning of several services,such as accomplishing better budgets,automating mult...The amalgamation of artificial intelligence(AI)with various areas has been in the picture for the past few years.AI has enhanced the functioning of several services,such as accomplishing better budgets,automating multiple tasks,and data-driven decision-making.Conducting hassle-free polling has been one of them.However,at the onset of the coronavirus in 2020,almost all worldly affairs occurred online,and many sectors switched to digital mode.This allows attackers to find security loopholes in digital systems and exploit them for their lucrative business.This paper proposes a three-layered deep learning(DL)-based authentication framework to develop a secure online polling system.It provides a novel way to overcome security breaches during the face identity(ID)recognition and verification process for online polling systems.This verification is done by training a pixel-2-pixel Pix2pix generative adversarial network(GAN)for face image reconstruction to remove facial objects present(if any).Furthermore,image-to-image matching is done by implementing the Siamese network and comparing the result of various metrics executed on feature embeddings to obtain the outcome,thus checking the electorate credentials.展开更多
Scaled-up industrial water electrolysis equipment that can be used with abundant seawater is key for affordable hydrogen production.The search for highly stable,dynamic,and economical electrocatalysts could have a sig...Scaled-up industrial water electrolysis equipment that can be used with abundant seawater is key for affordable hydrogen production.The search for highly stable,dynamic,and economical electrocatalysts could have a significant impact on hydrogen commercialization.Herein,we prepared energy-efficient,scalable,and engineering electronic structure modulated Mn-Ni bimetal oxides(Mn_(0.25)Ni_(0.75)O)through simple hydrothermal followed by calcination method.As-optimized Mn_(0.25)Ni_(0.75)O displayed enhanced oxygen and hydrogen evolution reaction(OER and HER)performance with overpotentials of 266 and115 mV at current densities of 10 mA cm^(-2)in alkaline KOH added seawater electrolyte solution.Additionally,Mn-Ni oxide catalytic benefits were attributed to the calculated electronic configurations and Gibbs free energy for OER,and HER values were estimated using first principles calculations.In real-time practical application,we mimicked industrial operating conditions with modified seawater electrolysis using Mn_(0.25)Ni_(0.75)O‖Mn_(0.25)Ni_(0.75)O under various temperature conditions,which performs superior to the commercial IrO_(2)‖Pt-C couple.These findings demonstrate an inexpensive and facile technique for feasible large-scale hydrogen production.展开更多
When designing a cell stack and developing an operational strategy for proton exchange membrane fuel cell,it is critical to characterize the local current,water and heat.To measure distributions of current density,rel...When designing a cell stack and developing an operational strategy for proton exchange membrane fuel cell,it is critical to characterize the local current,water and heat.To measure distributions of current density,relative humidity and temperature for both anode and cathode simultaneously along the straight parallel flow channels,this paper uses a segmented tool based on the multilayered printed circuit board flow field plates with embedded sensors.In this study,two kinds of experimental operations of fuel cell reactants are carried out for comparison:the co-flow operation with identical gas flow direction of hydrogen and air and the counter-flow operation with opposite gas flow directions.The detected relative humidity(RH)distributions of both anode and cathode indicate that the asymmetry of RH distribution at two sides of the membrane in counter-flow operation is better at holding water inside the fuel cell compared with the co-flow operation.The in situ measured performance distributions show that segments around the middle of the fuel cell contribute the highest current in counter-flow operation,while for co-flow operation,the current peak locates near the outlet of reactants.展开更多
It is demonstrated experimentally and confirmed theoretically that highly defective boron nitride showed outstanding performance for oxidative dehydrogenation of ethylbenzene.The catalyst is derived from carbon-doped ...It is demonstrated experimentally and confirmed theoretically that highly defective boron nitride showed outstanding performance for oxidative dehydrogenation of ethylbenzene.The catalyst is derived from carbon-doped hexagonal boron nitride nanosheets synthesized via a two-step reaction when participating the oxidative dehydrogenation reaction.The first step yields a polymeric precursor with the atomic positions of B,C,N relatively constrained,which is conducive for the formation of carbon atomic clusters uniformly dispersed throughout the BN framework.During the oxidative dehydrogenation of ethylbenzene to styrene,the nanoscale carbon clusters are removed and highly defective boron nitride(D-BN)is obtained,exposing boron-rich zigzag edges of BN that act as the catalytic sites.The catalytic performance of D-BN is therefore remarkably better than un-doped h-BN.Our results indicate that dispersed C-doping in h-BN is highly effective in terms of defect formation and resultant enhanced activity in oxidative dehydrogenation reactions.展开更多
Hydrogen storage in Liquid Organic Hydrogen Carrier(LOHC)systems is appealing for the safe storage and distribution of excess renewable energy via existing gasoline infrastructures to end-users.We present the eutectic...Hydrogen storage in Liquid Organic Hydrogen Carrier(LOHC)systems is appealing for the safe storage and distribution of excess renewable energy via existing gasoline infrastructures to end-users.We present the eutectic mixture of biphenyl and diphenyl ether of its first use as a LOHC material.The material is hydrogenated with 99%selectivity without the cleavage of C–O bond,with commercial heterogeneous catalysts,which is confirmed by nuclear magnetic spectroscopy and gas chromatography-mass spectrometry.Equilibrium concentration,dehydrogenation enthalpy,and thermo-neutral temperature are calculated using a density functional theory.The results indicate that O-atom-containing material exhibits more favorable dehydrogenation thermodynamics than that of the hydrocarbon analogue.The H2-rich material contains6.8 wt%of gravimetric hydrogen storage capacity.A preliminary study of catalytic dehydrogenation on a continuous reactor is presented to demonstrate a reversibility of this material.展开更多
Prolonged hydrothermal treatment for sulfonated poly(ether ether ketone) membranes induces mechanical degradation and developing hydrophilic-hydrophobic phase separation, simultaneously. The enhanced phase separation ...Prolonged hydrothermal treatment for sulfonated poly(ether ether ketone) membranes induces mechanical degradation and developing hydrophilic-hydrophobic phase separation, simultaneously. The enhanced phase separation provides incremental proton conductivity to the membranes, whereas mechanical degradation drastically reduces device stability. On this basis, we describe here the effects of two different ex situ aging processes on sulfonated poly(ether ether ketone) membranes: hydrationdehydration cycling and prolonged hydrothermal treatment. Both aged membranes exhibited enhanced phase separation under the hydrated conditions, as characterized by small angle X-ray scattering.However, when the aged membranes were dried again, the nanostructure of the membranes aged via the hydration-dehydration cycling was recoverable, whereas that of the membranes aged via prolonged hydrothermal treatment was irreversible. Furthermore, the two differently aged membranes showed clear differences in thermal, mechanical, and electrochemical properties. Finally, we implemented both aged membranes in fuel cell application. The sample aged via hydration-dehydration cycling maintained its improved cell performance, whereas the sample aged via hydrothermal treatment showed drastically reduced cell performance after durability test for 50 h.展开更多
The present study has been conducted to contribute,once and for all,filling the lack of structural information for the whole class of rare earth(RE)carbonates owning the tengerite-(Y)structure.A complete structural ch...The present study has been conducted to contribute,once and for all,filling the lack of structural information for the whole class of rare earth(RE)carbonates owning the tengerite-(Y)structure.A complete structural characterization,carried out by Rietveld refinement of X-ray powder diffraction(XRD)data,was comparatively performed for the first time on several hydrated RE carbonates,having the general chemical formula RE_(2)(CO_(3))_(3)·χH_(2)O,RE=Y,Gd,Tb,Dy,Ho and Er.All samples share the same space group and lattice parameters similar to tengerite-(Y);the structures are also closely related,consisting in all cases of a three-dimensional framework of nine-fold coordinated RE atom polyhedral,linked together by carbonate ions.In addition to relatively minor changes in fractional coordinates of atom sites and corresponding interatomic distances,the only perceivable difference lies in the lattice parameters affected by the ionic radius of RE^(3+).However,in the case of Er,which has the lowest cationic radius among the analyzed RE,the stabilization of tengerite structure is at its limit condition,because the carbonate groups are heavily distorted.Furthermore,FT-IR and Raman spectra confirm the main structural features obtained by Rietveld refinements.The observed morphology of the various samples is almost the same,being characterized by the presence of bidimensional rod-like particles grouped in agglomerates,typical of tengerite crystals,thus indicating that the crystallization mechanism occurring during the hydrothermal synthesis is the same,irrespective of the involved RE cation.展开更多
Solid oxide fuel cells(SOFCs)can directly convert renewable biogas into electricity with high efficiency at high temperature,however the long-term stability of SOFCs is significantly affected by the carbon deposition ...Solid oxide fuel cells(SOFCs)can directly convert renewable biogas into electricity with high efficiency at high temperature,however the long-term stability of SOFCs is significantly affected by the carbon deposition on the anode during cell operation.Herein,we report a novel carbon removal approach by high temperature infrared light driven photocatalytic oxidation.Upon the comparison of electrochemical performance of Ni-YSZ anode and TiO_(2)modified Ni-YSZ anode in the state-of-the-art single cell(Ni-YSZ/YSZ/LSCM),the modified anodes exhibit markedly improved peak powder density with simulated biogas fuel(70%CH_(4)+30%CO_(2))at 850℃with less coking after 40 h operation.The high activity and carbon deposition resistance of the modified anode is possibly attributed to the in situ generated hydroxyl radical from the reduced TiO_(x)powder under high temperature infrared light excitation,which is supported by detailed analysis of microstructural information of anodes and the powder-based thermo-photocatalytic experiments.展开更多
基金supported by the National Research Foundation (NRF) grant funded by the Korea government (NRF2022R1C1C1007619, NRF-2021M3H4A1A01002921, NRF2021M3I3A1084292)supported by the KIST Institutional Program (Project No. 2E32592-23-069)。
文摘PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula for Pr BSCF is AA'B_(2)O_(5+δ), with Pr(A-site) and Ba/Sr(A'-site) alternately stacked along the c-axis. Due to these structural features, the bulk oxygen ion diffusivity is significantly enhanced through the disorder-free channels in the PrO layer;thus, the A site cations(lanthanide ions) play a pivotal role in determining the overall electrochemical properties of layered perovskites. Consequently, previous research has predominantly focused on the electrical properties and oxygen bulk/surface kinetics of Ln cation effects,whereas the hydration properties for PCFC systems remain unidentified. Here, we thoroughly examined the proton uptake behavior and thermodynamic parameters for the hydration reaction to conclusively determine the changes in the electrochemical performances depending on LnBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(LnBSCF,Ln=Pr, Nd, and Gd) cathodes. At 500 ℃, the quantitative proton concentration of PrBSCF was 2.04 mol% and progressively decreased as the Ln cation size decreased. Similarly, the Gibbs free energy indicated that less energy was required for the formation of protonic defects in the order of Pr BSCF < Nd BSCF < Gd BSCF. To elucidate the close relationship between hydration properties and electrochemical performances in LnBSCF cathodes, PCFC single cell measurements and analysis of the distribution of relaxation time were further investigated.
基金supported by the National Natural Science Foundation of China (Grant No.22278123).
文摘Platinum-based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present,but an in-depth understanding of the relationship between their short-range structural information and catalytic performance is still lacking.Herein,we present a synthetic strategy that uses transition-metal oxide-assisted thermal diffusion.PtCo/C catalysts with localized tetragonal distortion were obtained by controlling the thermal diffusion process of transition-metal elements.This localized structural distortion induced a significant strain effect on the nanoparticle surface,which further shortened the length of the Pt-Pt bond,improved the electronic state of the Pt surface,and enhanced the performance of the catalyst.PtCo/C catalysts with special short-range structures achieved excellent mass activity(2.27 Amg_(Pt)^(-1))and specific activity(3.34 A cm^(-2)).In addition,the localized tetragonal distortion-induced surface compression of the Pt skin improved the stability of the catalyst.The mass activity decreased by only 13%after 30,000 cycles.Enhanced catalyst activity and excellent durability have also been demonstrated in the proton exchange membrane fuel cell configuration.This study provides valuable insights into the development of advanced Pt-based nanocatalysts and paves the way for reducing noble-metal loading and increasing the catalytic activity and catalyst stability.
基金supported by KIST (2E31871 and 2E32591)and Innovation Fund Denmark Denmark (DANFLOW—project#9090-00059)Korea Institute for Advancement of Technology (KIAT)through the International Cooperative R&D program (Project No.P0018437)Basic Science Research Program through the National Research Foundation of Korea (NRF)funded by the Ministry of Education (2021R1A6A1A03039981).
文摘A novel polybenzimidazole(PBI)-based trilayer membrane assembly is developed for application in vanadium redox flow battery(VRFB).The membrane comprises a 1μm thin cross-linked poly[2,2′-(p-oxydiphenylene)−5,5′-bibenzimidazole](OPBI)sandwiched between two 20μm thick porous OPBI membranes(p-OPBI)without further lamination steps.The trilayer membrane demonstrates exceptional properties,such as high conductivity and low area-specific resistance(ASR)of 51 mS cm−1 and 81mΩcm^(2),respectively.Contact with vanadium electrolyte increases the ASR of trilayer membrane only to 158mΩcm^(2),while that of Nafion is 193mΩcm^(2).VO^(2+)permeability is 2.73×10^(-9) cm^(2) min^(−1),about 150 times lower than that of Nafion NR212.In addition,the membrane has high mechanical strength and high chemical stability against VO^(2+).In VRFB,the combination of low resistance and low vanadium permeability results in excellent performance,revealing high Coulombic efficiency(>99%),high energy efficiency(EE;90.8%at current density of 80mA cm^(−2)),and long-term durability.The EE is one of the best reported to date.
基金support from the Hydrogen Materials-Advanced Research Consortium(HyMARC)supported by the National Research Foundation(NRF)of Korea grant funded by the Ministry of Science and ICT(2015M1A2A2074688)KIST institutional program funded by the Korea Institute of Science and Technology(2E29610)。
文摘In this perspective article,the synthesis and thermodynamic properties of aqueous solutions of formate salts(FS,HCO2-)are described in relationship to the concept of H2carriers.The physiochemical properties of solid FS,aqueous formate solutions,and aqueous bicarbonate solutions set the limitations for storage capacity,deliverable capacity,and usable H2capacity of these H2carriers,respectively.These parameters will help in the design of systems that use H2carriers for storage and transport of H2for fuel cell power applications.FS,as well as admixtures with formic acid(FA,H2CO2),have potential to address the goals outlined in the U.S.Department of Energy’s H2@scale initiative to store in chemical bonds a significant quantity of energy(hundreds of megawatts)obtained from large scale renewable resources.
基金funded by the Researchers Supporting Project Number(RSP2023R 102)King Saud University,Riyadh,Saudi Arabia.
文摘The amalgamation of artificial intelligence(AI)with various areas has been in the picture for the past few years.AI has enhanced the functioning of several services,such as accomplishing better budgets,automating multiple tasks,and data-driven decision-making.Conducting hassle-free polling has been one of them.However,at the onset of the coronavirus in 2020,almost all worldly affairs occurred online,and many sectors switched to digital mode.This allows attackers to find security loopholes in digital systems and exploit them for their lucrative business.This paper proposes a three-layered deep learning(DL)-based authentication framework to develop a secure online polling system.It provides a novel way to overcome security breaches during the face identity(ID)recognition and verification process for online polling systems.This verification is done by training a pixel-2-pixel Pix2pix generative adversarial network(GAN)for face image reconstruction to remove facial objects present(if any).Furthermore,image-to-image matching is done by implementing the Siamese network and comparing the result of various metrics executed on feature embeddings to obtain the outcome,thus checking the electorate credentials.
基金supported by the GEONJI Research support programsupported by Basic Science Research through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2021R1I1A1A01050905)+1 种基金supported by grants from the Medical Research Center Program(NRF-2017R1A5A2015061)through the National Research Foundation(NRF),which is funded by the Korean government(MSIP)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and Future Planning(NRF-2020R1A2B5B01001458)。
文摘Scaled-up industrial water electrolysis equipment that can be used with abundant seawater is key for affordable hydrogen production.The search for highly stable,dynamic,and economical electrocatalysts could have a significant impact on hydrogen commercialization.Herein,we prepared energy-efficient,scalable,and engineering electronic structure modulated Mn-Ni bimetal oxides(Mn_(0.25)Ni_(0.75)O)through simple hydrothermal followed by calcination method.As-optimized Mn_(0.25)Ni_(0.75)O displayed enhanced oxygen and hydrogen evolution reaction(OER and HER)performance with overpotentials of 266 and115 mV at current densities of 10 mA cm^(-2)in alkaline KOH added seawater electrolyte solution.Additionally,Mn-Ni oxide catalytic benefits were attributed to the calculated electronic configurations and Gibbs free energy for OER,and HER values were estimated using first principles calculations.In real-time practical application,we mimicked industrial operating conditions with modified seawater electrolysis using Mn_(0.25)Ni_(0.75)O‖Mn_(0.25)Ni_(0.75)O under various temperature conditions,which performs superior to the commercial IrO_(2)‖Pt-C couple.These findings demonstrate an inexpensive and facile technique for feasible large-scale hydrogen production.
基金National Key R&D Program of China(No.2018YFB1502500)Science and Technology Program of Sichuan Province(No.2019ZDZX0002 and No.2019YFG0002)Initiative Scientific Research Program of University of Electronic Science and Technology of China(No.ZYGX2018KYQD207 and No.ZYGX2018KYQD206).
文摘When designing a cell stack and developing an operational strategy for proton exchange membrane fuel cell,it is critical to characterize the local current,water and heat.To measure distributions of current density,relative humidity and temperature for both anode and cathode simultaneously along the straight parallel flow channels,this paper uses a segmented tool based on the multilayered printed circuit board flow field plates with embedded sensors.In this study,two kinds of experimental operations of fuel cell reactants are carried out for comparison:the co-flow operation with identical gas flow direction of hydrogen and air and the counter-flow operation with opposite gas flow directions.The detected relative humidity(RH)distributions of both anode and cathode indicate that the asymmetry of RH distribution at two sides of the membrane in counter-flow operation is better at holding water inside the fuel cell compared with the co-flow operation.The in situ measured performance distributions show that segments around the middle of the fuel cell contribute the highest current in counter-flow operation,while for co-flow operation,the current peak locates near the outlet of reactants.
基金support under the Australian Research Council’s Discovery Projects funding scheme(project number DP170101773)support from Alexander von Humboldt Foundation.T.T.+3 种基金financial support from the program of the Ministry of Education,Culture,Sports,Science,and Technology(MEXT,Japan)“Priority Issue on Post-K computer”(Development of new fundamental technologies for high-efficiency energy creation,conversion/storage and use)support from the Ministry of Science and Technology(2016YFA0204100)the National Natural Science Foundation of China(21961160722,91845201,21573254)the Liaoning Revitalization Talents Program XLYC1907055。
文摘It is demonstrated experimentally and confirmed theoretically that highly defective boron nitride showed outstanding performance for oxidative dehydrogenation of ethylbenzene.The catalyst is derived from carbon-doped hexagonal boron nitride nanosheets synthesized via a two-step reaction when participating the oxidative dehydrogenation reaction.The first step yields a polymeric precursor with the atomic positions of B,C,N relatively constrained,which is conducive for the formation of carbon atomic clusters uniformly dispersed throughout the BN framework.During the oxidative dehydrogenation of ethylbenzene to styrene,the nanoscale carbon clusters are removed and highly defective boron nitride(D-BN)is obtained,exposing boron-rich zigzag edges of BN that act as the catalytic sites.The catalytic performance of D-BN is therefore remarkably better than un-doped h-BN.Our results indicate that dispersed C-doping in h-BN is highly effective in terms of defect formation and resultant enhanced activity in oxidative dehydrogenation reactions.
基金supported by the Technology Development Program to Solve Climate Changes of the National Research Foundation(NRF)funded by the Ministry of Science,ICT,and Future Planning(2015M1A2A2074688)KISTI-HPC(KSC-2018-CRE-0022)for computational resourcesthe KIST institutional program funded by the Korea Institute of Science and Technology(2E29610).
文摘Hydrogen storage in Liquid Organic Hydrogen Carrier(LOHC)systems is appealing for the safe storage and distribution of excess renewable energy via existing gasoline infrastructures to end-users.We present the eutectic mixture of biphenyl and diphenyl ether of its first use as a LOHC material.The material is hydrogenated with 99%selectivity without the cleavage of C–O bond,with commercial heterogeneous catalysts,which is confirmed by nuclear magnetic spectroscopy and gas chromatography-mass spectrometry.Equilibrium concentration,dehydrogenation enthalpy,and thermo-neutral temperature are calculated using a density functional theory.The results indicate that O-atom-containing material exhibits more favorable dehydrogenation thermodynamics than that of the hydrocarbon analogue.The H2-rich material contains6.8 wt%of gravimetric hydrogen storage capacity.A preliminary study of catalytic dehydrogenation on a continuous reactor is presented to demonstrate a reversibility of this material.
基金Byoungseok Min of Pohang Accelerator Laboratory for SAXS technical support at 4C beamline.All authors have read the manuscript and agreed to its contents。
文摘Prolonged hydrothermal treatment for sulfonated poly(ether ether ketone) membranes induces mechanical degradation and developing hydrophilic-hydrophobic phase separation, simultaneously. The enhanced phase separation provides incremental proton conductivity to the membranes, whereas mechanical degradation drastically reduces device stability. On this basis, we describe here the effects of two different ex situ aging processes on sulfonated poly(ether ether ketone) membranes: hydrationdehydration cycling and prolonged hydrothermal treatment. Both aged membranes exhibited enhanced phase separation under the hydrated conditions, as characterized by small angle X-ray scattering.However, when the aged membranes were dried again, the nanostructure of the membranes aged via the hydration-dehydration cycling was recoverable, whereas that of the membranes aged via prolonged hydrothermal treatment was irreversible. Furthermore, the two differently aged membranes showed clear differences in thermal, mechanical, and electrochemical properties. Finally, we implemented both aged membranes in fuel cell application. The sample aged via hydration-dehydration cycling maintained its improved cell performance, whereas the sample aged via hydrothermal treatment showed drastically reduced cell performance after durability test for 50 h.
文摘The present study has been conducted to contribute,once and for all,filling the lack of structural information for the whole class of rare earth(RE)carbonates owning the tengerite-(Y)structure.A complete structural characterization,carried out by Rietveld refinement of X-ray powder diffraction(XRD)data,was comparatively performed for the first time on several hydrated RE carbonates,having the general chemical formula RE_(2)(CO_(3))_(3)·χH_(2)O,RE=Y,Gd,Tb,Dy,Ho and Er.All samples share the same space group and lattice parameters similar to tengerite-(Y);the structures are also closely related,consisting in all cases of a three-dimensional framework of nine-fold coordinated RE atom polyhedral,linked together by carbonate ions.In addition to relatively minor changes in fractional coordinates of atom sites and corresponding interatomic distances,the only perceivable difference lies in the lattice parameters affected by the ionic radius of RE^(3+).However,in the case of Er,which has the lowest cationic radius among the analyzed RE,the stabilization of tengerite structure is at its limit condition,because the carbonate groups are heavily distorted.Furthermore,FT-IR and Raman spectra confirm the main structural features obtained by Rietveld refinements.The observed morphology of the various samples is almost the same,being characterized by the presence of bidimensional rod-like particles grouped in agglomerates,typical of tengerite crystals,thus indicating that the crystallization mechanism occurring during the hydrothermal synthesis is the same,irrespective of the involved RE cation.
基金supported by Shenzhen Science and Technology Innovation Commission(No.JCYJ20190813171403664)Basic research program of Guangdong Province(No.2018A030313851)+1 种基金Longgang District Technology Supporting Project(No.LGKCKJPT2019074)the Fundamental Research Funds for the Central Universities(No.HIT.NSRIF.2020074).
文摘Solid oxide fuel cells(SOFCs)can directly convert renewable biogas into electricity with high efficiency at high temperature,however the long-term stability of SOFCs is significantly affected by the carbon deposition on the anode during cell operation.Herein,we report a novel carbon removal approach by high temperature infrared light driven photocatalytic oxidation.Upon the comparison of electrochemical performance of Ni-YSZ anode and TiO_(2)modified Ni-YSZ anode in the state-of-the-art single cell(Ni-YSZ/YSZ/LSCM),the modified anodes exhibit markedly improved peak powder density with simulated biogas fuel(70%CH_(4)+30%CO_(2))at 850℃with less coking after 40 h operation.The high activity and carbon deposition resistance of the modified anode is possibly attributed to the in situ generated hydroxyl radical from the reduced TiO_(x)powder under high temperature infrared light excitation,which is supported by detailed analysis of microstructural information of anodes and the powder-based thermo-photocatalytic experiments.
