Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundame...Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundamental understanding on how they control the electrochemical performances.Herein,by harnessing the electrostatic adsorption of one-dimensional nanofiller(i.e.,surface-charged halloysite nanotubes,d-HNTs),we successfully fabricate a high-performance polymer nanocomposite electrolyte enabled by strong surface adsorption,referred as adsorption-state polymer electrolyte(ASPE).This ASPE shows fast ion transport(0.71±0.05 mS cm^(-1)at room temperature),high mechanical strength and toughness(10.3±0.05 MPa;15.73 MJ m^(-3)),improved lithium-ion transference number,and long cycle life with lithium metal anode,in comparison with the sample without the d-HNT adsorption effect.To fundamentally understand these high performances,an anion-rich asymmetric solvent structure model is further proposed and evidenced by both experiments and simulation studies.Results show that the electrostatic adsorption among the d-HNT,ionic liquid electrolyte,and polymer chain generates a nano filler-supported fast ion-conduction pathway with asymmetric Li+-coordination microenvironment.Meanwhile,the anion-rich asymmetric solvent structure model of ASPE also generates a fast de-solvation and anion-derived stable solid-electrolyte interphase for lithium metal anode.The high performance and understanding of the mechanism for ASPE provide a promising path to develop advanced polymer electrolytes.展开更多
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional l...All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.展开更多
<div style="text-align:justify;"> Rainfall infiltration is a porous medium flow problem with variable saturation. Based on the theoretical analysis of the flow field, electrical conductivity of rocks, ...<div style="text-align:justify;"> Rainfall infiltration is a porous medium flow problem with variable saturation. Based on the theoretical analysis of the flow field, electrical conductivity of rocks, the electrical field, the paper simulates the coupling relationship between the water saturation in soil and the apparent resistivity distribution. It combines the Richards equation, the Archie formula and the Laplace equation. The experiment simulates the potential field data by the Wenner setting in electrical exploration on a two-layer geologic model with continuous rainfall during 5 days, which shows that the effective saturation in soil is increasing with the rainfall time, while the apparent resistivity is decreasing. This can provide a theoretical basis for the analyzing the rainfall infiltration and porosity of the soil by using high-density electrical method in the future. </div>展开更多
The selective oxidation of hydrocarbons can be used to produce oxygen-containing functional compounds such as alcohols, aldehydes or ketones and its efficient and green conversion lies in the development of efficient ...The selective oxidation of hydrocarbons can be used to produce oxygen-containing functional compounds such as alcohols, aldehydes or ketones and its efficient and green conversion lies in the development of efficient catalysts that activate C-H bonds and O_(2) simultaneously. In this work, the bimetallic organic framework (CoMnBDC) material with morphology of stacked nanosheets was synthesized using terephthalic acid as ligands to coordinate with Co^(2+) and Mn^(2+) cations under solvothermal conditions. As revealed by spectroscopic characterizations, the electron transfer from Mn to Co in the CoMnBDC resulted in the reduction of the Co average oxidation state and increase of the Mn average oxidation state. The CoMnBDC nanosheets were used as catalyst in catalytic oxidation of ethylbenzene, in which the redox effect promotes the effective electron transfer, the activation of O_(2) and benzyl C-H bond. The 96.2% conversion of ethylbenzene and 98.0% selectivity towards acetophenone could be obtained with oxygen as sole oxidant and solvent-free condition. The excellent catalytic performance is related to the structure of CoMnBDC and is also the best when compared with reported results. Various types of aromatic hydrocarbons containing benzyl C-H bonds can be effectively oxidized by CoMnBDC to produce corresponding ketone products. The density functional theory (DFT) calculation revealed that the redox effect leads to the relative enrichment of electrons on Co in CoMnBDC, which is conducive to the activation of O_(2);Mn with higher oxidation state is beneficial for the adsorption of ethylbenzene and activation of C-H bonds. The CoMnBDC has a lower energy barrier for transition state, making it easier for the ethylbenzene oxidation to produce acetophenone.展开更多
Silkworm silk and spider silk have been attracting numerous interests.Rapid solvation of silkworm silk protein and spider silk protein without hydrolysis of peptide bonds is highly desirable.Microwave irradiation has ...Silkworm silk and spider silk have been attracting numerous interests.Rapid solvation of silkworm silk protein and spider silk protein without hydrolysis of peptide bonds is highly desirable.Microwave irradiation has been proposed for facile extraction of water-soluble silk protein by various liquid media.However,microwave exposure can cause hydrolysis of peptide bonds,leading to irreversible degradation of silk protein.In this study,a series of representative dipeptides and a rationally designed recombinant protein derived from silk protein is employed to investigate the efect of microwave on the stability of the peptide bonds during a long time dissolution process,i.e.,heating at 60℃in a CaCl_(2):CH_(3)CH_(2)OH:H_(2)O(1:2:8)solution.Results demonstrate that microwave irradiation imposes a minor damage and a negligible cleavage of the peptide bonds,compared with the conventional heating method.The microwave irradiation treatment suggested in this is suitable for dissolution of silk protein.It is anticipated that this approach can be developed to a commercial level commercially.展开更多
Several process parameters affect product reliability.Traditional reliability improvement methods primarily focus on maximizing product lifetime,often overlooking the variation in product lifetime.Manufacturers,howeve...Several process parameters affect product reliability.Traditional reliability improvement methods primarily focus on maximizing product lifetime,often overlooking the variation in product lifetime.Manufacturers,however,aim to produce products with minimal variations in their performance.Robust parameter design offers an effective strategy to help manufacturers enhance product reliability while reducing process variations.In practice,reliability experiments frequently involve constrained randomization due to the selection of specific experimental protocols.This study proposes a framework to achieve robust product reliability under a constrained randomization experiment.To consider random effects,we develop a Bayesian method-based Weibull non-linear mixed model for the lifetime response.Important factors are identified according to Bayesian posterior credible intervals.Subsequently,we propose an integrated multi-objective optimization model to determine the optimal factor levels.This model simultaneously considers minimizing the total costs of the manufacturer,maximizing the product lifetime,and minimizing the lifetime variance.An industrial thermostat experiment is conducted to validate the proposed method.Compared to existing approaches,the proposed method demonstrates superior performance in reducing variance and total cost,particularly for long warranty periods.Finally,we discuss the practical implications of the optimal solutions for manufacturers,finding that variations remain tolerable within a certain range.展开更多
A damage identification system of carbon fiber reinforced plastics （CFRP） structures is investigated using fiber Bragg grating （FBG） sensors and back propagation （BP） neural network. FBG sensors are applied to c...A damage identification system of carbon fiber reinforced plastics （CFRP） structures is investigated using fiber Bragg grating （FBG） sensors and back propagation （BP） neural network. FBG sensors are applied to construct the sensing network to detect the structural dynamic response signals generated by active actuation. The damage identification model is built based on the BP neural network. The dynamic signal characteristics extracted by the Fourier transform are the inputs, and the damage states are the outputs of the model. Besides, damages are simulated by placing lumped masses with different weights instead of inducing real damages, which is confirmed to be feasible by finite element analysis （FEA）. At last, the damage identification system is verified on a CFRP plate with 300mm × 300mm experimental area, with the accurate identification of varied damage states. The system provides a practical way for CFRP structural damage identification.展开更多
Selective hydrogenation of the carbonyl bond inα,β-unsaturated carbonyl compounds is rather challenging owing to the more feasible hydrogenation of ethylenic bond from both thermodynamic and kinetic aspects.Here,we ...Selective hydrogenation of the carbonyl bond inα,β-unsaturated carbonyl compounds is rather challenging owing to the more feasible hydrogenation of ethylenic bond from both thermodynamic and kinetic aspects.Here,we demonstrate a facile emulsionbased molecule-nanoparticle self-assembly strategy for the atomic engineering of Ir species on three-dimensional CeO_(2)spheres(Ir1@CeO_(2)).When applied to the hydrogenation ofα,β-unsaturated aldehydes,Ir1@CeO_(2)catalyst remarkably exhibited~100%selectivity towards unsaturated alcohols,whereas the formation of Ir nanoparticles on CeO_(2)drastically decreased the selectivity for unsaturated alcohols.Spectroscopic studies revealed that strong metal-support interactions triggered the charge transfer from Ir to CeO_(2),leading to the partial reduction of Ce^(4+)to Ce^(3+)along with the formation new Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces.The electrophilic atomic Ir species at the Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces would therefore preferentially adsorb and facilitate hydrogenation of polar C=O bond to achieve exceptional selectivity.展开更多
Nickel-iron sulfide has shown attractive activity in electrocatalytic oxygen evolution reaction(OER).However,the effects of low valence sulfur(S^(2−))and metal species on OER in binary nickel-iron sulfide have rarely ...Nickel-iron sulfide has shown attractive activity in electrocatalytic oxygen evolution reaction(OER).However,the effects of low valence sulfur(S^(2−))and metal species on OER in binary nickel-iron sulfide have rarely been systematically studied.Works based on post-catalysis characterization have led to the assumption that the real active species are nickel-iron oxyhydroxide,and that nickel-iron sulfide acts only as a precatalyst.Therefore,to study the role of S,Ni,and Fe for the development of nickel-iron sulfide catalyst is of self-evident importance.Herein,a facile solvothermal method is used to synthesize acetylene black coated with nickel-iron sulfide nanosheets.Electrochemical tests show that the presence of low valence S species makes the catalyst have faster OER kinetics,larger active area,and intermediate active species adsorption area.Therefore,the present study reveals the enhancing effect of low valence sulfur species(S^(2−))on OER in binary nickel-iron sulfide.In situ Raman spectroscopy shows that the generation ofγ-NiOOH intermediate is essential and Fe does not directly participate in the oxygen production.Density functional theory(DFT)calculation shows that Ni-OH deprotonation is a rate-determining step for both binary nickel-iron sulfide and nickel sulfide.The addition of Fe into NiSx lightly increases the charge transfer of Ni atom to O atom,which makes deprotonation easier and thereby improves the OER performance.展开更多
基金financial support from the National Natural Science Foundation of China(52203123)the Sichuan Science and Technology Program(2023NSFSC0991)+2 种基金the State Key Laboratory of Polymer Materials Engineering(sklpme 2023-1-05 and sklpme 2024-2-04)the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundamental understanding on how they control the electrochemical performances.Herein,by harnessing the electrostatic adsorption of one-dimensional nanofiller(i.e.,surface-charged halloysite nanotubes,d-HNTs),we successfully fabricate a high-performance polymer nanocomposite electrolyte enabled by strong surface adsorption,referred as adsorption-state polymer electrolyte(ASPE).This ASPE shows fast ion transport(0.71±0.05 mS cm^(-1)at room temperature),high mechanical strength and toughness(10.3±0.05 MPa;15.73 MJ m^(-3)),improved lithium-ion transference number,and long cycle life with lithium metal anode,in comparison with the sample without the d-HNT adsorption effect.To fundamentally understand these high performances,an anion-rich asymmetric solvent structure model is further proposed and evidenced by both experiments and simulation studies.Results show that the electrostatic adsorption among the d-HNT,ionic liquid electrolyte,and polymer chain generates a nano filler-supported fast ion-conduction pathway with asymmetric Li+-coordination microenvironment.Meanwhile,the anion-rich asymmetric solvent structure model of ASPE also generates a fast de-solvation and anion-derived stable solid-electrolyte interphase for lithium metal anode.The high performance and understanding of the mechanism for ASPE provide a promising path to develop advanced polymer electrolytes.
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金National Natural Science Foundation of China (52203123)Sichuan Science and Technology Program (2023NSFSC0991)+2 种基金State Key Laboratory of Polymer Materials Engineering (sklpme-2023-1-05 and sklpme-2024-2-04)Fundamental Research Funds for the Central UniversitiesThis research was also partially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.
文摘<div style="text-align:justify;"> Rainfall infiltration is a porous medium flow problem with variable saturation. Based on the theoretical analysis of the flow field, electrical conductivity of rocks, the electrical field, the paper simulates the coupling relationship between the water saturation in soil and the apparent resistivity distribution. It combines the Richards equation, the Archie formula and the Laplace equation. The experiment simulates the potential field data by the Wenner setting in electrical exploration on a two-layer geologic model with continuous rainfall during 5 days, which shows that the effective saturation in soil is increasing with the rainfall time, while the apparent resistivity is decreasing. This can provide a theoretical basis for the analyzing the rainfall infiltration and porosity of the soil by using high-density electrical method in the future. </div>
基金supported by the Key Research and Development Project of Anhui Province(No.2022a05020048)the Open Project of Anhui Provincial Key Laboratory for Degradation and Monitoring of Pollution of the Environment(No.FSKFKT007D)+2 种基金the State Key Laboratory of Heavy Oil Processing(No.SKLHOP202202007)the Excellent Youth Research Project in Universities of Anhui Province(No.2023AH030050)the University Collaborative Innovation Project of Anhui Province(No.GXXT-2023-034).
文摘The selective oxidation of hydrocarbons can be used to produce oxygen-containing functional compounds such as alcohols, aldehydes or ketones and its efficient and green conversion lies in the development of efficient catalysts that activate C-H bonds and O_(2) simultaneously. In this work, the bimetallic organic framework (CoMnBDC) material with morphology of stacked nanosheets was synthesized using terephthalic acid as ligands to coordinate with Co^(2+) and Mn^(2+) cations under solvothermal conditions. As revealed by spectroscopic characterizations, the electron transfer from Mn to Co in the CoMnBDC resulted in the reduction of the Co average oxidation state and increase of the Mn average oxidation state. The CoMnBDC nanosheets were used as catalyst in catalytic oxidation of ethylbenzene, in which the redox effect promotes the effective electron transfer, the activation of O_(2) and benzyl C-H bond. The 96.2% conversion of ethylbenzene and 98.0% selectivity towards acetophenone could be obtained with oxygen as sole oxidant and solvent-free condition. The excellent catalytic performance is related to the structure of CoMnBDC and is also the best when compared with reported results. Various types of aromatic hydrocarbons containing benzyl C-H bonds can be effectively oxidized by CoMnBDC to produce corresponding ketone products. The density functional theory (DFT) calculation revealed that the redox effect leads to the relative enrichment of electrons on Co in CoMnBDC, which is conducive to the activation of O_(2);Mn with higher oxidation state is beneficial for the adsorption of ethylbenzene and activation of C-H bonds. The CoMnBDC has a lower energy barrier for transition state, making it easier for the ethylbenzene oxidation to produce acetophenone.
基金This work was supported by the National Natural Science Foundation of China[grant number:21972009]the National Key Research Program of China[grant number:2016YFA0201700/2016YFA0201701].
文摘Silkworm silk and spider silk have been attracting numerous interests.Rapid solvation of silkworm silk protein and spider silk protein without hydrolysis of peptide bonds is highly desirable.Microwave irradiation has been proposed for facile extraction of water-soluble silk protein by various liquid media.However,microwave exposure can cause hydrolysis of peptide bonds,leading to irreversible degradation of silk protein.In this study,a series of representative dipeptides and a rationally designed recombinant protein derived from silk protein is employed to investigate the efect of microwave on the stability of the peptide bonds during a long time dissolution process,i.e.,heating at 60℃in a CaCl_(2):CH_(3)CH_(2)OH:H_(2)O(1:2:8)solution.Results demonstrate that microwave irradiation imposes a minor damage and a negligible cleavage of the peptide bonds,compared with the conventional heating method.The microwave irradiation treatment suggested in this is suitable for dissolution of silk protein.It is anticipated that this approach can be developed to a commercial level commercially.
基金supported by the National Natural Science Foundation of China[grants numbers:72002066,71871204,72471172,and 71902138]。
文摘Several process parameters affect product reliability.Traditional reliability improvement methods primarily focus on maximizing product lifetime,often overlooking the variation in product lifetime.Manufacturers,however,aim to produce products with minimal variations in their performance.Robust parameter design offers an effective strategy to help manufacturers enhance product reliability while reducing process variations.In practice,reliability experiments frequently involve constrained randomization due to the selection of specific experimental protocols.This study proposes a framework to achieve robust product reliability under a constrained randomization experiment.To consider random effects,we develop a Bayesian method-based Weibull non-linear mixed model for the lifetime response.Important factors are identified according to Bayesian posterior credible intervals.Subsequently,we propose an integrated multi-objective optimization model to determine the optimal factor levels.This model simultaneously considers minimizing the total costs of the manufacturer,maximizing the product lifetime,and minimizing the lifetime variance.An industrial thermostat experiment is conducted to validate the proposed method.Compared to existing approaches,the proposed method demonstrates superior performance in reducing variance and total cost,particularly for long warranty periods.Finally,we discuss the practical implications of the optimal solutions for manufacturers,finding that variations remain tolerable within a certain range.
基金This work was supported by the National Natural Science Foundation of China under Grant Nos. 41472260 and 51373090, the Natural ScienceFoundation of Shandong Province, China under Grant Nos. 2014ZRE27372 and ZR2017BF007, the Fundamental research funds of Shandong University, China under Grant No. 2016JC012, and the Young Scholars Program of Shandong University under Grant No. 2016WLJH30.
文摘A damage identification system of carbon fiber reinforced plastics （CFRP） structures is investigated using fiber Bragg grating （FBG） sensors and back propagation （BP） neural network. FBG sensors are applied to construct the sensing network to detect the structural dynamic response signals generated by active actuation. The damage identification model is built based on the BP neural network. The dynamic signal characteristics extracted by the Fourier transform are the inputs, and the damage states are the outputs of the model. Besides, damages are simulated by placing lumped masses with different weights instead of inducing real damages, which is confirmed to be feasible by finite element analysis （FEA）. At last, the damage identification system is verified on a CFRP plate with 300mm × 300mm experimental area, with the accurate identification of varied damage states. The system provides a practical way for CFRP structural damage identification.
基金the National Natural Science Foundation of China(No.21901007)the Natural Science Foundation of Anhui Province(No.2008085QB83)+1 种基金the Science and Technology Development Fund(FDCT)of Macao SAR(No.0032/2021/ITP)the University of Macao(No.MYRG2020-00026-FST)。
文摘Selective hydrogenation of the carbonyl bond inα,β-unsaturated carbonyl compounds is rather challenging owing to the more feasible hydrogenation of ethylenic bond from both thermodynamic and kinetic aspects.Here,we demonstrate a facile emulsionbased molecule-nanoparticle self-assembly strategy for the atomic engineering of Ir species on three-dimensional CeO_(2)spheres(Ir1@CeO_(2)).When applied to the hydrogenation ofα,β-unsaturated aldehydes,Ir1@CeO_(2)catalyst remarkably exhibited~100%selectivity towards unsaturated alcohols,whereas the formation of Ir nanoparticles on CeO_(2)drastically decreased the selectivity for unsaturated alcohols.Spectroscopic studies revealed that strong metal-support interactions triggered the charge transfer from Ir to CeO_(2),leading to the partial reduction of Ce^(4+)to Ce^(3+)along with the formation new Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces.The electrophilic atomic Ir species at the Ir^(δ+)-O_(2)--Ce^(3+)(OV)interfaces would therefore preferentially adsorb and facilitate hydrogenation of polar C=O bond to achieve exceptional selectivity.
基金the National Natural Science Foundation of China(No.21901007)the Natural Science Foundation of Anhui Province(No.2008085QB83).
文摘Nickel-iron sulfide has shown attractive activity in electrocatalytic oxygen evolution reaction(OER).However,the effects of low valence sulfur(S^(2−))and metal species on OER in binary nickel-iron sulfide have rarely been systematically studied.Works based on post-catalysis characterization have led to the assumption that the real active species are nickel-iron oxyhydroxide,and that nickel-iron sulfide acts only as a precatalyst.Therefore,to study the role of S,Ni,and Fe for the development of nickel-iron sulfide catalyst is of self-evident importance.Herein,a facile solvothermal method is used to synthesize acetylene black coated with nickel-iron sulfide nanosheets.Electrochemical tests show that the presence of low valence S species makes the catalyst have faster OER kinetics,larger active area,and intermediate active species adsorption area.Therefore,the present study reveals the enhancing effect of low valence sulfur species(S^(2−))on OER in binary nickel-iron sulfide.In situ Raman spectroscopy shows that the generation ofγ-NiOOH intermediate is essential and Fe does not directly participate in the oxygen production.Density functional theory(DFT)calculation shows that Ni-OH deprotonation is a rate-determining step for both binary nickel-iron sulfide and nickel sulfide.The addition of Fe into NiSx lightly increases the charge transfer of Ni atom to O atom,which makes deprotonation easier and thereby improves the OER performance.
