MXene derivatives are notable two-dimensional nanomaterials with numerous prospective applications in the domains of energy development.MXene derivative,MBene,diversifies its focus on energy storage and harvesting due...MXene derivatives are notable two-dimensional nanomaterials with numerous prospective applications in the domains of energy development.MXene derivative,MBene,diversifies its focus on energy storage and harvesting due to its exceptional electrical conductivity,structural flexibility,and mechanical properties.This comprehensive review describes the sandwich-like structure of the synthesized MBene,derived from its multilayered parent material and its distinct chemical framework to date.The fields of focus encompass the investigation of novel MBenes,the study of phase-changing mechanisms,and the examination of hex-MBenes,ortho-MBenes,tetra-MBenes,tri-MBenes,and MXenes with identical transition metal components.A critical analysis is also provided on the electrochemical mechanism and performance of MBene in energy storage(Li/Na/Mg/Ca/Li–S batteries and supercapacitors),as well as conversion and harvesting(CO_(2) reduction,and nitrogen reduction reactions).The persistent difficulties associated with conducting experimental synthesis and establishing artificial intelligence-based forecasts are extensively deliberated alongside the potential and forthcoming prospects of MBenes.This review provides a single platform for an overview of the MBene’s potential in energy storage and harvesting.展开更多
The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conve...The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.展开更多
To address the challenges of air stability and slurry processability in layered transition metal oxide O_(3)-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)for sodium-ion batteries(SIBs),we have designed an innovative 500℃...To address the challenges of air stability and slurry processability in layered transition metal oxide O_(3)-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)for sodium-ion batteries(SIBs),we have designed an innovative 500℃reheating strategy.This method improves the surface properties of NFM without the need for additional coating layers,making it more efficient and suitable for large-scale applications.Pristine NFM(NFM-P)was first synthesized through a high-temperature solid-state method and then modified using this reheating approach(NFM-HT).This strategy significantly enhances air stability and electrochemical performance,yielding an initial discharge specific capacity of 151.46 mAh/g at 0.1C,with a remarkable capacity retention of 95.04%after 100 cycles at 0.5C.Additionally,a 1.7 Ah NFM‖HC(hard carbon)pouch cell demonstrates excellent long-term cycling stability(94.64%retention after 500 cycles at 1C),superior rate capability(86.48%retention at 9C),and strong low-temperature performance(77%retention at-25℃,continuing power supply at-40℃).Notably,even when overcharged to 8.29 V,the pouch cell remained safe without combustion or explosion.This reheating strategy,which eliminates the need for a coating layer,offers a simpler,more scalable solution for industrial production while maintaining outstanding electrochemical performance.These results pave the way for broader commercial adoption of NFM materials.展开更多
Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are ineffi...Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.展开更多
The rigorous operating condition of proton exchange membrane fuel cells(PEMFCs)poses a substantial hurdle for the long-term stability of Pt-based alloy catalysts;thus,the development of Pt-alloy catalysts with unique ...The rigorous operating condition of proton exchange membrane fuel cells(PEMFCs)poses a substantial hurdle for the long-term stability of Pt-based alloy catalysts;thus,the development of Pt-alloy catalysts with unique morphologies is crucial for enhancing the stability of PEMFCs.In this study,we synthesized a novel PtCu nano-dendrite(PtCuND)catalyst through a facile,one-step solvothermal process.The sub-nanometer particles and nanopores within this catalyst facilitate enhanced mass transport.In PEM single-cell tests,the PtCuND catalyst displays high activity and robust stability,achieving a mass activity of 0.65 A mgPt^(–1).Notably,after accelerated durability tests,the mass activity and the voltage at 0.8 A cm^(–2)of PtCuND exhibits only minimal decreases of 18.5%and 9 mV,respectively.The combined experimental results and theoretical calculations conclusively illustrate the optimized adsorption of oxygen species and the impact of compressive strain on the catalyst surface.The enhanced durability can be attributed to the maintained nano-dendritic morphology and the strengthened interaction within the Pt-Cu bonds.This work not only enhances the stability of PEMFCs but also provides a robust foundation for the future scaling up of catalyst production,paving the way for widespread application in sustainable energy systems.展开更多
CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at desi...CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at design and understanding of catalytic materials and electrolyte systems,the CO_(2) ER performance(such as current density,selectivity,stability,CO_(2) conversion,etc.)has been continually increased.Unfortunately,there has been relatively little attention paid to the large-scale CO 2 electrolyzers,which stand just as one obstacle,alongside series-parallel integration,challenging the practical application of this infant technology.In this review,the latest progress on the structures of low-temperature CO_(2) electrolyzers and scale-up studies was systematically overviewed.The influence of the CO_(2) electrolyzer configurations,such as the flow channel design,gas diffusion electrode(GDE)and ion exchange membrane(IEM),on the CO_(2) ER performance was further discussed.The review could provide inspiration for the design of large-scale CO_(2) electrolyzers so as to accelerate the industrial application of CO_(2) ER technology.展开更多
Ionic liquids(ILs)are an emerging class of media of fundamental importance for chemical engineering,especially due to their interaction with solid surfaces.Here,we explore the growth phenomenon of surface-confined ILs...Ionic liquids(ILs)are an emerging class of media of fundamental importance for chemical engineering,especially due to their interaction with solid surfaces.Here,we explore the growth phenomenon of surface-confined ILs and reveal a peculiar structural transition behavior from order to disorder above a threshold thickness.This behavior can be explained by the variation of interfacial forces with increasing distance from the solid surface.Direct structural observation of different ILs highlights the influence of the ionic structure on the growth process.Notably,the length of the alkyl chain in the cation is found to be a determining factor for the ordering trend.Also,the thermal stability of surface-confined ILs is investigated in depth by controlling annealing treatments.It is found that the ordered monolayer ILs exhibit high robustness against high temperatures.Our findings provide new perspectives on the properties of surface-confined ILs and open up potential avenues for manipulating the structures of nanometer-thick IL films for various applications.展开更多
Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a...Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a mesoporous CeO_(2)single-crystal formed with the regulation of ionic liquids,which catalyzed the effective carbonylation reaction with CO_(2)under mild reaction conditions.By altering the synthetic environment,a series of uniform mesoporous CeO_(2)particles with atomically aligned single-crystal frameworks were constructed,which have different surface physicochemical properties and primary aggregation degree.The prepared mesoporous CeO_(2)single-crystal achieved efficient activation of CO_(2)and alcohols at 0.5 MPa CO_(2)and 100℃,and the CeO_(2)-IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g^(–1)h^(–1),which was 50.6 times as high as that of the CeO_(2)obtained without ionic liquids.Subsequently,the catalytic pathway and mechanism of carbonylation reaction with CO_(2)on mesoporous CeO_(2)single-crystal were studied via React-IR spectra and C18O_(2)labeling experiments.The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials,aiming to develop novel catalytic materials to meet industrial needs.展开更多
Photothermal catalysis significantly enhances the efficiency of photocatalytic CO_(2) reduction,offering a promising strategy for accelerated CO_(2) resource utilization.Herein,a series of Cu_(x)In_(y)S photocatalysts...Photothermal catalysis significantly enhances the efficiency of photocatalytic CO_(2) reduction,offering a promising strategy for accelerated CO_(2) resource utilization.Herein,a series of Cu_(x)In_(y)S photocatalysts were synthesized,exhibiting tunable band gap energy by varying the Cu/In/S atomic ratios for photothermocatalytic CO_(2) conversion to C_(2)H_(4).The typical CuInS_(2) catalyst demonstrates a more negative conduction band,significantly enhancing the electron reduction ability and facilitating the multi-electron reduction of CO_(2) to C_(2)H_(4).Additionally,the abundant sulfur vacancies in CuInS_(2) generate additional active sites,enhance charge separation efficiency,and consequently improve catalytic activity.The generation rate of ethylene reaches 45.7μmol g^(−1) h^(−1) with a selectivity of 79.7%.This study provides a new avenue for producing ethylene in photothermal catalysis,as well as highlighting the superiorities of the CuInS_(2) catalyst.展开更多
The implementation of synthetic polymer membranes in gas separations,ranging from natural gas sweetening,hydrogen separation,helium recovery,carbon capture,oxygen/nitrogen enrichment,etc.,has stimulated the vigorous d...The implementation of synthetic polymer membranes in gas separations,ranging from natural gas sweetening,hydrogen separation,helium recovery,carbon capture,oxygen/nitrogen enrichment,etc.,has stimulated the vigorous development of high-performance membrane materials.However,size-sieving types of synthetic polymer membranes are frequently subject to a trade-off between permeability and selectivity,primarily due to the lack of ability to boost fractional free volume while simultaneously controlling the micropore size distribution.Herein,we review recent research progress on microporosity manipulation in high-free-volume polymeric gas separation membranes and their gas separation performance,with an emphasis on membranes with hourglass-shaped or bimodally distributed microcavities.State-of-the-art strategies to construct tailorable and hierarchically microporous structures,microporosity characterization,and microcavity architecture that govern gas separation performance are systematically summarized.展开更多
Ammonia,a hydrogen-rich and carbon-free energy carrier,possesses advantages such as high energy density and convenient liquefaction storage and serves as an optimal medium for hydrogen storage.Low-temperature direct a...Ammonia,a hydrogen-rich and carbon-free energy carrier,possesses advantages such as high energy density and convenient liquefaction storage and serves as an optimal medium for hydrogen storage.Low-temperature direct ammonia fuel cells(DAFCs)represent a highly promising pathway for the efficient utilization of ammonia energy.However,the sluggish kinetics of the low-temperature ammonia oxidation reaction(AOR),requires high loading of platinum-group metals(PGMs)catalysts,and their poisoning significantly hampers the performance of DAFCs,thereby limiting their large-scale commercial application.Therefore,it is crucial to design efficient,cost-effective,and stable catalysts.In this work,a detailed review of recent research efforts aimed at elucidating the mechanism underlying the AOR is presented.Building on this knowledge base,progress in the design and synthesis of both PGM and PGM-free catalysts for the AOR is discussed,as well as membrane electrode assembly(MEA)preparation processes for DAFCs.Furthermore,the results of the performance evaluation of AOR catalysts in single-cell tests are summarized.Finally,based on our findings from this research area thus far,potential design strategies for AOR catalysts that can promote the rapid development of low temperatures DAFCs are proposed.展开更多
Three-membered cyclic compounds are a fascinating class of compounds:they have the maximum torsional and angular strain(sp^(3)hybridization but bond angles deviate from 109°28’),and possess unique physical and c...Three-membered cyclic compounds are a fascinating class of compounds:they have the maximum torsional and angular strain(sp^(3)hybridization but bond angles deviate from 109°28’),and possess unique physical and chemical properties.A lot of effort has been devoted to their synthesis and applications in recent years.This review provides an overview of various synthesis strategies for three-membered cyclic compounds,and summarizes the proposed reaction mechanisms and key issues such as structure-property relationships through specific examples.Meanwhile,the advantages and disadvantages of different synthesis strategies were discussed,including the recently developed electrochemical synthesis methods.Finally,the prospects and challenges for further scientific research and practical applications of three-membered cyclic compounds were emphasized.The summary of three-membered cyclic compounds is beneficial for the development and utilization of novel functionalized molecules.展开更多
TiMn_(2)-based alloys hold significant application potential due to their moderate hydrogen storage operating conditions and exceptional volumetric hydrogen storage density.Industrial by-product hydrogen,which is wide...TiMn_(2)-based alloys hold significant application potential due to their moderate hydrogen storage operating conditions and exceptional volumetric hydrogen storage density.Industrial by-product hydrogen,which is widely available and relatively cheap,often contains components such as H_(2)S,CO,and CH_(4),whose poisoning mechanism on TiMn_(2)-based alloys in the process of hydrogen absorption and desorption remains to be elucidated.In this work,the poisoning mechanisms of H_(2)S,CO,and CH_(4)on Ti_(0.8)Zr_(0.2)Cr_(0.75)Mn_(1.25)Ce_(0.01)hydrogen storage alloy were investigated by isothermal adsorption curve,X-ray photoelectron spectroscopy(XPS),and scanning electron microscope-energy dispersive spectroscopy(SEM-EDS).The results showed that the toxicity of impurity gases on the alloy is CO>H_(2)S>CH_(4),and the regeneration difficulty was H_(2)S>CO>CH_(4).The hydrogen absorption of the Ti_(0.8)Zr_(0.2)Cr_(0.75)Mn_(1.25)Ce_(0.01)alloy was restored to 58.59%after five groups of H_(2)S poisoning-regeneration cycles.The hydrogen storage capacity retention rate decreased to 4.03%after five groups of CO poisoning,but the alloy recovered to 96.62%of the hydrogen absorption capacity after regeneration with pure hydrogen.The retention rate of the alloy was 100%after 100 cycles of CH_(4)poisoning.According to the results of XPS analysis,two metal sulfides(TiS and ZrS_(2))and one metal sulfate Zr(SO_(4))_(2)were formed after the Ti_(0.8)Zr_(0.2)Cr_(0.75)Mn_(1.25)Ce_(0.01)alloy was poisoned by H_(2)S.Therefore,H_(2)S poisoning belongs to irreversible adsorption and CO belongs to reversible adsorption.The poisoning mechanism may guide the design of alloys for the absorption/desorption of industrial by-product hydrogen.展开更多
Abnormalities in the transition betweenα-helices andβ-sheets(α-βtransition)may lead to devastating neurodegenerative diseases,such as Parkinson's syndrome and Alzheimer's disease.Ionic liquids(ILs)are pote...Abnormalities in the transition betweenα-helices andβ-sheets(α-βtransition)may lead to devastating neurodegenerative diseases,such as Parkinson's syndrome and Alzheimer's disease.Ionic liquids(ILs)are potential drugs for targeted therapies against these diseases because of their excellent bioactivity and designability of ILs.However,the mechanism through which ILs regulate the aα-βtransition remains unclear.Herein,a combination of GPU-accelerated microsecond molecular dynamics simulations,correlation analysis,and machine learning was used to probe the dynamicalα-βtransition process induced by ILs of 1-alkyl-3-methylimidazolium chloride([C_(n)mim]cl)and its molecular mechanism.Interestingly,the cation of [C_(n)mim]+in ILs can spontaneously insert into the peptides as free ions(n≤10)and clusters(n≥11).Such insertion can significantly inhibit theα-β,transition and the inhibiting ability for the clusters is more significant than that of free ions,where[Ciomim]+and[C_(12)mim]+can reduce the maximumβ-sheet content of the peptide by 18.5% and 44.9%,respectively.Furthermore,the correlation analysis and machine learning method were used to develop a predictive model accounting for the influencing factors on theα-βtransition,which could accurately predict the effect of ILs on theα-βtransition.Overall,these quantitative results may not only deepen the understanding of the role of ILs in theα-βtransition but also guide the development of the IL-based treatments for related diseases.展开更多
Electrocatalytic depolymerization of lignin into value-added chemicals offers a promising technique to make biorefining sustainable.Herein,we report a robust trimetallic PdNiBi electrocatalyst for reductive C–O bond ...Electrocatalytic depolymerization of lignin into value-added chemicals offers a promising technique to make biorefining sustainable.Herein,we report a robust trimetallic PdNiBi electrocatalyst for reductive C–O bond cleavage of different lignin model dimers and oxidized lignin under mild conditions.The reduction reaction proceeds with complete substrate conversion and excellent yields toward monomers of phenols(80%–99%)and acetophenones(75%–96%)in the presence of an ionic liquid electrolyte with operational stability.Systematic experimental investigations together with density functional theory(DFT)calculations reveal that the outstanding performance of the catalyst results from the synergistic effect of the metal elements,which facilitates the easier formation of a key Cαradical intermediate and the facile desorption of the as-formed products at the electrode.The results open up new opportunities for lignin valorization through the green electrocatalytic approach.展开更多
Developing single-atom Fe–N_(4)/C catalysts is crucial for the large-scale implementation of proton exchange membrane fuel cells(PEMFCs).While Fe–N_(4)/C catalysts are inherently active in accelerating the slow ORR ...Developing single-atom Fe–N_(4)/C catalysts is crucial for the large-scale implementation of proton exchange membrane fuel cells(PEMFCs).While Fe–N_(4)/C catalysts are inherently active in accelerating the slow ORR process,their performance is still inferior to that of Pt/C.Herein,a trace Co-doped Fe single-atom catalyst(Fe(tCo)–N–C)containing more active Fe_(2)N_(8) sites has been synthesized.Interestingly,compared with typical FeN4 sites in an Fe–N–C electrocatalyst,the Fe_(2)N_(8) sites generate a larger Fe–N bond length due to Co-doping.The elongated Fe–N bond in Fe_(2)N_(8) lowers the d-band center and charge density of iron sites,enhancing the ORR process by facilitating the formation of*OOH and generation and desorption of*OH.Fe(tCo)–N–C manifested excellent acidic and alkaline ORR activity,with a half-wave potential(E_(1/2))of 0.80 V in HClO_(4) solution and 0.89 V in KOH medium.More importantly,high peak power densities(Pmax)were realized by applying Fe(tCo)–N–C in PEMFCs,with the Pmax reaching 890 mW cm^(-2) in H_(2)–O_(2) and 380 mW cm^(-2) in H_(2)–air.Additionally,trace Co dopants in the catalyst improved carbon graphitization and provided high ORR catalytic stability.This research introduces an innovative approach to engineering highly active Fe_(2)N_(8) sites,providing valuable insights for the sustainable progress of PEMFC technology.展开更多
基金supported by the National Natural Science Foundation of China(No.52302241 and 22225801)the Major Science and Technology Programs of Henan Province(241100240200)the China Postdoctoral Science Foundation(No.2023M730940).
文摘MXene derivatives are notable two-dimensional nanomaterials with numerous prospective applications in the domains of energy development.MXene derivative,MBene,diversifies its focus on energy storage and harvesting due to its exceptional electrical conductivity,structural flexibility,and mechanical properties.This comprehensive review describes the sandwich-like structure of the synthesized MBene,derived from its multilayered parent material and its distinct chemical framework to date.The fields of focus encompass the investigation of novel MBenes,the study of phase-changing mechanisms,and the examination of hex-MBenes,ortho-MBenes,tetra-MBenes,tri-MBenes,and MXenes with identical transition metal components.A critical analysis is also provided on the electrochemical mechanism and performance of MBene in energy storage(Li/Na/Mg/Ca/Li–S batteries and supercapacitors),as well as conversion and harvesting(CO_(2) reduction,and nitrogen reduction reactions).The persistent difficulties associated with conducting experimental synthesis and establishing artificial intelligence-based forecasts are extensively deliberated alongside the potential and forthcoming prospects of MBenes.This review provides a single platform for an overview of the MBene’s potential in energy storage and harvesting.
文摘The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group,which enables us to conveniently bridge the gap between homo-and heterogeneous catalysis.In this study,we extend this general concept to the confinement of molecular rhodium phosphine complexes,including Rh-TPPTS,Rh-TPPMS and Rh-SXP,for olefin hydroformylation reactions.A series of hybrid catalyst materials consisting a modulated liquid interior([BMIM]NTf_(2),[BMIM]PF_(6),[BMIM]BF_(4) or H_(2)O)and a permeable silica crust were fabricated through our developed Pickering emulsion-based method,showing 9.4–24.2-fold activity enhancement and significantly improved aldehyde selectivity(from 72.2%,61.8%to 86.6%)compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene.Interestingly,the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool.The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.
基金the financial support provided by the Longzihu New Energy Laboratory Joint Fund of Henan Province(2023008)the Energy Storage Mater.and Processes Key Laboratory of Henan Province Open Fund(2021003)+1 种基金the Collaborative Innovation Team Project Fund of Industry-University-Research(32214085)the financial support received from Zhejiang Vast Na Technology Co.,Ltd.(24110380)。
文摘To address the challenges of air stability and slurry processability in layered transition metal oxide O_(3)-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)for sodium-ion batteries(SIBs),we have designed an innovative 500℃reheating strategy.This method improves the surface properties of NFM without the need for additional coating layers,making it more efficient and suitable for large-scale applications.Pristine NFM(NFM-P)was first synthesized through a high-temperature solid-state method and then modified using this reheating approach(NFM-HT).This strategy significantly enhances air stability and electrochemical performance,yielding an initial discharge specific capacity of 151.46 mAh/g at 0.1C,with a remarkable capacity retention of 95.04%after 100 cycles at 0.5C.Additionally,a 1.7 Ah NFM‖HC(hard carbon)pouch cell demonstrates excellent long-term cycling stability(94.64%retention after 500 cycles at 1C),superior rate capability(86.48%retention at 9C),and strong low-temperature performance(77%retention at-25℃,continuing power supply at-40℃).Notably,even when overcharged to 8.29 V,the pouch cell remained safe without combustion or explosion.This reheating strategy,which eliminates the need for a coating layer,offers a simpler,more scalable solution for industrial production while maintaining outstanding electrochemical performance.These results pave the way for broader commercial adoption of NFM materials.
基金supported by the National Key Research and Development Program of China(2022YFB3504702)support from Horizon-EIC,Pathfinder challenges(101070976)+3 种基金support from the National Natural Science Foundation of China(22278402,22478389)the Key Research and Development Program of Henan Province(231111241800)State Key Laboratory of Mesoscience and Engineering(MESO-23-A08)the Frontier Basic Research Projects of Institute of Process Engineering,CAS(QYJC-2023-03).
文摘Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.
文摘The rigorous operating condition of proton exchange membrane fuel cells(PEMFCs)poses a substantial hurdle for the long-term stability of Pt-based alloy catalysts;thus,the development of Pt-alloy catalysts with unique morphologies is crucial for enhancing the stability of PEMFCs.In this study,we synthesized a novel PtCu nano-dendrite(PtCuND)catalyst through a facile,one-step solvothermal process.The sub-nanometer particles and nanopores within this catalyst facilitate enhanced mass transport.In PEM single-cell tests,the PtCuND catalyst displays high activity and robust stability,achieving a mass activity of 0.65 A mgPt^(–1).Notably,after accelerated durability tests,the mass activity and the voltage at 0.8 A cm^(–2)of PtCuND exhibits only minimal decreases of 18.5%and 9 mV,respectively.The combined experimental results and theoretical calculations conclusively illustrate the optimized adsorption of oxygen species and the impact of compressive strain on the catalyst surface.The enhanced durability can be attributed to the maintained nano-dendritic morphology and the strengthened interaction within the Pt-Cu bonds.This work not only enhances the stability of PEMFCs but also provides a robust foundation for the future scaling up of catalyst production,paving the way for widespread application in sustainable energy systems.
基金supported by National Key R&D Program of China(2020YFA0710200)the National Natural Science Foundation of China(21838010,22122814)+2 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2018064)State Key Laboratory of Multiphase complex systems,Institute of Process Engineering,Chinese Academy of Sciences(No.MPCS-2022-A-03)Innovation Academy for Green Manufacture Institute,Chinese Academy of Science(IAGM2020C14).
文摘CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at design and understanding of catalytic materials and electrolyte systems,the CO_(2) ER performance(such as current density,selectivity,stability,CO_(2) conversion,etc.)has been continually increased.Unfortunately,there has been relatively little attention paid to the large-scale CO 2 electrolyzers,which stand just as one obstacle,alongside series-parallel integration,challenging the practical application of this infant technology.In this review,the latest progress on the structures of low-temperature CO_(2) electrolyzers and scale-up studies was systematically overviewed.The influence of the CO_(2) electrolyzer configurations,such as the flow channel design,gas diffusion electrode(GDE)and ion exchange membrane(IEM),on the CO_(2) ER performance was further discussed.The review could provide inspiration for the design of large-scale CO_(2) electrolyzers so as to accelerate the industrial application of CO_(2) ER technology.
基金supported by the National Key Research and Development Program of China(2021YFB3802600)the National Natural Science Foundation of China(22278396,22378392,22178344)+1 种基金the Youth Innovation Promotion Association CAS(Y2021022)the Open Research Fund of State Key Laboratory of Mesoscience and Engineering(MESO-23-D17)。
文摘Ionic liquids(ILs)are an emerging class of media of fundamental importance for chemical engineering,especially due to their interaction with solid surfaces.Here,we explore the growth phenomenon of surface-confined ILs and reveal a peculiar structural transition behavior from order to disorder above a threshold thickness.This behavior can be explained by the variation of interfacial forces with increasing distance from the solid surface.Direct structural observation of different ILs highlights the influence of the ionic structure on the growth process.Notably,the length of the alkyl chain in the cation is found to be a determining factor for the ordering trend.Also,the thermal stability of surface-confined ILs is investigated in depth by controlling annealing treatments.It is found that the ordered monolayer ILs exhibit high robustness against high temperatures.Our findings provide new perspectives on the properties of surface-confined ILs and open up potential avenues for manipulating the structures of nanometer-thick IL films for various applications.
文摘Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a mesoporous CeO_(2)single-crystal formed with the regulation of ionic liquids,which catalyzed the effective carbonylation reaction with CO_(2)under mild reaction conditions.By altering the synthetic environment,a series of uniform mesoporous CeO_(2)particles with atomically aligned single-crystal frameworks were constructed,which have different surface physicochemical properties and primary aggregation degree.The prepared mesoporous CeO_(2)single-crystal achieved efficient activation of CO_(2)and alcohols at 0.5 MPa CO_(2)and 100℃,and the CeO_(2)-IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g^(–1)h^(–1),which was 50.6 times as high as that of the CeO_(2)obtained without ionic liquids.Subsequently,the catalytic pathway and mechanism of carbonylation reaction with CO_(2)on mesoporous CeO_(2)single-crystal were studied via React-IR spectra and C18O_(2)labeling experiments.The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials,aiming to develop novel catalytic materials to meet industrial needs.
基金supported by the National Science Fund for Excellent Young Scholars(22222813)the National Key Research and Development Program of China(2023YFA1506803)+2 种基金the National Natural Science Foundation of China(22078338)the Young Scientists Fund of the National Natural Science Foundation of China(No.22408376)the Postdoctoral Fellowship Program of CPSF(GZC20232700)。
文摘Photothermal catalysis significantly enhances the efficiency of photocatalytic CO_(2) reduction,offering a promising strategy for accelerated CO_(2) resource utilization.Herein,a series of Cu_(x)In_(y)S photocatalysts were synthesized,exhibiting tunable band gap energy by varying the Cu/In/S atomic ratios for photothermocatalytic CO_(2) conversion to C_(2)H_(4).The typical CuInS_(2) catalyst demonstrates a more negative conduction band,significantly enhancing the electron reduction ability and facilitating the multi-electron reduction of CO_(2) to C_(2)H_(4).Additionally,the abundant sulfur vacancies in CuInS_(2) generate additional active sites,enhance charge separation efficiency,and consequently improve catalytic activity.The generation rate of ethylene reaches 45.7μmol g^(−1) h^(−1) with a selectivity of 79.7%.This study provides a new avenue for producing ethylene in photothermal catalysis,as well as highlighting the superiorities of the CuInS_(2) catalyst.
基金S.Luo and S.Zhang gratefully acknowledge the financial support from the National Natural Science Foundation of China(22008243,22090063,21890760)the International Partner Program of CAS(122111KYSB20200035)+1 种基金the Project of Stable Support for Youth Team in Basic Research Field of CAS(YSBR-017).R.Guo acknowledges the financial support from the Division of Chemical Sciences,Biosciences,and Geosciences,Office of Basic Energy Sciences of the U.S.Department of Energy(DOE),under award no.DE-SC0019024from the U.S.National Science Foundation under Cooperative Agreement No.EEC-1647722。
文摘The implementation of synthetic polymer membranes in gas separations,ranging from natural gas sweetening,hydrogen separation,helium recovery,carbon capture,oxygen/nitrogen enrichment,etc.,has stimulated the vigorous development of high-performance membrane materials.However,size-sieving types of synthetic polymer membranes are frequently subject to a trade-off between permeability and selectivity,primarily due to the lack of ability to boost fractional free volume while simultaneously controlling the micropore size distribution.Herein,we review recent research progress on microporosity manipulation in high-free-volume polymeric gas separation membranes and their gas separation performance,with an emphasis on membranes with hourglass-shaped or bimodally distributed microcavities.State-of-the-art strategies to construct tailorable and hierarchically microporous structures,microporosity characterization,and microcavity architecture that govern gas separation performance are systematically summarized.
基金supported by the National Key R&D Program(Nos.2022YFE0208300,2023YFE0108200)Beijing Natural Science Foundation(No.Z200012)+2 种基金the Key R&D Program of Henan Province(No.231111241800)Henan Provincial Science and Technology R&D Program Joint Fund(Advantageous Discipline Cultivation,No.222301420045)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001)。
文摘Ammonia,a hydrogen-rich and carbon-free energy carrier,possesses advantages such as high energy density and convenient liquefaction storage and serves as an optimal medium for hydrogen storage.Low-temperature direct ammonia fuel cells(DAFCs)represent a highly promising pathway for the efficient utilization of ammonia energy.However,the sluggish kinetics of the low-temperature ammonia oxidation reaction(AOR),requires high loading of platinum-group metals(PGMs)catalysts,and their poisoning significantly hampers the performance of DAFCs,thereby limiting their large-scale commercial application.Therefore,it is crucial to design efficient,cost-effective,and stable catalysts.In this work,a detailed review of recent research efforts aimed at elucidating the mechanism underlying the AOR is presented.Building on this knowledge base,progress in the design and synthesis of both PGM and PGM-free catalysts for the AOR is discussed,as well as membrane electrode assembly(MEA)preparation processes for DAFCs.Furthermore,the results of the performance evaluation of AOR catalysts in single-cell tests are summarized.Finally,based on our findings from this research area thus far,potential design strategies for AOR catalysts that can promote the rapid development of low temperatures DAFCs are proposed.
基金supported by the National Natural Science Foundation of China(Nos.U21A20307,22178359,and 22308087)CAS Project for Young Scientists in Basic Research(No.YSBR-052).
文摘Three-membered cyclic compounds are a fascinating class of compounds:they have the maximum torsional and angular strain(sp^(3)hybridization but bond angles deviate from 109°28’),and possess unique physical and chemical properties.A lot of effort has been devoted to their synthesis and applications in recent years.This review provides an overview of various synthesis strategies for three-membered cyclic compounds,and summarizes the proposed reaction mechanisms and key issues such as structure-property relationships through specific examples.Meanwhile,the advantages and disadvantages of different synthesis strategies were discussed,including the recently developed electrochemical synthesis methods.Finally,the prospects and challenges for further scientific research and practical applications of three-membered cyclic compounds were emphasized.The summary of three-membered cyclic compounds is beneficial for the development and utilization of novel functionalized molecules.
基金supported by the National Key R&D Program of China(No.2022YFB3504702)the National Natural Science Foundation of China(Nos.22278402 and 22478389)+2 种基金the Key R&D Program of Henan Province(No.231111241800)State Key Laboratory of Mesoscience and Engineering(No.MESO-23-A08)the Frontier Basic Research Projects of Institute of Process Engineering,CAS(No.QYJC-2023-03).
文摘TiMn_(2)-based alloys hold significant application potential due to their moderate hydrogen storage operating conditions and exceptional volumetric hydrogen storage density.Industrial by-product hydrogen,which is widely available and relatively cheap,often contains components such as H_(2)S,CO,and CH_(4),whose poisoning mechanism on TiMn_(2)-based alloys in the process of hydrogen absorption and desorption remains to be elucidated.In this work,the poisoning mechanisms of H_(2)S,CO,and CH_(4)on Ti_(0.8)Zr_(0.2)Cr_(0.75)Mn_(1.25)Ce_(0.01)hydrogen storage alloy were investigated by isothermal adsorption curve,X-ray photoelectron spectroscopy(XPS),and scanning electron microscope-energy dispersive spectroscopy(SEM-EDS).The results showed that the toxicity of impurity gases on the alloy is CO>H_(2)S>CH_(4),and the regeneration difficulty was H_(2)S>CO>CH_(4).The hydrogen absorption of the Ti_(0.8)Zr_(0.2)Cr_(0.75)Mn_(1.25)Ce_(0.01)alloy was restored to 58.59%after five groups of H_(2)S poisoning-regeneration cycles.The hydrogen storage capacity retention rate decreased to 4.03%after five groups of CO poisoning,but the alloy recovered to 96.62%of the hydrogen absorption capacity after regeneration with pure hydrogen.The retention rate of the alloy was 100%after 100 cycles of CH_(4)poisoning.According to the results of XPS analysis,two metal sulfides(TiS and ZrS_(2))and one metal sulfate Zr(SO_(4))_(2)were formed after the Ti_(0.8)Zr_(0.2)Cr_(0.75)Mn_(1.25)Ce_(0.01)alloy was poisoned by H_(2)S.Therefore,H_(2)S poisoning belongs to irreversible adsorption and CO belongs to reversible adsorption.The poisoning mechanism may guide the design of alloys for the absorption/desorption of industrial by-product hydrogen.
基金the National Natural Science Foundation of China(21834006,22078322,21978293,and 21978027)the Youth Innovation Promotion Association of CAS(2021046,Y2021046)State Key Laboratory of Treatments and Recycling for Organic Effluents by Adsorption in Petroleum and Chemical Industry(SDHY2114).
文摘Abnormalities in the transition betweenα-helices andβ-sheets(α-βtransition)may lead to devastating neurodegenerative diseases,such as Parkinson's syndrome and Alzheimer's disease.Ionic liquids(ILs)are potential drugs for targeted therapies against these diseases because of their excellent bioactivity and designability of ILs.However,the mechanism through which ILs regulate the aα-βtransition remains unclear.Herein,a combination of GPU-accelerated microsecond molecular dynamics simulations,correlation analysis,and machine learning was used to probe the dynamicalα-βtransition process induced by ILs of 1-alkyl-3-methylimidazolium chloride([C_(n)mim]cl)and its molecular mechanism.Interestingly,the cation of [C_(n)mim]+in ILs can spontaneously insert into the peptides as free ions(n≤10)and clusters(n≥11).Such insertion can significantly inhibit theα-β,transition and the inhibiting ability for the clusters is more significant than that of free ions,where[Ciomim]+and[C_(12)mim]+can reduce the maximumβ-sheet content of the peptide by 18.5% and 44.9%,respectively.Furthermore,the correlation analysis and machine learning method were used to develop a predictive model accounting for the influencing factors on theα-βtransition,which could accurately predict the effect of ILs on theα-βtransition.Overall,these quantitative results may not only deepen the understanding of the role of ILs in theα-βtransition but also guide the development of the IL-based treatments for related diseases.
基金supported by the National Natural Science Foundation of China(Nos.22078322,21890762,22178344,and 21834006)the Youth Innovation Promotion Association CAS(No.Y2021022).
文摘Electrocatalytic depolymerization of lignin into value-added chemicals offers a promising technique to make biorefining sustainable.Herein,we report a robust trimetallic PdNiBi electrocatalyst for reductive C–O bond cleavage of different lignin model dimers and oxidized lignin under mild conditions.The reduction reaction proceeds with complete substrate conversion and excellent yields toward monomers of phenols(80%–99%)and acetophenones(75%–96%)in the presence of an ionic liquid electrolyte with operational stability.Systematic experimental investigations together with density functional theory(DFT)calculations reveal that the outstanding performance of the catalyst results from the synergistic effect of the metal elements,which facilitates the easier formation of a key Cαradical intermediate and the facile desorption of the as-formed products at the electrode.The results open up new opportunities for lignin valorization through the green electrocatalytic approach.
基金This work was supported by the Beijing Natural Science Foundation(No.2202052 and Z200012)National Natural Science Foundation of China(No.92061125)+2 种基金Hebei Natural Science Foundation(B2020103043)Science and Technology Program of Inner Mongolia(2021GG0237)Key R&D Program of Henan Province(No.231111241800).
文摘Developing single-atom Fe–N_(4)/C catalysts is crucial for the large-scale implementation of proton exchange membrane fuel cells(PEMFCs).While Fe–N_(4)/C catalysts are inherently active in accelerating the slow ORR process,their performance is still inferior to that of Pt/C.Herein,a trace Co-doped Fe single-atom catalyst(Fe(tCo)–N–C)containing more active Fe_(2)N_(8) sites has been synthesized.Interestingly,compared with typical FeN4 sites in an Fe–N–C electrocatalyst,the Fe_(2)N_(8) sites generate a larger Fe–N bond length due to Co-doping.The elongated Fe–N bond in Fe_(2)N_(8) lowers the d-band center and charge density of iron sites,enhancing the ORR process by facilitating the formation of*OOH and generation and desorption of*OH.Fe(tCo)–N–C manifested excellent acidic and alkaline ORR activity,with a half-wave potential(E_(1/2))of 0.80 V in HClO_(4) solution and 0.89 V in KOH medium.More importantly,high peak power densities(Pmax)were realized by applying Fe(tCo)–N–C in PEMFCs,with the Pmax reaching 890 mW cm^(-2) in H_(2)–O_(2) and 380 mW cm^(-2) in H_(2)–air.Additionally,trace Co dopants in the catalyst improved carbon graphitization and provided high ORR catalytic stability.This research introduces an innovative approach to engineering highly active Fe_(2)N_(8) sites,providing valuable insights for the sustainable progress of PEMFC technology.
