Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challeng...Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.展开更多
TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperat...TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.展开更多
Hollow engineering plays a crucial role in enhancing interfacial polarization,which is an essential factor in microwave absorption.Herein,an in-situ growth approach was adopted to successively coating C layer and WS_(...Hollow engineering plays a crucial role in enhancing interfacial polarization,which is an essential factor in microwave absorption.Herein,an in-situ growth approach was adopted to successively coating C layer and WS_(2) nanosheets on the surface SiO_(2) nanosphere.The obtained results suggested that the formed SiO_(2)@Void@C@WS_(2) multi-component nanocomposites(MCNCs)reveal a representative flower-like yolk-shell structure,which were manufactured massively through a simple channel.Additionally,the obtained SiO_(2)@Void@C@WS_(2) MCNCs presented a more and more obvious yolk-shell structure and reduced WS_(2) content with decreasing the addition of SiO_(2)@C or tungsten and sulfur sources.Because of their distinc-tive structures and remarkable cooperative effects,the SiO_(2)@Void@C@WS_(2) displayed excellent microwave absorption performances.Through the majorization of hollow structure and WS_(2),improved properties of SiO_(2)@Void@C@WS_(2) MCNCs could be acquired owing to their boosted polarization and conductive loss capabilities.Amongst,the resulting SiO_(2)@Void@C@WS_(2) MCNCs exhibited the effective absorption band and minimum reflection loss values of 5.40 GHz and−45.50 dB with matching thicknesses of 1.78 and 1.55 mm,respectively.Therefore,our findings employed hollow engineering and optimization strategies for components to design and fabricate the yolk-shell structure flower-like MCNCs,which acted as highly efficient wide-band microwave absorbing materials.展开更多
In recent years,two-dimensional layered transition metal dichalcogenides-based multicomponent com-posites(MCCs)acting as electromagnetic wave(EMW)materials have received intensive investiga-tions.However,the vulcanica...In recent years,two-dimensional layered transition metal dichalcogenides-based multicomponent com-posites(MCCs)acting as electromagnetic wave(EMW)materials have received intensive investiga-tions.However,the vulcanication of metal greatly hindered their enhancement of EMW absorption per-formances(EMWAPs).Herein,a combined metal-organic frameworks-derived and hydrothermal strat-egy was presented to produce yolk-shell structure(YSS)CoNi@Air@C@MoS_(2) MCCs.The results showed that the thermal and hydrothermal treatments resulted in the generation of YSS and two-dimensional MoS_(2) nanosheets,which maintained the original morphology of CoNi Prussian blue analogues.The pro-tection of thick C layer well inhibited the vulcanization of inner CoNi alloy.The formed sheet-like MoS_(2) further optimized impedance matching characteristics,which led to the satisfactory EMWAPs of CoNi@Air@C@MoS_(2) MCCs.Furthermore,the EMWAPs could be further improved by optimizing the Ni:Co atom ratios CoNi@Air@C@MoS_(2) MCCs,which stemmed from their boosted impedance matching perfor-mances,EMW attention and polarization loss abilities.The absorption bandwidth and reflection loss val-ues for YSS CoNi@Air@C@MoS_(2) MCCs are 8 GHz and−60.83 dB,which covered almost all C-Ku bands.In general,our research work provided a valid strategy to produce YSS magnetic CoNi@Air@C@MoS_(2) MCCs with high efficiency,which well avoided the vulcanization of metal nanoparticles,made best of hollow engineering and atomic ratio optimization strategy to boost the comprehensive EMWAPs.展开更多
Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))using covalent organic frameworks(COFs)as photocatalysts holds promise for future applications.However,the influence of linkage chemistry on the photoelectroch...Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))using covalent organic frameworks(COFs)as photocatalysts holds promise for future applications.However,the influence of linkage chemistry on the photoelectrochemical properties and photocatalytic performance of COFs remains a significant challenge.Herein,we designed and synthesized a model system with different linkages,including imine-,amine-,azo-linked COFs,then investigated their photocatalytic activity of overall H_(2)O_(2)production.The photocatalytic results revealed varying activities for H_(2)O_(2)synthesis among these COFs,with the azo-linked TTA-Azo-COF(COF synthesized by 4,4’,4’’-(1,3,5-triazine-2,4,6-triyl)-trianiline and terephthalaldehyde)demonstrating the highest overall H2O2 photosynthesis activity of 2516μmol g^(–1)h^(–1)in an O2 atmosphere without any sacrificial agents,which is 6.72 and 2.85 times higher than that of imine-linked TTA-COF and amine-linked TTA-COF-AR,respectively.Furthermore,TTA-Azo-COF maintained a high photosynthesis H2O2 activity of 2116μmol g^(–1)h^(–1)under an air atmosphere,outperforming most COF-based photocatalytic systems under similar reaction conditions.Further characterizations and density functional theory calculations reveal these various linkages in different COFs result in distinct visible-light absorption,charge transfer capacities and formation energy barriers of key intermediates.This work revealed the significant impact of linkages on COFs and provided comprehensive guidance for the rational design of COFs with tailored linkages to fulfill specific requirements for future applications.展开更多
Three large π-conjugated and imine-based COFs,named TFP-TAB,TFP-TTA,and TTA-TTB,were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural unit...Three large π-conjugated and imine-based COFs,named TFP-TAB,TFP-TTA,and TTA-TTB,were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural units affect the efficiency of CO_(2)photoreduction.Results from both experiments and density-functional theory(DFT)calculations indicate the separation and transfer of the photoinduced charges is highly related to the triazine-N content and the conjugation degree in the skeletons of COFs.High-efficiency CO_(2)photoreduction can be achieved by rationally adjusting the number and position of both benzene and triazine rings in the COFs.Specifically,TTA-TTB,with orderly interlaced triazine-benzene heterojunctions,can suppress the recombination probability of electrons and holes,which effectively immobilizes the key species(COOH)and lowers the free energy change of the potential-determining step,and thus exhibits a superior visible-light-induced photocatalytic activity that yields 121.7 μmol HCOOH g^(-1)h^(-1).This research,therefore,helps to elucidate the effects of the different structural blocks in COFs on inherent heterogeneous photocatalysis for CO_(2)reduction at a molecular level.展开更多
Aqueous iron-ion batteries are regarded as one of the most promising candidates for grid applications owing to their low cost,high theoretical capacity,and excellent stability of iron in aqueous electrolytes.However,t...Aqueous iron-ion batteries are regarded as one of the most promising candidates for grid applications owing to their low cost,high theoretical capacity,and excellent stability of iron in aqueous electrolytes.However,the slow Fe(de)insertion caused by the high polarity of Fe^(2+)makes it difficult to match suitable cathode materials.Herein,defect-rich MoS_(2)with abundant 1T phase is synthesized and successfully applied in aqueous iron-ion batteries.Benefit from abundant active sites generated by the heteroatom incorporation and S vacancy,as well as the highly conductive 1T phase,it can deliver a specific capacity of 123 mAh/g at a current density of 100mA/g,and demonstrates an impressive capacity retention of 88%after 600 cycles at 200mA/g.This work presents a novel pathway for the advancement of cathode materials for aqueous iron-ion batteries.展开更多
The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates ...The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.展开更多
The issues of reducing CO_2 levels in the atmo-sphere, sustainably utilizing natural mineral resources,and dealing with indus trial waste offer challenging opportunities for sustainable development in energy and the e...The issues of reducing CO_2 levels in the atmo-sphere, sustainably utilizing natural mineral resources,and dealing with indus trial waste offer challenging opportunities for sustainable development in energy and the environment. The latest advances in CO_2 mineralization technology involving natural minerals and industrial waste are summarized in this paper, with great emphasis on the advancement of fundamental science, economic evaluation, and engineering applications. We discuss several lead-ing large-scale CO_2 mineralization methodologies from a techn ical and engineering-science perspective. For each technology option, we give an overview of the technical parameters, reaction pathway, reactivity, procedural scheme, and laboratorial and pilot devices. Furthermore, we present a discussion of each technology based on experimental results and the literature. Finally, current gaps in knowledge are identified in the conclusion, and an overview of the challenges and opportunities for future research in this field is provided.展开更多
Lithium-carbon dioxide(Li-CO_(2))batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality.However,bidirectional catalysts design for improving the sluggis...Lithium-carbon dioxide(Li-CO_(2))batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality.However,bidirectional catalysts design for improving the sluggish CO_(2)reduction reaction(CO_(2)RR)/CO_(2)evolution reaction(CO_(2)ER)kinetics remains a huge challenge.In this work,an advanced catalyst with fast-interfacial charge transfer was subtly synthesized through element segregation,which significantly improves the electrocatalytic activity for both CO_(2)RR and CO_(2)ER.Theoretical calculations and characterization analysis demonstrate local charge redistribution at the constructed interface,which leads to optimized binding affinity towards reactants and preferred Li_(2)CO_(3)decomposition behavior,enabling excellent catalytic activity during CO_(2)redox.Benefiting from the enhanced charge transfer ability,the designed highly efficient catalyst with dual active centers and large exposed catalytic area can maintain an ultra-small voltage gap of 0.33 V and high energy efficiency of 90.2%.This work provides an attractive strategy to construct robust catalysts by interface engineering,which could inspire further design of superior bidirectional catalysts for Li-CO_(2)batteries.展开更多
The utilization of covalent organic frameworks(COFs)holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure.In this work,we show that a si...The utilization of covalent organic frameworks(COFs)holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure.In this work,we show that a single-point structural alteration in the linkage within a nickel phthalocyanine(NiPc)-based series effectively modulates the catalytic performance of the COFs in electrochemical CO_(2)reduction reaction(CO_(2)RR).A Ni Pc-based COF series with three members which possess the same Ni Pc unit but different linkages,including piperazine,dioxin,and dithiine,have been constructed by nucleophilic aromatic substitution reaction between octafluorophthalocyanine nickel and tetrasubstituted benzene linkers with different bridging groups.Among these COFs,the dioxin-linked COF showed the best activity of CO_(2)RR with a current density of CO(j_(CO))=-27.99 m A cm^(-2)at-1.0 V(versus reversible hydrogen electrode,RHE),while the COF with piperazine linkage demonstrated an excellent selectivity of Faradaic efficiency for CO(FECO)up to 90.7%at a pretty low overpotential of 0.39 V.In addition,both a high FECO value close to 100%and a reasonable jCO of-8.20 m A cm^(-2)at the potential of-0.8 V(versus RHE)were obtained by the piperazine-linked COF,making it one of the most competitive candidates among COF-based materials.Mechanistic studies exhibited that single-point structural alteration could tailor the electron density in Ni sites and alter the interaction between the active sites and the key intermediates adsorbed and desorbed,thereby tuning the electrochemical performance during CO_(2)RR process.展开更多
基金supported by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang Province of China(No.2024C01056)。
文摘Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.
基金supported by the National Natural Science Foundation of China(22279026,2247090373)the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX1401)+2 种基金the China Postdoctoral Science Foundation(2024M764198)the National Natural Science Foundation of China(22509044)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.
基金supported by the Guizhou Provincial Science and Technology Projects for Platform and Talent Team Plan(No.GCC[2023]007)the Innovation Group of Guizhou University([2024]08)+1 种基金Fok Ying Tung Education Foundation(No.171095)the National Natural Science Foundation of China(No.11964006).
文摘Hollow engineering plays a crucial role in enhancing interfacial polarization,which is an essential factor in microwave absorption.Herein,an in-situ growth approach was adopted to successively coating C layer and WS_(2) nanosheets on the surface SiO_(2) nanosphere.The obtained results suggested that the formed SiO_(2)@Void@C@WS_(2) multi-component nanocomposites(MCNCs)reveal a representative flower-like yolk-shell structure,which were manufactured massively through a simple channel.Additionally,the obtained SiO_(2)@Void@C@WS_(2) MCNCs presented a more and more obvious yolk-shell structure and reduced WS_(2) content with decreasing the addition of SiO_(2)@C or tungsten and sulfur sources.Because of their distinc-tive structures and remarkable cooperative effects,the SiO_(2)@Void@C@WS_(2) displayed excellent microwave absorption performances.Through the majorization of hollow structure and WS_(2),improved properties of SiO_(2)@Void@C@WS_(2) MCNCs could be acquired owing to their boosted polarization and conductive loss capabilities.Amongst,the resulting SiO_(2)@Void@C@WS_(2) MCNCs exhibited the effective absorption band and minimum reflection loss values of 5.40 GHz and−45.50 dB with matching thicknesses of 1.78 and 1.55 mm,respectively.Therefore,our findings employed hollow engineering and optimization strategies for components to design and fabricate the yolk-shell structure flower-like MCNCs,which acted as highly efficient wide-band microwave absorbing materials.
基金supported by the Guizhou Provincial Science and Technology Projects for Platform and Talent Team Plan(No.GCC[2023]007)the Innovation Group of Guizhou University(No.[2024]08)+1 种基金Fok Ying Tung Education Foundation(No.171095)the National Natural Science Foundation of China(No.11964006).
文摘In recent years,two-dimensional layered transition metal dichalcogenides-based multicomponent com-posites(MCCs)acting as electromagnetic wave(EMW)materials have received intensive investiga-tions.However,the vulcanication of metal greatly hindered their enhancement of EMW absorption per-formances(EMWAPs).Herein,a combined metal-organic frameworks-derived and hydrothermal strat-egy was presented to produce yolk-shell structure(YSS)CoNi@Air@C@MoS_(2) MCCs.The results showed that the thermal and hydrothermal treatments resulted in the generation of YSS and two-dimensional MoS_(2) nanosheets,which maintained the original morphology of CoNi Prussian blue analogues.The pro-tection of thick C layer well inhibited the vulcanization of inner CoNi alloy.The formed sheet-like MoS_(2) further optimized impedance matching characteristics,which led to the satisfactory EMWAPs of CoNi@Air@C@MoS_(2) MCCs.Furthermore,the EMWAPs could be further improved by optimizing the Ni:Co atom ratios CoNi@Air@C@MoS_(2) MCCs,which stemmed from their boosted impedance matching perfor-mances,EMW attention and polarization loss abilities.The absorption bandwidth and reflection loss val-ues for YSS CoNi@Air@C@MoS_(2) MCCs are 8 GHz and−60.83 dB,which covered almost all C-Ku bands.In general,our research work provided a valid strategy to produce YSS magnetic CoNi@Air@C@MoS_(2) MCCs with high efficiency,which well avoided the vulcanization of metal nanoparticles,made best of hollow engineering and atomic ratio optimization strategy to boost the comprehensive EMWAPs.
文摘Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))using covalent organic frameworks(COFs)as photocatalysts holds promise for future applications.However,the influence of linkage chemistry on the photoelectrochemical properties and photocatalytic performance of COFs remains a significant challenge.Herein,we designed and synthesized a model system with different linkages,including imine-,amine-,azo-linked COFs,then investigated their photocatalytic activity of overall H_(2)O_(2)production.The photocatalytic results revealed varying activities for H_(2)O_(2)synthesis among these COFs,with the azo-linked TTA-Azo-COF(COF synthesized by 4,4’,4’’-(1,3,5-triazine-2,4,6-triyl)-trianiline and terephthalaldehyde)demonstrating the highest overall H2O2 photosynthesis activity of 2516μmol g^(–1)h^(–1)in an O2 atmosphere without any sacrificial agents,which is 6.72 and 2.85 times higher than that of imine-linked TTA-COF and amine-linked TTA-COF-AR,respectively.Furthermore,TTA-Azo-COF maintained a high photosynthesis H2O2 activity of 2116μmol g^(–1)h^(–1)under an air atmosphere,outperforming most COF-based photocatalytic systems under similar reaction conditions.Further characterizations and density functional theory calculations reveal these various linkages in different COFs result in distinct visible-light absorption,charge transfer capacities and formation energy barriers of key intermediates.This work revealed the significant impact of linkages on COFs and provided comprehensive guidance for the rational design of COFs with tailored linkages to fulfill specific requirements for future applications.
基金support from the Scientific Research Fund of Zhejiang Provincial Education Department(Y202353855)the Zhejiang Provincial Key R&D Project(2021C01056)+1 种基金the Programme of Introducing Talents of Discipline to Universities(No.D17008)the National Natural Science Foundation of China(22208312).
文摘Three large π-conjugated and imine-based COFs,named TFP-TAB,TFP-TTA,and TTA-TTB,were synthesized via the ordered incorporation of benzene and triazine rings in the same host framework to study how the structural units affect the efficiency of CO_(2)photoreduction.Results from both experiments and density-functional theory(DFT)calculations indicate the separation and transfer of the photoinduced charges is highly related to the triazine-N content and the conjugation degree in the skeletons of COFs.High-efficiency CO_(2)photoreduction can be achieved by rationally adjusting the number and position of both benzene and triazine rings in the COFs.Specifically,TTA-TTB,with orderly interlaced triazine-benzene heterojunctions,can suppress the recombination probability of electrons and holes,which effectively immobilizes the key species(COOH)and lowers the free energy change of the potential-determining step,and thus exhibits a superior visible-light-induced photocatalytic activity that yields 121.7 μmol HCOOH g^(-1)h^(-1).This research,therefore,helps to elucidate the effects of the different structural blocks in COFs on inherent heterogeneous photocatalysis for CO_(2)reduction at a molecular level.
基金supported by Shenzhen Fundamental Research Program(No.GXWD20201231165807007-20200802205241003).
文摘Aqueous iron-ion batteries are regarded as one of the most promising candidates for grid applications owing to their low cost,high theoretical capacity,and excellent stability of iron in aqueous electrolytes.However,the slow Fe(de)insertion caused by the high polarity of Fe^(2+)makes it difficult to match suitable cathode materials.Herein,defect-rich MoS_(2)with abundant 1T phase is synthesized and successfully applied in aqueous iron-ion batteries.Benefit from abundant active sites generated by the heteroatom incorporation and S vacancy,as well as the highly conductive 1T phase,it can deliver a specific capacity of 123 mAh/g at a current density of 100mA/g,and demonstrates an impressive capacity retention of 88%after 600 cycles at 200mA/g.This work presents a novel pathway for the advancement of cathode materials for aqueous iron-ion batteries.
基金supported by the Natural Science Foundation of Hunan Province(No.2023JJ30650)the Central South University Innovation-Driven Research Programme(No.2023CXQD061)。
文摘The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.
基金finance support of the Ministry of Science and Technology (State Key Research Plan, 2013BAC12B00)the National Natural Science Foundation of China (21336004 and 51254002)
文摘The issues of reducing CO_2 levels in the atmo-sphere, sustainably utilizing natural mineral resources,and dealing with indus trial waste offer challenging opportunities for sustainable development in energy and the environment. The latest advances in CO_2 mineralization technology involving natural minerals and industrial waste are summarized in this paper, with great emphasis on the advancement of fundamental science, economic evaluation, and engineering applications. We discuss several lead-ing large-scale CO_2 mineralization methodologies from a techn ical and engineering-science perspective. For each technology option, we give an overview of the technical parameters, reaction pathway, reactivity, procedural scheme, and laboratorial and pilot devices. Furthermore, we present a discussion of each technology based on experimental results and the literature. Finally, current gaps in knowledge are identified in the conclusion, and an overview of the challenges and opportunities for future research in this field is provided.
基金supported by the National Key Research and Development Program of China(2019YFA0705700)Guangdong Innovative and Entrepreneurial Research Team Program(2021ZT09L197)+2 种基金Shenzhen Science and Technology Program(KQTD20210811090112002)Interdisciplinary Research and Innovation Fund of Tsinghua Shenzhen International Graduate School,National Natural Science Foundation of China(No.52373233)the SIAT International Joint Lab Project(No.E3G113).
文摘Lithium-carbon dioxide(Li-CO_(2))batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality.However,bidirectional catalysts design for improving the sluggish CO_(2)reduction reaction(CO_(2)RR)/CO_(2)evolution reaction(CO_(2)ER)kinetics remains a huge challenge.In this work,an advanced catalyst with fast-interfacial charge transfer was subtly synthesized through element segregation,which significantly improves the electrocatalytic activity for both CO_(2)RR and CO_(2)ER.Theoretical calculations and characterization analysis demonstrate local charge redistribution at the constructed interface,which leads to optimized binding affinity towards reactants and preferred Li_(2)CO_(3)decomposition behavior,enabling excellent catalytic activity during CO_(2)redox.Benefiting from the enhanced charge transfer ability,the designed highly efficient catalyst with dual active centers and large exposed catalytic area can maintain an ultra-small voltage gap of 0.33 V and high energy efficiency of 90.2%.This work provides an attractive strategy to construct robust catalysts by interface engineering,which could inspire further design of superior bidirectional catalysts for Li-CO_(2)batteries.
基金supported by the National Natural Science Foundation of China(22305238)the Anhui Provincial Natural Science Foundation(2308085MB35)。
文摘The utilization of covalent organic frameworks(COFs)holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure.In this work,we show that a single-point structural alteration in the linkage within a nickel phthalocyanine(NiPc)-based series effectively modulates the catalytic performance of the COFs in electrochemical CO_(2)reduction reaction(CO_(2)RR).A Ni Pc-based COF series with three members which possess the same Ni Pc unit but different linkages,including piperazine,dioxin,and dithiine,have been constructed by nucleophilic aromatic substitution reaction between octafluorophthalocyanine nickel and tetrasubstituted benzene linkers with different bridging groups.Among these COFs,the dioxin-linked COF showed the best activity of CO_(2)RR with a current density of CO(j_(CO))=-27.99 m A cm^(-2)at-1.0 V(versus reversible hydrogen electrode,RHE),while the COF with piperazine linkage demonstrated an excellent selectivity of Faradaic efficiency for CO(FECO)up to 90.7%at a pretty low overpotential of 0.39 V.In addition,both a high FECO value close to 100%and a reasonable jCO of-8.20 m A cm^(-2)at the potential of-0.8 V(versus RHE)were obtained by the piperazine-linked COF,making it one of the most competitive candidates among COF-based materials.Mechanistic studies exhibited that single-point structural alteration could tailor the electron density in Ni sites and alter the interaction between the active sites and the key intermediates adsorbed and desorbed,thereby tuning the electrochemical performance during CO_(2)RR process.
