Since the discovery of enzyme-like activity of Fe3O4 nanoparticles in 2007,nanozymes are becoming the promising substitutes for natural enzymes due to their advantages of high catalytic activity,low cost,mild reaction...Since the discovery of enzyme-like activity of Fe3O4 nanoparticles in 2007,nanozymes are becoming the promising substitutes for natural enzymes due to their advantages of high catalytic activity,low cost,mild reaction conditions,good stability,and suitable for large-scale production.Recently,with the cross fusion of nanomedicine and nanocatalysis,nanozyme-based theranostic strategies attract great attention,since the enzymatic reactions can be triggered in the tumor microenvironment to achieve good curative effect with substrate specificity and low side effects.Thus,various nanozymes have been developed and used for tumor therapy.In this review,more than 270 research articles are discussed systematically to present progress in the past five years.First,the discovery and development of nanozymes are summarized.Second,classification and catalytic mechanism of nanozymes are discussed.Third,activity prediction and rational design of nanozymes are focused by highlighting the methods of density functional theory,machine learning,biomimetic and chemical design.Then,synergistic theranostic strategy of nanozymes are introduced.Finally,current challenges and future prospects of nanozymes used for tumor theranostic are outlined,including selectivity,biosafety,repeatability and stability,in-depth catalytic mechanism,predicting and evaluating activities.展开更多
Fracturing operations can effectively improve the production of low-permeable reservoirs. The performance of fracturing fluids directly affects the fracturing efficiency and back flow capacity. As polymerbased fractur...Fracturing operations can effectively improve the production of low-permeable reservoirs. The performance of fracturing fluids directly affects the fracturing efficiency and back flow capacity. As polymerbased fracturing fluids(such as guar gum(GG), polyacrylamide(HPAM), etc.) are high-viscosity fluids formed by viscosifiers and crosslinking agents, the degree of gel breakage after the fracturing operation directly influences the damage degree to the reservoir matrix and the mobility of oil angd gas produced from the reservoir into the wellbore. This study compared the viscosity, molecular weight, and particle size of the fracturing fluid after gel breakage prepared by GG and HPAM as viscosifiers, as well as evaluate their damage to the core. Results show that the viscosities of the gel-breaking fluid increased with the concentration of the viscosifier for both the HPAM-based and GG-based fracturing fluids. For the breaking fluid with the same viscosity, the molecular weight in the HPAM-based gel-breaking fluid was much larger than that in the GG-based system. Moreover, for the gel-breaking fluid with the same viscosity, the molecular particle size of the residual polymers in the HPAM-based system was smaller than that in the GG-based system. The damage to the core with the permeability of 1 × 10^(-3)μm^(2) caused by both the HPAM-based and GG-based gel-breaking fluids decreased with the increase in the solution viscosity. For the gel-breaking fluid systems with the same viscosity(i.e., 2-4 mPa s), the damage of HPAM-based fracturing fluid to low-permeability cores was greater than the GG-based fracturing fluid(45.6%-80.2%) since it had a smaller molecular particle size, ranging from 66.2% to 77.0%. This paper proposed that the damage caused by hydraulic fracturing in rock cores was related to the partilce size of residual polymers in gel-breaking solution, rather than its molecular weight. It was helpful for screening and optimizing viscosifiers used in hydraulic fracturing process.展开更多
The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate ...The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate their useless components(mainly the degraded solid electrolyte interphase,SEI)and reconstruct their damaged structure.Herein,a facile and efficient strategy is proposed to recycle the spent graphite on the basis of the careful investigation of the composition of the cycled graphite anodes and the rational design of the regeneration processes.The regenerated graphite,which is revitalized by calcination treatment and acid leaching,delivers superb rate performance and a high specific capacity of 370 mAh g^(-1)(~99% of its theoretical capacity)after 100 cycles at 0.1 C,superior to the commercial graphite anodes.The improved electrochemical performance could be attributed to unchoked Li^(+) transport channels and enhanced charge transfer reaction due to the effective destruction of the degraded SEI and the full recovery of the damaged structure of the spent graphite.This work clarifies that the electrochemical performance of the regenerated graphite could be deteriorated by even a trace amount of the residual“impurity”and provides a facile method for the efficient regeneration of graphite anodes.展开更多
Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-pot...Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.展开更多
Developing the highly active, cost-effective, environmental-friendly, and ultra-stable nonprecious electrocatalysts for hydrogen evolution reaction(HER) is distinctly indispensable for the large-scale practical applic...Developing the highly active, cost-effective, environmental-friendly, and ultra-stable nonprecious electrocatalysts for hydrogen evolution reaction(HER) is distinctly indispensable for the large-scale practical applications of hydrolytic hydrogen production. Herein, we report the synthesis of well-integrated electrode, NiV layered double hydroxide nanosheet array grown in-situ on porous nickel foam(abbreviated as in-NiV-LDH/NF) via the facile one-step hydrothermal route. Interestingly, the valence configuration of vanadium(V) sites in such NiV-LDH are well dominated by the innovative use of NF as the reducing regulator, achieving the reassembled in-NiV-LDH/NF with a high proportion of trivalent V ions(V3+), and then an enhanced intrinsic electrocatalytic HER activity. The HER testing results show that the in-NiVLDH/NF drives the current densities of 10 and 100 mA cm-2 at extremely low overpotentials of 114 and 245 mV without iR-compensation respectively, even outperforms commercial 20 wt% Pt/C at the large current density of over 80 mA cm-2 in alkaline media, as well as gives robust catalytic durability of at least 100 h in both alkaline and neutral media. More importantly, this work provides a fresh perspective for designing bimetal(oxy) hydroxides electrocatalysts with efficient hydrogen generation.展开更多
Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.De...Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.展开更多
The development of sodium-ion full cells is seriously suppressed by the incompatibility between electrodes and electrolytes. Most representatively, high-voltage ester-based electrolytes required by the cathodes presen...The development of sodium-ion full cells is seriously suppressed by the incompatibility between electrodes and electrolytes. Most representatively, high-voltage ester-based electrolytes required by the cathodes present poor interfacial compatibility with the anodes due to unstable solid electrode interphase(SEI). Herein, Fe S@N,S-C(spindle-like Fe S nanoparticles individually encapsulated in N,S-doped carbon) with excellent structural stability is synthesized as a potential sodium anode material. It exhibits exceptional interfacial stability in ester-based electrolyte(1 M NaClO_(4) in ethylene carbonate/propylene carbonate with 5% fluoroethylene carbonate) with long-cycling lifespan(294 days) in Na|Fe S@N,S-C coin cell and remarkable cyclability in pouch cell(capacity retention of 82.2% after 170 cycles at 0.2 A g^(-1)).DFT calculation reveals that N,S-doping on electrode surface could drive strong repulsion to solvated Na_(2) and preferential adsorption to ClO_(4)^(-) anion, guiding the anion-rich inner Helmholtz plane.Consequently, a robust SEI with rich inorganic species(NaCl and Na_(2)O) through the whole depth stabilizes the electrode–electrolyte interface and protects its integrity. This work brings new insight into the role of electrode’s surface properties in interfacial compatibility that can guide the design of more versatile electrodes for advanced rechargeable metal-ion batteries.展开更多
Lithium(Li)metal electrodes show significantly different reversibility in the electrolytes with different salts.However,the understanding on how the salts impact on the Li loss remains unclear.Herein,using the electro...Lithium(Li)metal electrodes show significantly different reversibility in the electrolytes with different salts.However,the understanding on how the salts impact on the Li loss remains unclear.Herein,using the electrolytes with different salts(e.g.,lithium hexafluorophosphate(LiPF_(6)),lithium difluoro(oxalato)borate(LiDFOB),and lithium bis(fluorosulfonyl)amide(LiFSI))as examples,we decouple the irreversible Li loss(SEI Li^(+)and“dead”Li)during cycling.It is found that the accumulation of both SEI Li^(+)and“dead”Li may be responsible to the irreversible Li loss for the Li metal in the electrolyte with LiPF_(6)salt.While for the electrolytes with LiDFOB and LiFSI salts,the accumulation of“dead”Li predominates the Li loss.We also demonstrate that lithium nitrate and fluoroethylene carbonate additives could,respectively,function as the“dead”Li and SEI Li^(+)inhibitors.Inspired by the above understandings,we propose a universal procedure for the electrolyte design of Li metal batteries(LMBs):(i)decouple and find the main reason for the irreversible Li loss;(ii)add the corresponding electrolyte additive.With such a Li-loss-targeted strategy,the Li reversibility was significantly enhanced in the electrolytes with 1,2-dimethoxyethane,triethyl phosphate,and tetrahydrofuran solvents.Our strategy may broaden the scope of electrolyte design toward practical LMBs.展开更多
基金S.G.acknowledges the financial support from the National Natural Science Foundation of China(NSFC 52272144,51972076)the Heilongjiang Provincial Natural Science Foundation of China(JQ2022E001)+4 种基金the Natural Science Foundation of Shandong Province(ZR2020ZD42)the Fundamental Research Funds for the Central Universities.H.D.acknowledges the financial support from the National Natural Science Foundation of China(NSFC 22205048)China Postdoctoral Science Foundation(2022M710931 and 2023T160154)Heilongjiang Postdoctoral Science Foundation(LBH-Z22010)G.Y.acknowledges the financial support from the National Science Foundation of Heilongjiang Education Department(324022075).
文摘Since the discovery of enzyme-like activity of Fe3O4 nanoparticles in 2007,nanozymes are becoming the promising substitutes for natural enzymes due to their advantages of high catalytic activity,low cost,mild reaction conditions,good stability,and suitable for large-scale production.Recently,with the cross fusion of nanomedicine and nanocatalysis,nanozyme-based theranostic strategies attract great attention,since the enzymatic reactions can be triggered in the tumor microenvironment to achieve good curative effect with substrate specificity and low side effects.Thus,various nanozymes have been developed and used for tumor therapy.In this review,more than 270 research articles are discussed systematically to present progress in the past five years.First,the discovery and development of nanozymes are summarized.Second,classification and catalytic mechanism of nanozymes are discussed.Third,activity prediction and rational design of nanozymes are focused by highlighting the methods of density functional theory,machine learning,biomimetic and chemical design.Then,synergistic theranostic strategy of nanozymes are introduced.Finally,current challenges and future prospects of nanozymes used for tumor theranostic are outlined,including selectivity,biosafety,repeatability and stability,in-depth catalytic mechanism,predicting and evaluating activities.
文摘Fracturing operations can effectively improve the production of low-permeable reservoirs. The performance of fracturing fluids directly affects the fracturing efficiency and back flow capacity. As polymerbased fracturing fluids(such as guar gum(GG), polyacrylamide(HPAM), etc.) are high-viscosity fluids formed by viscosifiers and crosslinking agents, the degree of gel breakage after the fracturing operation directly influences the damage degree to the reservoir matrix and the mobility of oil angd gas produced from the reservoir into the wellbore. This study compared the viscosity, molecular weight, and particle size of the fracturing fluid after gel breakage prepared by GG and HPAM as viscosifiers, as well as evaluate their damage to the core. Results show that the viscosities of the gel-breaking fluid increased with the concentration of the viscosifier for both the HPAM-based and GG-based fracturing fluids. For the breaking fluid with the same viscosity, the molecular weight in the HPAM-based gel-breaking fluid was much larger than that in the GG-based system. Moreover, for the gel-breaking fluid with the same viscosity, the molecular particle size of the residual polymers in the HPAM-based system was smaller than that in the GG-based system. The damage to the core with the permeability of 1 × 10^(-3)μm^(2) caused by both the HPAM-based and GG-based gel-breaking fluids decreased with the increase in the solution viscosity. For the gel-breaking fluid systems with the same viscosity(i.e., 2-4 mPa s), the damage of HPAM-based fracturing fluid to low-permeability cores was greater than the GG-based fracturing fluid(45.6%-80.2%) since it had a smaller molecular particle size, ranging from 66.2% to 77.0%. This paper proposed that the damage caused by hydraulic fracturing in rock cores was related to the partilce size of residual polymers in gel-breaking solution, rather than its molecular weight. It was helpful for screening and optimizing viscosifiers used in hydraulic fracturing process.
基金supported by the National Key R&D Program of China(2021YFB2400300)Key R&D Program of Hubei Province of China(2020BAB088)+2 种基金National Natural Science Foundation of China(52002277)the Fundamental Research Funds for the Central Universities(2021GCRC001)Guangdong Basic and Applied Basic Reuter Foundation(2021A1515011748).
文摘The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate their useless components(mainly the degraded solid electrolyte interphase,SEI)and reconstruct their damaged structure.Herein,a facile and efficient strategy is proposed to recycle the spent graphite on the basis of the careful investigation of the composition of the cycled graphite anodes and the rational design of the regeneration processes.The regenerated graphite,which is revitalized by calcination treatment and acid leaching,delivers superb rate performance and a high specific capacity of 370 mAh g^(-1)(~99% of its theoretical capacity)after 100 cycles at 0.1 C,superior to the commercial graphite anodes.The improved electrochemical performance could be attributed to unchoked Li^(+) transport channels and enhanced charge transfer reaction due to the effective destruction of the degraded SEI and the full recovery of the damaged structure of the spent graphite.This work clarifies that the electrochemical performance of the regenerated graphite could be deteriorated by even a trace amount of the residual“impurity”and provides a facile method for the efficient regeneration of graphite anodes.
基金supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205,U1804126)Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.
基金supported by the National Natural Science Foundation of China (Nos.21701107, 51672165)Natural Science Foundation of Shaanxi Province (2019JQ-018)+3 种基金Doctoral Scientific Research Startup Foundation of Shaanxi University of Science and Technology (2016QNBT-07)Platform construction Fund for Imported talent of Shaanxi University of Science and Technology (134080038)National Key R&D Program of China (2017YFB0308300)Xi’an Key Laboratory of Green Manufacture of Ceramic materials Foundation (2019220214SYS017CG039)。
文摘Developing the highly active, cost-effective, environmental-friendly, and ultra-stable nonprecious electrocatalysts for hydrogen evolution reaction(HER) is distinctly indispensable for the large-scale practical applications of hydrolytic hydrogen production. Herein, we report the synthesis of well-integrated electrode, NiV layered double hydroxide nanosheet array grown in-situ on porous nickel foam(abbreviated as in-NiV-LDH/NF) via the facile one-step hydrothermal route. Interestingly, the valence configuration of vanadium(V) sites in such NiV-LDH are well dominated by the innovative use of NF as the reducing regulator, achieving the reassembled in-NiV-LDH/NF with a high proportion of trivalent V ions(V3+), and then an enhanced intrinsic electrocatalytic HER activity. The HER testing results show that the in-NiVLDH/NF drives the current densities of 10 and 100 mA cm-2 at extremely low overpotentials of 114 and 245 mV without iR-compensation respectively, even outperforms commercial 20 wt% Pt/C at the large current density of over 80 mA cm-2 in alkaline media, as well as gives robust catalytic durability of at least 100 h in both alkaline and neutral media. More importantly, this work provides a fresh perspective for designing bimetal(oxy) hydroxides electrocatalysts with efficient hydrogen generation.
基金the National Key R&D Research Program of China(Grant No.2018YFB0905400)the National Natural Science Foundation of China(Grant Nos.51872277,21606003,51902062,51972067,51802044,51925207 and U1910210)+2 种基金the Fundamental Research Funds for the Central Universities(WK2060140026)the DNL cooperation Fund,CAS(DNL180310)the Guangdong Natural Science Funds for Distinguished Young Scholar(Grant No.2019B151502039)。
文摘Alkali metal ion batteries(AMIBs)are playing an irreplaceable part in the energy revolution,due to their intrinsic advantages of large capacity/power density and abundance of alkali metal ions in the earth’s crust.Despite their great promise,the inborn deficiencies of commercial graphite and other anodes being researched so far call for the quest of better alternatives that exhibit all-round performance with the balance of energy/power density and cycling stability.Gallium-based materials,with impressive capacity utilization and self-healing ability,provide an anticipated solution to this conundrum.In this review,an overview on the recent progress of gallium-based anodes and their storage mechanism is presented.The current strategies used as engineering solutions to meet the scientific challenges ahead are discussed,in addition to the insightful outlook for possible future study.
基金supported by the National Natural Science Foundation of China (U1804129, 21771164)the Program for Young Scholar of Changjiang Scholars+1 种基金Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘The development of sodium-ion full cells is seriously suppressed by the incompatibility between electrodes and electrolytes. Most representatively, high-voltage ester-based electrolytes required by the cathodes present poor interfacial compatibility with the anodes due to unstable solid electrode interphase(SEI). Herein, Fe S@N,S-C(spindle-like Fe S nanoparticles individually encapsulated in N,S-doped carbon) with excellent structural stability is synthesized as a potential sodium anode material. It exhibits exceptional interfacial stability in ester-based electrolyte(1 M NaClO_(4) in ethylene carbonate/propylene carbonate with 5% fluoroethylene carbonate) with long-cycling lifespan(294 days) in Na|Fe S@N,S-C coin cell and remarkable cyclability in pouch cell(capacity retention of 82.2% after 170 cycles at 0.2 A g^(-1)).DFT calculation reveals that N,S-doping on electrode surface could drive strong repulsion to solvated Na_(2) and preferential adsorption to ClO_(4)^(-) anion, guiding the anion-rich inner Helmholtz plane.Consequently, a robust SEI with rich inorganic species(NaCl and Na_(2)O) through the whole depth stabilizes the electrode–electrolyte interface and protects its integrity. This work brings new insight into the role of electrode’s surface properties in interfacial compatibility that can guide the design of more versatile electrodes for advanced rechargeable metal-ion batteries.
基金This work was supported by the National Key Research and Development Program(2021YFB2400300)the National Natural Science Foundation of China(52272203)the Fundamental Research Funds for the Central Universities(2021GCRC001).
文摘Lithium(Li)metal electrodes show significantly different reversibility in the electrolytes with different salts.However,the understanding on how the salts impact on the Li loss remains unclear.Herein,using the electrolytes with different salts(e.g.,lithium hexafluorophosphate(LiPF_(6)),lithium difluoro(oxalato)borate(LiDFOB),and lithium bis(fluorosulfonyl)amide(LiFSI))as examples,we decouple the irreversible Li loss(SEI Li^(+)and“dead”Li)during cycling.It is found that the accumulation of both SEI Li^(+)and“dead”Li may be responsible to the irreversible Li loss for the Li metal in the electrolyte with LiPF_(6)salt.While for the electrolytes with LiDFOB and LiFSI salts,the accumulation of“dead”Li predominates the Li loss.We also demonstrate that lithium nitrate and fluoroethylene carbonate additives could,respectively,function as the“dead”Li and SEI Li^(+)inhibitors.Inspired by the above understandings,we propose a universal procedure for the electrolyte design of Li metal batteries(LMBs):(i)decouple and find the main reason for the irreversible Li loss;(ii)add the corresponding electrolyte additive.With such a Li-loss-targeted strategy,the Li reversibility was significantly enhanced in the electrolytes with 1,2-dimethoxyethane,triethyl phosphate,and tetrahydrofuran solvents.Our strategy may broaden the scope of electrolyte design toward practical LMBs.
