H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an elec...H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.展开更多
Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their m...Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.展开更多
Objective: The significance of isolated high-grade prostatic intraepithelial neoplasia in initial biopsy as an predic-tor for prostate cancer has been extensively research, and the true relationship remnant is no clea...Objective: The significance of isolated high-grade prostatic intraepithelial neoplasia in initial biopsy as an predic-tor for prostate cancer has been extensively research, and the true relationship remnant is no clear till now. The aim of this study is to evaluate prediction value of cancer on repeat biopsy in patients with high-grade prostatic intraepithelial neoplasia, using multivariate analysis. Methods: Thirty-eight men with a diagnosis of isolated high-grade prostatic intraepithelial neo-plasia in initial needle biopsy were studies, in the Fist Affiliated Hospital of Medical School of Xi'an Jiaotong University, from January 2003 to March 2009. These samples were using immunostaining of p63 and 34βE12 and P504s, with a median fol-low-up of 525 (range, 7 to 1650) days, and to researched the incidence of subsequent prostate cancer, and to predicted the risk of prostate cancer in clinicopathological parameters of isolated high-grade prostatic intraepithelial neoplasia on repeat biopsies by logistic regression analysis. Results: There were 10 of 38 (26.3%) men with prostate cancer on repeat biopsies after diagnosis isolated high-grade prostatic intraepithelial neoplasia in initial biopsy, of the rates of prostate cancer were 80% for micropapillary and 75% for cribriform high-grade prostatic intraepithelial neoplasia (P < 0.05), respectively. The positive cores of isolated high-grade prostatic intraepithelial neoplasia was the important for the risk of prostate cancer using Multi-factor logistic regression analysis. The time range in 30 to 690 days was stronger risk for prostate cancer detection after diagnosis isolated HGPIN in initial biopsy. p63 and 34βE12 were disrupted positive expression, and P504S was weak posi-tive expression in the 61% isolated high-grade prostatic intraepithelial neoplasia. Conclusion: Isolated high-grade prostatic intraepithelial neoplasia on repeat biopsy conferred a 26.3% risk of prostate cancer, and this risk level is lower than the previ-ously reported risk of 24% to 58%. The number of positive cores and the histopathological pattern with high-grade prostatic intraepithelial neoplasia on initial biopsy was significantly associated with the risk of cancer.展开更多
Li-CO_(2)batteries(LCBs)suffer from high overpotentials caused by sluggish CO_(2)reaction kinetics.This work designs a Te-doped Fe_(3)O_(4)(Te-Fe_(3)O_(4))flower-like microsphere catalyst to lower the overpotential an...Li-CO_(2)batteries(LCBs)suffer from high overpotentials caused by sluggish CO_(2)reaction kinetics.This work designs a Te-doped Fe_(3)O_(4)(Te-Fe_(3)O_(4))flower-like microsphere catalyst to lower the overpotential and improve the reversibility of LCBs.Experimental results reveal that Te doping modifies the electronic structure of Fe_(3)O_(4)and reduces the overpotential.The stable Te-O bond between Te and C_(2)O^(2-)_(4)could effectively inhibit the dispro-portionation reaction of the latter,enabling the Te-Fe_(3)O_(4)cathodes to exhibit a remarkable capacity(9485 mAh g^(-1))and a long cycling life(155 cycles)with an overpotential of 1.21 V and an energy efficiency of about 80%at a high current density(2000 mA g^(-1)).Through the interaction between Te and Li_(2)C_(2)O_(4)to inhibit the dispro-portionation reaction,this work successfully achieves long-term cycling of LCBs with low overpotential at high current density.展开更多
The application of Li-O_(2)batteries(LOBs)with ultra-high theoretical energy density is limited due to the slow redox kinetics and serious side reactions,especially in high-rate cycles.Herein,CeO_(2)is constructed on ...The application of Li-O_(2)batteries(LOBs)with ultra-high theoretical energy density is limited due to the slow redox kinetics and serious side reactions,especially in high-rate cycles.Herein,CeO_(2)is constructed on the surface of Mn_(2)O_(3)through an interface engineering strategy,and Mn_(2)O_(3)@CeO_(2)heterojunction with good activity and stability at high current density is prepared.The interfacial properties of catalyst and formation mechanism of Li_(2)O_(2)are deeply studied by density functional theory(DFT)and experiments,revealing the charge-discharge reaction mechanism of LOBs.The results show that the strong electron coupling between Mn_(2)O_(3)and CeO_(2)can promote the formation of oxygen vacancies.Heterojunction combined with oxygen vacancy can improve the affinity for O_(2)and LiO_(2)reaction intermediates,inducing the formation of thin-film Li_(2)O_(2)with low potential and easy decomposition,thus improving the cycle stability at high current density.Consequently,it achieved a high specific capacity of 12545 at 1000 mA g^(-1)and good cyclability of 120 cycles at 4000 mA g^(-1).This work thus sheds light on designing efficient and stable catalysts for LOBs under high current density.展开更多
基金supported by the National Natural Science Foundation of China(22479031,22162004)the Natural Science Foundation of Guangxi(2022JJD120011).
文摘H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.
文摘Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.
基金Supported by a grant from the Key Sci-tech Research Project of Shanxi Province, China (No. 2003K10-G38)
文摘Objective: The significance of isolated high-grade prostatic intraepithelial neoplasia in initial biopsy as an predic-tor for prostate cancer has been extensively research, and the true relationship remnant is no clear till now. The aim of this study is to evaluate prediction value of cancer on repeat biopsy in patients with high-grade prostatic intraepithelial neoplasia, using multivariate analysis. Methods: Thirty-eight men with a diagnosis of isolated high-grade prostatic intraepithelial neo-plasia in initial needle biopsy were studies, in the Fist Affiliated Hospital of Medical School of Xi'an Jiaotong University, from January 2003 to March 2009. These samples were using immunostaining of p63 and 34βE12 and P504s, with a median fol-low-up of 525 (range, 7 to 1650) days, and to researched the incidence of subsequent prostate cancer, and to predicted the risk of prostate cancer in clinicopathological parameters of isolated high-grade prostatic intraepithelial neoplasia on repeat biopsies by logistic regression analysis. Results: There were 10 of 38 (26.3%) men with prostate cancer on repeat biopsies after diagnosis isolated high-grade prostatic intraepithelial neoplasia in initial biopsy, of the rates of prostate cancer were 80% for micropapillary and 75% for cribriform high-grade prostatic intraepithelial neoplasia (P < 0.05), respectively. The positive cores of isolated high-grade prostatic intraepithelial neoplasia was the important for the risk of prostate cancer using Multi-factor logistic regression analysis. The time range in 30 to 690 days was stronger risk for prostate cancer detection after diagnosis isolated HGPIN in initial biopsy. p63 and 34βE12 were disrupted positive expression, and P504S was weak posi-tive expression in the 61% isolated high-grade prostatic intraepithelial neoplasia. Conclusion: Isolated high-grade prostatic intraepithelial neoplasia on repeat biopsy conferred a 26.3% risk of prostate cancer, and this risk level is lower than the previ-ously reported risk of 24% to 58%. The number of positive cores and the histopathological pattern with high-grade prostatic intraepithelial neoplasia on initial biopsy was significantly associated with the risk of cancer.
基金supported by the National Natural Science Foundation of China(22162004)the Natural Science Foundation of Guangxi Province(2022JJD120011)the Innovation Project of Guangxi Graduate Education(YCBZ2023012,YCSW2023115,YCBZ2023048).
文摘Li-CO_(2)batteries(LCBs)suffer from high overpotentials caused by sluggish CO_(2)reaction kinetics.This work designs a Te-doped Fe_(3)O_(4)(Te-Fe_(3)O_(4))flower-like microsphere catalyst to lower the overpotential and improve the reversibility of LCBs.Experimental results reveal that Te doping modifies the electronic structure of Fe_(3)O_(4)and reduces the overpotential.The stable Te-O bond between Te and C_(2)O^(2-)_(4)could effectively inhibit the dispro-portionation reaction of the latter,enabling the Te-Fe_(3)O_(4)cathodes to exhibit a remarkable capacity(9485 mAh g^(-1))and a long cycling life(155 cycles)with an overpotential of 1.21 V and an energy efficiency of about 80%at a high current density(2000 mA g^(-1)).Through the interaction between Te and Li_(2)C_(2)O_(4)to inhibit the dispro-portionation reaction,this work successfully achieves long-term cycling of LCBs with low overpotential at high current density.
基金supported by the National Natural Science Foundation of China(22162004)the Natural Science Foundation of Guangxi Province(2022JJD120011)+1 种基金the Innovation Project of Guangxi Graduate Education(YCBZ2023012)the High-performance Computing Platform of Guangxi University.
文摘The application of Li-O_(2)batteries(LOBs)with ultra-high theoretical energy density is limited due to the slow redox kinetics and serious side reactions,especially in high-rate cycles.Herein,CeO_(2)is constructed on the surface of Mn_(2)O_(3)through an interface engineering strategy,and Mn_(2)O_(3)@CeO_(2)heterojunction with good activity and stability at high current density is prepared.The interfacial properties of catalyst and formation mechanism of Li_(2)O_(2)are deeply studied by density functional theory(DFT)and experiments,revealing the charge-discharge reaction mechanism of LOBs.The results show that the strong electron coupling between Mn_(2)O_(3)and CeO_(2)can promote the formation of oxygen vacancies.Heterojunction combined with oxygen vacancy can improve the affinity for O_(2)and LiO_(2)reaction intermediates,inducing the formation of thin-film Li_(2)O_(2)with low potential and easy decomposition,thus improving the cycle stability at high current density.Consequently,it achieved a high specific capacity of 12545 at 1000 mA g^(-1)and good cyclability of 120 cycles at 4000 mA g^(-1).This work thus sheds light on designing efficient and stable catalysts for LOBs under high current density.
