TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its el...TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its electrochemical activity.Herein,narrow bandgap manganese oxide(MnO_(x))was composited with TiO_(2)nanotube arrays(TiO_(2)NTAs)that in-situ oxidized on porous Ti sponge,forming the MnO_(x)-TiO_(2)NTAs anode.XANES and XPS analysis further proved that the composition of MnO_(x)is Mn2O3.Electrochemical characterizations revealed that increasing the composited concentration of MnO_(x)can improve the conductivity and reduce oxygen evolution potential so as to improve the electrochemical activity of the composited MnO_(x)-TiO_(2)NTAs anode.Meanwhile,the optimal degradation rate of benzoic acid(BA)was achieved using MnO_(x)-TiO_(2)NTAs with a MnO_(x)concentration of 0.1 mmol L^(-1),and the role of MnO_(x)was proposed based on DFT calculation.Additionally,the required electrical energy(EE/O)to destroy BA was optimized by varying the composited concentration of MnO_(x)and the degradation voltage.These quantitative results are of great significance for the design and application of high-performance materials for EAOPs.展开更多
Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches ...Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches regarding indispensable cathode materials for PIBs are badly absent.Herein,we synthesize K-deficient layered manganese-based oxides(P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2))and investigate them as cathode of PIBs for the first time.As the newcomer of potassium-containing layered manganese-based oxides(K_(x)MnO_(2))group,P2-K_(0.21)MnO_(2) delivers high discharge capacity of 99.3 mAh g^(-1) and P3-K_(0.23)MnO_(2) exhibits remarkable capacity retention rate of 75.5%.Besides,in-situ XRD and ex-situ XRD measurements reveal the reversible phase transition of P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2) with the potassium-ions extraction and reinsertion,respectively.This work contributes to a better understanding for the potassium storage in K-deficient layered K_(x)MnO_(2)(x≤0.23),possessing an important basic scientific significance for the exploitation and application of layered K_(x)MnO_(2) in PIBs.展开更多
Various Mn-based catalysts for NO oxidation were prepared using MnO_(x)as active compound,while Ti O_(2)and Al_(2)O_(3)were adopted as catalyst support.The performance of the catalysts was tested to study the effect o...Various Mn-based catalysts for NO oxidation were prepared using MnO_(x)as active compound,while Ti O_(2)and Al_(2)O_(3)were adopted as catalyst support.The performance of the catalysts was tested to study the effect of support on Mn-based catalyst activity.Performance of the catalysts followed as Mn_(0.4)/Al>Mn_(0.2)/Al>Mn_(0.4)/Ti>Mn_(0.2)/Ti>MnO_(x)>Al_(2)O_(3)on the whole,indicating the synergism of MnO_(x)and Al_(2)O_(3)for NO catalytic oxidation.Results were analyzed according to characterization data.Adsorbed oxygen on catalyst rather than lattice oxygen was detected as the active oxidizer for NO oxidation.As catalyst support,Al_(2)O_(3)provided more sites to carry surface adsorbed oxygen than TiO_(2),resulting in the presence of more active oxygen on Mn O_(x)/Al_(2)O_(3)than on MnO_(x)/TiO_(2).Moreover,MnO_(x)/Al_(2)O_(3)possessed high surface area and pore volume,which greatly benefited the adsorption of NO on catalyst and further favored the oxidation of NO by active oxygen.All these advantages helped Mn_(0.4)/Al exhibited the best catalytic efficiency.展开更多
Low-frequency resistance noise spectroscopy is applied to investigate bulk single crystals of the intercalated ironselenide K_(x)Fe_(2-y)Se_(2) superconductors with different iron vacancy orders.Based on a generalized...Low-frequency resistance noise spectroscopy is applied to investigate bulk single crystals of the intercalated ironselenide K_(x)Fe_(2-y)Se_(2) superconductors with different iron vacancy orders.Based on a generalized fluctuation model,the well-observed resistance hump above 100 K is interpreted as an insulator-metal phase transition with a characteristic transition energy of 0.1-0.6 eV,indicating a highly inhomogeneous energy distribution configuration.In the superconducting transition regime,we find that the normalized resistance noise scales with resistance R excellently as S_(R)/R^(2)∝R^(l_(rs)) with the noise exponent lrs≈1.4.With reduced iron vacancy disordering in enhanced superconductivity K_(x)Fe_(2-y)Se_(2) crystals,the level of resistance fluctuations is greatly suppressed,suggesting a geometrical phase transition for conduction channel,which is directly related to the microstructure of the crystals.展开更多
The performance of catalysts used in after-treatment systems is the key factor for the removal of diesel soot,which is an important component of atmosphericfine particle emissions.Herein,three-dimensionally ordered ma...The performance of catalysts used in after-treatment systems is the key factor for the removal of diesel soot,which is an important component of atmosphericfine particle emissions.Herein,three-dimensionally ordered macroporous–mesoporous Ti_(x)Si+(1-x)O_(2)(3DOM-m Ti_(x)Si+(1-x)O_(2)) and its supported MnO_(x)catalysts doped with different alkali/alkaline-earth metals (AMnO_(x)/3 DOM-m Ti_(0.7)Si_(0.3)O_(2)(A:Li,Na,K,Ru,Cs,Mg,Ca,Sr,Ba)) were prepared by mesoporous template (P123)-assisted colloidal crystal template (CCT) and incipient wetness impregnation methods,respectively.Physicochemical characterizations of the catalysts were performed using scanning electron microscopy,X-ray diffraction,N_(2)adsorption–desorption,H_(2)temperature-programmed reduction,O_(2)temperature-programmed desorption,NO temperature-programmed oxidation,and Raman spectroscopy techniques;then,we evaluated their catalytic performances for the removal of diesel soot particles.The results show that the 3DOM-m Ti_(0.7)Si_(0.3)O_(2)supports exhibited a well-defined 3DOM-m nanostructure,and AMnO_(x)nanoparticles with 10–50 nm were evenly dispersed on the inner walls of the uniform macropores.In addition,the as-prepared catalysts exhibited good catalytic performance for soot combustion.Among the prepared catalysts,CsMnO_(x)/3DOM-m Ti_(0.7)Si_(0.3)O_(2)had the highest catalytic activity for soot combustion,with T10,T50,and T90(the temperatures corresponding to soot conversion rates of 10%,50%,and 90%) values of 285,355,and 393℃,respectively.The high catalytic activity of the CsMnO_(x)/3 DOM-m Ti_(0.7)Si_(0.3)O_(2)catalysts was attributed to their excellent low-temperature reducibility and homogeneous macroporous–mesoporous structure,as well as to the synergistic effects between Cs and Mn species and between CsMnO_(x)and the Ti_(0.7)Si_(0.3)O_(2)support.展开更多
The selective catalytic reduction(SCR) of NO_(x) with NH_(3)(NH_(3)-SCR) technology has been widely applied for reducing NO_(x) emissions from stationary and mobile sources.In this work,the extruded monolith MnO_(x)-C...The selective catalytic reduction(SCR) of NO_(x) with NH_(3)(NH_(3)-SCR) technology has been widely applied for reducing NO_(x) emissions from stationary and mobile sources.In this work,the extruded monolith MnO_(x)-CeO_(2)-TiO_(2) catalyst was installed in a cement kiln for NH_(3)-SCR of NO_(x),where the flue gas temperature was 110-140℃.It is found that the monolith catalyst is severely deactivated after operating for about 200 h with almost no NO_(x) conversion at 160℃ under GHSV of 50000 h^(-1),while the fresh monolith catalyst remains 60% NO_(x) conversion.Scanning electron microscopy-energy dispersive spectroscopy(SEM-EDS),X-ray photoelectron spectroscopy(XPS),temperature-programmed desorption of SO_(2)(SO_(2)-TPD) and thermogravimetric-differential thermal analysis(TG-DTG) experiments reveal that both MnO_(x) and CeO_(2) oxides in monolith are severely sulfated to manganese sulfate and cerium sulfate,and the external monolith walls are covered by massive ceria sulfate and little ammonium nitrate.In situ diffuse reflectance infrared Fourier trans form spectroscopy(DRIFTS) analysis demonstrates that the formation of nitrates at low temperatures is inhibited due to the occupation of active sites in MnO_(x)-CeO_(2)-TiO_(2) by sulfates,resulting in the decrease of low temperature activity.After washing with water,the activity of deactivated monolith catalyst can be partially recovered,together with significant loss of manganese and cerium from monolith.展开更多
基金the support from the Brook Byers Institute for Sustainable Systems,Hightower ChairGeorgia Research Alliance at the Georgia Institute of Technology。
文摘TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its electrochemical activity.Herein,narrow bandgap manganese oxide(MnO_(x))was composited with TiO_(2)nanotube arrays(TiO_(2)NTAs)that in-situ oxidized on porous Ti sponge,forming the MnO_(x)-TiO_(2)NTAs anode.XANES and XPS analysis further proved that the composition of MnO_(x)is Mn2O3.Electrochemical characterizations revealed that increasing the composited concentration of MnO_(x)can improve the conductivity and reduce oxygen evolution potential so as to improve the electrochemical activity of the composited MnO_(x)-TiO_(2)NTAs anode.Meanwhile,the optimal degradation rate of benzoic acid(BA)was achieved using MnO_(x)-TiO_(2)NTAs with a MnO_(x)concentration of 0.1 mmol L^(-1),and the role of MnO_(x)was proposed based on DFT calculation.Additionally,the required electrical energy(EE/O)to destroy BA was optimized by varying the composited concentration of MnO_(x)and the degradation voltage.These quantitative results are of great significance for the design and application of high-performance materials for EAOPs.
基金support from the Key Project of Guangdong Province Nature Science Foundation (No. 2017B030311013)the Scientific and Technological Plan of Guangdong Province, Guangzhou and Qingyuan City, China (Nos. 2019B090905005, 2019B090911004, 2017B020227009, 2019DZX008, 2019A004)+2 种基金the financial support from the National Key R&D Program of China (2018YFB1502600)the National Natural Science Foundation of China (No. 51922042 and 51872098)the Sino-Singapore International Joint Research Institute (SSIJRI), Guangzhou 510700, China.
文摘Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches regarding indispensable cathode materials for PIBs are badly absent.Herein,we synthesize K-deficient layered manganese-based oxides(P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2))and investigate them as cathode of PIBs for the first time.As the newcomer of potassium-containing layered manganese-based oxides(K_(x)MnO_(2))group,P2-K_(0.21)MnO_(2) delivers high discharge capacity of 99.3 mAh g^(-1) and P3-K_(0.23)MnO_(2) exhibits remarkable capacity retention rate of 75.5%.Besides,in-situ XRD and ex-situ XRD measurements reveal the reversible phase transition of P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2) with the potassium-ions extraction and reinsertion,respectively.This work contributes to a better understanding for the potassium storage in K-deficient layered K_(x)MnO_(2)(x≤0.23),possessing an important basic scientific significance for the exploitation and application of layered K_(x)MnO_(2) in PIBs.
基金supported by the National Natural Science Foundation of China(51906193)the Fundamental Research Funds for the Central Universities(xjh012019013)+1 种基金the Basic Research Program of Natural Science in Shaanxi Province(2020JQ-039)support from Young Talent Support Program of Xi'an Association for Science and Technology。
文摘Various Mn-based catalysts for NO oxidation were prepared using MnO_(x)as active compound,while Ti O_(2)and Al_(2)O_(3)were adopted as catalyst support.The performance of the catalysts was tested to study the effect of support on Mn-based catalyst activity.Performance of the catalysts followed as Mn_(0.4)/Al>Mn_(0.2)/Al>Mn_(0.4)/Ti>Mn_(0.2)/Ti>MnO_(x)>Al_(2)O_(3)on the whole,indicating the synergism of MnO_(x)and Al_(2)O_(3)for NO catalytic oxidation.Results were analyzed according to characterization data.Adsorbed oxygen on catalyst rather than lattice oxygen was detected as the active oxidizer for NO oxidation.As catalyst support,Al_(2)O_(3)provided more sites to carry surface adsorbed oxygen than TiO_(2),resulting in the presence of more active oxygen on Mn O_(x)/Al_(2)O_(3)than on MnO_(x)/TiO_(2).Moreover,MnO_(x)/Al_(2)O_(3)possessed high surface area and pore volume,which greatly benefited the adsorption of NO on catalyst and further favored the oxidation of NO by active oxygen.All these advantages helped Mn_(0.4)/Al exhibited the best catalytic efficiency.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11774303 and 11574373)Joint Fund of Yunnan Provincial Science and Technology Department,China(Grant No.2019FY003008)。
文摘Low-frequency resistance noise spectroscopy is applied to investigate bulk single crystals of the intercalated ironselenide K_(x)Fe_(2-y)Se_(2) superconductors with different iron vacancy orders.Based on a generalized fluctuation model,the well-observed resistance hump above 100 K is interpreted as an insulator-metal phase transition with a characteristic transition energy of 0.1-0.6 eV,indicating a highly inhomogeneous energy distribution configuration.In the superconducting transition regime,we find that the normalized resistance noise scales with resistance R excellently as S_(R)/R^(2)∝R^(l_(rs)) with the noise exponent lrs≈1.4.With reduced iron vacancy disordering in enhanced superconductivity K_(x)Fe_(2-y)Se_(2) crystals,the level of resistance fluctuations is greatly suppressed,suggesting a geometrical phase transition for conduction channel,which is directly related to the microstructure of the crystals.
基金supported by Key Research and Development Program of Ministry of Science and Technology of the People’s Republic of China (MOST) (No. 2017YFE0131200) for collaboration between China and PolandNational Nature Science Foundation of China (NSFC) (Nos. 22072095, U1908204, 21761162016)+3 种基金General Projects of Liaoning Province Natural Fund (No. 2019-MS-284)National Engineering Laboratory for Mobile Source Emission Control Technology (No. NELMS2018A04)University level innovation team of Shenyang Normal University, Major Incubation Program of Shenyang Normal University (No. ZD201901)supported by the Research Grants Council (RGC) of Hong Kong through NSFC/RGC Joint Research Scheme (No. N_CUHK451/17)。
文摘The performance of catalysts used in after-treatment systems is the key factor for the removal of diesel soot,which is an important component of atmosphericfine particle emissions.Herein,three-dimensionally ordered macroporous–mesoporous Ti_(x)Si+(1-x)O_(2)(3DOM-m Ti_(x)Si+(1-x)O_(2)) and its supported MnO_(x)catalysts doped with different alkali/alkaline-earth metals (AMnO_(x)/3 DOM-m Ti_(0.7)Si_(0.3)O_(2)(A:Li,Na,K,Ru,Cs,Mg,Ca,Sr,Ba)) were prepared by mesoporous template (P123)-assisted colloidal crystal template (CCT) and incipient wetness impregnation methods,respectively.Physicochemical characterizations of the catalysts were performed using scanning electron microscopy,X-ray diffraction,N_(2)adsorption–desorption,H_(2)temperature-programmed reduction,O_(2)temperature-programmed desorption,NO temperature-programmed oxidation,and Raman spectroscopy techniques;then,we evaluated their catalytic performances for the removal of diesel soot particles.The results show that the 3DOM-m Ti_(0.7)Si_(0.3)O_(2)supports exhibited a well-defined 3DOM-m nanostructure,and AMnO_(x)nanoparticles with 10–50 nm were evenly dispersed on the inner walls of the uniform macropores.In addition,the as-prepared catalysts exhibited good catalytic performance for soot combustion.Among the prepared catalysts,CsMnO_(x)/3DOM-m Ti_(0.7)Si_(0.3)O_(2)had the highest catalytic activity for soot combustion,with T10,T50,and T90(the temperatures corresponding to soot conversion rates of 10%,50%,and 90%) values of 285,355,and 393℃,respectively.The high catalytic activity of the CsMnO_(x)/3 DOM-m Ti_(0.7)Si_(0.3)O_(2)catalysts was attributed to their excellent low-temperature reducibility and homogeneous macroporous–mesoporous structure,as well as to the synergistic effects between Cs and Mn species and between CsMnO_(x)and the Ti_(0.7)Si_(0.3)O_(2)support.
基金supported by the National Natural Science Foundation of China (22188102,22072179)Cultivating Project of Strategic Priority Research Program of Chinese Academy of Sciences (XDPB190201)。
文摘The selective catalytic reduction(SCR) of NO_(x) with NH_(3)(NH_(3)-SCR) technology has been widely applied for reducing NO_(x) emissions from stationary and mobile sources.In this work,the extruded monolith MnO_(x)-CeO_(2)-TiO_(2) catalyst was installed in a cement kiln for NH_(3)-SCR of NO_(x),where the flue gas temperature was 110-140℃.It is found that the monolith catalyst is severely deactivated after operating for about 200 h with almost no NO_(x) conversion at 160℃ under GHSV of 50000 h^(-1),while the fresh monolith catalyst remains 60% NO_(x) conversion.Scanning electron microscopy-energy dispersive spectroscopy(SEM-EDS),X-ray photoelectron spectroscopy(XPS),temperature-programmed desorption of SO_(2)(SO_(2)-TPD) and thermogravimetric-differential thermal analysis(TG-DTG) experiments reveal that both MnO_(x) and CeO_(2) oxides in monolith are severely sulfated to manganese sulfate and cerium sulfate,and the external monolith walls are covered by massive ceria sulfate and little ammonium nitrate.In situ diffuse reflectance infrared Fourier trans form spectroscopy(DRIFTS) analysis demonstrates that the formation of nitrates at low temperatures is inhibited due to the occupation of active sites in MnO_(x)-CeO_(2)-TiO_(2) by sulfates,resulting in the decrease of low temperature activity.After washing with water,the activity of deactivated monolith catalyst can be partially recovered,together with significant loss of manganese and cerium from monolith.
