Polyoxymethylene dimethyl ethers(OMEs)with physical properties similar to those of diesel has received significant attention as green additives for soot emission suppression.Herein,series of SO_(4)^(2-)/ZrO_(2)-TiO_(2...Polyoxymethylene dimethyl ethers(OMEs)with physical properties similar to those of diesel has received significant attention as green additives for soot emission suppression.Herein,series of SO_(4)^(2-)/ZrO_(2)-TiO_(2)catalysts were developed for OMEs production from dimethoxymethane(DMM)and1,3,5-trioxane through sequential formaldehyde monomer insertion into C-O bond of DMM.Not Lewis but Bronsted acid sites were identified to be active for the decomposition of 1,3,5-trioxane into formaldehyde unit,however,both of them are effective for the chain propagation of DMM via formaldehyde unit insertion into C-O bond.Kinetic studies indicated each chain growth step exhibited the same parameters and activation barrier on corresponding Bronsted and Lewis acid sites due to the same reaction mechanism and very similar chemical structure of OMEs.Also,the catalytic stability investigation suggested the deactivation behavior was derived from the carbon deposition,and the decay factor could be exponentially correlated with the amount of coke accumulation.展开更多
Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst...Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst in polycrystalline state could be clearly observed by transmission electron microscopy(TEM).Mesopores were detected by N2 adsorption-desorption isotherms which further confirmed the MoO_(3)/ZrO_(2)-TiO_(2)structural characteristics of catalyst.The results of NH_(3)-TPD showed that the calcination temperatures had a great influence on the acidity of the catalyst,and the weak acidic site had a strong catalytic activity for the catalytic hydrolysis of CFC-12.Moreover,ZrO_(2)-TiO_(2)was highly dispersed in the MoO_(3)framework,suggested by powder X-ray diffraction(XRD)and N_(2)adsorption-desorption results.The effects of the catalyst calcination temperatures on the conversion rate of CFC-12 were studied.The effects of catalytic hydrolysis temperatures and water vapor concentration on the catalytic hydrolysis rate of CFC-12 were also studied.The solid acid MoO_(3)/ZrO_(2)-TiO_(2)was calcined at 500℃for 3 h at a catalytic hydrolysis temperature of 400℃and water vapor concentration of 83.18%,and catalytic hydrolysis rate of CFC-12 reached 98.65%.The hydrolysis rate of CFC-12 remained above 65.34%after 30 hours continuous reaction.展开更多
超高镍层状材料LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(简称NCM92)因其具有较高的能量密度和价格优势,已成为锂离子电池重要的正极材料来源之一。然而,由于该材料的界面不稳定和不可逆相变,商业应用面临特别是在高截止电压下快速的容量衰...超高镍层状材料LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(简称NCM92)因其具有较高的能量密度和价格优势,已成为锂离子电池重要的正极材料来源之一。然而,由于该材料的界面不稳定和不可逆相变,商业应用面临特别是在高截止电压下快速的容量衰落和严重的结构退化的问题。本研究设计了一种ZrO_(2)/Li_(2)ZrO_(3)双包覆层改性超高镍单晶正极材料,同时材料表面均匀掺杂有Zr元素,通过双包覆层协同策略显著增强了正极的高压性能和结构稳定性。研究结果表明,ZrO_(2)/Li_(2)ZrO_(3)双包覆层可以有效缓解超高镍正极材料H2-H3相变的不可逆性,提高力学稳定性和界面稳定性,同时表面Zr掺杂进入晶体结构中的TM层与Li位抑制Li/Ni混排并扩宽了晶格间距,ZrO_(2)/Li_(2)ZrO_(3)双包覆层与Zr掺杂改性的材料(NCM92-Zr)展现出优异的电化学性能,在0.5 C(200 mA·g^(-1))电流密度下,2.75~4.4 V电压范围内循环150圈后仍有155.2 mA h g^(-1)的放电比容量,容量保持率高达75.5%。此研究为在高截止电压下超高镍正极的复杂机制和改进的结构稳定性提供了新的思路。展开更多
The multilevel storage capability of nonvolatile resistive random access memory(ReRAM)is greatly de-sired to accomplish high functioning memory density.In this study,Ta_(2)O_(5) thin film with different thick-nesses(2...The multilevel storage capability of nonvolatile resistive random access memory(ReRAM)is greatly de-sired to accomplish high functioning memory density.In this study,Ta_(2)O_(5) thin film with different thick-nesses(2,4,and 6 nm)was exploited as an appropriate interfacial barrier layer for limiting the formation of the interfacial layer between the 10 nm thick sputtering deposited resistive switching(RS)layer and Ta ohmic electrode to improve the switching cycle endurance and uniformity.Results show that lower form-ing voltage,narrow distribution of SET-voltages,good dc switching cycles(10^(3)),high pulse endurance(10^(6) cycles),long retention time(10^(4) s at room temperature and 100℃),and reliable multilevel resis-tance states were obtained at an appropriate thickness of∼2 nm Ta_(2)O_(5) interfacial barrier layer instead of without Ta_(2)O_(5) and with∼4 nm,and∼6 nm Ta_(2)O_(5) barrier layer,ZrO_(2)-based memristive devices.Besides,multilevel resistance states have been scientifically investigated via modulating the compliance current(CC)and RESET-stop voltages,which displays that all of the resistance states were distinct and stayed stable without any considerable deprivation over 10^(4) s retention time and 104 pulse endurance cycles.The I-V characteristics of RESET-stop voltage(from−1.7 to−2.3 V)of HRS are found to be a good linear fit with the Schottky equation.It can be seen that Schottky barrier height rises by increasing the stop-voltage during RESET-operation,resulting in enhancing the data storage memory window(on/offratio).Moreover,RESET-voltage and CC control of HRS and LRS revealed the physical origin of the RS mecha-nism,which entails the formation and rupture of conducting nanofilaments.It is thoroughly investigated that proper optimization of the barrier layer at the ohmic interface and the switching layer is essential in memristive devices.These results demonstrate that the ZrO_(2)-based memristive device with an optimized∼2 nm Ta_(2)O_(5) barrier layer is a promising candidate for multilevel data storage memory applications.展开更多
The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants.Coupled ZrO_(2)/ZnO photocatalyst was prepared with a simple precipitation method with cheap ra...The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants.Coupled ZrO_(2)/ZnO photocatalyst was prepared with a simple precipitation method with cheap raw materials zinc acetate and zirconium oxychloride,and was character-ized by X-ray diffraction(XRD)and transmission electron microscopy(TEM).Reactive brilliant red X-3B was used as a model compound to investigate the photocatalytic activity of synthesized catalysts in water under 254 nm UV irradia-tion.Results show that the optimal calcination temperature and coupling molar ratio of Zr were 350°C and 2.5%,respec-tively.At the calcination temperature of 350°C,ZrO_(2) was dispersed on the surface of hexagonal ZnO in the form of amorphous clusters.The particle size of ZrO_(2)/ZnO decreased with the decrease of calcination temperature and the increase of Zr coupling amount.ZrO_(2)/ZnO has better photocatalytic activity for degradation of reactive brilliant red(RBR)X-3B than pure ZnO and P25-TiO_(2).展开更多
层状无机材料的弱层间耦合和大面积表面为构建低导热性无机固体材料提供了基本框架.合成具有足够散射和非谐波性的稳定层状材料,从而降低热导率,仍是一项挑战.本文在层状无机FeOCl材料体系中,通过一步氧化还原反应成功获得了一种结构稳...层状无机材料的弱层间耦合和大面积表面为构建低导热性无机固体材料提供了基本框架.合成具有足够散射和非谐波性的稳定层状材料,从而降低热导率,仍是一项挑战.本文在层状无机FeOCl材料体系中,通过一步氧化还原反应成功获得了一种结构稳定的富含Fe^(2+)的层状材料,实现了表面和界面的同步改性,并实现了超低的热导率.具体而言,系统的X射线吸收精细结构(XAFS)分析和电子能量损失光谱(EELS)分析表明,碱金属原子的层间插层和表面缺陷的引入诱导了大量Fe^(2+)的存在,从而增强了其非谐波性和声子散射.此外,声子态密度(PDOS)分布也提供了确凿的证据,证明了散射概率的提高和声子模式整体的软化.所制得的层状无机材料Fe(III)_(1−n)Fe(II)_(n)O_(1−x)Cl[K^(+)]_(m)不仅结构稳定,而且在298 K时的热导率比原始FeOCl降低了近60%,低至0.29 W m^(−1) K^(−1),这在层状无机材料中是极低的.这项研究为低导热层状材料的设计提供了新的视角.展开更多
基金the fund from the National Natural Science Foundation of China(22208349)the Innovation Academy for Green Manufacture(Chinese Academy of Sciences,IAGM2020C20)+1 种基金Shandong Provincial Natural Science Youth Fund(ZR2022QB244)Japan Society for the Promotion of Science(P20345)。
文摘Polyoxymethylene dimethyl ethers(OMEs)with physical properties similar to those of diesel has received significant attention as green additives for soot emission suppression.Herein,series of SO_(4)^(2-)/ZrO_(2)-TiO_(2)catalysts were developed for OMEs production from dimethoxymethane(DMM)and1,3,5-trioxane through sequential formaldehyde monomer insertion into C-O bond of DMM.Not Lewis but Bronsted acid sites were identified to be active for the decomposition of 1,3,5-trioxane into formaldehyde unit,however,both of them are effective for the chain propagation of DMM via formaldehyde unit insertion into C-O bond.Kinetic studies indicated each chain growth step exhibited the same parameters and activation barrier on corresponding Bronsted and Lewis acid sites due to the same reaction mechanism and very similar chemical structure of OMEs.Also,the catalytic stability investigation suggested the deactivation behavior was derived from the carbon deposition,and the decay factor could be exponentially correlated with the amount of coke accumulation.
基金Funded by the National Natural Science Foundation of China(No.51568068)the Young and Middle-aged Academic and Technical Leaders Reserve Talent Program(No.202105AC160054)。
文摘Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst in polycrystalline state could be clearly observed by transmission electron microscopy(TEM).Mesopores were detected by N2 adsorption-desorption isotherms which further confirmed the MoO_(3)/ZrO_(2)-TiO_(2)structural characteristics of catalyst.The results of NH_(3)-TPD showed that the calcination temperatures had a great influence on the acidity of the catalyst,and the weak acidic site had a strong catalytic activity for the catalytic hydrolysis of CFC-12.Moreover,ZrO_(2)-TiO_(2)was highly dispersed in the MoO_(3)framework,suggested by powder X-ray diffraction(XRD)and N_(2)adsorption-desorption results.The effects of the catalyst calcination temperatures on the conversion rate of CFC-12 were studied.The effects of catalytic hydrolysis temperatures and water vapor concentration on the catalytic hydrolysis rate of CFC-12 were also studied.The solid acid MoO_(3)/ZrO_(2)-TiO_(2)was calcined at 500℃for 3 h at a catalytic hydrolysis temperature of 400℃and water vapor concentration of 83.18%,and catalytic hydrolysis rate of CFC-12 reached 98.65%.The hydrolysis rate of CFC-12 remained above 65.34%after 30 hours continuous reaction.
文摘超高镍层状材料LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(简称NCM92)因其具有较高的能量密度和价格优势,已成为锂离子电池重要的正极材料来源之一。然而,由于该材料的界面不稳定和不可逆相变,商业应用面临特别是在高截止电压下快速的容量衰落和严重的结构退化的问题。本研究设计了一种ZrO_(2)/Li_(2)ZrO_(3)双包覆层改性超高镍单晶正极材料,同时材料表面均匀掺杂有Zr元素,通过双包覆层协同策略显著增强了正极的高压性能和结构稳定性。研究结果表明,ZrO_(2)/Li_(2)ZrO_(3)双包覆层可以有效缓解超高镍正极材料H2-H3相变的不可逆性,提高力学稳定性和界面稳定性,同时表面Zr掺杂进入晶体结构中的TM层与Li位抑制Li/Ni混排并扩宽了晶格间距,ZrO_(2)/Li_(2)ZrO_(3)双包覆层与Zr掺杂改性的材料(NCM92-Zr)展现出优异的电化学性能,在0.5 C(200 mA·g^(-1))电流密度下,2.75~4.4 V电压范围内循环150圈后仍有155.2 mA h g^(-1)的放电比容量,容量保持率高达75.5%。此研究为在高截止电压下超高镍正极的复杂机制和改进的结构稳定性提供了新的思路。
基金supported in part by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (No.2021R1C1C1004422)the Dongguk University Research Fund of 2020supported through the National Research Foundation of Korea (NRF) funded by the Ministry of Science,ICT & Future Planning (Nos.NRF2020M3F3A2A02082449 and NRF-2016R1A6A1A03013422)。
文摘The multilevel storage capability of nonvolatile resistive random access memory(ReRAM)is greatly de-sired to accomplish high functioning memory density.In this study,Ta_(2)O_(5) thin film with different thick-nesses(2,4,and 6 nm)was exploited as an appropriate interfacial barrier layer for limiting the formation of the interfacial layer between the 10 nm thick sputtering deposited resistive switching(RS)layer and Ta ohmic electrode to improve the switching cycle endurance and uniformity.Results show that lower form-ing voltage,narrow distribution of SET-voltages,good dc switching cycles(10^(3)),high pulse endurance(10^(6) cycles),long retention time(10^(4) s at room temperature and 100℃),and reliable multilevel resis-tance states were obtained at an appropriate thickness of∼2 nm Ta_(2)O_(5) interfacial barrier layer instead of without Ta_(2)O_(5) and with∼4 nm,and∼6 nm Ta_(2)O_(5) barrier layer,ZrO_(2)-based memristive devices.Besides,multilevel resistance states have been scientifically investigated via modulating the compliance current(CC)and RESET-stop voltages,which displays that all of the resistance states were distinct and stayed stable without any considerable deprivation over 10^(4) s retention time and 104 pulse endurance cycles.The I-V characteristics of RESET-stop voltage(from−1.7 to−2.3 V)of HRS are found to be a good linear fit with the Schottky equation.It can be seen that Schottky barrier height rises by increasing the stop-voltage during RESET-operation,resulting in enhancing the data storage memory window(on/offratio).Moreover,RESET-voltage and CC control of HRS and LRS revealed the physical origin of the RS mecha-nism,which entails the formation and rupture of conducting nanofilaments.It is thoroughly investigated that proper optimization of the barrier layer at the ohmic interface and the switching layer is essential in memristive devices.These results demonstrate that the ZrO_(2)-based memristive device with an optimized∼2 nm Ta_(2)O_(5) barrier layer is a promising candidate for multilevel data storage memory applications.
文摘The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants.Coupled ZrO_(2)/ZnO photocatalyst was prepared with a simple precipitation method with cheap raw materials zinc acetate and zirconium oxychloride,and was character-ized by X-ray diffraction(XRD)and transmission electron microscopy(TEM).Reactive brilliant red X-3B was used as a model compound to investigate the photocatalytic activity of synthesized catalysts in water under 254 nm UV irradia-tion.Results show that the optimal calcination temperature and coupling molar ratio of Zr were 350°C and 2.5%,respec-tively.At the calcination temperature of 350°C,ZrO_(2) was dispersed on the surface of hexagonal ZnO in the form of amorphous clusters.The particle size of ZrO_(2)/ZnO decreased with the decrease of calcination temperature and the increase of Zr coupling amount.ZrO_(2)/ZnO has better photocatalytic activity for degradation of reactive brilliant red(RBR)X-3B than pure ZnO and P25-TiO_(2).
基金supported by the Chinese Academy of Sciences(CAS)Project for Young Scientists in Basic Research(YSBR-070)the National Natural Science Foundation of China(21925110,22321001 and 12147105)+5 种基金the USTC Research Funds of the Double FirstClass Initiative(YD2060002004)the National Key Research and Development Program of China(2022YFA1203600)the Anhui Provincial Key Research and Development Project(202004a050200760)the Key R&D Program of Shandong Province(2021CXGC010302)the Fellowship of China Postdoctoral Science Foundation(2022M710141)the Open Foundation of the Key Lab(Center)of Engineering Research Center of Building Energy Efficiency Control and Evaluation,Ministry of Education(AHJZNX-2023-04).
文摘层状无机材料的弱层间耦合和大面积表面为构建低导热性无机固体材料提供了基本框架.合成具有足够散射和非谐波性的稳定层状材料,从而降低热导率,仍是一项挑战.本文在层状无机FeOCl材料体系中,通过一步氧化还原反应成功获得了一种结构稳定的富含Fe^(2+)的层状材料,实现了表面和界面的同步改性,并实现了超低的热导率.具体而言,系统的X射线吸收精细结构(XAFS)分析和电子能量损失光谱(EELS)分析表明,碱金属原子的层间插层和表面缺陷的引入诱导了大量Fe^(2+)的存在,从而增强了其非谐波性和声子散射.此外,声子态密度(PDOS)分布也提供了确凿的证据,证明了散射概率的提高和声子模式整体的软化.所制得的层状无机材料Fe(III)_(1−n)Fe(II)_(n)O_(1−x)Cl[K^(+)]_(m)不仅结构稳定,而且在298 K时的热导率比原始FeOCl降低了近60%,低至0.29 W m^(−1) K^(−1),这在层状无机材料中是极低的.这项研究为低导热层状材料的设计提供了新的视角.
