The first observation of Mo5+ in the passivation layer of Mo2N

Molybdenum nitride powder with sg of 115 m2·g-1 (passivated) has been prepared by a temperature programmed reaction of MoO3 in H2/N2 mixture. It exhibited high catalytic activity in CO oxidation at low temperature. XPS, EPR and LRS studies have shown the existence of mixed valence states of Mo ions, especially Mo5+ ion (g⊥=1.932, g‖=1.892) observed for the first time, in the passivation layer of molybdenum nitride. A surface superoxide species, O-2(g = 2.001, Raman band 1 124 cm-1), was found to be produced accompanying the transformation of Mo5+/Mo4+ redox pair. Evidence has been given to suggest that this surface superoxide might be responsible for CO oxidation over Mo2N catalyst.     

Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

Surface interactions of MoO3/ α-Fe2O3 system

α-Fe₂O₃ -supported molybdena catalysts have been prepared by heating a mixture of MoO₃ and α-Fe₂O₃. XRD, XPS, LRS, TG-DTA and Mössbauer spectroscopy were used to characterize the interactions between MoO₃ and α-Fe₂O₃. The dispersion capacity of MoO₃ on the surface of α-Fe₂O₃ determined by XRD and XPS was 0.8 mmol/100m² α-Fe₂O₃ in the samples calcined at 420 . For the sample with low MoO₃ loading, LRS and FT-IR results showed that Mo⁶⁺ ions were located in the tetrahedral vacant sites on the surface of α-Fe₂O₃, signed as Mo- . The amount of Mo-II species, formed by Mo6+ ions incorporated into the octahedral vacant sites, increased with the MoO₃ loading. Based on the assumption that the (001) plane of α-Fe₂O₃ is preferentially exposed, almost all the Mo⁶⁺ ions of the dispersed molybdena species existed at the surface octahedral sites for the sample with MoO₃ loading close or beyond the dispersion capacity, and formed the Mo-II species. In this case, the capping O^2- ions linking with the incorporated Mo⁶⁺ ions formed a surface epitaxial structure, which was in good agreement with the results predicted by the incorporation model proposed previously. XRD and Mössbauer spectroscopy of the MoO₃ α-Fe₂O₃ samples calcined at different temperatures showed that the calcination temperature could strongly influence the interaction extent: ( i) at 420 , MoO₃ dispersed on the surface of α-Fe₂O₃ and formed surface Mo species; (ii ) at 500 , MoO₃ reacted with the bulk of α-Fe₂O₃ and formed Fe₂(MoO₄)₃ compound.     

Surface state of molybdenum cations in MoO3/CeO2

Conclusion  

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Synthesis of layered LiMnO2 byin situ oxidation-intercalation and a study of the reaction mechanism and electrochemical performance

Using Mn(OH)₂ as precursor, LiOH as lithiating agent and (NH₄)₂S₂O₈ as oxidant, layeredo-LiMnO₂ was obtained by a novel method—in situ oxidation-intercalation under mild conditions (80 °C). The product was characterized by XRD, ICP, TEM and⁷Li-NMR. The results reveal that orthorhombic LiMnO₂ with high purity and good crystallinity can be obtained by this method. During electrochemical tests, a LiMnO₂/Li cell shows an initial reversible capacity of 208 mAh · g⁻¹ and a reversible capacity of 180 mAh · g⁻¹ after 30 cycles at room temperature.     

Correlation between structure and hardness of magnetron sputtering deposited CNx films

Carbon nitride films are deposited on Si (001) substrates by reactive dc magnetron sputtering graphite in a pure N2 discharge. The structure of carbon nitride films has been probed using Fourier transformation infrared, near edge X-ray absorption fine structure (NEXAFS) and high resolution electron microscopy (HREM), and the hardness has been evaluated in nanoin-dentation experiments. FTIR spectra show that N atoms are bound to sp1, sp2, and sp3 hybridized C atoms. C1s NEXAFS spectra show that the intensity of π* resonance is the lowest for the film grown at substrate temperature TS = 350℃, with a turbostratic-like structure and high hardness, while it is the highest for the film grown at TS = 100℃, with an amorphous structure and low hardness. The correlation between the structure and hardness of carbon nitride films has been discussed.     

Rapid synthesis of MoSi2-Si3N4 nanocomposite via reaction milling of Si and Mo powder mixture

The nanocomposite of MoSi2-SiaN4 （molybdenum disilicide-silicon nitride） was synthesized by reaction milling of the Mo and Si powder mixture. Changing the processing parameters led to the formation of different products such as a- and B-MoSi2, SiaN4, Mo2N, and M05Si3 at various milling times. A thermodynamic appraisal showed that the milling of Moa2Siss powder mixture was associated with highly exothermic mechanically induced self-sustaining reaction （MSR） between Mo and Si. The MSR took place around 5 h of milling led to the formation of a-MoSi2 and the reaction between Si and N2 to produce Si3N4 under a nitrogen pressure of 1 MPa. By increasing the nitrogen pressure to 5 MPa, more heat is released, resulting in the dissociation of Si3N4 and the transformation of a-MoSi2 to β-MoSi2. Heat treatment was also performed on the milled samples and led to the formation of Mo2N and the transformation of a-MoSi2 to β-MoSi2 at the milling times of 10 and 40 h, respectively.     

CuO/CeO2催化剂在温度变动过程中的CO-PROX催化性能

采用浸渍方法制备不同Cu/Ce原子比的CuO/CeO₂催化剂,用于富氢气体中CO优先氧化反应(CO-PROX),考察其在温度变动情况下的催化性能. 利用X射线衍射(XRD)、程序升温还原(TPR)方法对反应前后催化剂样品进行了表征. XRD测试表明,催化反应后的催化剂中有金属Cu0生成. 这与文献结果一致. 与不含CO₂的情况比较,当模拟富氢气体中含有CO₂时,低温段催化活性明显下降. Cu/Ce原子比为10%的催化剂在温度变动过程中具有较稳定的催化性能.      

Synthesis mechanism of LiNiVO4 by wet chemical method and mixed valence of nickel and vanadium

The single phase LiNiVO₄ has been successfully synthesized by adopting a new mild liquid route with oxalic acid as both complexant and precipitant, and this method is named the CPG method. The products were obtained by sintering the dry gel precursor which was prepared by the CPG method at 200—850℃ for 2—10 h in air. The products were tested by XRD, XPS, ESR and TGA-DTA, and the results indicate that the single phase LiNiVO₄ could be obtained at 450℃ for 2—3 h in air and LiNiVO₄ was still steady at 850℃ for 10 h. The valence analyses show that in LiNiVO₄ the valence of lithium is +1, both nickel and vanadium have the mixed valence, namely +2, +3 for nickel and +4, +5 for vanadium respectively. The LiNiVO₄ can be expressed as LiNi³⁺_xNi²⁺_1-xV⁴⁺_xV⁵⁺_1-xO₄ (0≤x<1). The pyrolysis mechanism of the dry gel is also discussed.     

Mn2+和Mo6+对棉花幼苗生长耐盐性的影响

研究了Mn²⁺和Mo⁶⁺混合液浸种对棉花幼苗生长耐盐性的影响.结果表明,适宜浓度的Mn²⁺和Mo⁶⁺能明显提高盐渍土中棉花幼苗长度、根系活力、叶片叶绿素含量、过氧化物酶(POD)活性,即提高了棉花幼苗生长的耐盐性,其中以1 000 mg·L^-1 Mn2++200 mg·L^-1 Mo⁶⁺效果最佳.     

二维Ti3C2Tx MXene材料的制备与工艺优化

二维（2D）过渡金属碳/氮化物（MXene）材料是当前最受关注的二维材料之一,其中二维碳化钛（Ti₃C₂T_x MXene）材料的研究最为广泛。该材料目前主要通过刻蚀三元碳化物或氮化物（MAX相）后进一步插层得到,因此MAX相材料的纯度和制备工艺条件直接决定了Ti₃C₂T_x MXene材料的物化性质。主要完成了不同Ti₃AlC₂ MAX相材料的筛选,选择氢氟酸（HF）刻蚀,并优化了不同的插层方法,制备了一系列Ti₃C₂T_x MXene材料。通过X射线衍射（XRD）、场发射扫描电镜（FESEM）、透射电子显微镜（TEM）、原子力显微镜（AFM）和X射线光电子能谱（XPS）等表征,确定使用原位锂离子（Li⁺）插层法可有效获得单层Ti₃C₂T_x MXene材料。制备的单层Ti₃C₂T_x MXene材料的表面平整,片径约为150 nm,厚度约为2 nm。同时,创新性地采用涡旋震荡辅助材料分层,极大地缩短了超声时间,提高了单层Ti₃C₂T_x MXene材料的产率（可达70%）,并且可以避免材料氧化,为Ti₃C₂T_x MXene材料未来应用提供了新方法。     

High-pressure synthesis and properties of CeO2-ZrO2 solid solution

Using nanoparticles of CeO₂ and ZrO₂ prepared by the chemical precipitation method as starting materials, the singlephase cubic Ce_0.5Zr_0.5O₂ solid solution (cCe_0.5Zr_0.5O₂) has been synthesized under 3.1 GPa at 1073 K for the first time. The structure of the c-Ce_0.5Zr_0.5O₂ has not been changed before and after annealing at 773 K for 1 h. Only an unknown EPR signal (g =1.990) has been observed in the c-Ce_0.5Zr_0.5O₂ and not varied after annealing at 773 K for 1 h, which exhibited that there exists no Ce³⁺ in the c-Ce_0.5Zr_0.5O₂ and the Ce⁴⁺ has not been reduced into Ce³⁺ after annealing. The transport mechanism is ionic for the c-Ce_0.5Zr_0.5O₂. The bulk conductivity (σ =1.2 ×10⁻⁵ S/cm at 823 K, σ=2.1 × 10⁻³ S/cm at 1123 K) is the same as that of CeO₂, but smaller than that of Y₂O₃-stabilized ZrO₂. A marked curvature at T = 823 K has been observed in the Arrhenius plot of the bulk conductivity. The activation energy below 823 K is lower than that above 823 K, and the reason has been discussed.     

氮化碳自组装包裹对SnO2TiO2复合锂离子电池负极材料电化学性能的影响

通过简单的石墨相氮化碳(g-C₃N₄)纳米片自组装沉积法,制备了g-C₃N₄包裹的SnO₂-TiO₂纳米复合材料.扫描电子显微镜观察显示,g-C₃N₄均匀地包裹在SnO₂-TiO₂纳米颗粒上.SnO₂-TiO₂-C₃N₄纳米复合材料被用作锂离子电池的负极材料,在0.2C的倍率下循环20次后,比容量达到380.2 mA·h·g^-1,明显高于未经g-C₃N₄包裹的纯的SnO₂(51.6 mA·h·g^-1)和SnO₂-TiO₂纳米复合材料.在0.1~0.5C的倍率充放电测试中,SnO₂-TiO₂-C₃N₄纳米复合材料的比容量仅从490 mA·h·g^-1衰减到330 mA·h·g^-1,高倍率下抗衰减性能优于同类材料.材料优异的电化学性能归功于g-C₃N₄的包裹处理,这不仅增强了固体电解质界面(SEI)的稳定性,也抑制了锂离子嵌入-脱出时SnO₂和TiO₂纳米颗粒的体积变化.     

石墨相氮化碳表面包覆改善锂离子电池正极材料LiCoO2电化学性能的研究

通过简单的固相法和液相法,分别制备出石墨相氮化碳（g-C₃N₄）表面改性的商品化LiCoO₂复合材料,采用扫描电子显微镜观察改性后的材料,发现g-C₃N₄都均匀地包裹在LiCoO₂表面。两种g-C₃N₄-LiCoO₂复合材料被用作锂离子电池的正极材料,电化学测试结果显示,固相法制得的g-C₃N₄-LiCoO₂复合材料在0.2 C的倍率下充放电测试,首次比容量达167 mA·h·g^-1,循环80次后,比容量仍达132 mA·h·g^-1,高于未经g-C₃N₄包裹的纯LiCoO₂（98 mA·h·g^-1）;液相法制得的Y-C₃N₄-LiCoO₂复合材料循环稳定性明显优于同类材料,循环80次后容量保持率均在95%以上。试验证实,g-C₃N₄表面改性的策略具有一定的实用价值,改性后,材料优异的电化学性能归因于g-C₃N₄的包裹处理,这不仅增强了固体电解质界面（SEI）的稳定性,也抑制了锂离子嵌入/脱出电极材料时引起LiCoO₂体积的变化。     

Au/CexZr1-xO2催化剂在高浓度CO室温催化氧化中的活性

 以柠檬酸溶胶凝胶法制备的铈锆氧化物为载体,采用沉积-沉淀法制备了Au/Ce_xZr_1-xO₂催化剂.探讨了载体组成、焙烧温度、金担载量对该催化剂催化氧化一氧化碳性能的影响,并对催化剂进行XRD表征,优化了制备条件.结果表明:当载体为Ce_0.75Zr_0.25O₂,焙烧温度为550℃,金担载量为4.7%的催化剂在室温下催化氧化CO的效果最好.该催化剂的优点是具有较强的耐水性;在用量少,一氧化碳浓度高的条件下仍能氧化CO₃0%~40%左右.     

CuO/CeO_2空心球的制备及其对CO的氧化性能研究(英文)

报道了一种利用PS模板制备CuO负载CeO_2空心球的简便方法。用扫描电镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、N_2吸附-脱吸等温线和X射线光电子能谱(XPS)对CuO/CeO_2空心球的结构特征进行了表征。为了评价CuO/CeO_2空心球之间的催化性能差异,采用工业CeO_2和CeO_2空心球,H_2温度程序还原(H_2-TPR)和CO氧化试验。结果表明,合成的样品形貌好,比表面积大,纯度高。H_2-TPR分析表明,CuO/CeO_2空心球的还原性具有多种表面活性物。CuO掺杂的CeO_2空心球表现出比CeO_2空心球和商业CeO_2在CO氧化中的更好的性能,因为铜通过氧缺陷的增加和协同效应有效增强了样品对CO催化活性。     

Refinement of the crystal structure for a new mineral──antimonselite

The crystal structure of a new mineral of the stibnite group, Sb-2Se-3, has been determined. The cell constants, obtained by least-squares calculation from direct θ -value's measurements on the diffractometer are: a =1.158 8(5), b =1.174 4(4), c =0.395 5(2) nm; orthorhombic; V =0.538 23 nm+3; Z =4. The space group is Pbnm. X-ray single crystal data, using Mo K α radiation, were measured on a RIGAKU RASA-5RP automated diffractometer and refined to a final R index of 0.048 1. Sb-2Se-3 is isostructural with Sb-2S-3 and Bi-2S-3. Each Sb(1) atom is six-coordinated by 3 Se(1), 1 Se(2) and 2 Se(3) atoms at distances 0.266 0-0.323 6 nm. Each Sb(2) atom is seven-coordinated by 2 Se(1), 2 Se(2) and 3 Se(3) atoms at distances of 0.258 1- 0.346 7 nm. The crystal structure consists of chains parallel to c or needle axis. The strongest bonds (shortest separations) are within the chains. Many important physical properties of antimonselite (optical, ferroelectric, etc.) are related to its crystal structure.     

尿素辅助模板法合成介孔氮掺杂CeO2及其CO2捕获应用研究

以硝酸铈为前驱物,以尿素为助剂,采用一种简单的模板法合成了介孔氮掺杂CeO₂材料.利用X射线衍射仪(XRD)、吸附-脱附仪(BET)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FT-IR)等设备对合成材料进行表征.多种测试结果证明:试验得到的纳米材料具有均一的介孔结构和较高的比表面积(124.8 m²·g^-1)并掺杂了氮元素.同时,测定了介孔CeO₂材料对于CO₂的吸附性能,并研究了氮掺杂对CeO₂材料的CO₂吸附性能的影响.结果表明:相比未掺杂氮的介孔CeO₂,氮掺杂的介孔CeO₂具有更好的CO₂吸附性能和循环吸附脱附性能.     

A possible configuration of H 5 + cluster

On the basis of our previous work, a configuration of H ₅ ⁺ has been presented that is a square center structure, and the energy for the structure of H ₅ ⁺ has been obtained by IACQM. The result showed that there is an extreme energy E_e: −2.45981 [2 Ry] atR = 2.50a ₀. It indicates that the square center structure of H ₅ ⁺ system has the certain stability, which is a possible configuration of H ₅ ⁺ .