盐酸后处理制备高效制氢光催化剂Zn2In2S5

采用水热法制备了ZnIn₂S₄固溶体, 并通过用盐酸对其进行后处理获得了系列Zn_mIn₂S_m+3(m≥2, 整数)固溶体. 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线光电子能谱(XPS)、 紫外-可见漫反射光谱(UV-Vis DRS)、 荧光光谱(PL)和电化学测试对催化剂的组成、 结构和性能进行了表征. 研究了系列固溶体可见光光催化制氢活性. 结果表明, ZnIn₂S₄固溶体经0.5 mol/L HCl处理后能转化为Zn₂In₂S₅固溶体, 其制氢活性为ZnIn₂S₄固溶体的2.2倍, 并且具有良好的稳定性.     

Pu在Gd2Zr2O7基质中的模拟固化: (Gd1-xCex)2Zr2O7+x的热物理性能研究

采用高温固相反应,以NaF作助熔剂,在1000 ℃的温度下合成了锕系元素Pu的模拟固化体(Gd_1-xCe_x)₂Zr₂O_7+x (0 ≤ x ≤ 0.7).研究了模拟固化体的物相、热膨胀系数(TEC)、热导率(TC)随温度及组成的变化规律.粉末X射线衍射(XRD)测试结果表明: Gd₂Zr₂O₇基质本身呈弱有序烧绿石结构,而用Ce⁴⁺取代Gd³⁺的模拟固化体都呈缺陷萤石结构. (Gd_1-xCe_x)₂Zr₂O_7+x的Ce(3d) X射线光电子能谱(XPS)有六个峰,结合能分别位于881.7, 888.1, 897.8, 900.4, 907.1, 916.1 eV处,与CeO2的XPS图谱非常相似,说明Ce为四价.随着温度的升高,所有样品的热膨胀系数总体上呈增大趋势.在室温至750 ℃附近,大部分样品的热导率随温度的升高而降低,之后热导率又呈小幅上升.在相同温度下,固化体(Gd_1-xCe_x)₂Zr₂O_7+x (0 ≤ x ≤ 0.7)的热膨胀系数及热导率随组成变化呈相同趋势:在0 ≤ x ≤ 0.1范围内随x的增大而增大,随后在x = 0.1-0.7时逐渐减小.     

杂多酸/离子液体杂化材料催化苯的高选择性羟基化

制备了V取代的磷钼酸H_3+xPMo_12-xV_xO₄₀（x=0,1,2）及1-丁基-3-甲基咪唑溴盐离子液体（[C₄mim]Br）,并采用离子交换的方法制备了系列杂化材料（[C₄mim]3+xPMo_12-xV_xO₄₀,x=0,1,2）;采用X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、紫外-可见漫反射光谱（UV-Vis DRS）对所制备样品进行了表征;以H₂O₂为氧化剂,考察了所得样品催化苯羟基化制苯酚的活性。结果表明,和相应的离子液体及杂多酸相比,杂化材料的催化活性得到了很大的提高,尤其是催化剂[C₄mim]₅PMo₁₀V₂O₄₀,在优化后的条件下,苯的转化率可达到21%,苯酚的选择性在99%以上。而且,该催化剂具有很好的可重复使用性,连续使用五次后,苯的转化率和苯酚的选择性没有明显降低。     

空心NiCo2S4纳米球助催化剂担载ZnIn2S4纳米片用于可见光催化制氢

纳米片与空心球上之间的合理界面调控是开发高效太阳能制氢光催化剂的潜在策略。在各类光催化材料中,金属硫化物由于具有相对较窄的带隙和优越的可见光响应能力而被广泛研究。ZnIn₂S₄是一种层状的三元过渡金属半导体光催化剂,其带隙可控(约2.4 eV)。在众多金属硫化物光催化剂中,ZnIn₂S₄引起了广泛兴趣。然而,单纯的ZnIn₂S₄光催化活性仍然相对较差,主要是因为光生载流子的复合率较高、迁移速率较慢。在半导体光催化剂上负载助催化剂是提升光催化剂性能的一种有效方法,因为它不仅可以加速光生电子和空穴的分离,而且还可以降低质子还原反应的活化能。作为一种三元过渡金属硫化物,NiCo₂S₄表现出较高的导电性、较低的电负性、丰富的氧化还原特性以及优越的电催化活性。这些特性表明,NiCo₂S₄可以作为光催化制氢的助催化剂,以加速电荷分离和转移。此外,NiCo₂S₄和ZnIn₂S₄都属于三元尖晶石的晶体结构,这可能有助于构建具有紧密界面接触的NiCo₂S₄/ZnIn₂S₄复合物,从而提高光催化性能。本文中,将超薄ZnIn₂S₄纳米片原位生长到非贵金属助催化剂NiCo₂S₄空心球上,形成具有强耦合界面和可见光吸收的NiCo₂S₄@ZnIn₂S₄分级空心异质结构光催化剂。最优NiCo₂S₄@ZnIn₂S₄复合样品(NiCo₂S₄含量：ca. 3.1%)的析氢速率高达78 μmol·h^-1,约是纳米片组装ZnIn₂S₄光催化剂析氢速率的9倍、约是1% (w, 质量分数)Pt/ZnIn₂S₄样品析氢速率的3倍。此外,该复合光催化剂在反应中表现出良好的稳定性。荧光和电化学测试结果表明,NiCo₂S₄空心球是一种有效的助催化剂,可促进光生载流子的分离和传输,并降低析氢反应的活化能。最后,提出了NiCo₂S₄@ZnIn₂S₄光催化析氢的可能反应机理。在NiCo₂S₄@ZnIn₂S₄复合光催化剂中,具有高导电性的NiCo₂S₄助催化剂可快速接受ZnIn₂S₄上的光生电子,用以还原质子生成氢气,而电子牺牲剂TEOA捕获光生空穴,进而完成光催化氧化还原循环。该研究有望为基于纳米片为次级结构的分级空心异质结光催化剂的设计合成及其光催化制氢研究提供一定的指导。     

ZnIn2S4/g-C3N4复合材料的制备及可见光催化制氢性能

采用水热方法制备了ZnIn₂S₄/g-C₃N₄复合材料, 并通过X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 紫外-可见漫反射光谱(UV-Vis DRS)、 透射电子显微镜(TEM)和荧光光谱(PL)等手段对其结构和性能进行表征. 结果表明, 当ZnIn₂S₄的负载量为20%(质量分数)时, 复合材料表现出最佳的光催化制氢性能, 制氢速率可达到637.08 μmol·g^-1·h^-1, 分别为纯ZnIn₂S₄和纯g-C₃N₄的4倍和37倍. 其原因在于ZnIn₂S₄和g-C₃N₄之间具有紧密的异质结结构, 两者有效的结合改善了组分的能带匹配和界面电荷转移, 从而大幅增强了载流子的分离和迁移, 进而提高光催化的性能.     

柠檬酸溶胶-凝胶法制备的Ce1-xZrxO2: 结构及其氧移动性

采用 XRF、XRD、Raman、XPS、H₂-TPR 以及与氩离子刻蚀相结合的XPS等表征技术对柠檬酸溶胶-凝胶法制备的Ce_1-xZr_xO₂ (0≤x≤1)样品的结构及其氧移动性进行了研究. 结果表明, Ce_1-xZr_xO₂ 样品的晶型结构对其中氧的移动性有明显影响. 当x≤0.15 时, Ce_1-xZr_xO₂ 以立方CeO₂相 Ce-Zr-O 固溶体存在, 随着Zr含量的逐渐增加, CeO₂晶胞体积减小、氧空位浓度增加, 氧移动性逐渐增强; 当x＞0.15时, 形成四方ZrO₂相和立方CeO₂相Ce-Zr-O固溶体的混合物, 随着Zr含量的逐渐增加, 四方ZrO₂相的含量增加、氧空位浓度减小, 氧移动性逐渐减弱. 因此, Ce_0.852Zr_0.152O₂样品具有最高的氧移动性.     

Synthesis and electrochemical properties of Li1-xVxCryFe1-yPO4/C as a cathode material

Composites Li1-xVxCryFe1-yPO4/C（x=0.01, 0.02; y = 0.01, 0.02） were synthesized by solid-state reaction method. The influence of the content of doping vanadium and chromium on the structure of Li1-xVxCryFe1-yPO4/C was investigated by XRD, while the morphology of powders was observed by SEM. The investigation of the electrochemical performances showed that the Li0.99V0.01Cr0.02Fe0.98PO4/C material has a higher capacity. At 0.1 C discharging rate, it is capable of delivering reversible specific capacity of 163.8 mAh/g with fairly stable cycleability.     

All-solid-state BiVO4/ZnIn2S4 Z-scheme composite with efficient charge separations for improved visible light photocatalytic organics degradation

Constructing a Z-scheme is a significant approach to improve the separation of photogene rated carriers for effective organic pollutant degradation.Herein,a BiVO4/ZnIn2S4(BZ) Z-scheme composite was successfully synthesized,and applied to photodegrade methyl orange(MO) irradiated by a LED lamp.Anchoring the BiVO4 on the ZnIn2S4 nanoparticles promoted the separation of photogenerated electronholes and broadened the light response range.The detailed characterizations,including surface morphology,elements valence state,and photocurrent performance,demonstrated that the enhanced separation of photogenerated carriers was the pivotal reason for the enhanced photocatalysis reaction.Benefiting from the excellent photocatalytic characteristics,the 5% mass ratio of BZ composite presented the highest MO degradation rate of 0.00997 min^-1,which was 1.9 and 10.3 times greater than the virgin ZnIn2S4 and BiVO4,respectively.Furthermore,the BZ hybrid materials indicated a well photo-stability in the four recycling tests.     

微波辅助快速制备2D/1D ZnIn2S4/TiO2 S型异质结及其光催化制氢性能

The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO₂ has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO₂ nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO₂ NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO₂ NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO₂ NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn₂S₄). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO₂ NFs, we report a 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn₂S₄nanosheets decorated on 1D TiO₂ NFs. The loading of ZnIn₂S₄ nanoplates on the TiO₂ NFs could be easily controlled by adjusting the molar ratios of ZnIn₂S₄ precursors to TiO₂ NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn₂S₄/TiO₂ composites was significantly improved, and the obtained ZnIn₂S₄/TiO₂ composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn₂S₄/TiO₂= 0.5) sample was 8774 μmol·g^-1·h^-1, which is considerably higher than those of pure TiO₂ NFs (3312 μmol·g^-1·h^-1) and ZnIn₂S₄nanoplates (3114 μmol·g^-1·h^-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn₂S₄ and TiO₂ was proposed to interpret the enhanced HER activity of the ZnIn₂S₄/TiO₂heterojunctionphotocatalysts.      

TiN/HfxZr1-xO2/TiN铁电电容器的原位生长与表征

HfO₂基铁电电容器,特别是TiN/Hf_xZr_1-xO₂/TiN金属-绝缘体-金属电容器,由于其良好的稳定性、高性能和互补金属氧化物半导体(CMOS)兼容性,在新一代非易失性存储器中有着广阔的应用前景。由于TiN/Hf_xZr_1-xO₂/TiN电容器的电性能与Hf_xZr_1-xO₂铁电薄膜与TiN电极层界面质量相关,因此控制TiN/Hf_xZr_1-xO₂/TiN异质结构的制备和表征至关重要。本文报道了一种三明治结构：Hf_xZr_1-xO₂铁电薄膜夹在两个TiN电极之间的新的制备方法,通过超高真空系统互连的原子层沉积(ALD)和磁控溅射设备实现。原位生长和表征结果表明,ZrO₂掺杂浓度和快速热退火温度可以调节TiN/Hf_xZr_1-xO₂/TiN异质结的铁电性能,并能很好地被互连系统监控。在该体系中,通过在HfO₂中掺杂50% (molar fraction, x) ZrO₂并且在600 ℃下快速热退火(RTA),获得了21.5 μC·cm^-2的高剩余极化率和1.35 V的低矫顽电压。     

Ir2S3/ZnIn2S4催化下可见光诱导发生的烯烃/炔烃的高效硫氢化反应:Ir2S3的作用

C–S键的构建在化学中具有非常重要的意义.利用硫醇和烯烃/炔烃的硫氢化反应来构建C?S键是一种绿色、可持续和低成本的方法.本文以ZnCl₂,InCl₃,硫代乙酰胺为前驱体,在微量IrCl₃存在条件下,通过一步溶剂热法制备得到了含有不同Ir摩尔比(0.5 mol%,1 mol%和2 mol%)的Ir₂S₃/ZnIn₂S₄纳米复合材料,并考察了它在可见光下诱导烯烃/炔烃的硫氢化反应中的催化性能.以苄基硫醇和苯乙炔的硫氢化反应为模型反应,发现在ZnIn₂S₄中引入微量的Ir₂S₃可明显提升其性能,其中以0.5 mol%Ir₂S₃/ZnIn₂S₄为催化剂时反应性能最佳;反应15 h后苄基硫醇的转化率为97%,苄基苯乙烯基硫醚的产率为95%,明显高于以未修饰的ZnIn₂S₄为催化剂时的转化率和产率.在反应中加入自由基捕获剂TEMPO之后可淬灭该反应,表明与未修饰的ZnIn₂S₄相同,以Ir₂S₃/ZnIn₂S₄复合材料催化的硫氢化反应同样是由硫醇自由基诱发的反应.这种微量Ir₂S₃对ZnIn₂S₄上光诱导硫氢化反应的提升作用在所考察的多个系列底物的反应中都有不同程度的体现,尤其对于一些空间体积较大的底物,其提升作用尤为明显,表明微量Ir₂S₃的存在对ZnIn₂S₄上光诱导硫醇和烯烃/炔烃硫氢化反应的提升作用具有普适性.通过研究负载不同助催化剂(MoS₂,NiS和Pd)的ZnIn₂S₄纳米复合材料在烯烃/炔烃硫氢化反应中的性能及其电化学交流阻抗,我们发现,Ir₂S₃的存在可促进ZnIn₂S₄上光生电子空穴的分离,从而有利于巯基自由基的生成,同时还抑制了副物氢气的产生,因此,烯烃/炔烃的硫氢化反应性能显著提高.该文提出了一种在可见光下利用半导体光催化来构建C?S键的绿色途径,对于理解和设计新的光催化有机合成反应体系具有一定的指导意义.     

Bimetallic Sulfide/Sulfur Doped T3C2Tx MXene Nanocomposites as High-performance Anode Materials for Sodium-ion Batteries

The application of transition metal dichalcogenides(TMDs) as anode materials in sodium-ion batteries (SIBs) has been hindered by low conductivity and poor cyclability. Herein, we report the synthesis of Co_xFe_1-xS₂ bimetallic sulfide/sulfur-doped Ti₃C₂ MXene nanocomposites(Co_xFe_1-xS₂@S-Ti₃C₂) by a facile co-precipitation process and thermal-sulfurization reaction. The interconnected 3D frameworks consisting of MXene nanosheets can effectively buffer the volume change and enhance the charge transfer. In particular, sulfur-doped MXene nanosheets provide rich active sites for sodium storage and restrain sulfur loss during charging/discharging processes, leading the increase of specific capacity and cycling the stability of anode materials. As a result, Co_xFe_1-xS₂@S-Ti₃C₂ anodes exhibited high capacity, high rate capability and long cycle life(399 mA·h/g at 5 A/g with an 94% capacity retention after 600 cycles).     

Mechanism of Lithium and Cobalt Recovery from Spent Lithium-ion Batteries by Sulfation Roasting Process

Different from the traditional pyrometallurgical recovery process of Li and Co from spent lithium-ion batteries, a new recovery method for Li and Co was established by converting LiCoO₂ into water-soluble metal sulfates by roasting a mixture of LiCoO₂ and NaHSO₄·H₂O. The evolution law of the mixture with increased roasting temperature was investigated by thermogravimetry-differential scanning calorimetry(TG-DSC), in situ X-ray diffraction(XRD), XRD, and X-ray photoelectron spectroscopy(XPS). The results show that the phase transition of LiCoO₂ mixed with NaHSO₄·H₂O with increased temperature proceeded as follows:LiCoO₂, NaHSO₄·H₂O→LiCoO₂, NaHSO₄→Li_1-xCoO₂, LiNaSO₄, Na₂S₂O₇, Na₂SO₄→Li_1-xCoO₂, Co₃O₄, LiNaSO₄, Na₂SO₄→Co₃O₄, LiNaSO₄. The reaction mechanism of this roasting process may be as follows:LiCoO₂+NaHSO₄·H₂O→1/2Li₂SO₄+ 1/2Na₂SO₄+1/3Co₃O₄+1/12O₂+3/2H₂O, Li₂SO₄+Na₂SO₄=2LiNaSO₄.     

Synthesis of ferrocenyl-1,2-diketones and related compounds: Crystal and molecular structures of 1,2-diferrocenylethanedione and 1-ferrocenyl-2-(4-biphenylyl) ethanedione

Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C₅H₅)Fe(C₅H₄)] can be prepared by oxidation of acylferrocenes FcCOCH₂R or, more efficiently, by oxidation of the isomeric ketones FcCH₂COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH₂PPh₃)⁺I⁻ via the acylated salts [FcCH(COR)PPh₃]⁺I⁻. The haloacylferocenes FcCOCCl_x H_3−x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel—Crafts acylation of ferrocene using CCl_xH_3−xCOCl/AlCl₃, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCCl_xH_3−x and the other giving the reduced products FcCOCCl_x−1H_4−x. Two diketones FcCOCOFc 3b and FcCOCOC₆H₄Ph 3c have been structurally characterised by single-crystal X-ray diffraction.     

Positronium as a tool to monitor changes of chemical structure

The applicability of positron annihilation spectroscopy for chemical structural problems is demonstrated by two examples: For the swelling dynamics of an amphiphilic polymer network, very quick structural changes were indicated by positronium lifetime parameters at very low swelling ratios and a hydration mechanism was proposed accordingly. For the series [Fe_xZn_1−x(propyltetrazole)₆](BF₄)₂(x=1, 0.6, 0.4, 0.1, 0), changes in the dynamic structure were revealed by positronium lifetime spectroscopy. For compounds of x>0, temperature-induced spin-crossover was detected.     

Transition metal sulfur dioxide hexafluoroarsenates and hexafluoroantimonates

The preparation and characterization by X-ray crystallography of transition metal sulfur dioxide hexafluoroarsenates of the general formula [M(SO₂)_x](AsF₆)₂ 1 (1a: M=Mn, x=2; 1c: M=Co, x=4; 1e: M=Cu, x=4) and the hexafluoroantimonate [Co(SO₂)₂](SbF₆)₂ 3 is reported. The structural features of the compounds mentioned are compared with those of [Fe(SO₂)₄](AsF₆)₂ (1b) and [Ni(SO₂)₆](AsF₆)₂ (1d), reported previously. The structural diversity of transition metal sulfur dioxide complexes is discussed.     

Thermodynamics of (1,4-difluorobenzene + an n-alkane) and of (hexafluorobenzene + an n-alkane)

Excess molar enthalpies H^E and excess molar volumes V^E have been measured, as a function of mole fraction x₁, at 298.15 K and atmospheric pressure for the five liquid mixtures (x₁1,4-C₆H₄F₂ + x₂n-C_lH_2l+2), l = 7, 8, 10, 12 and 16. In addition, H^E and excess molar heat capacities C_P^E at constant pressure have been determined for the two liquid mixtures (x₁C₆F₆ + x₂n-C_lH_2l+2), l = 7 and 14, at the same temperature and pressure. The instruments used were flow microcalorimeters of the Picker design (the H^E version was equipped with separators) and a vibrating-tube densimeter, respectively.

The excess enthalpies of the five difluorobenzene mixtures are all positive and quite large; they increase with increasing chain length l of the n-alkane from H^E(x₁ = 0.5)/(J mol⁻¹) = 1050 for l = 7 to 1359 for l = 16. The corresponding excess volumes V^E are all positive and also increase with increasing l: V^E(x₁ = 0.5)/(cm³ mol⁻¹) = 0.650 for l = 7 and 1.080 for l = 16. Interestingly, the excess enthalphies of the corresponding mixtures with hexafluorobenzene are only about 5% larger, whereas the excess volumes of (x₁C₆F₆ + x₂n-C_lH_2l+2) are roughly twice as large as those of their counterparts in the series containing 1,4-C₆H₄F₂. Specifically, at 298.15 K H^E(x₁ = 0.5)/(J mol⁻¹) = 1119 for (x₁C₆F₆ + x₂n-C₇H₁₆) and 1324 for (x₁C₆F₆ + x₂n-C₁₄H₃₀), and for the same mixtures V^E(x₁ = 0.5)/(cm³ mol⁻¹) = 1.882 and 2.093, respectively. The excess heat capacities for both systems are negative and of about the same magnitude as the excess heat capacities of mixtures of fluorobenzene with the same n-alkanes (Roux et al., 1984): C_P^E(x₁ = 0.5)/(J K⁻¹ mol⁻¹) = −1.18 for (x₁C₆F₆ + x₂n-C₇H₁₆), and −2.25 for (x₁C₆F₆ + x₂n-C₁₄H₃₀). The curve C_P^E vs. (x₁ for x₁C₆F₆ + x₂n-C₁₄H₃₀) shows a sort of “hump” for x₁ 0.5, which is presumed to indicate emerging W-shape composition dependence at lower temperatures.     

Nanotubes of lepidocrocite titanates

Titanate nanotubes were synthesized in hydrothermal treatment of anatase titania powders and concentrated NaOH solution and their structure was investigated. It was suggested that the nanotubes might be constructed from lepidocrocite H_xTi_{2− x/4}□_x/4O₄ (x0.7, □: vacancy) sheets. The newly proposed lepidocrocite titanate nanotube model was supported by X-ray diffraction, electron diffraction, and thermogravimetry studies.     

Regioselective Magneto-optical Heteronanorods Enabling Chiroptical Activity

Synthesis of colloidal heterostructures with rational design and controllable precision represents a promising strategy for achieving novel properties and applications. Most recently, Zhuang et al. reported a "double-buffer-layer engineering" concept that was capable of regioselectively growing magnetic Fe₃O₄ nanodomains only at single ends of semiconductor Zn_xCd_1-xS(0 ≤ x ≤ 1) nanorods. The resulting composite nanostructures exhibited chiroptical activity due to the local magnetic fields introduced by regiospecific magnetic nanodomains, highlighting the promise of controlled colloidal chemistry in synthesizing chiroptical nanostructures in the absence of chiral molecules and helical geometries. The work has been published online in Nature Nanotechnology on January 20, 2020.     

Structure and redox properties of CexPr1−xO2−δ mixed oxides and their catalytic activities for CO, CH3OH and CH4 combustion

A series of Ce_xPr_1−xO_2−δ mixed oxides were synthesized by a sol–gel method and characterized by Raman, XRD and TPR techniques. The oxidation activity for CO, CH₃OH and CH₄ on these mixed oxides was investigated. When the value x was changed from 1.0 to 0.8, only a cubic phase CeO₂ was observed. The samples were greatly crystallized in the range of the value x from 0.99 to 0.80, which is due to the formation of solid solutions caused by the complete insertion of Pr into the CeO₂ crystal lattices. Raman bands at 465 and 1150 cm⁻¹ in Ce_xPr_1−xO_2−δ samples are attributed to the Raman active F_2g mode of CeO₂. The broad band at around 570 cm⁻¹ in the region of 0.3 ≤ x ≤ 0.99 can be linked to oxygen vacancies. The new band at 195 cm⁻¹ may be ascribed to the asymmetric vibration caused by the formation of oxygen vacancies. The TPR profile of Pr₆O₁₁ shows two reduction peaks and the reduction process is followed: . The reduction temperature of Ce_xPr_1−xO_2−δ mixed oxides is lower than those of Pr₆O₁₁ or CeO₂. TPR results indicate that Ce_xPr_1−xO_2−δ mixed oxides have higher redox properties because of the formation of Ce_xPr_1−xO_2−δ solid solutions. The presence of the oxygen vacancies favors CO and CH₃OH oxidation, while the activity of CH₄ oxidation is mostly related to reduction temperatures and redox properties.