Role of A-sites in pyrochlore lanthanide ruthenate for electrocatalysis of oxygen evolution reaction

Developing highly stable and efficient catalysts for oxygen evolution reaction(OER)is extremely important to sustainable energy conversion and storage,but improved efficiency is largely hindered by sluggish reaction kinetics.Dense and bimetal ruthenates have emerged as one of the promising substitutes to replace single-metal ruthenium or iridium oxides,but the fundamental understanding the role of A-site cations is still blurring.Herein,a family of lanthanides(Ln=all the lanthanides except Pm)are applied to synthesize pyrochlore lanthanide ruthenates(Ln_(2)Ru_(2)O_(7)),and only Ln_(2)Ru_(2)O_(7)(Ln=Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,or Lu)with pure phase can be obtained by the ambient-pressure calcination.Compared with the perovskite ruthenates(SrRuO_(3))and rutile RuO_(2),the[RuO_(6)]units in these Ln_(2)Ru_(2)O_(7) present the largely distorted configurations and different energy level splitting to prevent the excessive Ru oxidation and dissolution,which leads the primary improvement in the electrocatalytic OER performance.In the similar crystalline field split states,the charge transfer between[RuO6]units and Ln^(3+)cations also affect catalytic activities,even in the Ln_(2)Ru_(2)O_(7) surface reconstruction during the OER process.Consequently,Tb_(2)Ru_(2)O_(7) showed the highest OER performance among all the prepared Ln_(2)Ru_(2)O_(7) with similar morphologies and crystallization.This systematic work gives fundamental cognition to rational design of high-performance OER electrocatalysts in proper water electrolysis technologies.

离子注入诱发YSZ相变和Pyrochlore纳米晶的电子显微研究

通过剖面电子显微技术研究了离子注入在单晶YSZ中诱发生成Pyrochlore纳米晶(约10nm),并使萤石结构的YSZ局部相变为焦绿石结构。在YSZ单晶中注入180keVTi+离子,注入温度为常温,Ti+注量为1×1017ions/cm2,随后在1100℃的氩气中退火2h。电子显微研究表明,Y(钇)稳定的立方ZrO2转变成为点阵常数a≈(1.024±0.005)nm的焦绿石结构A2B2O7(Y2(TixZr1-x)2O7)。生成的Y2(TixZr1-x)2O7与母相保持共格,有[110]YSZ∥[110]P和(11-1)YSZ∥(11-1)P的取向关系。阳离子有序和化学成分的重新分布被认为是这种相变发生的机理。

Hydroxycalciopyrochlore, A New Mineral Species from Sichuan, China

Hydroxycalciopyrochlore,ideally （Ca,Na,U,□）2（Nb,Ti）2O6（OH）,cubic,is a new mineral species （IMA2011-026） within the pyrochlore supergroup that was found occurring at the Maoniuping mine,Mianning County,Xichang prefecture,Sichuan Province,southwest China.The mineral is found in an alkali feldspar granite rare-earth ore deposit （26-27 Ma）.Associated minerals include calcite,barite,celestine,albite,aegirine,aegirine-augite,fluorite,parasite-（Ce）,thorite,thorianite,zircon,galena,sphalerite,magnetite,and pyrite.Crystals occur mostly as octahedra,and less often as dodecahedra and tetrahexahedra or combinations thereof.Some occur with an allotriomorphic habit with a thick triangular tabular form.Crystals generally range from 0.1 to 1 mm in size.The mineral is brownishblack,greenish-black and black on fresh sections with a brown streak.The crystal is translucent,and has a greasy lustre on fresh sections.It is metamict without any observed parting or cleavage and with a conchoidal fracture.The Vickers microhardness is 572 kg/mm2 （5-6 on the Mohs hardness scale）.The density measured by hydrostatic weighing is 5.10（3） g/cm3.The strongest four reflections in the X-ray powder-diffraction pattern [d in（A） （Ⅰ） hkl] are：2.9657 （100） 2 2 2,1.8142 （34） 0 4 4,1.5463 （21） 2 2 6,2.5688 （18） 0 0 4.The unit-cell parameters are a =10.381（4） （A）,V=1118.7（7）（A）3,Z =8.The structure was solved and refined in the space group Fd3m with R =0.09.The empirical formula is （Ca0.74Na0.5sU0.40Ce0.05Fe0.02□0.21）2.00（Nb1.15Ti0.s0Ta0.03Al0.01Mg0.01）2.00O6.02 [（OH）1.01F0.09]1.10,on the basis of 2 atoms of B pfu; the simplified formula is （Ca,Na,U,□）2（Nb,Ti）2O6（OH）.Type material is deposited in the Geological Museum of China,Beijing,People＇s Republic of China,catalogue number M11800.

Hydrothermal Synthesis and Characterization of Pyrochlore Titanate R_2Ti_2O_7(R=Gd^(3+),Tb^(3+),Dy^(3+))

Pyrochlore titanate oxides, R2Ti2O7（R=Gd3＋, Tb3＋, Dy3＋）, were synthesized under mild hydrothermal conditions. The crystal growth of pyrochlore titanate oxides and taking place of chemical reaction in the hydrothermal processing were sensitive to the alkalinity, temperature, reaction time, the nature of the rare earth ion and the composition of initial reaction mixture. The as-prepared samples were characterized by powder X-ray diffraction, scanning electron microscopy, Raman spectrum and variable temperature dc magnetic susceptibility（Superconductivity quantum interference device, SQUIDS）. The magnetic studies gave 7.29×10-23 A·m2/Gd3＋ and -8.28 K, 8.75×10-23 A·m2/ Tb3＋ and -19.7 K, and 8.85×10-23 A·m2/Dy3＋ and 0.84 K effective moments and Weiss constants for Gd2Ti2O7, Tb2Ti2O7 and Dy2Ti2O7, respectively.

First-principles calculation of structural and electronic properties of pyrochlore Lu_2Sn_2O_7

A Density functional theory method within generalized gradient approximation has been performed to obtain the static lattice parameters, oxygen positional parameter, bond length and bond angle and electronic properties of ideal Lu2Sn207 pyrochlore. The results are in excellent agreement with available experimental measurements. Density of states （DOS） of this compound was presented and analysed. We also notice the presence of the hybridization between oxygen and Lu metal. The band structure calculations show that the compound has direct band gap of 2.67 eV at the F point in the Brillouin zone and this indicates that the material has a semi-conducting feature.

Phase and Rietveld Refinement of Pyrochlore Gd_2Zr_2O_7 Used for Immobilization of Pu(Ⅳ)

The phase of pyrochlore Gd_2Zr_2O_7 used for immobilization of Pu （Ⅳ） was investigated, tetravalent cerium was used as the simulacrum for plutonium with tetravalence, and the compounds in the system Gd_2Zr_2-_xCe_xO_7 （0.0≤x≤2.0） were synthesized via a high temperature solid reaction method with Gd_2O_3 and ZrO_2 powders being used as the starting materials. Based on the collected XRD data of the gained samples, the phase and microstructural change of compounds were calculated by means of rietveld structural refinement method. The experimental results indicated that the phases of compounds were changed from pyrochlore to fluorite-type phase with the increasing x. The linear relation between a and x was discovered in the range of fluorite-type phase, which accorded with a = 0.52748 ＋ 0.00825 x （0.2≤x≤2.0）, while V= 0.14668 ＋ 0.00711 x （0.2≤x≤2.0） was also achieved.

Study of High-Temperature Stability of Pyrochlore Zirconates

Based on defect chemistry theory and molecular dynamics,the defect formation energy and its relationship with the mechanism of pyrochlore-fluorite phase change were investigated,so as to reveal the underlying mechanism of high-temperature stability of pyrochlore zirconates.Results showed that with the rise of the atom mass of A,the defect formation energies decreased that meant the crystal structure tended to become more disordered.Noticeably,the first nearest cation antisite dominated the pyrochlore disorder transformation process.In addition,it was found that the diffusion of oxygen atoms was far higher than that of cations,and was increased with the temperature,thus also promoting the pyrochlore-fluorite transformation process.

Self-propagating High-temperature Synthesis of Sm and Zr Co-doped Gd2Ti2O7 Pyrochlore Ceramics as Nuclear Waste Forms

We reported a rapid synthesis of Sm^(3+)/Zr^(4+)co-doped Gd2Ti2O7 pyrochlore simulated nuclear wastes solidification by self-propagation plus quick pressing technique.With increment excess contents of Sm2O3 and ZrO2 from 0 to 10wt%,the phase composition of the products is a mixed phase of pyrochlore structure and defective fluorite structure by X-ray diffraction(XRD)analysis and Raman spectrum.In addition,the SEM results demonstrate the fracture surface and microstructure of Gd2Ti2O7-based pyrochlore.The densified pyrochlore waste form exhibits high bulk density of 5.56 g·cm^(-3) and vickers hardness of 11.20±0.2 GPa.The leaching tests show that the elemental leaching rates of Gd,Sm,and Cu after 42 days are 1.92×10^(-4),1.51×10^(-4),and 3.90×10^(-3) g·m^(-2)·d^(-1),respectively.

The Complex Magnetism in the Breathing Pyrochlore LiIn(Cr_(1-x)Rh_x)_4O_8

We perform a detailed investigation of the new ＇breathing＇ pyrochlore compound LiInCr4O8 through Rh substi- tution with measurements of magnetic susceptibility, specific heat, and x-ray powder diffraction. The antiferro- magnetic phase of LiInCr4O8 is found to be slowly suppressed with increasing Rh, up to the critical concentration of x = 0.1 where the antiferromagnetic phase is still observed with the peak in specific heat Tp = 12.5 K, slightly lower than Tp =14.3 K for the x = 0 compound. From tile measurements of magnetization we also uncover evidence that substitution increases the amount of frustration. Comparisons are made with the LiGayIn1-yCr4O8 system as well as other frustrated pyrochlore-related materials and comparable amounts of frustration are found. The results of this work show that the engineered breathing pyrochlores present an important method to further understand the complex magnetism in frustrated systems.

Vibrational modes in La2Zr2O7 pyrochlore irradiated with disparate electrical energy losses

Polycrystalline samples of La2Zr2O7 pyrochlore are irradiated by different energetic heavy ions to investigate the dependence of the vibrational mode variations on the irradiation parameters. The applied electronic energy loss(d E/dx)e increases from about 5.2 keV/nm to 39.6 keV/nm. The ion fluence ranges from 1× 10^11 ions/cm^2 to 6× 10^15 ions/cm^2.Vibrational modes of irradiated pyrochlore are analyzed by using Raman spectrum. Infrared active modes F1 uat 192, 308,and 651 cm^-1 appear in Raman spectra, and the F2 gband at 265 cm-1 rises up due to the irradiation by 200-MeV Kr ions with(d E/dx)e of 16.0 keV/nm. Differently, for the pyrochlore irradiated by 1750-MeV Bi ions with(d E/dx)e of 39.6 keV/nm, in spite of the appearance of infrared active mode F1 u651 cm^-1, the amorphous structure occurs according to the vibrational mode variations of pyrochlore irradiated at higher ion fluences. Amorphous tracks are observed in the samples, which confirm the occurrence of pyrochlore–amorphous transition in pyrochlore irradiated with(d E/dx)e of 39.6 keV/nm.

Stable CuO/La_(2)Sn_(2)O_(7) catalysts for soot combustion:Study on the monolayer dispersion behavior of CuO over a La_(2)Sn_(2)O_(7) pyrochlore support

To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.

Enrichment of Nb and Ti from carbonatite pyrochlore ore via calcining-slaking followed by gravity separation

In this work,a novel process consisting of calcining-slaking followed by gravity separation for the enrichment of niobium(Nb)and titanium(Ti)from carbonatite pyrochlore ore was proposed,validated and compared with the current mainstream flotation method.During calcining of the pyrochlore ore,within which the carbonates were transformed into lime.Subsequently,when the calcined ore was slaked,lime was transformed into hydroxide with fine particles which were amenable to gravity separation.After calcining at 900℃for 60 min,slaking at 90℃for 10 min with a liquid–solid ratio of 3:1(mL/g),approximately 40%of tailings can be removed by gravity separation,the recoveries of Nb and Ti were 94.7%and 91.0%,and the enrichment ratios of Nb and Ti were 1.61 and 1.43,respectively.The new approach exhibits high separation efficiency of carbonate gangue minerals and valuable minerals,satisfactory recoveries of niobium as well as titanium can be achieved.

High pressure synthesis and characterization of the pyrochlore Dy2Pt2O7:A new spin ice material

The cubic pyrochlore Dy2Pt2O7 was synthesized under 4 GPa and 1000℃ and its magnetic and thermodynamic properties were characterized by DC and AC magnetic susceptibility and specific heat down to 0.1 K.We found that Dy2Pt2O7 does not form long-range magnetic order,but displays characteristics of canonical spin ice such as Dy2Pt2O7,including(1)a large effective moment 9.64μB close to the theoretical value and a small positive Curie-Weiss temperatureθCW=+0.77 K signaling a dominant ferromagnetic interaction among the Ising spins;(2)a saturation moment ~4.5μB being half of the total moment due to the local<111>Ising anisotropy;(3)thermally activated spin relaxation behaviors in the low(~1 K)and high(~20 K)temperature regions with different energy barriers and characteristic relaxation time;and most importantly,(4)the presence of a residual entropy close to Pauling’s estimation for water ice.

Heavy-Ion Radiation Stability of Gd_2Zr_2O_7-Pyrochlore Glass-Ceramic Wasteforms Doped by Simulated Actinides

To research the structure radiation stability of simulated Gd2Zr2O7-pyrochlore glass-ceramic wasteforms Nd3+, Ce4+ were selected as the simulated nuclide of An3+ and An4+ radionuclides respectively. A series of compounds with the general formula Gd2-xNdxZr2-xCexO7 (0.0≤ x ≤2.0) were prepared by High-temperature sintering method at 1623 K for 48 h in air atmosphere. The heavy-ion irradiation experiments were done at room temperature and atmospheric pressure. The structure and microscopic morphology of Gd2-xNdxZr2-xCexO7 (0.0≤ x ≤2.0) glass-ceramic wasteforms before and after irradiation experiments were investigated by the X-ray diffraction and scanning electron microscopy.

Bolshetagninskoe Deposit Microcline-Pyrochlore Ore Process Mineralogy

Bolshetagninskoe deposit is one of the most important Russia niobium potential sources. It is confined to carbonatite complex of the same name that is situated in the Sayan Mountains, Eastern Siberia. In the result of VIMS exploration niobium ores reserves have been applied by Russian State Reserve Committee in 2012 year. Ores contain about 1% Nb2O5 and are unique in that the economic pyrochlore mineralization is concentrated in alkaline metasomatic rocks but not in carbonatites[1]. During exploration 47 borehole samples and 6 bulk samples were collected and studied by process mineralogy techniques (optic mineralogical analyze, optic image analyzer system, XRD, EPMA). 26 borehole samples and 2 bulk samples were tested by rougher floatation to define geometallurgical items and to understand the ore’s behavior. Four volumetric samples have been tested by commissioned flowsheet (radiometric separation → impact milling → selective floatation → pyrochlore leaching → ferroniobium). There are three ore types in the Bolshetagninskoe deposit: microcline-pyrochlore (MP), biotite-columbite-pyrochlore (BCP) and carbonate-pyrochlore (CP). MP type is the most important one. MP ore consists of microcline (59wt%–70wt%) with minor carbonates, apatite, sulfides, goethite. Pyrochlore, the essential Nb mineral (94% of ore Nb content), occurs as fine grains (weighted average grain size is 57 μn). Since pyrochlore grains are fine and friable, the ore preparation size and method is a main problem of its treatment. While primary ore processing is effective to remove about 30% waste material it is important to evaluate its influence on floatation feed grade.

Radiation effects of pyrochlore-rich synroc by heavy-ion irradiation

Heavy-ion irradiation is commonly used to study radiation damage of high level radioactive waste (HLW) forms, but S ion was never used before. In this investigation, 100 MeV 32S ions produced by tandem accelerator was used to study radiation effects on pyrochlore-rich synroc which contained simulated actinides. The amorphization and amorphous doses were determined by X-ray diffractometer (XRD) and transmission electron microscopy /select area electron diffraction (TEM/SAED). The vacancy defects induced by heavy-ion irradiation were characterized by using positron annihilation technique (PAT). The experimental results show that the amorphous dose is 0.5 dpa, the defects produced by heavy-ion irradiation are mainly voids, and irradiation could continue to intensify the vacancy defects even after the amorphous dose was reached.

苯甲羟肟酸体系烧绿石与方解石分离及机理研究

方解石是影响碳酸盐型烧绿石浮选回收的重要因素。目前在实际应用中主要采用反浮选除去碳酸盐类矿物,然后以选择性较差的阳离子为捕收剂直接浮选烧绿石,但存在流程较复杂、回收率不高的问题。以油酸和苯甲羟肟酸为捕收剂,通过单矿物试验研究不同捕收剂对烧绿石和方解石浮选的影响,探索正浮选流程下烧绿石和方解石浮选分离的可行性,并通过浮选溶液化学、红外光谱分析、络合物化学分析等方法探究苯甲羟肟酸体系下药剂在两种矿物表面的作用机理。单矿物试验结果表明,在最佳的pH条件下,油酸、苯甲羟肟酸对烧绿石和方解石都具有较好的捕收能力,但苯甲羟肟酸的选择性要优于油酸,可作为潜在捕收剂。在pH=6时,Pb^(2+)可以扩大苯甲羟肟酸对烧绿石和方解石的可浮性差异,使两者能够有效分离,同时Pb2+的存在可以降低苯甲羟肟酸的用量。动电位和红外光谱结果表明,苯甲羟肟酸在烧绿石和方解石表面发生了化学吸附作用;螯合剂产物分析结果表明,苯甲羟肟酸在矿物表面以苯甲氧肟酸和金属离子活性点作用形成的五元环螯合产物为主,Pb^(2+)的加入可以增加矿物表面的活性点,有助于苯甲羟肟酸在矿物表面的化学吸附。与方解石相比,苯甲羟肟酸在烧绿石表面的吸附强度更大,从而实现两者的分离。

高熵稀土萤石型氧化物陶瓷研究进展

萤石型氧化物具有高熔点、低热导率、抗烧结等优异性能,是目前研究最为广泛且具有很高应用前景的高熵材料结构体系。烧绿石结构可以认为是一种有序缺陷萤石结构,因此本文将烧绿石结构归入萤石型系列。国内外高熵稀土萤石型氧化物结构体系可以分为四类:AO_(2)型、A_(2)B_(2)O_(7)型、A_(2)B_(2)O_(6)O′型、双相RE_(2)Zr_(2)O_(7)型,对各个结构体系的研究现状进行了综述,对高熵稀土萤石型氧化物的发展方向进行了展望。