Synthesis and characterization of Rh3(μ-PPh2)3(CO)3(PPh3)2: a novel triangular rhodium cluster

Thermal decomposition of RhH(CO)(PPh₃)₃ (Ph = phenyl) in nonane at 120°C yielded a green solid in high yield. The complex was established as Rh₃(μ-PPh₂)₃(CO)₃(PPh₃)₂, (I), X-ray crystallography. I was found to be coordinately unsaturated in the solid state and in solution.     

Hydrothermal synthesis of single-crystal CeCO3OH and their thermal conversion to CeO2

Hexagonal single-crystalline cerium carbonate hydroxide （CeCO3OH） precursors with dendrite morphologies have been synthesized by a facile hydrothermal method at 180 C using CeCl3-7H2O as the cerium source, triethylenetetramine as both an alkaline and carbon source, with triethylenete- tramine also playing an important role in the formation of the dendrite structure. Polycrystalline ceria （CeO2） have been obtained by calcining the precursor at 500 C for 4 h. Tile morphology of the precursor was partly maintained during the heating process. The optical absorption spectra indicate the CeO2 nano/microstructures have a direct band gap of 2.92 eV, which is lower than values of the bulk powder due to the quantum size effect. The high absorption in the UV region for CeO2 nano/microstructure indicated that this material was expected to be used as UV-blocking materials.     

Synthesis and characterisation of cobalt hydroxy carbonate Co2CO3(OH)2 nanomaterials

In an attempt to make nanofibres based upon cobalt oxides, a novel compound hydrated cobalt hydroxy carbonate was formed. This compound is related to the minerals of the rosasite mineral group. X-ray diffraction (XRD) showed that the formed compound was a cobalt hydroxy carbonate, and scanning electron microscopy (SEM) displayed bundles of fibres on the micron scale in length and nanoscale in width. The morphology was compared with that of the rosasite mineral group. X-ray photoelectron spectroscopy (XPS) proved two bond energies for cobalt and three for oxygen in the compound. The compound was characterised by vibrational spectroscopy and the spectra related to minerals of the rosasite mineral group. The stability of the synthetic mineral was limited to temperatures below 200°C.     

Synthesis, characterization, and electrochemical application of Ca(OH)2-, Co(OH)2-, and Y(OH)3-Coated Ni(OH)2 tubes

We report on the synthesis, characterization, and electrochemical application of Ca(OH)2-, Co(OH)2-, and Y(OH)3-coated Ni(OH)2 tubes with mesoscale dimensions. These composite tubes were prepared via a two-step chemical precipitation within an anodic alumina membrane under ambient conditions. The morphology and structure of the as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) equipped with energy dispersive spectroscopy (EDS). The results showed that the size of the tubes was of mesoscale dimension and the proportion of the tube morphology was about 95%. The as-prepared composite tubes were further investigated as the positive-electrode materials of rechargeable alkaline batteries. Electrochemical measurements revealed that the Ni(OH)2 tubes coated with Ca(OH)2, Co(OH)2, and Y(OH)3 exhibited superior electrode properties including high discharge capacity, excellent high-temperature and high-rate discharge ability, and good cycling reversibility. The mechanism analysis suggests that both the coated layers and the unique hollow-tube structures play an indispensable role in optimizing the electrochemical performance of nickel hydroxide electrodes.     

Infrared study of some synthetic phases of malachite (Cu2(OH)2CO3)-hydrozincite (Zn5(OH)6(CO3)2) series

Synthetic malachite, hydrozincite and five monophasic mixed copper-zinc hydroxycarbonates have been studied by Fourier transform infrared (FTIR) spectroscopy at ambient and liquid nitrogen temperature in the region of 4000-400 cm(-1). The analysis of the spectra reveals that the samples containing up to 20% zinc retain the malachite lattice, thus forming solid solutions. The inclusion of zinc ions in malachite reflects on the positions and intensity of the bands corresponding to the internal modes of the carbonate ion, to the OH librations and to the Me-O interactions. For example, the higher and the lower frequency components of v3 shift to higher and lower frequencies, respectively. The intensity of the bands corresponding to v2 decreases with the zinc content increase. The spectrum of the sample Cu1.31Zn0.69(OH)2CO3 become diffuse and ill-resolved in the region of the Me-O interactions (region below 600 cm(-1)) and the corresponding bands are shifted to lower frequencies due to the weaker Zn-O interactions as compared with those of the copper ions. The internal modes of the carbonate ions in hydrozincite and aurichalcite are assigned and discussed taking into account the site symmetry and factor group symmetry. The OH and OD stretches (matrix-isolated HDO molecules) and the hydrogen bond strengths are interpreted in terms of Me-O interactions (synergetic effect), hydrogen bond angles and different hydrogen bond acceptor strengths of the oxygen atoms from the carbonate ions. It proves that the hydrogen bonds in hydrozincite are stronger as compared with those in malachite, irrespective of both the larger hydrogen bond lengths and the weaker Zn-O interactions in hydrozincite due to the higher hydrogen bond acceptor strength of the non-coordinated oxygen atom and the formation of bifurcated hydrogen bonds.     

Pb3(CO3)2(OH)2 Is an Active Phase in Electrocatalytic CO2 Reduction to Formate

Determining the catalytically active phase in electrochemical CO₂ reduction has been challenging. In their work recently published in Nature Communications on July 8, 2020, Zhang et al. studied the phase transition of a tannin-lead(II) complex in electrochemical CO₂ reduction and revealed that the in-situ formed hydrocerussite[Pb₃(CO₃)₂(OH)₂] is the stable active phase for formate production. This new finding may help settle the debate on the real active site of Pb-based materials for CO₂ electroreduction.     

Synthesis of single-crystal beta-Ni(OH)2 nanodisks and alpha-Fe2O3 nanocrystals in C2H5OH-NaOH-NH3 x H2O system

Circular beta-Ni(OH)2 nanodisks and rhombohedral and hexagonal alpha-Fe2O3 nanocrystals were prepared using the C2H5OH-NaOH-NH3 x H2O system under hydrothermal conditions. The C2H5OH/H2O solvent is an appropriate one for the growth of these two materials with their thermodynamically favored morphologies. The possible formation mechanisms are discussed.     

Synthesis of 99mTc(CO)3-NOET via [99mTc(OH2)3(CO)3]+ precursor and comparative biological studies with 99mTcN-noet

Summary The organometallic precursor fac-[^99mTc(CO)₃(H₂O)₃]⁺ was reacted with N-ethoxy, N-ethyl dithiocarbamate (NOET) in phosphate buffered saline (pH 7.4) at room temperature for 30 minutes to produce the ^99mTc(CO)₃-NOET complex. The radiochemical purity (RCP) of the product was over 90% as measured by thin layer chromatography (TLC). No decomposition of the complex at room temperature (RT) was observed over a period of 6 hours. Its partition coefficient indicated that it was a lipophilic complex. The biodistribution comparison in mice of the ^99mTc(CO)₃-NOET complex and the ^99mTcN-NOET complex showed that the former had a lower heart and brain uptake as compared to that of the latter, suggesting the incorporation of the [^99mTc(CO)₃]⁺ core into the NOET ligand does not improve the biological features as a myocardial imaging agent.     

碱式碳酸铜微球的表面改性和组装

报道了通过分散聚合反应在碱式碳酸铜微球表面锚接聚苯乙烯纳米粒子, 以调节其亲水/亲油性的方法. 结果表明, 锚接的聚苯乙烯纳米粒子尺寸愈大, 所得的改性碱式碳酸铜微球疏水性愈强. 用对油和水润湿性适中的改性碱式碳酸铜微球为乳化剂, 能够制备出稳定的油包水型Pickering乳液. 改性碱式碳酸铜微球组装在Pickering乳液的分散相液滴表面, 形成一个固体壳层. 将Pickering 乳液的分散相水核凝胶化, 合成出分级结构琼脂糖凝胶微球.     

Basische Carbonate des Dysprosiums: Dy2O2(CO3) und Dy(OH)(CO3)

Basic Carbonates of Dysprosium: Dy₂O₂(CO₃) and Dy(OH)(CO₃) Single crystals of the basic carbonates Dy₂O₂(CO₃) and Dy(OH)(CO₃) are obtained via hydrothermal synthesis from a mixture of DyCl₃ · 6 H₂O and K₂CO₃ and Cs₂CO₃, respectively, as well as CO₂ and H₂O in a steel autoclave at 480 and 400 °C, respectively. The crystal structures are isotypic with those of II‐Nd₂O₂(CO₃) and B–Nd(OH)(CO₃), respectively; Dy₂O₂(CO₃): hexagonal, P6₃/mmc, Z = 2; a = 386.9(2), c = 1516.3(3) pm; Dy(OH) · (CO₃): hexagonal, P‐6, Z = 18; a = 1201.0(1), c = 971.8(9) pm.     

双核有机锡(Ⅳ)配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)-SnPh_3]·2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH的合成、表征和晶体结构

利用三苯基氯化锡和对苯二甲酸二钠、哌嗪荒酸二钠在甲醇中反应 ,合成了双核有机锡 (Ⅳ )配合物 [Ph3 Sn (CH3 OH)O2 CC6H4 CO2 (CH3 OH)SnPh3 ]·2CH3 OH (1)和 [Ph3 SnS2 CN(CH2 CH2 ) 2 NCS2 SnPh3 ]·2CH3 OH (2 ) .通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征 .用X射线单晶衍射测定了这两个化合物的晶体结构 .化合物 1为单斜晶系 ,空间群P2 1/n ,a =1.5 199(5 )nm ,b =0 .90 0 0 (3)nm ,c =1.82 0 6 (6 )nm ,β =113.970 (5 )° ,Z =2 ,V =2 .2 75 5(13)nm3 ,Dc=1.413g/cm3 ,μ =1.146mm-1,F(0 0 0 ) =980 ,R1=0 .0 35 3,wR2 =0 .0 6 0 6 .化合物 2为单斜晶系 ,空间群P2 1/c,a =1.5 0 6 6 (5 )nm ,b =1.0 875 (4 )nm ,c =1.35 42 (5 )nm ,β =91.6 14(5 )°,Z =2 ,V =2 .2 178(14)nm3 ,Dc=1.498g/cm3 ,μ =1.35 1mm-1,F(0 0 0 ) =10 0 8,R1=0 .0 40 1,wR2 =0 .1148.在 1和 2的晶体中 ,锡原子呈五配位畸变三角双锥构型 .配合物 1由未配位的甲醇分子通过氢键作用形成二维网状结构     

Y(OH)CO3在AgI上的覆盖及中空粒子的制备

用银配合物制备均匀球形AgI纳米粒子,粒径20～100 nm范围内可自由调控.用AgI作为内置核,在尿素存在下,将Y(NO3)3进行升温水解,在预置粒子上包覆Y(OH)CO3形成复合粒子,并符合表面膜机理.结合X射线、电镜照片,考察了Y(NO3)3、尿素、银配合物、内置核的浓度,反应时间,水解温度,表面电荷对反应体系的影响.并加入配合剂Na2S2O3,运用生成稳定配合物的方法溶解内置核,最终得到Y(OH)CO3中空粒子.     

乳液聚合法制备P(St/BA)-KAl(OH)2CO3纳米复合物

利用乳液聚合法制备了一种含KAl(OH)2CO3纳米粒子的聚苯乙烯／丙烯酸丁酯复合物．Zeta电位、粒径分布、扫描电镜(SEM)和透射电镜(TEM)等分析表明KAl(OH)2CO3粒子能够稳定地分散于苯丙乳液的乳胶粒中,形成核一壳结构．热失重(TG)分析表明KAl(OH)2CO3粒子的加入能提高复合物的热稳定性,使其在阻燃涂料领域有着潜在的应用前景．     

配合物Ni(Pybox) (SCN)2(CH3OH)的合成、表征与晶体结构

本文合成了含N原子的三齿配体2,6-吡啶二噁唑啉(Pybox),由Pybox与NiCl2·6H2O和KSCN在甲醇溶液中反应制得标题配合物Ni(Pybox)(SCN)2(CH3OH),并进行了元素分析、红外光谱、电子光谱、X-射线衍射等表征.结果表明:此配合物属单斜晶系,空间群为P2(1)/n,晶体学参数为:a=7.9...     

Synthesis,characterization and thermal behaviour of Fe4(OH)11NO3·2H2O

A new iron basic salt, Fe₄(OH)₁₁NO₃·2H₂O, has been prepared by partially hydrolyzing a solution of Fe(NO₃)₃·9H₂O with urea. The X-ray powder diffraction pattern has been indexed within a monoclinic cella=9.99(3) ?,b=9.48(2) ?,c=3.074(3) ? andβ=90.57(1)°. Thermal decomposition reactions in still air and nitrogen flow have been studied by DTA and TG analysis, and the intermediate and final products have been characterized by X-ray diffraction and IR spectroscopy. When this material is thermally decomposed in an X-ray high temperature diffraction chamber, pure iron is formed at 900 °C together with Fe(III) and Fe(II) oxides.

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Zusammenfassung Mittels Hydrolyse einer L?sung von Fe(NO)₃)₃·9H₂O mit Karbamid wurde das neue basische Eisensalz Fe₄(OH)₁₁NO₃·2H₂O dargestellt. Aus einem R?ntgenpulververfahren resultierena=9,55(3) ?,b=9,48(2) ?,c=3,074(3) ? undβ=90,57(1)° für eine monozyklische Zelle. Mittels DTA- und TG-Untersuchungen wurden die thermischen Zersetzungsreaktionen an Luft und im Stickstoffflu? untersucht und die Zwischen- und Endprodukte mit r?ntgendiffraktionsverfahren und IR-Spectroskopie charakterisiert. Bei einer thermischen Zersetzung dieses Stoffes in einer Hochtemperatur-r?ntgendiffraktionskammer wird bei 900 °C elementares Eisen zusammen mit Fe(II)- und Fe(III)-oxiden gebildet.

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Резюме Частичным гидролизо м раствора соли Fe(NO₃)₃ · 9H₂O с мочевиной получен а новая основная соль Fe₄(OH)₁₁NO₃ · 2Н₂О, для которой методо м порошкового рентген оструктурного анализа была установ лена моноклинная стр уктура с параметрами ячейкиа=9,55(3) А,b=9,48(2) ?,c=3,074(3) ? иβ=90,57(1)°. Термиче ское разложение соли изучено методом ДТА и ТГ в динамическо й атмосфере воздуха и азота, а образующиеся промеж уточные и конечные продукты ре акции были охарактер изованы рентгенофазовым ана лизом и ИК спектроскопией. ˉПри термическом разложе нии соли в высокотемпературно й рентгено-диффракци онной камере при 900° образует ся чистое железо вмес те с оксидами двух- и трехвалентного желе за.

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The authors are greateful to Dr. R. M. Rojas for his helpful suggestions.     

First-principles characterization of formate and carboxyl adsorption on stoichiometric CeO2(111) and CeO2(110) surfaces

Molecular adsorption of formate and carboxyl on stoichiometric CeO₂(111) and CeO₂(110) surfaces was studied using periodic density functional theory (DFT+U) calculations. Two distinguishable adsorption modes (strong and weak) of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO₂(110) surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Finally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO₂ surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters (U = 0, 5, and 7). However, the calculated adsorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes (<0.2 eV). The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is negatively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.     

Structural characterization of nanosized CeO(2)-SiO(2), CeO(2)-TiO(2), and CeO(2)-ZrO(2) catalysts by XRD, Raman, and HREM techniques

Structural characteristics of nanosized ceria-silica, ceria-titania, and ceria-zirconia mixed oxide catalysts have been investigated using X-ray diffraction (XRD), Raman spectroscopy, BET surface area, thermogravimetry, and high-resolution transmission electron microscopy (HREM). The effect of support oxides on the crystal modification of ceria cubic lattice was mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahighly dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO(2)-SiO(2) sample primarily consists of nanocrystalline CeO(2) on the amorphous SiO(2) surface. Both crystalline CeO(2) and TiO(2) anatase phases were noted in the case of CeO(2)-TiO(2) sample. Formation of cubic Ce(0.75)Zr(0.25)O(2) and Ce(0.6)Zr(0.4)O(2) (at 1073 K) were observed in the case of the CeO(2)-ZrO(2) sample. Raman measurements disclose the fluorite structure of ceria and the presence of oxygen vacancies/Ce(3+). The HREM results reveal well-dispersed CeO(2) nanocrystals over the amorphous SiO(2) matrix in the cases of CeO(2)-SiO(2), isolated CeO(2), and TiO(2) (anatase) nanocrystals, some overlapping regions in the case of CeO(2)-TiO(2), and nanosized CeO(2) and Ce-Zr oxides in the case of CeO(2)-ZrO(2) sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO(2) is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of the mixed oxide systems is more than that of pure CeO(2) and is system dependent.     

Synthesis of RuH2(CO)(PPh3)3 in a CO2 and H2 atmosphere

Summary RuH₂(CO)(PPh₃)₃ was prepared in a CO₂ and H₂ atmosphere from RuCl₃ and PPh₃ in the presence of alcohol and Et₃N. Introduction of CO into the system lead to the formation of other complexes e.g. Ru(CO)₃-(PPh₃)₂. Addition of alkali in place of Et₃N resulted in a decrease in the RuH₂(CO)(PPh₃)₃ yield.Author to whom all correspondence should be directed.     

Stabilization of CeO(2) nanoparticles in a CO(2) rich solvent

Here it is shown that the chemical nature of outer organic surfactant layers, used to stabilize inorganic nanoparticles (NPs), is a key factor controlling solubility in a mixed liquid CO(2)-heptane (10% vol) solvent.