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1.
Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher-ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems.  相似文献   

2.
Guo  Zengzeng  Wu  Chunlei 《Kinetics and Catalysis》2022,62(1):S21-S29
Kinetics and Catalysis - The monolithic catalyst was prepared by hydrothermal synthesis of Co3O4 crystals on metal foams (Ni, Cu, Fe) and named Co3O4@X. Then ZIF-67 nanoparticles were grown in situ...  相似文献   

3.
We report the synthesis, crystal structures, and spectral, thermal, and magnetic properties of a family of metal–organic perovskite ABX3, [C(NH2)3][MII(HCOO)3], in which A=C(NH2)3 is guanidinium, B=M is a divalent metal ion (Mn, Fe, Co, Ni, Cu, or Zn), and X is the formate HCOO?. The compounds could be synthesized by either diffusion or hydrothermal methods from water or water‐rich solutions depending on the metal. The five members (Mn, Fe, Co, Ni, and Zn) are isostructural and crystallize in the orthorhombic space group Pnna, while the Cu member in Pna21. In the perovskite structures, the octahedrally coordinated metal ions are connected by the antianti formate bridges, thus forming the anionic NaCl‐type [M(HCOO)3]? frameworks, with the guanidinium in the nearly cubic cavities of the frameworks. The Jahn–Teller effect of Cu2+ results in a distorted anionic Cu–formate framework that can be regarded as Cu–formate chains through short basal Cu? O bonds linked by the long axial Cu? O bonds. These materials show higher thermal stability than other metal–organic perovskite series of [AmineH][M(HCOO)3] templated by the organic monoammonium cations (AmineH+) as a result of the stronger hydrogen bonding between guanidinium and the formate of the framework. A magnetic study revealed that the five magnetic members (except Zn) display spin‐canted antiferromagnetism, with a Néel temperature of 8.8 (Mn), 10.0 (Fe), 14.2 (Co), 34.2 (Ni), and 4.6 K (Cu). In addition to the general spin‐canted antiferromagnetism, the Fe compound shows two isothermal transformations (a spin‐flop and a spin‐flip to the paramagnetic phase) within 50 kOe. The Co member possesses quite a large canting angle. The Cu member is a magnetic system with low dimensional character and shows slow magnetic relaxation that probably results from the domain dynamics.  相似文献   

4.
通过催化剂将CO转化为无毒气体仍然是目前减少CO污染的主要手段.随着纳米技术的快速发展,纳米催化剂因其在催化反应中呈现出的独特结构效应(如形貌效应、尺寸效应等)而受到人们的广泛关注.已有大量研究表明,纳米Co3O4作为一种非贵金属氧化物催化剂具有强烈的催化形貌效应,展现出优异的CO低温催化活性.因此,通过合理的设计来调控催化剂粒子的形貌,从而进一步改善催化剂的性能已成为近年来催化剂领域的重要研究方向.对于Co3O4纳米催化剂的可控制备,水热法具有反应温和、操作简便和产品形貌易控等特点.早期的研究主要围绕于Co3O4形貌的可控合成以及不同形貌Co3O4催化剂对其催化活性产生的影响,较少有对其形貌形成机制的报道.特别是在水热反应中,系统研究各反应参数对催化剂各异形貌的形成影响鲜有报道.
  本文在前人的研究基础上,重点研究了水热反应过程中各主要反应参数对产品形貌控制的影响,绘制了一副不同形貌Co3O4材料的合成过程图,并研究了Co3O4纳米催化剂催化CO氧化的形貌效应.通过水热法先成功合成了三种不同形貌(纳米棒、纳米片和纳米立方)的碱式碳酸钴纳米粒子,然后将其焙烧得到了Co3O4纳米粒子.采用扫描电子显微镜(SEM),透射电子显微镜(TEM), X射线粉末衍射仪(XRD),程序升温还原(H2-TPR和CO-TPR),氮气吸附-脱附比表面积测试(BET),氧气程序升温脱附(O2-TPD), X射线光电子能谱(XPS)等表征手段研究了不同反应参数对纳米碱式碳酸钴前驱体形貌形成的作用和各异形貌Co3O4纳米粒子在催化CO氧化反应中催化性能的差异及原因.
  结果表明, Co3O4较好地继承了碱式碳酸钴的形貌,在较低温度条件下(≤140°C),钴源(CoCl2或Co(NO3)2)是影响前驱体形貌的关键因素,反应时间只对粒子的尺寸产生较大影响.低温下, CoCl2作为钴源易诱导生产纳米棒状碱式碳酸钴,而Co(NO3)2则有利于纳米片状生成.当温度高于140°C后,无论何种钴源,最终均制得纳米立方体.表面活性剂CTAB对前驱体的均一性和粒子的分散性产生重要影响,加入CTAB后得到的产品尺寸更均一,形貌更加规整.对比于其他两种形貌的样品, Co3O4纳米片显示出更好的CO催化氧化活性.
   XPS结果表明,各形貌Co3O4纳米材料的表面组成存在明显差异,活性物种Co3+含量的不同是影响催化活性差异的重要原因. Co3O4纳米片具有更多的Co3+活性位,立方纳米Co3O4表面吸附氧含量较高, Co3O4纳米棒则暴露出相对更多的Co2+.因此,在三种形貌催化剂上CO氧化反应中, Co3O4纳米片表现出最优的催化活性,纳米立方次之,而纳米棒最差. H2-TPR, CO-TPR和O2-TPD等结果也表明, Co3O4纳米片拥有更强的还原性能和脱附氧能力,其次是纳米立方Co3O4.这与XPS结果一致,证实了不同形貌Co3O4纳米催化剂上暴露活性位的数量和表面氧物种的不同是造成彼此间催化CO氧化活性差异的重要原因.此外,通过稳定性测试发现Co3O4纳米片具有较高的催化稳定性,在水蒸气存在的情况下Co3O4纳米片逐渐失活,但随后在干燥条件下其催化活性又逐渐得到恢复.  相似文献   

5.
We report the synthesis, crystal structures, thermal and magnetic characterizations of a family of metal‐organic frameworks adopting the niccolite (NiAs) structure, [dmenH22+][M2(HCOO)62−] (dmen=N,N′‐dimethylethylenediamine; M=divalent Mn, 1Mn ; Fe, 2Fe ; Co, 3Co ; Ni, 4Ni ; Cu, 5Cu ; and Zn, 6Zn ). The compounds could be synthesized by either a diffusion method or directly mixing reactants in methanol or methanol–water mixed solvents. The five members, 1Mn , 2Fe , 3Co , 4Ni , and 6Zn are isostructural and crystallize in the trigonal space group P 1c, while 5Cu crystallizes in C2/c. In the structures, the octahedrally coordinated metal ions are connected by anti–anti formate bridges, thus forming the anionic NiAs‐type frameworks of [M2(HCOO)62−], with dmenH22+ located in the cavities of the frameworks. Owing to the Jahn–Teller effect of the Cu2+ ion, the 3D framework of 5Cu consists of zigzag Cu‐formate chains with Cu OCHO Cu connections through short basal Cu O bonds, further linked by the long axial Cu O bonds. 6Zn exhibits a phase transition probably as a result of the order–disorder transition of the dmenH22+ cation around 300 K, confirmed by differential scanning calorimetry and single crystal X‐ray diffraction patterns under different temperatures. Magnetic investigation reveals that the four magnetic members, 1Mn , 2Fe , 3Co , and 4Ni , display spin‐canted antiferromagnetism, with a Néel temperature of 8.6 K, 19.8 K, 16.4 K, and 33.7 K, respectively. The Mn, Fe, and Ni members show spin‐flop transitions below 50 kOe. 2Fe possesses a large hysteresis loop with a large coercive field of 10.8 kOe. The Cu member, 5Cu , shows overall antiferromagnetism (both inter‐ and intra‐chains) with low‐dimensional characteristics.  相似文献   

6.
Three novel nanosized Cu(II), Co(II) and Ni(II) complexes of imine ligand attained from the condensation of 2‐amino‐3‐hydroxypyridine and 3‐methoxysalicylaldehyde have been prepared and investigated using diverse chemical methods such as NMR, CHN analysis, conductance, IR, Spectral studies, TGA and magnetic moment measurements. The obtained data confirmed that the synthesized complexes have metal: ligand ratio of 1:1 and octahedral geometry for Co(II) and Ni(II) complexes. Interestingly, The complexes are used as precursors for producing CuO, Co2O3 and NiO nanoparticles by calcination at 500 °C and their structures were described by powder x‐ray and transmittance electron microscopy. Furthermore, to investigate the feasibility of using the synthesized materials for semiconductor based nanodevices, the electrical properties of the prepared imine complexes and their corresponding metal oxides were investigated by measuring the electrical conductivity over a temperature range 373‐593 K. The data confirm that the materials are semiconductor. The electrical conduction process in the complexes is governed by intermolecular and intramolecular transfer of the charge carriers. But, the conduction mechanism arises from the contribution of the phonon‐assisted small polaron hopping in NiO nanoparticles and charge carrier hopping in CuO and Co2O3 nanoparticles. The results indicate that the complexes under study are promising candidates for wide scale of organic based semiconducting devices.  相似文献   

7.
A facile approach to bimetallic phosphides, Co‐Fe‐P, by a high‐temperature (300 °C) reaction between Co‐Fe‐O nanoparticles and trioctylphosphine is presented. The growth of Co‐Fe‐P from the Co‐Fe‐O is anisotropic. As a result, Co‐Fe‐P nanorods (from the polyhedral Co‐Fe‐O nanoparticles) and sea‐urchin‐like Co‐Fe‐P (from the cubic Co‐Fe‐O nanoparticles) are synthesized with both the nanorod and the sea‐urchin‐arm dimensions controlled by Co/Fe ratios. The Co‐Fe‐P structure, especially the sea‐urchin‐like (Co0.54Fe0.46)2P, shows enhanced catalysis for the oxygen evolution reaction in KOH with its catalytic efficiency surpassing the commercial Ir catalyst. Our synthesis is simple and may be readily extended to the preparation of other multimetallic phosphides for important catalysis and energy storage applications.  相似文献   

8.
9.
Preparation of large quantities of high‐performance supported Pt‐alloy electrocatalysts is crucial for the faster development and implementation of low‐temperature proton exchange membrane fuel cells (PEMFCs). One of the prospective nanofabrication synthesis methods is based on the galvanic displacement (GD) reaction. A facile, highly reproducible, gram scale, water‐based double passivation GD method is now presented for the synthesis of carbon‐supported Pt‐M nanoparticles (M=Cu, Ni, Co). It offers great flexibility over the catalyst design, such as the choice of the sacrificial metal (M), variation of the chemical composition of alloy, variation of total metal loading (Pt+M) on carbon support, or even variation of the carbon support itself. The obtained Pt‐alloy catalysts are several times more active compared to a Pt reference and exhibits better stability during accelerated degradation tests performed at 60 °C.  相似文献   

10.
4-(1H-Pyrazolo (3,4-d) pyrimidin-4-ylazo) benzene-1,3-diol was synthesized and characterized by various spectral and analytical techniques. Semiempirical quantum calculations using the AM1 method have been performed in order to evaluate the geometry and electronic structure of the title azodye in the ground state. The complex formation between Co(II), Ni(II) and Cu(II) ions and the title azodye was studied conductometrically and spectrophotometrically. The spectrophotometric determination of the title metal ions and titration using EDTA are reported. Co(II), Ni(II) and Cu(II) complexes of the title azodye have been synthesized and characterized by elemental analysis, conductivity, magnetic susceptibility, IR, UV-Vis and thermal analysis (TGA and DTA).The spectral and magnetic data suggested the octahedral geometry for Co(II) and Ni(II) complexes while Cu(II) complexes have square planar geometry. The thermal studies confirmed the chemical formulations of the title complexes. The thermal degradation takes place in two or three steps depending on the type of the metal and the geometry of the complexes. The kinetics of the decomposition was examined by using Coats-Redfern relation. The activation energies and other activation parameters (DeltaH, DeltaS and DeltaG) were computed and related to the bonding and stereochemistry of the complexes.  相似文献   

11.
A new hydrazone (LH2) derived from the condensation of 2‐(4‐fluorobenzamido)benzohydrazide with 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde was used to synthesize Co(III), Ni(II) and Cu(II) complexes. These were characterized using various physicochemical, thermal, spectroscopic and single‐crystal X‐ray diffraction techniques. All the complexes crystallize in a monoclinic crystal system with P21/n space group and Z = 4. Structural studies of [Co(L)(LH)]?H2O indicate the presence of both amido and imidol tautomeric forms of the ligand, resulting in a distorted octahedral geometry around the Co(III) ion. On the other hand, in the [Ni(L)(DMF)] and [Cu(L)(H2O)] complexes, the ligand coordinates to the metal through imidol form resulting in distorted square planar geometry, in which the fourth position is occupied by the oxygen of coordinated DMF in [Ni(L)(DMF)] and by a water molecule in [Cu(L)(H2O)]. Hirshfeld surface calculations were performed to explore hydrogen bonding and C―H???π interactions. Molecular docking studies were carried out to study the interaction between the synthesized compounds and proteins (cyclooxygenase‐2 and 5‐lipoxygenase). The complexes along with the parent ligand were screened for their in vivo anti‐inflammatory activity, using the carrageenan‐induced rat paw oedema method. The complexes show significant anti‐inflammatory potencies.  相似文献   

12.
Pt/Co‐core Au‐shell nanoparticles were synthesized via a two‐step route using NaBH4 as a reducing agent. The nanoparticles are characterized by UV‐vis spectroscopy, transmission electron microscopy (TEM) and powder X‐ray diffraction (XRD). The results indicate that the as‐synthesized Pt/Co‐core Au‐shell nanoparticles have a disordered face centered cubic (fcc) structure, whereas the annealed Pt/Co‐core Au‐shell nanoparticles exhibit an ordered face centered tetragonal (fct) structure. Superconducting quantum interference device (SQUID) studies reveal that the coercivity of the annealed Pt/Co‐core Au‐shell nanoparticles increases to 510 Oe after heat treatment at 500 °C for 2 h.  相似文献   

13.
The properties of supported non‐noble metal particles with a size of less than 1 nm are unknown because their synthesis is a challenge. A strategy has now been created to immobilize ultrafine non‐noble metal particles on supports using metal–organic frameworks (MOFs) as metal precursors. Ni/SiO2 and Co/SiO2 catalysts were synthesized with an average metal particle size of 0.9 nm. The metal nanoparticles were immobilized uniformly on the support with a metal loading of about 20 wt %. Interestingly, the ultrafine non‐noble metal particles exhibited very high activity for liquid‐phase hydrogenation of benzene to cyclohexane even at 80 °C, while Ni/SiO2 with larger Ni particles fabricated by a conventional method was not active under the same conditions.  相似文献   

14.
We synthesized magnetic spinel ferrites from trimetallic single-source precursors. Fe(II), Co(II), and Ni(II) ferrite nanoparticles in the range of 9-25 nm were synthesized by solvothermal decomposition of trimetallic acetate complex precursors in benzyl ether in the presence of oleic acid and oleylamine, using 1,2-dodecanediol as the reducing agent. For comparison, spinel ferrite nanoparticles were synthesized by stoichiometric mixtures of metal acetate or acetylacetonate salts. The nanoparticles (NP) were characterized by TEM, DLS, powder XRD, and Raman spectroscopy; and their magnetic properties were characterized by ZFC-FC and M(H) measurements. The ferrite-NP were more homogeneous and had a narrower size distribution when trimetallic complexes were used as precursors. As a consequence, the magnetic properties of these ferrite-NP are closer to the aimed room temperature superparamagnetic behavior, than are those of other ferrites obtained by a mixture of salts.  相似文献   

15.
A new asymmetric Salamo‐based ligand H2L was synthesized using 3‐tertbutyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H2L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}2], and [{Ni(L)(CH3COO)(CH3CH2OH)}2Ni] with the ligand H2L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H2L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.  相似文献   

16.
Novel cobalt, nickel and copper complexes were synthesized by regular reflux method and nano sized Co(II), Ni(II) and Cu(II) metal complexes were synthesized by a facile hydrothermal method using green solvent at various temperatures without the addition of any capping agent. The structural characterization was done by magnetic susceptibility, molar conductance, elemental analysis, thermal analysis, FT‐IR, 1H NMR, 13C NMR, ESI mass, UV–Visible analysis. The morphology and size of the nano metal complexes were determined using FE‐Scanning electron microscopy, powder X‐ray diffraction data and atomic force microscopic techniques. All the spectral and analytical results reveal 1:2 metal to ligand ratios having [ML2(H2O)2] stoichiometry, here M=Co(II), Ni(II) and Cu(II), L=deprotonated ligand. The non‐electrolytic nature of the compound was confirmed by molar conductance experiment. The synthesized Schiff base and its metal complexes (7, 8 and 9) were tested for their biological activity. All the tested compounds exhibit decent anticancer and DNA cleavage activity and copper complex shows better activity results than other tested compounds.  相似文献   

17.
A formaldehyde‐assisted metal–ligand crosslinking strategy is used for the synthesis of metal–phenolic coordination spheres based on sol–gel chemistry. A range of mono‐metal (Co, Fe, Al, Ni, Cu, Zn, Ce), bi‐metal (Fe‐Co, Co‐Zn) and multi‐metal (Fe‐Co‐Ni‐Cu‐Zn) species can be incorporated into the frameworks of the colloidal spheres. The formation of coordination spheres involves the pre‐crosslinking of plant polyphenol (such as tannic acid) by formaldehyde in alkaline ethanol/water solvents, followed by the aggregation assembly of polyphenol oligomers via metal–ligand crosslinking. The coordination spheres can be used as sensors for the analysis of nucleic acid variants with single‐nucleotide discrimination, and a versatile precursor for electrode materials with high electrocatalytic performance.  相似文献   

18.
γ‐Alumina supported 3d transition‐metal nanoparticles are commonly used catalysts for several industrial reactions, such as Fischer‐Tropsch, reforming, methanation, and hydrogenation reactions. However, the activity of such catalyst is often limited by the low metal dispersion and a high content of irreducible metal, inherent to the conventional preparation methods in aqueous phase. In this context, we have recently shown that [{Ni(μ2‐OCHO)(OCHO)(tmeda)}2(μ2‐OH2)] (tmeda=tetramethylethylenediamine) is a suitable molecular precursor for the formation of 1–2 nm large nanoparticles onto alumina. Here, we explore the synthesis of the corresponding Fe, Co, and Cu molecular precursors, namely [{Fe(μ2‐OCHO)(OCHO)(tmeda)}4], [{Co(μ2‐OCHO)(OCHO)(tmeda)}2(μ2‐OH2 )], [Cu(κ2‐OCHO)2(tmeda)], which are, like the Ni precursor, soluble in a range of solvents, rendering them convenient metal precursors for the preparation of supported metallic nanoparticles on γ‐alumina. Using a specific adsorption of the molecular precursor on γ‐alumina in a suitable organic solvent, treatment under H2 provides small and narrowly distributed Fe (2.5±0.9 nm), Co (3.0±1.2 nm), Ni (1.7±0.5 nm), and Cu (2.1±1.5 nm) nanoparticles. XAS shows that the proportion of MAl2O4 (M = Co, Ni, Cu) is small, thus illustrating the advantage of using these tailor‐made molecular precursors.  相似文献   

19.
The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were obtained with sizes ranging from 20 and 60 nm. Through careful control of the reaction conditions, single-phase nanoparticular antimonides were synthesized. The nanophases were investigated by powder X-ray diffraction and (high resolution) electron microscopy. The approach is based on activated metal nanoparticles as precursors for the synthesis of the intermetallic compounds. X-ray powder diffraction studies of reaction intermediates allowed monitoring of the reaction kinetics. The small particle size of the reactants ensures short diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis.  相似文献   

20.
A-site ordered perovskite (BiMn3)Mn4O12 was synthesized through a high-pressure synthesis route at 5 GPa and found to exhibit two magnetic transitions and to show either a positive or a negative magnetodielectric effect depending on the temperature range/magnetic state.  相似文献   

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