Dispersed Nickel Cobalt Oxyphosphide Nanoparticles Confined in Multichannel Hollow Carbon Fibers for Photocatalytic CO2 Reduction

Materials for high‐efficiency photocatalytic CO₂ reduction are desirable for solar‐to‐carbon fuel conversion. Herein, highly dispersed nickel cobalt oxyphosphide nanoparticles (NiCoOP NPs) were confined in multichannel hollow carbon fibers (MHCFs) to construct the NiCoOP‐NPs@MHCFs catalysts for efficient CO₂ photoreduction. The synthesis involves electrospinning, phosphidation, and carbonization steps and permits facile tuning of chemical composition. In the catalyst, the mixed metal oxyphosphide NPs with ultrasmall size and high dispersion offer abundant catalytically active sites for redox reactions. At the same time, the multichannel hollow carbon matrix with high conductivity and open ends will effectively promote mass/charge transfer, improve CO₂ adsorption, and prevent the metal oxyphosphide NPs from aggregation. The optimized hetero‐metal oxyphosphide catalyst exhibits considerable activity for photosensitized CO₂ reduction, affording a high CO evolution rate of 16.6 μmol h^?1 (per 0.1 mg of catalyst).     

Synthesis and characterization of titanates of the formula MTiO3 (M = Mn,Fe, Co,Ni and Cd) by co-precipitation of mixed metal oxalates

When divalent metal chloride solutions of Mn, Fe, Co, Ni and Cd were mixed with potassium titanyl oxalate solution, mixed metal oxalates were obtained in the case of Fe, Co and Ni at room temperature in the pH range 1.5–3. In the case of manganese, heating was found to be necessary to induce precipitation and complete precipitation occurred at 80 °C. Mixed cadmium and titanyl oxalate precipitation was complete at a pH of 3 at room temperature. Various physico-chemical techniques were employed to characterize the as-dried oxalate precursors and the final MTiO₃ oxide powders (M = Mn, Fe, Co, Ni and Cd) obtained on thermal decomposition. All these experimental results relating to the synthesis and characterizations of MTiO₃ oxides are presented in this paper. The results suggest that the reaction of potassium titanyl oxalate and metal chloride solutions may not lead to the formation of a single molecular precursor by direct salt elimination reaction in the pH range 1.5–3.     

Molecular Mixed‐Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts

Well‐defined mixed‐metal [CoMn₃O₄] and [NiMn₃O₄] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure‐function relationships of the electrocatalysts’ heterometallic composition. Depending on preparation conditions, the Co‐Mn oxide was found to change metal composition during catalysis, while the Ni–Mn oxides maintained the NiMn₃ ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn₃O₄ cubane‐like geometry was maintained in the absence of thermal treatment ( 2‐Ni ). In contrast, the thermally generated 3‐Ni develops an oxide‐like extended structure. Both 2‐Ni and 3‐Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen‐evolving complex in Photosystem II, including the MMn₃O₄ cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.     

Effect of Various Synthesis methods on the Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2

Layered LiNi1/3Co1/3Mn1/3O2 has the isostructure of α-NaFeO2 and shows high rate capacity with stable cycleability. Furthermore, the thermal behavior of this material is milder than that of lithium nickel oxide and lithium cobalt oxide. In addition, it is expected to be stable at elevated temperatures. Therefore LiNi1/3Co1/3Mn1/3O2 may be the most promising cathode materials of lithium-ion secondary battery.In this research, LiNi1/3Co1/3Mn1/3O2 was prepared by solid-state reaction, sol-gel method and mixed hydroxide method. The influences of synthesis method on the physical and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), charge/discharge cycling cyclic voltammetry and differential scanning calorimetry (DSC). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the LiNi1/3Co1/3Mn1/3O2 compound are 2+, 3+ and 4+. From the voltage profile and cyclic voltammetry, the redox processes occurring at ～3.8V and ～4.5V are assigned to the Ni2+/Ni3+ and Co3+/Co4+ couples, respectively. Different preparation methods result in the difference in morphology (shape, particle size and specific surface area) and electrochemical behaviors. A sample prepared by solid-state reaction has the worst electrochemical performance among these three methods. Sample synthesized by mixed hydroxide method displays the better rate capacity than that prepared by sol-gel method, while the capacity retention of sample prepared by sol-gel method is superior to that synthesized by mixed hydroxide method.     

Oxidation does not (always) kill reactivity of transition metals: solution-phase conversion of nanoscale transition metal oxides to phosphides and sulfides

Unexpected reactivity on the part of oxide nanoparticles that enables their transformation into phosphides or sulfides by solution-phase reaction with trioctylphosphine (TOP) or sulfur, respectively, at temperatures of ≤370 °C is reported. Impressively, single-phase phosphide products are produced, in some cases with controlled anisotropy and narrow polydispersity. The generality of the approach is demonstrated for Ni, Fe, and Co, and while manganese oxides are not sufficiently reactive toward TOP to form phosphides, they do yield MnS upon reaction with sulfur. The reactivity can be attributed to the small size of the precursor particles, since attempts to convert bulk oxides or even particles with sizes approaching 50 nm were unsuccessful. Overall, the use of oxide nanoparticles, which are easily accessed via reaction of inexpensive salts with air, in lieu of organometallic reagents (e.g., metal carbonyls), which may or may not be transformed into metal nanoparticles, greatly simplifies the production of nanoscale phosphides and sulfides. The precursor nanoparticles can easily be produced in large quantities and stored in the solid state without concern that "oxidation" will limit their reactivity.     

“Metal‐Free” Catalytic Oxygen Reduction Reaction on Heteroatom‐Doped Graphene is Caused by Trace Metal Impurities

The oxygen reduction reaction (ORR) is of high industrial importance. There is a large body of literature showing that metal‐based catalytic nanoparticles (e.g. Co, Mn, Fe or hybrid Mn/Co‐based nanoparticles) supported on graphene act as efficient catalysts for the ORR. A significant research effort is also directed to the so‐called “metal‐free” oxygen reduction reaction on heteroatom‐doped graphene surfaces. While such studies of the ORR on nonmetallic heteroatom‐doped graphene are advertised as “metal‐free” there is typically no sufficient effort to characterize the doped materials to verify that they are indeed free of any trace metal. Here we argue that the claimed “metal‐free” electrocatalysis of the oxygen reduction reaction on heteroatom‐doped graphene is caused by metallic impurities present within the graphene materials.     

Co-M(M=La,Ce, Fe,Mn, Cu,Cr)复合金属氧化物催化分解N2O

通过共沉淀法制备了一系列Co-M(M= La, Ce, Fe, Mn, Cu, Cr)复合金属氧化物及纯Co3O4催化剂, 考察了其催化分解N2O 的活性. 结果表明在研究的系列催化剂中, Co-Ce 复合氧化物催化剂具有最好的催化分解N2O的活性; 其活性与Ce/Co 摩尔比有直接的关系, 当Ce/Co 摩尔比为0.05 时(CoCe0.05 催化剂)催化活性最佳; 当有NO 和O2共存时, 可能在催化剂活性中心上形成表面硝酸盐或亚硝酸盐吸附物种而使其活性受到较大影响. 通过对Co-M 催化剂的XRD、BET、O2-TPD及H2-TPR 等表征结果的分析, 发现作为主要活性位的Co2+的氧化还原能力是影响催化剂活性的主要原因. 这是因为根据反应机理, N2O 的表面分解步骤与Co2+氧化成Co3+的能力相关, 而吸附氧的脱附与Co3+还原成Co2+的能力相关. 在所研究的催化剂中, 添加除CeO2之外的其它过渡金属氧化物时, 催化剂中Co3+/Co2+的氧化还原能力降低, 因此其催化性能降低. 另外, 添加不同过渡金属氧化物也改变了N2O 催化分解反应的速控步骤.     

密度泛函理论计算研究金属-N4大环化合物在酸性介质中的稳定性

质子交换膜燃料电池(PEMFCs)是一种能够有效地将化学能转换成电能的装置,其具有较高的效率及功率密度,还兼具环境友好的优点,因而在电动车和分布式电站等领域有广泛应用前景.然而,昂贵的价格及较差的耐久性阻碍了 PEMFCs的广泛应用.阴极氧还原反应(ORR)缓慢的动力学是限制 PEMFCs性能的主要因素.目前, Pt及其合金仍然是最有效的 ORR催化剂.有限的 Pt供应量是 PEMFC商业化的主要障碍之一.因此,具有较高 ORR活性的非贵金属催化剂越来越多的引起了人们的关注.在众多非贵金属 ORR催化剂中, Fe, Co等金属与氮共掺杂的碳材料最有望取代 Pt.一般认为,这类材料中起催化作用的活性中心是与金属酞菁(MPc)和卟啉(MP)等大环分子类似的金属-N4配位结构.无论是 MPc和 MP,还是掺杂碳材料催化剂,在酸性介质中的耐久性都不够好.具体原因至今仍没有定论.一些研究者认为中心金属离子与酸性介质中的质子交换引起的去金属中心是原因之一.我们通过密度泛函理论计算和热力学分析研究酸性介质(pH=1)中金属大环分子中金属离子和溶液中质子的交换反应,探讨去金属中心是否是造成金属大环类分子催化剂和金属与氮共掺杂碳基催化剂在酸性介质中不稳定的原因.
　　我们建立了研究金属大环化合物中心金属离子与溶液中质子的交换反应的热力学分析方法.在此基础上借助密度泛函理论计算获得各种金属酞菁和卟啉在强酸性介质中的金属离子平衡浓度,以确定相应金属大环分子的稳定性.研究结果表明,在酸性介质中铬、锰、锌类酞菁和卟啉分子很容易被质子化而形成相应的非金属酞菁和卟啉,原因可能是这三类金属的二价阳离子的3d轨道均为半充满或者全充满状态,使得它们与氮的配位能力下降;而铁、钴、镍、铜类酞菁和卟啉在酸性介质中金属化离子的平衡浓度几乎为零,表明它们基本上不发生金属离子与质子的交换反应,且稳定性趋势为 CoPc > NiPc > FePc > CuPc和 CoP > NiP > CuP > FeP,同时,相应的金属酞菁比金属卟啉更稳定.这表明具有氧还原活性的铁、钴类大环分子催化剂及铁、钴与氮共掺杂的碳材料在酸性溶液中的活性衰减并不是由于金属离子与质子的交换引起的.
　　我们还考察了取代基对大环分子中金属离子与质子交换反应的影响,结果发现,给电子取代基(甲基,氨基,叔丁基)会极大地增强酞菁铁和酞菁钴在酸性介质中的稳定性.对于酞菁铁而言,具有中等强度吸电子效应的四氯、四氟和十六氯取代后,其在酸性中稳定性有一定程度的增强,而具有强烈吸电子效应的四硝基及十六氟取代后,稳定性则降低.对于酞菁钴而言,上面提到的所有吸电子取代基都会使得其在酸性介质中变得更加不稳定,并且其不稳定程度随着取代基吸电子能力的增强而上升.     

Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts

The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO₂ utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO₂ catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.     

Self‐Templated Formation of Uniform NiCo2O4 Hollow Spheres with Complex Interior Structures for Lithium‐Ion Batteries and Supercapacitors

Despite the significant advancement in preparing metal oxide hollow structures, most approaches rely on template‐based multistep procedures for tailoring the interior structure. In this work, we develop a new generally applicable strategy toward the synthesis of mixed‐metal‐oxide complex hollow spheres. Starting with metal glycerate solid spheres, we show that subsequent thermal annealing in air leads to the formation of complex hollow spheres of the resulting metal oxide. We demonstrate the concept by synthesizing highly uniform NiCo₂O₄ hollow spheres with a complex interior structure. With the small primary building nanoparticles, high structural integrity, complex interior architectures, and enlarged surface area, these unique NiCo₂O₄ hollow spheres exhibit superior electrochemical performances as advanced electrode materials for both lithium‐ion batteries and supercapacitors. This approach can be an efficient self‐templated strategy for the preparation of mixed‐metal‐oxide hollow spheres with complex interior structures and functionalities.     

Bimetallic oxide nanoparticles confined in ZIF‐67‐derived carbon for highly selective oxidation of saturated C–H bond in alkyl arenes

Zeolite imidazolate frameworks (ZIFs) have recently emerged as an ideal type of carbon precursors with abundant tailorability. In this work, a series of ZIF‐derived porous carbon catalysts have been prepared with encapsulation of bimetallic oxide nanoparticles via simple thermal treatment. The composition and structure of these catalysts were confirmed in detail by different characterization methods. The bimetallic oxide (Mn/Co, Fe/Co, and Cu/Co) nanoparticles were encapsulated in the nitrogen‐doped graphitized carbon matrix. Moreover, the hierarchically porous structure and carbon defects were successfully constructed in the carbon catalysts. Additionally, in the selective oxidation of saturated C–H bonds in alkyl arenes, the carbon catalysts demonstrate outstanding performance for the oxidation of C–H bonds to corresponding carboxyl groups. This was due to their unique structure can greatly promote mass transfer and molecular oxygen activation, resulting in high conversion and high selectivity. Remarkably, this work here could also provide a novel strategy to the controllable synthesis of metal–organic frameworks (MOFs)‐derived carbon catalysts for enhanced performance in heterogeneous catalysis.     

Shape Engineering of Oxide Nanoparticles for Heterogeneous Catalysis

The fabrication of oxide particles with tunable sizes and shapes at the nanoscale is one of the most crucial issues for the design and development of highly efficient heterogeneous catalysts. The shape of oxide nanoparticles has been demonstrated to affect their catalytic properties remarkably. Tuning the shape of oxide particles allows preferential exposure of specific reactive facets; this can maximize the number of active sites available to the reactants, which can improve the activity and also mediate the reaction route to a specific channel to achieve higher selectivity for a particular chemical reaction. In addition, the shape of the oxide particles affects their interaction with metal particles or clusters, and this involves interfacial strain and charge transfer. Metal particles or clusters dispersed on the reactive or polar facets of the oxide support often provide superior catalytic performance, primarily because of strong metal–support interactions. However, the geometric and electronic features of the metal‐oxide interface may change during the course of the reaction, induced by chemisorption of reactive molecules at elevated temperatures, which should be taken into account in proposing a structure–reactivity relationship.     

Synthesis of Multifunctional Metal‐ and Metal Oxide Core@Mesoporous Silica Shell Structures by Using a Wet Chemical Approach

We demonstrate a facile wet chemical approach for fabricating spherical metal/metal‐oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO₂) shells were fabricated over the pre‐synthesized spherical SiO₂ nanoparticles through a three‐step strategy: 1) synthesis of core materials, 2) covering the core with an organic–inorganic composite layer, and 3) removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO₂, into the pores of an mSiO₂ shell. Mn and TiO₂ cluster‐ incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero‐element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications.     

生物基碳包覆纳米材料(Mn,Co)的制备

提出了一种制备碳包覆纳米材料的新方法.以生物蛋白为前驱体材料，蛋白质肽链构成的空心结构作为合成碳包覆纳米材料的模板反应器;在热处理时，蛋白肽链发生分解,残留的碳作为碳源形成富勒烯类空心纳米材料的壳体，并将填充在蛋白质空心结构内部的金属材料包覆起来.以此技术制备了铁磁性金属锰和钴的碳包覆纳米级材料，初步验证是可行的.讨论了蛋白的矿化组装和蛋白的炭化反应机理.     

Electrospun titania sol–gel‐based ceramic composite nanofibers for online micro‐ solid‐phase extraction with high‐performance liquid chromatography

Titanium(IV) tetraisopropoxide was employed as a metal oxide sol–gel precursor to prepare ceramic composite nanofibers by the electrospinning system. To facilitate this process and obtain the desired nanofibers with higher aspect ratios and surface area, poly(vinylpyrrolidone) was added to the sol of titania. Four ceramic nanofibers sheets based on titania were prepared while each sheet contained different transition metals such as Fe‐Mn, Fe‐Ni, Fe‐Co, and Fe‐Mn‐Co‐Ni. The scanning electron microscope images showed good homogeneity for all the prepared ceramic composites with a diameter range of 100–250 nm. The sorption efficiency was investigated by a micro‐solid‐phase extraction setup in online combination with high‐performance liquid chromatography for the determination of naproxen and clobetasol. All the prepared composites exhibited comparable efficiencies for the desired analytes and the type of metal showed insignificant effect. For the selected composite with Fe‐Mn, the linearity of the analytes was in the range of 1–1000 μg/L and the limit of detection values were found to be 2 and 0.3 μg/L for naproxen and clobetasol, respectively. The developed method was extended to the analysis of urine and blood plasma samples and acceptable relative standard deviations were obtained at two concentration levels.     

Enhanced Pseudocapacitance in Multicomponent Transition‐Metal Oxides by Local Distortion of Oxygen Octahedra

Anomalously high pseudocapacitance of a metal oxide was observed when Ni, Co, and Mn were mixed in a solid solution. Analysis by X‐ray absorption near‐edge spectroscopy (XANES) identified a wider redox swing of Ni as the origin of the enlarged pseudocapacitance. Ab initio DFT calculations revealed that aliovalent species resulting from the copresence of multiple transition metals can generate permanent local distortions of [NiO₆] octahedra. As this type of distortion breaks the degenerate e_g level of Ni²⁺, the Jahn–Teller lattice instability necessary for the Ni^2+/3+ redox flip can be effectively diminished during charge–discharge, thus resulting in the significantly increased capacitance. Our findings highlight the importance of understanding structure–property correlation related to local structural distortions in improving the performance of pseudocapacitors.     

Synchrotron radiation-based multi-analytical approach for studying underglaze color: The microstructure of Chinese Qinghua blue decors (Ming dynasty)

In this paper, we develop a methodological approach combining macro-X-ray fluorescence and synchrotron radiation-based techniques (μXRF, full-field XANES and μXRD) to determine the composition and microstructure of underglaze decors of Qinghua porcelains (Ming dynasty). Various transition metal elements (Fe, Mn, Co) are present in the blue decoration of these ceramics and the approach proposed allows for establishing the feature of each. Thus it shows that Fe ions are distributed homogeneously over the whole glaze without any significant difference in blue and white parts. They do not play a significant role in the color. In contrast, Co ions exhibit a heterogeneous distribution with CoAl₂O₄ particles close to the body/glaze interphase. These particles play a key role in the blue color and, the hue variations seem in greater part to link to their density and repartition. Co dispersed in the glassy matrix is also bivalent and mainly in tetragonal coordination, leading also to a blue color. Mn ion distribution is similar to the one of Co but without presenting local high concentrations associated to Mn based particles. Mn affects the darkness of the color and for the sample without CoAl₂O₄ particle; it is the main color contribution. The presence of CoAl₂O₄ crystals was confirmed by μXRD, which revealed, in addition, a variation of cell parameters certainly linking to a Co partial substitution.     

Single‐Crystal‐like Nanoporous Spinel Oxides: A Strategy for Synthesis of Nanoporous Metal Oxides Utilizing Metal‐Cyanide Hybrid Coordination Polymers

Development of a new method to synthesize nanoporous metal oxides with highly crystallized frameworks is of great interest because of their wide use in practical applications. Here we demonstrate a thermal decomposition of metal‐cyanide hybrid coordination polymers (CPs) to prepare nanoporous metal oxides. During the thermal treatment, the organic units (carbon and nitrogen) are completely removed, and only metal contents are retained to prepare nanoporous metal oxides. The original nanocube shapes are well‐retained even after the thermal treatment. When both Fe and Co atoms are contained in the precursors, nanoporous Fe?Co oxide with a highly oriented crystalline framework is obtained. On the other hand, when nanoporous Co oxide and Fe oxide are obtained from Co‐ and Fe‐contacting precursors, their frameworks are amorphous and/or poorly crystallized. Single‐crystal‐like nanoporous Fe?Co oxide shows a stable magnetic property at room temperature compared to poly‐crystalline metal oxides. We further extend this concept to prepare nanoporous metal oxides with hollow interiors. Core‐shell heterostructures consisting of different metal‐cyanide hybrid CPs are prepared first. Then the cores are dissolved by chemical etching using a hydrochloric acid solution (i.e., the cores are used as sacrificial templates), leading to the formation of hollow interiors in the nanocubes. These hollow nanocubes are also successfully converted to nanoporous metal oxides with hollow interiors by thermal treatment. The present approach is entirely different from the surfactant‐templating approaches that traditionally have been utilized for the preparation of mesoporous metal oxides. We believe the present work proves a new way to synthesize nanoporous metal oxides with controlled crystalline frameworks and architectures.     

Electrothermal atomization with a metal micro-tube in atomic absorption spectrometry

The processes of atom formation and dissipation in a molybdenum micro-tube atomizer have been studied to obtain information on the reaction involved. Vapor temperature was found to be close to atomizer surface temperature. Appearance temperatures and activation energies were obtained for Al, Co, Cu, Mn, Pb, Sb, Se, Sn and Te in argon and argon-hydrogen atmospheres. The atom formation processes are divided into two groups : the reduction of the metal oxide followed by the atomization of free metal, and thermal dissociation of the metal oxide. Hydrogen significantly changes atom formation processes for some metals compared to those in pure argon. The dissipation process of atoms from the micro-tube atomizer appears to be purely gas-phase diffusional.     

Shifting Oxygen Charge Towards Octahedral Metal: A Way to Promote Water Oxidation on Cobalt Spinel Oxides

Cobalt spinel oxides are a class of promising transition metal (TM) oxides for catalyzing oxygen evolution reaction (OER). Their catalytic activity depends on the electronic structure. In a spinel oxide lattice, each oxygen anion is shared amongst its four nearest transition metal cations, of which one is located within the tetrahedral interstices and the remaining three cations are in the octahedral interstices. This work uncovered the influence of oxygen anion charge distribution on the electronic structure of the redox‐active building block Co?O. The charge of oxygen anion tends to shift toward the octahedral‐occupied Co instead of tetrahedral‐occupied Co, which hence produces strong orbital interaction between octahedral Co and O. Thus, the OER activity can be promoted by pushing more Co into the octahedral site or shifting the oxygen charge towards the redox‐active metal center in CoO₆ octahedra.