Czesław Kapusta

Co–NC–W and Fe–NC–W Electron‐Transfer Channels for Thermal Bistability in Trimetallic {Fe6Co3[W(CN)8]6} Cyanido‐Bridged Cluster

The design and construction of switchable materials attracts tremendous interest owing to the potential in information storing and processing or molecular sensing. The archetypal examples involve a diversity of Fe-, 6] Feor Cobased spin-crossover (SCO) compounds, Co-catecholate/semiquinone systems, 11] as well as d-d bimetallic and sd-d trimetallic cyanide-bridged systems revealing chargetransfer-induced spin transitions (CTIST). Some of these compounds, for example Prussian blue analogues, are particularly promising from the point of view of photoswitching between nonmagnetic and magnetized (that is, TB, TC) states, owing to magnetic coupling through molecular bridges in discrete species 15] and extended networks. 18] Such bistability also emerged in the magnetochemistry of octacyanidometalates, exploiting metal-to-metal electron transfer in CoL[W(CN)8] 3 (L = pyrimidine, 4-methylpyridine) or canonical SCO in FeL[Nb(CN)8] 4 extended networks (L = 4-pyridinealdoxime). A magnetic hysteresis loop with a coercivity of 1–3 T were observed in an optically excited low-temperature metastable phase. As a continuing effort to obtain innovative bistable systems, we explored the simultaneous embedding of Co and Fe cations into one octacyanido-bridged coordination skeleton. We have engineered and isolated the novel trimetallic {Co3Fe II 6[W (CN)8]6(MeOH)24}·x MeOH (1) material built of nanosized (ca. 20 ) pentadecanuclear six-capped body-centered cubic Co3Fe6W6 clusters with MeOH molecules of crystallization (see the Supporting Information). The {M9M’ V 6(CN)48(L)24}·n solv compound family (M = Mn, Co, Ni; M’= Mo, W; L = blocking ligands; Figure 1) reveal high-

Exploring the formation of 3D ferromagnetic cyano-bridged CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2x}·yH2O networks

Two novel non-stoichiometric 3D cyano-bridged coordination networks of general formula CuII2+x{CuII4[WV(CN)8]4−2x[WIV(CN)8]2x}·yH2O were obtained according to two different synthetic strategies. The heterogeneous reaction between solid 2D cyano-bridged network (dienH3){CuII[WV(CN)8]}3·4H2O (1) (dienH33+ = protonated diethylenetriamine) and an aqueous solution of DyIII(NO3)3 results in the removal of dienH33+ cations and the formation of a 3D cyano-bridged CuII2.44{CuII4[WV(CN)8]3.12[WIV(CN)8]0.88}·5H2O (2) network. The direct combination of [CuII(H2O)6]2+ and [WV(CN)8]3− in aqueous media leads to the structurally related CuII2.97{CuII4[WV(CN)8]2.06[WIV(CN)8]1.94}·4H2O (3) assembly. The assemblies 2 and 3 were characterised by X-ray powder diffraction along with IR, X-ray absorption spectroscopy (XAS), proton induced X-ray emission (PIXE) and magnetic measurements. 2 and 3 crystallise in a tetragonal system, space group I4/mmm with cell parameters a = b = 7.2695(9) A; c = 28.268(5) A; Z = 2 (2) and a = b = 7.2858(9) A, c = 28.282(5) A, Z = 2 (3). Both networks are characterised by the increase of TC from 33 K to 40 K and coercivity from 0.2 to 2–2.5 kOe compared to 1. Despite their general structural and magnetic similarity, 2 and 3 reveal significant differences in magnetic dimensionality: compound 2 exhibits the features of a metamagnet with a threshold field of 1.8 kOe at 4.2 K, while compound 3 resembles a classical magnet with 3D ordering. This difference is discussed in terms of non-stoichiometry of the networks accompanied by the appearance of different numbers of non-magnetic “defects” due to the formation of diamagnetic W(IV) centres.

Perspective on the phase diagram of cuprate high-temperature superconductors

Universal scaling laws can guide the understanding of new phenomena, and for cuprate high-temperature superconductivity the influential Uemura relation showed, early on, that the maximum critical temperature of superconductivity correlates with the density of the superfluid measured at low temperatures. Here we show that the charge content of the bonding orbitals of copper and oxygen in the ubiquitous CuO2 plane, measured with nuclear magnetic resonance, reproduces this scaling. The charge transfer of the nominal copper hole to planar oxygen sets the maximum critical temperature. A three-dimensional phase diagram in terms of the charge content at copper as well as oxygen is introduced, which has the different cuprate families sorted with respect to their maximum critical temperature. We suggest that the critical temperature could be raised substantially if one were able to synthesize materials that lead to an increased planar oxygen hole content at the expense of that of planar copper.

Study of N-doped TiO2 thin films forphotoelectrochemical hydrogengeneration from water

Abstract The present work deals with nitrogen-doped stoichiometric TiO2:N and non-stoichiometric TiO2−x:N thin films deposited by means of dc-pulsed reactive sputtering for application as photoanodes for hydrogen generation from water, using solar energy. Stoichiometric thin films of TiO2 crystallize as a mixture of anatase and rutile while rutile phase predominates in TiO2:N at higher nitrogen flow rates as shown by X-ray diffraction at grazing incidence, XRD GID. Lack of bulk nitridation of stoichiometric TiO2:N is indicated by valence-to-core X-ray emission spectroscopy, XES, analysis. The energy band gap as well as flat band potential remain almost unaffected by increasing nitrogen flow rate in this case. In contrast to that, non-stoichiometric thin films of TiO2‑x:N demonstrate systematic evolution of the structural, morphological, optical and photolectrochemical properties upon increasing level of nitrogen doping. Pronounced changes in the growth pattern of non-stoichiometric TiO2-x:N upon varied nitrogen flow rate, demonstrated by scanning electron microscopy, SEM, can be easily correlated with the crystallographic properties studied by XRD GID. Relative positions of Kβ’’ XES lines of the TiO2-x:N thin films, which depend strongly on the nature of the ligands and their local coordination, change with the increasing nitrogen flow. Doping of nonstoichiometric titanium dioxide with nitrogen shifts the absorption spectrum towards the visible range and increases considerably the flat band potential which is beneficial for water photolysis. Graphical Abstract

Correction: Formation of pure Cu nanocrystals upon post-growth annealing of Cu-C material obtained from focused electron beam induced deposition: comparison of different methods.

Summary In this paper we study in detail the post-growth annealing of a copper-containing material deposited with focused electron beam induced deposition (FEBID). The organometallic precursor Cu(II)(hfac)2 was used for deposition and the results were compared to that of compared to earlier experiments with (hfac)Cu(I)(VTMS) and (hfac)Cu(I)(DMB). Transmission electron microscopy revealed the deposition of amorphous material from Cu(II)(hfac)2. In contrast, as-deposited material from (hfac)Cu(I)(VTMS) and (hfac)Cu(I)(DMB) was nano-composite with Cu nanocrystals dispersed in a carbonaceous matrix. After annealing at around 150–200 °C all deposits showed the formation of pure Cu nanocrystals at the outer surface of the initial deposit due to the migration of Cu atoms from the carbonaceous matrix containing the elements carbon, oxygen, and fluorine. Post-irradiation of deposits with 200 keV electrons in a transmission electron microscope favored the formation of Cu nanocrystals within the carbonaceous matrix of freestanding rods and suppressed the formation on their surface. Electrical four-point measurements on FEBID lines from Cu(hfac)2 showed five orders of magnitude improvement in conductivity when being annealed conventionally and by laser-induced heating in the scanning electron microscope chamber.

Enhanced thermal conductivity of graphene nanoplatelets epoxy composites

Abstract Efficient heat dissipation from modern electronic devices is a key issue for their proper performance. An important role in the assembly of electronic devices is played by polymers, due to their simple application and easiness of processing. The thermal conductivity of pure polymers is relatively low and addition of thermally conductive particles into polymer matrix is the method to enhance the overall thermal conductivity of the composite. The aim of the presented work is to examine a possibility of increasing the thermal conductivity of the filled epoxy resin systems, applicable for electrical insulation, by the use of composites filled with graphene nanoplatelets. It is remarkable that the addition of only 4 wt.% of graphene could lead to 132 % increase in thermal conductivity. In this study, several new aspects of graphene composites such as sedimentation effects or temperature dependence of thermal conductivity have been presented. The thermal conductivity results were also compared with the newest model. The obtained results show potential for application of the graphene nanocomposites for electrical insulation with enhanced thermal conductivity. This paper also presents and discusses the unique temperature dependencies of thermal conductivity in a wide temperature range, significant for full understanding thermal transport mechanisms.

Magnetic Properties of the Bi6Fe2Ti3O18 Aurivillius Phase Prepared by Hydrothermal Method

The multiferroic Aurivillius phases in the Bi-Fe-Ti-O system are built from alternate (Bi2O2)2+ and (Bin-1XnO3n+1)2 layers, where X = Fe3+, Ti4+ and “n” refers to the number of perovskite-like layers between Bi2O2 layers. Detailed magnetic studies should be done to understand electromagnetic interactions and multiferroic coupling effects. In the present paper, a powder composed of the Aurivillius phase with n = 5, Bi6Fe2Ti3O18, was successfully prepared by the hydrothermal method. The powder was sintered, obtaining dense polycrystalline materials. It was stated that both powder and sintered bodies were paramagnets with a possible antiferromagnetic ordering or a spin-glass state at the liquid helium temperatures.

Determination of oxygen vacancy limit in Mn substituted yttria stabilized zirconia

A series of Mnx(Y0.148Zr0.852)1−xO2−δ ceramics was systematically studied by means of X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) and DC magnetic susceptibility. The XAS and XES results show the changes in manganese oxidation state and a gradual evolution of the local atomic environment around Mn ions upon increasing dopant contents, which is due to structural relaxation caused by the growing amount of oxygen vacancies. Magnetic susceptibility measurements reveal that Mn3O4 precipitates are formed for x ≥ 0.1 and enable independent determination of the actual quantity of Mn ions dissolved in Yttria Stabilized Zirconia (YSZ) solid solution. We show that the amount of oxygen vacancies generated by manganese doping into YSZ is limited to ∼0.17 per formula unit.

Direct Electron Beam Writing of Silver-Based Nanostructures

Direct writing utilizing a focused electron beam constitutes an interesting alternative to resist-based techniques, as it allows for precise and flexible growth onto any conductive substrate in a single-step process. One important challenge, however, is the identification of appropriate precursors which allow for deposition of the material of choice, e.g., for envisaged applications in nano-optics. In this regard the coinage metal silver is of particular interest since it shows a relatively high plasma frequency and, thus, excellent plasmonic properties in the visible range. By utilizing the precursor compound AgO2Me2Bu, direct writing of silver-based nanostructures via local electron beam induced deposition could be realized for the first time. Interestingly, the silver deposition was strongly dependent on electron dose; at low doses of 30 nC/μm2 a dominant formation of pure silver crystals was observed, while at higher electron doses around 104 nC/μm2 large carbon contents were measured. A scheme for the enhanced silver deposition under low electron fluxes by an electronic activation of precursor dissociation below thermal CVD temperature is proposed and validated using material characterization techniques. Finally, the knowledge gained was employed to fabricate well-defined two-dimensional deposits with maximized silver content approaching 75 at. %, which was achieved by proper adjustment of the deposition parameters. The corresponding deposits consist of plasmonically active silver crystallites and demonstrate a pronounced Raman signal enhancement of the carbonaceous matrix.

Novel nanostructural contrast for magnetic resonance imaging of endothelial inflammation: targeting SPIONs to vascular endothelium

This study aimed to develop superparamagnetic iron oxide nanoparticles (SPIONs) targeted to the areas of vascular endothelium changed in the initial inflammation process, a first step of numerous cardiovascular diseases. Iron oxide nanoparticles coated with a cationic derivative of chitosan (CCh) and having attached monoclonal antibodies (anti VCAM-1 and anti P-selectin) were successfully prepared. Owing to electrostatic stabilization, they form a stable colloidal dispersion in aqueous media. The superparamagnetic properties of the resulting SPION-CCh-anti-VCAM-1 maghemite nanoparticles were proved by magnetometric and Mossbauer measurements. In vitro studies confirmed the specific interaction of anti-VCAM-1 antibodies bound to the surface of SPIONs with endothelial cells of aorta of db/db mice, known to display endothelial inflammation associated with diabetes. The nanoparticles obtained were also visualized using MRI in the aortic arch of ApoE/LDLR−/− mice displaying endothelial inflammation associated with atherosclerosis.