Pair Distribution Function Analysis and Electrochemical Performance of Mesoporous Carbon Nanomaterials Synthesized Through KOH and ZnCl2 Activation

Mesoporous carbon has been synthesized by activating carbonized biogas slurry residues with ZnCl2 and KOH simultaneously. The carbon to activating agent mass ratios were kept at 1:4, while the ZnCl2 to KOH mass ratio varied from 4:0, 3:1, 2:2, 1:3, to 0:4. The highest BET specific surface area of 361 m2 g-1, micropore surface area of 231 m2 g‒1, mesopore surface area of 125 m2 g‒1, and total pore volume of 0.23 cm3 g‒1 which amounted to 78% mesopore content, were obtained for the sample with 3:1 ZnCl2 to KOH mass ratio. Scanning electron microscope (SEM) images were acquired to determine the surface morphology and energy dispersive X-ray (EDX) was used to determine surface composition of the samples. The short, medium, and long-range orders of the synthesized materials were studied using pair distribution function (PDF) analysis. PDF showed that in addition to the locally ordered carbon and silica phase components, samples activated using combined ZnCl2 and KOH also contained crystalline Zn2SiO4 phase with the willemite structure. Electrochemical studies in three-electrode cell system revealed maximum specific capacitance of 216 F g‒1 exhibited by sample with a ZnCl2: KOH mass ratio of 3:1 at a scan rate of 5 mV s‒1. Keywords: Mesoporous carbon; Pair distribution function, Specific capacitance, supercapacitor &nbsp

Local atomic and magnetic structure of dilute magnetic semiconductor (Ba,K)(Zn,Mn)2_2As2_2

We have studied the atomic and magnetic structure of the dilute ferromagnetic semiconductor system (Ba,K)(Zn,Mn)$_2$As$_2$ through atomic and magnetic pair distribution function analysis of temperature-dependent x-ray and neutron total scattering data. We detected a change in curvature of the temperature-dependent unit cell volume of the average tetragonal crystallographic structure at a temperature coinciding with the onset of ferromagnetic order. We also observed the existence of a well-defined local orthorhombic structure on a short length scale of $\lesssim 5$ \AA, resulting in a rather asymmetrical local environment of the Mn and As ions. Finally, the magnetic PDF revealed ferromagnetic alignment of Mn spins along the crystallographic $c$-axis, with robust nearest-neighbor ferromagnetic correlations that exist even above the ferromagnetic ordering temperature. We discuss these results in the context of other experiments and theoretical studies on this system

Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite

Lead halide perovskites such as methylammonium lead triiodide (MAPI) have outstanding optical and electronic properties for photovoltaic applications, yet a full understanding of how this solution processable material works so well is currently missing. Previous research has revealed that MAPI possesses multiple forms of static disorder regardless of preparation method, which is surprising in light of its excellent performance. Using high energy resolution inelastic X-ray (HERIX) scattering, we measure phonon dispersions in MAPI and find direct evidence for another form of disorder in single crystals: large amplitude anharmonic zone-edge rotational instabilities of the PbI_6 octahedra that persist to room temperature and above, left over from structural phase transitions that take place tens to hundreds of degrees below. Phonon calculations show that the orientations of the methylammonium couple strongly and cooperatively to these modes. The result is a non-centrosymmetric, instantaneous local structure, which we observe in atomic pair distribution function (PDF) measurements. This local symmetry breaking is unobservable by Bragg diffraction, but can explain key material properties such as the structural phase sequence, ultra low thermal transport, and large minority charge carrier lifetimes despite moderate carrier mobility.Comment: 30 pages, 11 figure

Development of devices and systems of growth of gallium arsenide ingots for micro, nano electronics and photovoltaics

У роботі представлені результати розробки системи керування процесом вирощування зливків арсеніду галія, теплового вузла, методу й системи виміру внутрішніх напружень у пластинах арсеніду галію. Представлені в роботі технічні рішення дозволили одержати злитки кремнію діаметром 100 мм. с рухливістю, см² В⁻¹ с⁻¹ - 2500 ÷ 3500; концентрацій носіїв заряду, см⁻³ - 5×10¹⁷ ÷ 5×10¹⁸; густиною дислокацій, см⁻² - до 8×10⁴.Gallium arsenide is a perspective semiconductor, the need for which is constantly in-creasing. This is associated with the development of electronic components operating in excess of the high frequency range and development of terrestrial photovoltaics based on gallium arsenide solar cells. Increase in diameter of grown ingots leads to a deterioration in their performance, which is caused by the imperfection of growing technology. The paper presents the results of the development of systems and devices which help to improve existing technology to produce GaAs ingots and wafers with a diameter of 100 mm with the best technical parameters. Developed a system to manage growing GaAs ingot. As a sensor of diameter ingot it uses a weighting method provides a measurement error in the process of growing ± 1,0 mm. The system allows to grow GaAs ingots with an error of ± 2 mm. For the formation of temperature gradients developed thermal unit, which provides a gradient of 51 .. 53 K/cm in growing of ingots with diameter of 100 mm. For adjusting the process parameters were developed measuring device of the internal stresses that are generated in the ingot during the growth of the GaAs ingot. Presented in paper technical solutions provided a silicon ingot with a diameter of 100 mm. with mobility, cm² V⁻¹ s⁻¹ - 2500 ÷ 3500, the charge carrier density, cm⁻³ - 5×10¹⁷ ÷ 5×10¹⁸; dislocation density, cm⁻² - to 8×10⁴.В работе представлены результаты разработки системы управления процессом выращивания слитков арсенида галлия, теплового узла, метода и системы измерения внутренних напряжений в пластинах арсенида галлия. Представленные в работе технические решения позволили получить слитки кремния диаметром 100 мм. подвижностью, см² В⁻¹ с⁻¹ - 2500 ÷ 3500; концентраций носителей заряда, см⁻³ - 5×10¹⁷ ÷ 5×10¹⁸; плотность дислокаций, см⁻² - до 8×10⁴

Total scattering reveals the hidden stacking disorder in a 2D covalent organic framework

Interactions between extended π-systems are often invoked as the main driving force for stacking and crystallization of 2D organic polymers. In covalent organic frameworks (COFs), the stacking strongly influences properties such as the accessibility of functional sites, pore geometry, and surface states, but the exact nature of the interlayer interactions is mostly elusive. The stacking mode is often identified as eclipsed based on observed high symmetry diffraction patterns. However, as pointed out by various studies, the energetics of eclipsed stacking are not favorable and offset stacking is preferred. This work presents lower and higher apparent symmetry modifications of the imine-linked TTI-COF prepared through high- and low-temperature reactions. Through local structure investigation by pair distribution function analysis and simulations of stacking disorder, we observe random local layer offsets in the low temperature modification. We show that while stacking disorder can be easily overlooked due to the apparent crystallographic symmetry of these materials, total scattering methods can help clarify this information and suggest that defective local structures could be much more prevalent in COFs than previously thought. A detailed analysis of the local structure helps to improve the search for and design of highly porous tailor-made materials

Light-driven molecular motors embedded in covalent organic frameworks

The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host-guest phenomena in well-defined 3D solid materials. In this work, we detail the synthesis of a diamine-based light-driven molecular motor and its incorporation into a series of imine-based polymers and covalent organic frameworks (COF). We study structural and dynamic properties of the molecular building blocks and derived self-assembled solids with a series of spectroscopic, diffraction, and theoretical methods. Using an acid-catalyzed synthesis approach, we are able to obtain the first crystalline 2D COF with stacked hexagonal layers that contains 20 mol% molecular motors. The COF features a specific pore volume and surface area of up to 0.45 cm(3) g(-1) and 604 m(2) g(-1), respectively. Given the molecular structure and bulkiness of the diamine motor, we study the supramolecular assembly of the COF layers and detail stacking disorders between adjacent layers. We finally probe the motor dynamics with in situ spectroscopic techniques revealing current limitations in the analysis of these new materials and derive important analysis and design criteria as well as synthetic access to new generations of motorized porous framework materials

pH-Responsive Relaxometric Behaviour of Coordination Polymer Nanoparticles Made of a Stable Macrocyclic Gadolinium Chelate

Lanthanide-containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gdchelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd-DOTA-4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r=16.4 mmsat 10 MHz), but also for a pH responsiveness (Δr=108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd-DOTA-4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity

Characterizing the atomic structure in low concentrations of weakly ordered, weakly scattering materials using the pair distribution function

Nanoscale structural characterization is critical to understanding the physical underpinnings of properties and behavior in materials with technological applications. The work herein shows how the pair distribution function technique can be applied to x-ray total scattering data for material systems which weakly scatter x-rays, a typically difficult task due to the poor signal-to-noise obtained from the structures of interest. Characterization and structural modeling are demonstrated for a variety of molecular and porous systems, along with the detection and characterization of disordered, minority phases and components. In particular, reliable detection and quantitative analysis are demonstrated for nanocrystals of an active pharmaceutical ingredient suspended in dilute solution down to a concentration of 0.25 wt. %, giving a practical limit of detection for ordered nanoscale phases within a disordered matrix. Further work shows that minority nanocrystalline phases can be detected, fingerprinted, and modeled for mixed crystalline and amorphous systems of small molecules and polymers. The crystallization of amorphous lactose is followed under accelerated aging conditions. Melt quenching is shown to produce a different local structure than spray drying or freeze drying, along with increased resistance to crystallization. The initial phases which form in the spray dried formulation are identified as a mixture of polymorphs different from the final α-lactose monohydrate form. Hard domain formation in thermoplastic polyurethanes is also characterized as a function of methylene diphenyl diisocyanate and butanediol component ratio, showing that distinct and different hard phase structures can form and are solved by indexing with structures derived from molecular dynamics relaxation. In both cases, phase fractions can be quantified in the mixed crystalline and amorphous systems by fitting with both standards or structure models. Later chapters, demonstrate pair distribution characterization of particle incorporation, structure, and synthesis of nanoporous materials. Nanoparticle size distributions are extracted from platinum nanoparticles nucleating within a zeolite matrix through structural modeling, and validated by transmission electron microscope studies. The structure of zirconium phosphonate-phosphate unconventional metal organic framework is determined to consist of turbostratically disordered nanocrystalline layers of Zr-phenylphosphonate, and the local environment of terbium intercalated between the layers is found to resemble the local environment in scheelite-type terbium phosphate. Finally, the early stages of reaction between aqueous zinc dinitrate hexahydrate and methanolic 2-methylimidazole are characterized using in situ total scattering measurements, showing that secondary building units of tetrahedrally coordinated by 2-methylimidazole initially form upon reaction. Overall, the methodologies are developed and applied toward phase detection, identification, solution, and behavior in pharmaceuticals, polymers, and nanoporous materials along with advice for carrying out experiments and analysis on such materials such that they can be extended to other similar systems

Розробка пристроїв і систем вирощування злитків арсеніду галію для виробів мікро, нано електроніки та фотовольтаіки

Gallium arsenide is a perspective semiconductor, the need for which is constantly increasing. This is associated with the development of electronic components operating in excess of the high frequency range and development of terrestrial photovoltaics based on gallium arsenide solar cells. Increase in diameter of grown ingots leads to a deterioration in their performance, which is caused by the imperfection of growing technology. The paper presents the results of the development of systems and devices which help to improve existing technology to produce GaAs ingots and wafers with a diameter of 100 mm with the best technical parameters. Developed a system to manage growing GaAs ingot. As a sensor of diameter ingot it uses a weighting method provides a measurement error in the process of growing ± 1,0 mm. The system allows to grow GaAs ingots with an error of ± 2 mm. For the formation of temperature gradients developed thermal unit, which provides a gradient of 51 .. 53 K cm in growing of ingots with diameter of 100 mm. For adjusting the process parameters were developed measuring device of the internal stresses that are generated in the ingot during the growth of the GaAs ingot. Presented in paper technical solutions provided a silicon ingot with a diameter of 100 mm. with mobility, cm2 V-1 s-1 - 2500 ÷ 3500, the charge carrier density, cm-3 - 5x1017 ÷ 5x1018; dislocation density, cm-2 - to 8x104.В работе представлены результаты разработки системы управления процессом выращивания слитков арсенида галлия, теплового узла, метода и системы измерения внутренних напряжений в пластинах арсенида галлия. Представленные в работе технические решения позволили получить слитки кремния диаметром 100 мм. с подвижностью,  см2 В-1 с-1 -   2500 ÷ 3500; концентраций носителей заряда, см-3 - 5x1017 ÷ 5x1018; плотность дислокаций, см-2 - до 8х104.Розробка пристроїв і систем вирощування  злитків арсеніду галію для виробів мікро, нано електроніки та фотовольтаіки. У роботі представлені результати розробки системи керування процесом вирощування зливків арсеніду галія, теплового вузла, методу й системи виміру внутрішніх напружень у пластинах арсеніду галію. Представлені в роботі технічні рішення дозволили одержати злитки кремнію діаметром 100 мм. с рухливістю,  см2 В-1 с-1 -   2500 ÷ 3500; концентрацій носіїв заряду, см-3 - 5x1017 ÷ 5x1018; густиною дислокацій, см-2 - до 8x104