Crystal Imperfections of Industrial Vanadium Phosphorous Oxide Catalysts

This study presents information about crystal imperfections in the main phase of industrial vanadium phosphorous oxide catalysts that are used to catalyze the oxidation of n-butane to maleic anhydride, being an important intermediate in the chemical industry. The mechanism of this reaction is still debated, and the catalytically active and selective surface centers have not yet been identified. The results presented are based on X-ray diffraction data obtained by both laboratory-scale and synchrotron powder diffraction experiments, as well as laboratory-scale single-crystal diffraction experiments. It has been proven that pronounced Bragg reflection broadening effects found in laboratory-scale powder diffraction patterns of industrial VPO catalysts are real and not due to an insufficient 2-θ resolution of the apparatus. In the framework of this work, a powder diffraction full profile fitting strategy was developed using the TOPAS software, which was applied to analyze the X-ray diffraction data of four differently activated industrial catalyst samples, originating from one batch after they had been catalytically tested. It was found that the reflection broadening is mainly caused by an anisotropic crystal size, which results in platelet-shaped crystallites of vanadyl pyrophosphate. A further contribution to the reflex broadening, especially for (111), was found to be a result of stacking faults perpendicular to the a direction in the crystal structure of vanadyl pyrophosphate. These results were used to elaborate on possible correlations between structural proxies and catalytic performance. A direct correlation between the extension of coherently scattering domains in the z direction and the catalyst�s selectivity could be proven, whereas the activity turned out to be dependent on the crystallite shape. Regarding the phase contents, it could be shown that sample catalysts containing a higher amount of β-VO(PO3)2 showed increased catalytic activity

Role of crystal size on swing-effect and adsorption induced structure transition of ZIF-8.

The flexibility and structure transition behaviour of ZIF-8 in a series of samples with different particle size has been studied using a combination of high-resolution N2 gas adsorption isotherms and, for the first time, a broad in situ PXRD and Rietveld analysis. During the stepped adsorption process, large particles showed a narrow adsorption/desorption pressure range with a shorter equilibrium time due to lower kinetic hindrance, deriving from higher amount of active sites. In situ PXRD showed that both the rotation of imidazole ring and a bend in the methyl group led to the gate opening of ZIF-8.This work was funded by the EPSRC IAA Partnership Development Award (RG/75759). D.F.-J. thanks the Royal Society for funding through a University Research Fellowship. We thank Diamond Light Source for beamtime at beamline I11 (visit EE9750).This is the author accepted manuscript. The final version is available from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C6DT00565

Role of crystal size on swing-effect and adsorption induced structure transition of ZIF-8

The flexibility and structure transition behaviour of ZIF-8 in a series of samples with different particle size has been studied using a combination of high-resolution N2 gas adsorption isotherms and, for the first time, a broad in situ PXRD and Rietveld analysis. During the stepped adsorption process, large particles showed a narrow adsorption/desorption pressure range with a shorter equilibrium time due to lower kinetic hindrance, deriving from higher amount of active sites. In situ PXRD showed that both the rotation of imidazole ring and a bend in the methyl group led to the gate opening of ZIF-8.This work was funded by the EPSRC IAA Partnership Development Award (RG/75759). D. F.-J. thanks the Royal Society for funding through a University Research Fellowship. We thank Diamond Light Source for beamtime at beamline I11 (visit EE9750).Peer reviewe

A breathing zirconium metal-organic framework with reversible loss of crystallinity by correlated nanodomain formation

The isoreticular analogue of the metal-organic framework UiO-66(Zr), synthesized with the flexible trans-1,4-cyclohexanedicarboxylic acid as linker, shows a peculiar breathing behavior by reversibly losing long-range crystalline order upon evacuation. The underlying flexibility is attributed to a concerted conformational contraction of up to two thirds of the linkers, which breaks the local lattice symmetry. X-ray scattering data are described well by a nanodomain model in which differently oriented tetragonal-type distortions propagate over about 7-10 unit cells

Pt accelerated coarsening of A15 precipitates in Cr-Si alloys

The effect of alloying Cr-rich Cr-Si alloys with Pt was investigated by a combination of complementary experimental methods and atomic scale modelling. The investigated Cr-Si and Cr-Si-Pt (Cr ⩾86 at.%) alloys developed a two-phase microstructure consisting of Cr solid solution (Crss) matrix and strengthened by A15 precipitates during annealing at 1200\ub0C. It was found that additions of 2 at.% Pt increase the coarsening rate by almost five times considering annealing times up to 522 h. Pt was found to change the precipitate matrix orientation relationship, despite its low influence on the Crss matrix/A15 precipitate misfit. Through this experimental and modelling approach new insight has been gained into mechanisms of enhanced coarsening by Pt addition. The increased coarsening is principally attributed to a change in interface composition and structure resulting in different thermodynamic stabilities: Pt-containing A15 phase was found to have a broader compositional range if both elements, Pt and Si, are present compared to only Si. Additionally, the Crss phase was found to have a higher solubility of Pt and Si over just Si. Both factors additionally facilitated Ostwald ripening

Phase Transitions in Zeolitic Imidazolate Framework 7: The Importance of Framework Flexibility and Guest-Induced Instability

A study of the phase transitions in ZIF-7 (zeolitic imidazolate frameworks- (Zn(PhIm)2, PhIm = benzimidazolate)) as a function of guest occupancy and temperature was reported. Raman spectra of an as-synthesized sample were collected in air between 297 and 421 K. The major contributions of the spectra come from the vibrational modes of the benzimidazolate ligand. Upon heating, most of the Raman bands remain similar and keep the same frequencies until 357 K, indicating that the structure of ZIF-7 seems to be stable in this temperature range. Above 357 K, strong modifications are observed in the regions corresponding to the lattice modes. The formation of ZIF-7-II is attributed to the loss of dimethylformamide (DMF) solvent molecules from the ZIF-7-I framework. This can be confirmed by the differential scanning calorimetry and thermogravimetric analysis traces of ZIF-7-I. The highly-distorted and locally-strained nature of ZIF-7-II leads to its poor crystallinity, reflected by X-ray powder diffraction and scanning electron microscope

Pressure promoted low-temperature melting of metal–organic frameworks

International audienceMetal–organic frameworks (MOFs) are microporous materials with huge potential for chemical processes. Structural collapse at high pressure, and transitions to liquid states at high temperature, have recently been observed in the zeolitic imidazolate framework (ZIF) family of MOFs. Here, we show that simultaneous high-pressure and high-temperature conditions result in complex behaviour in ZIF-62 and ZIF-4, with distinct high- and low-density amorphous phases occurring over different regions of the pressure–temperature phase diagram. In situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF state expands substantially towards lower temperatures at intermediate, industrially achievable pressures and first-principles molecular dynamics show that softening of the framework coordination with pressure makes melting thermodynamically easier. Furthermore, the MOF glass formed by melt quenching the high-temperature liquid possesses permanent, accessible porosity. Our results thus imply a route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition on heating at ambient pressure

Enhancement of terahertz photoconductive antenna operation by optical nanoantennas

Photoconductive antennas are promising sources of terahertz radiation that is widely used for spectroscopy, characterization, and imaging of biological objects, deep space studies, scanning of surfaces, and detection of potentially hazardous substances. These antennas are compact and allow for generation of both ultrabroadband pulses and tunable continuous wave terahertz signals at room temperatures, with no need for high-power optical sources. However, such antennas have relatively low energy conversion efficiency of femtosecond laser pulses or two close pump wavelengths (photomixers) into the pulsed and continuous terahertz radiation, correspondingly. Recently, an approach to solving this problem that involves known methods of nanophotonics applied to terahertz photoconductive antennas and photomixers has been proposed. This approach comprises the use of optical nanoantennas for enhancing the absorption of pump laser radiation in the antenna gap, reducing the lifetime of photoexcited carriers, and improving the antenna thermal efficiency. This Review is intended to systematize the main results obtained by researchers in this promising field of hybrid optical-to-terahertz photoconductive antennas and photomixers. We summarize the main results on hybrid THz antennas, compare the approaches to their implementation, and offer further perspectives of their development including an application of all-dielectric nanoantennas instead of plasmonic ones

Synthesis of porous metal phosphonate frameworks for applications in gas separation and storage

Porous metal phosphonate framework materials were synthesised by solvothermal reaction of bis(α-aminomethylenephosphonic acid) ligands with divalent and trivalent metal cations. The syntheses and characterisation by NMR and, where possible, single crystal X-ray diffraction of seven bisphosphonic acid ligands, including N,N′-piperazinebis(methylenephosphonic acid) (H₄L), its racemic and enantiopure (R) 2-methyl (H₄L′ and R-H₄L′) and 2,5-dimethyl (H₄L′′) derivatives, and N,N′-4,4′-bipiperidinebis(methylenephosphonic acid) (H₄LL) are reported. Syntheses of the known phase Y₂(LH₂)₃·5H₂O and the new phases, STA-13(Y) (St Andrews microporous material No. 13) and Y₂(R-L′H₂)₃·4H₂O, from reactions of Y(AcO)₃ with H₄L, H₄L′ and R-H₄L′ respectively are reported. The as-prepared and dehydrated structures of each phase have been determined from either laboratory or synchrotron powder X-ray diffraction data. Reaction of Y(AcO)₃ and H₄L′′ is shown to form a phase with a different structure. The features determining which structure crystallises are discussed. Syntheses of other rare-earth forms of STA-13 (Sc³⁺, Gd³⁺–Yb³⁺) and the porosity of each phase to N₂ are reported. STA-13(Y) is the most porous form with loadings of ∼3 mmol g⁻¹ and ∼4 mmol g⁻¹ for N₂ and CO₂ respectively. MIL-91(Fe) was synthesised for the first time from reactions of Fe³⁺ cations with H₄L. Its structure was confirmed by Rietveld refinement, but it was not porous. The first syntheses of [Fe₄L₁.₅(AcO)₁.₅(OH,H₂O)₃]·0.5NH₄5.5H₂O (L= L or L′) are reported, from reactions of H₄L or H₄L′ in the presence of an excess of Fe³⁺ cations. The phase is related to a previously reported Co phase. The synthesis of divalent metal bisphosphonate STA-12(Mg) (Mg₂(H₂O)₂L·5.6H₂O) was reported for the first time and its structure determined from single crystal X-ray diffraction. The dehydration behaviour of this material was compared with the known forms of STA-12. STA-12(Mg) is porous to both N₂ (∼5.5 mmol g⁻¹) and CO₂ (~ 8.5 mmol g⁻¹). Reaction of H₄LL with Co²⁺ and Ni²⁺ gave two materials isoreticular with STA-12, labelled STA-16(Co) and STA-16(Ni). The structures of both materials were solved from synchrotron powder X-ray diffraction data. On dehydration, STA-16(Co) undergoes a reversible structural transition to an unknown structure. By contrast, STA-16(Ni) retains the same symmetry in the dehydrated form and its structure was determined from synchrotron powder X-ray diffraction data. Both materials are porous to N₂, with an uptake of up to 22.2 mmol g⁻¹, and CO₂ with maximum loading of 21.7 mmol g⁻¹. NLDFT analysis of N₂ adsorption data confirm the crystallographically determined pore radii. Syntheses of other frameworks with divalent cations and initial reactions of H₄LL with trivalent cations are also reported