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

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

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

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

In Atrial Fibrillation, Omnipolar Voltage Maps More Accurately Delineate Scar Than Bipolar Voltage Maps.

BACKGROUND: Optimal method for voltage assessment in AF remains unclear. OBJECTIVES: This study evaluated different methods for assessing atrial voltage and their accuracy in identifying pulmonary vein reconnection sites (PVRSs) in atrial fibrillation (AF). METHODS: Patients with persistent AF undergoing ablation were included. De novo procedures: voltage assessment in AF with omnipolar voltage (OV) and bipolar voltage (BV) methodology and BV assessment in sinus rhythm (SR). Activation vector and fractionation maps were reviewed at voltage discrepancy sites on OV and BV maps in AF. AF voltage maps were compared with SR BV maps. Repeat ablation procedures: OV and BV maps in AF were compared to detect gaps in wide area circumferential ablation (WACA) lines that correlated with PVRS. RESULTS: Forty patients were included: 20 de novo and 20 repeat procedures. De novo procedure: OV vs BV maps in AF; average voltage 0.55 ± 0.18 mV vs 0.38 ± 0.12 mV; P = 0.002, voltage difference of 0.20 ± 0.07 mV; P = 0.003 at coregistered points and proportion of left atrium (LA) area occupied by low-voltage zones (LVZs) was smaller on OV maps (42.4% ± 12.8% OV vs 66.7% ± 12.7% BV; P < 0.001). LVZs identified on BV maps and not on OV maps correlated frequently to wavefront collision and fractionation sites (94.7%). OV AF maps agreed better with BV SR maps (voltage difference at coregistered points 0.09 ± 0.03 mV; P = 0.24) unlike BV AF maps (0.17 ± 0.07 mV, P = 0.002). Repeat ablation procedure: OV was superior in identifying WACA line gaps that correlated with PVRS than BV maps (area under the curve = 0.89, P < 0.001). CONCLUSIONS: OV AF maps improve voltage assessment by overcoming the impact of wavefront collision and fractionation. OV AF maps correlate better with BV maps in SR and more accurately delineate gaps on WACA lines at PVRS

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

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

Exploiting SMART pass filter deactivation detection to minimize inappropriate subcutaneous implantable cardioverter defibrillator therapies: a real-world single-centre experience and management guide

AIMS: The SMART Pass™ (SP) algorithm is a high-pass filter that aims to reduce inappropriate therapy (IT) in subcutaneous internal cardiac defibrillator (S-ICD), but SP can deactivate due to low amplitude sensed R waves or asystole. The association between IT and SP deactivation and management strategies were evaluated, hypothesizing SP deactivation increases the risk of IT and device re-programming, or lead/generator re-positioning could reduce this risk. METHODS AND RESULTS: Retrospective single-centre audit of Emblem™ S-ICD devices implanted 2016 to 2020 utilizing health records and remote monitoring data. Cox regression models evaluated associations between SP deactivation and IT. A total of 348 patients (27 ± 16.6 months follow-up) were studied: 73% primary prevention. Thirty-eight patients (11.8%) received 83 shocks with 27 patients (7.8%) receiving a total of 44 IT. Causes of IT were oversensing (98%) and aberrantly conducted atrial fibrillation (2%). SP deactivation occurred in 32 of 348 patients (9%) and was significantly associated with increased risk of IT (hazard ratio 5.36, 95% CI 2.37-12.13). SP deactivation was due to low amplitude R waves (94%), associated with a higher defibrillation threshold at implant and presence of arrhythmogenic right ventricular cardiomyopathy. No further IT occurred 16 ± 15.5 months after corrective interventions, with changing the sensing vector being successful in 59% of cases. CONCLUSION: To reduce the risk of IT, the cause of the SP deactivation should be investigated, and appropriate reprogramming, device, or lead modifications made. Utilizing the alert for SP deactivation and electrograms could pro-actively prevent IT