Modulator-controlled synthesis of microporous STA-26, an interpenetrated 8,3-connected zirconium MOF with the the-i topology, and its reversible lattice shift

The authors acknowledge the support of the EPSRC/St Andrews Criticat CDT (RRRP, PAW) and the European Community Seventh Framework Program (FP7/2007-2013) number 608490 (project M4CO2) (KKC, MYM, KIH, PAW). SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. The research data (and/or materials) supporting this publication can be accessed at DOI: http://dx.doi.org/10.17630/6ffeed8a-e75f-4648-968f-3ed32a94e9a0.A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-26 (St Andrews porous material-26), has been prepared using the 4,4',4"-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoate (TMTB) tritopic linker with formic acid as a modulating agent. In the as-prepared form STA-26 possesses Im-3m symmetry compared with the Pm-3m symmetry of the non-interpenetrated analogue, NU-1200, prepared using benzoic acid as a modulator. Upon removal of residual solvent there is a shift between the interpenetrating lattices and a resultant symmetry change to Cmcm which is fully reversible. This is observed by X-ray diffraction and 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 nodes leaving coordinatively unsaturated Zr4+ sites, as shown by IR spectroscopy using CO and CD3CN as probe molecules. Nitrogen adsorption at 77 K together with grand canonical Monte Carlo simulations confirms a microporous, fully interpenetrated, structure with pore volume 0.53 cm3 g−1 while CO2 adsorption at 196 K reaches 300 cm3 STP g−1 at 1 bar. While the pore volume is smaller than that of its non-interpenetrated mesoporous analogue, interpenetration makes the structure more stable to moisture adsorption and introduces shape selectivity in adsorption.PostprintPeer reviewe

General data protection regulation

Mit der Allgemeinen Datenschutzverordnung (DSGVO) wurde der neue Datenschutzrahmen in der Europäischen Union festgelegt und der bisherige Rechtsakt - die Richtlinie 95/46/EG des Europäischen Parlaments und des Rates vom 24. Oktober 1995 zum Schutz natürlicher Personen bei der Verarbeitung personenbezogener Daten und zum freien Datenverkehr - aufgehoben. Ziel des neuen Gesetzes war es jedoch nicht, das EU-Datenschutzrecht zu revolutionieren. Ziel war es vielmehr, die Zersplitterung und Unterschiede zwischen den Rechtsvorschriften der Mitgliedstaaten im Rahmen der früheren Regelung zu beseitigen und damit das EU-Datenschutzrecht vollständig zu harmonisieren und die Hindernisse für den Fluss personenbezogener Daten in der Union zu beseitigen. Das Problem ist jedoch, dass die DSGVO zahlreiche Öffnungsklauseln enthält, die es den Mitgliedstaaten ermöglichen, ihre eigenen Rechtsvorschriften zu erlassen, indem sie die Anforderungen der Verordnung genauer spezifizieren. Diese Flexibilität wiederum droht, den EU-Datenschutzrahmen erneut zu fragmentieren. Darüber hinaus scheint die Beseitigung der Kollisionsnormen des früheren Datenschutzregimes das Problem weiter zu verschärfen. Der Zweck dieses Papiers ist die Beantwortung von zwei Hauptfragen. Erstens, ob die große Anzahl der Eröffnungsklauseln in der DSGVO tatsächlich ihren Zweck untergräbt, ein einheitliches Datenschutzsystem in der Union zu schaffen. Zweitens: Wie könnte angesichts der zu erwartenden Unterschiede im nationalen Recht aufgrund der Eröffnungsklauseln und der fehlenden Kollisionsnormen ein Kollisionsproblem im Rahmen der neuen Datenschutzregelung gelöst werden? Um diese Fragen zu beantworten, beginnt Kapitel II dieses Papiers mit einem Überblick über die Eröffnungsklauseln. Darüber hinaus werden die Eröffnungsklauseln, die aus praktischer Sicht für die alltäglichen Geschäftstätigkeiten von Unternehmen der Privatwirtschaft von größerer Bedeutung sind, im Detail erörtert. In Kapitel III wird die Herangehensweise von fünf verschiedenen Mitgliedstaaten an die Eröffnungsklauseln untersucht, um zu bewerten, ob die Mitgliedstaaten tatsächlich von der gebotenen Möglichkeit Gebrauch machen, Rechtsvorschriften innerhalb der delegierten Zuständigkeit zu erlassen und damit ein abweichendes Datenschutzrecht innerhalb der Union zu schaffen. Schließlich wird in Kapitel IV geprüft, ob die DSGVO eine Lösung für das anwendbare Recht bietet, falls die Bestimmungen der Eröffnungsklauseln von einem Mitgliedstaat zum anderen unterschiedlich sind und wenn nicht, welche anderen Lösungen es gibt. Die Schlussfolgerung des Papiers zur ersten Frage lautet nicht nur, dass es in der Tat zu viele Eröffnungsklauseln gibt, sondern dass die Mitgliedstaaten im Rahmen der übertragenen Kompetenzen aktiv Gesetze erlassen, und diese manchmal sogar überschreiten. Dies führt zu Inkonsistenzen im Datenschutzregime innerhalb der EU und untergräbt damit das Ziel der DSGVO, einen einheitlichen Rechtsrahmen zu schaffen. Abschließend zur zweiten Frage: Die DSGVO enthält keine allgemeinen Bestimmungen zu Kollisionsnormen, was wiederum die durch die unterschiedlichen nationalen Rechtsvorschriften verursachten Probleme weiter verschärft. Die Rechtsliteratur bietet jedoch mögliche Lösungen für das Problem. Zum Beispiel: Analog zu den Regeln zur Bestimmung der federführenden Aufsichtsbehörde, unter Berufung auf allgemeine EU-Kollisionsnormen (z. B. Rom I-Verordnung), unter Berufung auf nationale Kollisionsnormen oder anwendbares Recht von den Angaben bestimmter Öffnungsklauseln zu bestimmen. Es bleibt abzuwarten, ob weitere Leitlinien des Europäischen Datenschutzausschusses oder die Rechtsprechung des Gerichtshofs der Europäischen Union die kollisionsrechtlichen Situationen klären und problematische nationale Bestimmungen, die der DSGVO zuwiderlaufen, angehen werden.The General Data Protection Regulation (“GDPR”) established the new data protection framework in the European Union and repealed the previous legal act which regulated that matter - the Directive 95/46/EC of the European Parliament and of the Council of 24 October 1995 on the protection of individuals with regard to the processing of personal data and on the free movement of such data. However, the aim of the new legal act was not to revolutionise EU data protection law, but rather to eliminate the fragmentation and differences between Member State laws under the previous regime, and thereby to fully harmonise EU data protection law and remove the obstacles to flows of personal data within the Union. The problem, however, is that the GDPR contains a significant amount of opening clauses, which enable Member States to enact their own legislation by further specifying the requirements of the regulation. In turn, these flexibilities threaten to once again fragment the EU data protection framework. In addition, the removal of the conflict of laws provisions which existed under the previous data protection regime, seems to further exacerbate the problem. The purpose of this thesis is to answer two main questions. First, whether the amount of the opening clauses in the GDPR indeed undermines its purpose to establish a uniform data protection regime in the Union. Second, given the expected differences in national law due to the opening clauses and the lack of general applicable law rule, how could an eventual conflict of laws issue be resolved under the new data protection regime? In order to answer these questions, Section II of this thesis starts with an overview of the opening clauses, focusing in detail on the opening clauses which are more important from a practical perspective for the day-to-day business activities of controllers and processors in the private sector. Section III examines the approach of five different Member States to the opening clauses in order to evaluate whether Member States in fact make use of the provided opportunity to enact legislation within the delegated competence, and thereby creating diverging data protection law within the Union. Finally, Section IV examines whether the GDPR provides a solution for establishing the applicable law in case provisions enacted within the opening clauses differ from one Member State to another, and if not what other solutions are there. The conclusion of the thesis to the first question is not only that there indeed are too many opening clauses, but also that Member States actively legislate within the delegated competences, sometimes even arguably beyond them. This leads to inconsistencies in the data protection regime within the EU and thus undermines the aim of the GDPR to establish a uniform legal framework. As regards the second question, the GDPR does not provide general conflict of laws provisions which further exacerbates the issues caused by the diverging national legislation. However, the law literature provides possible solutions to the issue, such as analogy to the rules for determining lead supervisory authority, relying on general EU conflict of laws rules (e.g., Rome I Regulation), relying on national conflict of laws rules, or deriving applicable law indications from certain opening clauses. It remains to be seen whether further guidance of the European Data Protection Board or case law of the Court of Justice of the European Union would clarify the conflict of laws concerns and address problematic national provisions contrary to the GDPR

FTIR Evidence of Different Bonding of Methane to OH Groups on H–ZSM-5, HY, and SiO₂

Low-temperature adsorption of CH₄ and ¹⁵N₂ on H–ZSM-5, SiO₂, and HY is comparatively studied. Partly and fully deuteroxylated samples were also investigated. It was established that methane forms H bonds simultaneously with oxygen and hydrogen from the Si–OH groups, which reflects in enhanced shift of the OH modes to lower frequency as compared to the case if methane was bound to the proton only. In contrast, methane is attached to highly acidic hydroxyls forming a bond mainly with the proton. At high methane equilibrium pressure, a second methane molecule is bound to the same acidic OH group

OH/OD Isotopic Shift Factors of Isolated and H‑Bonded Surface Silanol Groups

The OH/OD isotopic shift factors (<i>i = </i>ν_OH/ν_OD) of isolated silanols on SiO₂ and [Si]­BEA are between 1.3563 and 1.3568, values lower than the theoretical shift of 1.3744. However, <i>i</i> of the harmonic OH modes almost coincides with the theoretical value which indicates that the experimental deviations in this case are mainly due to anharmonicity. The anharmonicity slightly decreases when the OH groups participate in weak H-bonding with adsorbed CH₄ or CO which should lead to an increase of <i>i</i>. However, contrary to these expectations, <i>i</i> additionally decreases. This is attributed to the lower acidity of the OD groups as compared to the respective OHs. The value of <i>i</i> is also lower for H-bonded silanols as compared to isolated SiOH groups. It is concluded that <i>i</i> depends on the extent of H-bonding which allows easy distinguishing between isolated and H-bonded surface hydroxyls

Purification of Hydrogen from CO with Cu/ZSM-5 Adsorbents

The transition to a hydrogen economy requires the development of cost-effective methods for purifying hydrogen from CO. In this study, we explore the possibilities of Cu/ZSM-5 as an adsorbent for this purpose. Samples obtained by cation exchange from aqueous solution (AE) and solid-state exchange with CuCl (SE) were characterized by in situ EPR and FTIR, H2-TPR, CO-TPD, etc. The AE samples possess mainly isolated Cu2+ cations not adsorbing CO. Reduction generates Cu+ sites demonstrating different affinity to CO, with the strongest centres desorbing CO at about 350 &deg;C. The SE samples have about twice higher Cu/Al ratios, as one H+ is exchanged with one Cu+ cation. Although some of the introduced Cu+ sites are oxidized to Cu2+ upon contact with air, they easily recover their original oxidation state after thermal treatment in vacuum or under inert gas stream. In addition, these Cu+ centres regenerate at relatively low temperatures. It is important that water does not block the CO adsorption sites because of the formation of Cu+(CO)(H2O)x complexes. Dynamic adsorption studies show that Cu/ZSM-5 selectively adsorbs CO in the presence of hydrogen. The results indicate that the SE samples are very perspective materials for purification of H2 from CO

Understanding the Role of the Acid Sites in 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid Reaction over Gold Catalysts: Surface Investigation on CexZr1- xO2 Compounds

A series of CexZr1-xO2 supports with different Ce/Zr molar ratios were utilized for the preparation of gold catalyst used in the selective oxidation of 5-hydroxymethyl-2-furfural to 2,5-furandicarboxylic acid. The used method of gold deposition allows the preparation of gold particles with homogeneous size and shape distribution, a formulation very useful for studies dedicated to revealing the support participation in the reaction. The supports are characterized by Fourier transform infrared spectroscopy using CO as probe molecule, and the sample catalytic activity is thereafter correlated to the support acid site distribution. The possible participation of its Lewis/Br\uf8nsted acidity in the reaction mechanism is also proposed