Synthesis and activation for catalysis of Fe-SAPO-34 prepared using iron polyamine complexes as structure directing agents

This work was supported by Johnson Matthey PLC, UK. Solid-state NMR spectra were obtained at the EPSRC UK National Solid-state NMR Service at Durham.The use of transition metal cations complexed by polyamines as structure directing agents (SDAs) for silicoaluminophosphate (SAPO) zeotypes provides a route, via removal of the organic by calcination, to microporous solids with well-distributed, catalytically-active extra-framework cations and avoids the need for post-synthesis aqueous cation exchange. Iron(II) complexed with tetraethylenepentamine (TEPA) is found to be an effective SDA for SAPO- 34, giving as-prepared solids where Fe2+-TEPA complexes reside within the cha cages, as indicated by Mössbauer, optical and X-ray absorption near edge spectroscopies. By contrast, when non-coordinating tetraethylammonium ions are used as the SDAs in Fe-SAPO-34 preparations, iron is included as octahedral Fe3+ within the framework. The complex- containing Fe-SAPO-34(TEPA) materials give a characteristic visible absorption band at 550 nm (and purple colouration) when dried in air that is attributed to oxygen chemisorption. Some other Fe2+ polyamine complexes (diethylenetriamine, triethylenetetramine and pentaethylenehexamine) show similar behaviour. After calcination in flowing oxygen at 550 °C, ‘one-pot’ Fe(TEPA) materials possess Fe3+ cations and a characteristic UV-visible spectrum: they also show appreciable activity in the selective catalytic reduction of NO with NH3.PostprintPostprintPeer reviewe

Understanding the structure directing action of copper-polyamine complexes in the direct synthesis of Cu-SAPO-34 and Cu-SAPO-18 catalysts for the selective catalytic reduction of NO with NH3

This work has been supported by Johnson Matthey PLC, UK.Cu2+ cations complexed by linear polyamines have been studied as structure-directing agents (SDAs) for the direct synthesis of copper-containing microporous silicoaluminophosphate (SAPO) materials. The complexing ligands diethylenetriamine (DETA), N-(2-hydroxyethyl)ethylenediamine (HEEDA), triethylenetetramine (TETA), N,N′-bis(2-aminoethyl)-1,3-propanediamine (232), 1,2-bis(3-aminopropylamino)ethane (323), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) have been investigated. For comparison, syntheses have been performed using the analogous nickel-polyamine complexes. Cu2+ and Ni2+ forms of both SAPO-18 and SAPO-34 materials have been prepared. While most polyamine complexes direct crystallisation to SAPO-34, SAPO-18 has been prepared with Cu2+(232), Ni2+(232) and Ni2+(TETA). The coordination geometry of the included metal complexes was studied by UV-visible and EPR spectroscopy and computer simulation. SAPO-18 is favoured by the smaller square planar complexes or octahedral species (with 2 water molecules) of 232 and TETA. Calcination leaves extra-framework Cu2+ and Ni2+ cations within SAPO-18 and SAPO-34 frameworks. In situ synchrotron IR spectroscopy of Ni-SAPO-18 has shown thermal template degradation occurs via nitrile intermediates. Rietveld structural analysis located extra-framework Cu2+ and Ni2+ cations released by calcination. In SAPO-34, Cu2+ and Ni2+ were located in the 8R window of the cha cage. A second site was found for Ni2+ at the centre of the six-membered rings (6Rs) of the double-six-ring (D6R) sub-units. In SAPO-18 both Cu2+ and Ni2+ cations were located only in the 6Rs of the D6R sub-units. Selected copper SAPO-18 and SAPO-34 samples were tested in the selective catalytic reduction of NO with ammonia (NH3-SCR); both showed high activity.PostprintPostprintPeer reviewe

A retrosynthetic co-templating method for the preparation of silicoaluminophosphate molecular sieves

This work has been supported by Johnson Matthey PLC, UK. Solid-state NMR spectra were obtained at the EPSRC UK National Solid-state NMR Service at Durham.A retrosynthetic method has been developed to design the synthesis of target zeotypes whose frameworks belong to the ABC-6 structural family and which contain gme cages. This permits the preparation of silicoaluminophosphate versions of AFX (SAPO-56), SFW (STA- 18) and GME (STA-19) topology types. The method makes simultaneous use of two organic structure directing agents (SDAs) to promote the formation of structural features such as cages or channels of the target framework. Computational modelling was used to identify SDAs for gme and other cages or channels in the target structures. The trimethylammonium cation was found to be the most favourable SDA for the gme cage while bisdiazabicyclooctane (DABCO) alkane cations and quaternary ammonium oligomers of DABCO with connecting polymethylene chain lengths of 4 to 8 methylene units acted as 1 templates for the additional cages or channels, respectively. The incorporation of each of the co-SDAs in the as-prepared materials was confirmed by chemical analysis, 13C MAS NMR and Rietveld refinement combined with computational modeling. Calcination of the SAPO- 56, STA-18 and some of the STA-19 materials gives microporous, fully tetrahedrally- coordinated framework solids with AFX, SFW and GME topologies: other STA-19 samples convert topotactically to SAPO-5. These results show that SAPOs in the ABC-6 family can be prepared via a targeted co-templating approach.PostprintPostprintPeer reviewe

STA-20 : an ABC-6 zeotype structure prepared by co-templating and solved via a hypothetical structure database and STEM-ADF imaging

This work has been supported by Johnson Matthey PLC, UK. AEW acknowledges funding from an EPSRC/Johnson Matthey Industrial CASE PhD award EP/N50936X/1. We acknowledge Diamond Light Source for time on beamline I11 under the funded Proposal EE11830-1.A microporous silicoaluminophosphate with a novel topology type, STA-20, has been prepared via a dual templating method using hexamethylene bisdiazabicyclooctane (diDABCO-C6) and trimethylamine as co-templates. Its structure has been solved and confirmed using a multi-technique approach that included the use of a hypothetical zeolite database to obtain a candidate starting structure, followed by scanning transmission electron microscopy with annular dark field imaging and Rietveld refinement. STA-20 is a member of the ABC-6 family of zeotype structures. The structure has trigonal symmetry, P-31c, with a = 13.15497(18) Å and c = 30.5833(4) Å in the calcined form. It has a 12-layer stacking sequence of 6-rings (6Rs), AABAABAACAAC(A), which contains single and double 6R units. As well as d6r, can and gme cages, STA-20 possesses the longest cage observed in an ordered ABC-6 material, giving a 3D-connected pore system limited by 8R windows. Models for the location of the templates within cages of the framework were obtained by combining elemental analysis, 13C MAS NMR, computer modelling and Rietveld refinement.PostprintPostprintPeer reviewe

Integrating Diverse Datasets Improves Developmental Enhancer Prediction

Gene-regulatory enhancers have been identified using various approaches, including evolutionary conservation, regulatory protein binding, chromatin modifications, and DNA sequence motifs. To integrate these different approaches, we developed EnhancerFinder, a two-step method for distinguishing developmental enhancers from the genomic background and then predicting their tissue specificity. EnhancerFinder uses a multiple kernel learning approach to integrate DNA sequence motifs, evolutionary patterns, and diverse functional genomics datasets from a variety of cell types. In contrast with prediction approaches that define enhancers based on histone marks or p300 sites from a single cell line, we trained EnhancerFinder on hundreds of experimentally verified human developmental enhancers from the VISTA Enhancer Browser. We comprehensively evaluated EnhancerFinder using cross validation and found that our integrative method improves the identification of enhancers over approaches that consider a single type of data, such as sequence motifs, evolutionary conservation, or the binding of enhancer-associated proteins. We find that VISTA enhancers active in embryonic heart are easier to identify than enhancers active in several other embryonic tissues, likely due to their uniquely high GC content. We applied EnhancerFinder to the entire human genome and predicted 84,301 developmental enhancers and their tissue specificity. These predictions provide specific functional annotations for large amounts of human non-coding DNA, and are significantly enriched near genes with annotated roles in their predicted tissues and lead SNPs from genome-wide association studies. We demonstrate the utility of EnhancerFinder predictions through in vivo validation of novel embryonic gene regulatory enhancers from three developmental transcription factor loci. Our genome-wide developmental enhancer predictions are freely available as a UCSC Genome Browser track, which we hope will enable researchers to further investigate questions in developmental biology. © 2014 Erwin et al

Insights into Brønsted acid sites in the Zeolite Mordenite

The unique feature of the zeolite catalysts is the presence of catalytically active acidic hydroxyls, also known as Brønsted acid sites (BAS), in the zeolite micropores of molecular dimensions. The accessibility and catalytic properties of BAS depend on their local environment, and it is therefore important to know the exact locations of BAS and the number of BAS in these locations. This paper reports a detailed FT-IR investigation into BAS present in the acidic and partially Na-exchanged samples of industrially important mordenite (MOR) zeolite. Our results demonstrate the existence of (at least) six distinct BAS that can be visualized by six single bands in Fourier self-deconvolution traces of the IR spectra. The quantitative estimates for the amounts of these distinct BAS were obtained using the six-band deconvolution method developed in this work. These estimates show that in the purely acidic H-MOR sample about 25% of BAS are located in eight-membered ring (8-MR) channels (O1–H and O9–H hydroxyls), ∼13% of BAS are at the intersections between the side pockets and 12-MR channels (O5–H hydroxyls), and ∼62% of BAS are located in 12-MR channels (∼39% correspond to O2–H and/or O10–H hydroxyls and the remaining 23% to O3–H and O7–H hydroxyls). These quantitative data demonstrate that the acid sites are distributed quite evenly between oxygen atoms in different crystallographic positions, thus revealing the complexity of the experimental identification of distinct BAS in mordenites and explaining the variety of the earlier suggestions regarding their positions in these zeolites