Geopolymers are promising materials for safe immobilisation and disposal of complex radioactive waste streams. This work investigates the effect of Sr incorporation and alkali-activator chemistry on 1) geopolymer chemistry, phase assemblage and nanostructure, 2) chemical binding mechanism of Sr2+ into the aluminosilicate framework of (N,K)-A-S-H gels in geopolymers, and 3) mass transport of Sr2+ during leaching, using high-field solid-state nuclear magnetic resonance spectroscopy and synchrotron-based X-ray absorption spectroscopy measurements. All geopolymers studied comprise a fully polymerised, X-ray amorphous Al-rich (N,K)-A-S-H type gel. Si exists predominantly in tetrahedral Q4(4Al) and Q4(3Al) sites and Al exists in tetrahedral sites, resulting in a net negative charge that is balanced by Na+ and/or K+ in extra-framework sites. Sr2+ was incorporated into extra-framework sites within (N,K)-A-S-H gels, without altering the local structure of the aluminosilicate framework by directly substituting for both Na+ and K+ in charge-balancing sites to form a (N,K,Sr)-A-S-H gel, at loadings equal to or below Sr/Na = 0.005. Above this limit, SrCO3 is formed, and the geopolymers simultaneously chemically bind Sr within a (N,Sr,K)-A-S-H gel, and physically encapsulate excess Sr as SrCO3. These findings have significant implications for use of geopolymers as materials for encapsulation and/or immobilisation of radioactive waste containing 90Sr.

Potassium substituted double perovskite nanocrystals of the form Cs2KxAg1−xInCl6:Bi (x = 0–1) exhibit improved PLQY behaviour and structural diversity.

Natural zeolite and kaolin are abundant in Indonesia especially in Java and Belitung islands. These materials generally contain high aluminosilicate minerals that can be used as silica and alumina sources for the formation of NaY zeolite. This research aimed to identify the modification of NaY zeolite structure using Bayat natural zeolite as alumina source and Belitung kaolin as silica source and its catalytic activity for n-hexadecane cracking. Pretreatment of materials were performed in several steps: activation, purification, fragmentation for Bayat-Klaten natural zeolite, and silica extraction for Belitung kaolin. The synthesis of NaY was performed hydrothermally using seed-assisted method with crystallization times of 24 and 48 h. The surface area analysis showed a typical surface area of microporous zeolite (i.e., a pore diameter of 1.897 nm) and surface area of 309.4 cm2/g. Meanwhile, powder X-ray diffraction characterization showed that the as-synthesized materials have the structure of NaY zeolite. The optimum crystallization time was 24 h with Si/Al ratio of 4.10. Furthermore, both synthetic and natural sourced NaY zeolites were converted into HY zeolites and employed as cracking catalyst of n-hexadecane in a fixed-bed reactor at 500 degrees C for 75 s. The natural sourced HY resulted in 59.80% conversion and 59.80% yield of gasoline product (C-9-C-12). These values were lower than the results given by synthetic HY (80%).

Inorganic cesium lead halide perovskite nanocrystals are promising materials for optoelectronic applications as they exhibit high thermal stability alongside precise color tunability and high color purity; however, their optical properties are degraded by surface defects. This work demonstrates a room temperature synthesis of CsPbBr3 nanocrystals facilitating in situ surface passivation via the incorporation of Zn2+ cations. The facile incorporation ZnBr2+ into the precursor solution facilitates Zn2+ and Br- substitution into the nanocrystal surface/subsurface layers to induce passivation of existing Pb2+ and Br- vacancies and increase the photoluminescence quantum yield from similar to 48 to 86%. The XPS and solid-state H-1 MAS NMR techniques show that the key modification is a reduction of the octylamine:oleic acid ratio leading to a near-neutral surface charge; this is accompanied by the appearance of larger nanosheets and nanowires observed by quantitative powder XRD and HR-TEM. The suitability of these perovskite nanocrystals for electrically driven applications was confirmed by the fabrication of light-emitting diodes, which demonstrate that the in situ Zn2+ passivation strategy enhanced the external quantum efficiency by similar to 60%.

Ceramics based around silicon aluminum oxynitrides are of both fundamental structural chemistry and technological interest. Certain oxynitride crystal structures allow very significant compositional variation through extensive Si/N exchange for Al/O, which implies a degree of atomic ordering. In this study, solid-state Si-29 MAS NMR and variable field 1D and 2D Al-27 MAS NMR measurements are combined with density functional theory calculations of both the structural and NMR interaction parameters for various points across the Y4Si2O7N2-Y4Al2O9 compositional range. This series provides numerous possibilities for significant variation of atomic ordering in the local ditetrahedral (Si,Al)(2)O7-xNx units. The two slightly structurally inequivalent aluminum sites in Y4Al2O9 are unambiguously assigned to the observed resonances. Computational findings on Y4Si2O7N2 demonstrate that the single observed Si-29 NMR resonance covers a range of local inequivalent silicon environments. For the first time, the MAS NMR and neutron diffraction data from the Y4SiAlO8N structure have been directly reconciled, thus establishing aspects of atomic order and disorder that characterize this system. This comparison suggests that, although the diffraction data indicates long-range structural order supporting a highly crystalline character, the short-range information afforded by the solid-state NMR measurements indicates significant atomic disorder throughout the (Si,Al)(2)O7-xNx units.

This study demonstrates the use of gallium and tin modified Y zeolites as catalysts for the conversion of glucose into fructose, mannose and 5-Hydroxymethyl furfural. These catalysts can be synthesised via a simple and scalable procedure that uses commercially available Y zeolite. The catalysts were characterised by various techniques including elemental analysis, electron microscopy, nitrogen physisorption, X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, solid state nuclear magnetic resonance spectroscopy and X-ray absorption near edge spectro-scopy. It is found that tin containing Y zeolite generate a glucose conversion of 36 % and total product yield of 17 % in water. Meanwhile, gallium containing Y zeolite shows an HMF yield of 33 % when reactions were conducted in DMSO. The recyclability of tin and gallium containing Y zeolites were studied in DMSO and the activities of both materials were shown to remain stable. Furthermore, the spent catalysts can be regenerated via calcination in air.

Novel Cs-containing triple cation perovskite nanocrystals produce high-performance LEDs as a result of improved surface passivation and environmental stability.

Inorganic metal halide perovskite nanocrystals (NCs) are promising materials for emission-based applications; however, the inclusion of toxic lead may limit their commercial viability. This paper describes two cesium cupriferous iodides as nontoxic alternatives to lead containing perovskites. These nanocrystals were synthesized with tailored composition and morphology by a hot-injection colloidal route to produce hexagonal nanoplates (NPs) of blue-emitting Cs3Cu2I5 and nanorods (NRs) of yellow-emitting CsCu2I3. Phase purity was confirmed by Rietveld refinement of X-ray powder diffraction patterns and solid state 133Cs MAS NMR with both compounds exhibiting high thermal stability suitable for optoelectronic technologies. Phase mixing allows linear tuning of Commission Internationale de l’Eclairage (CIE) coordinates from (0.145, 0.055) to (0.418, 0.541) such that a 1:8 molar ratio of Cs3Cu2I5 NPs and CsCu2I3 NRs yields white emission, while the 133Cs MAS NMR demonstrates that these photophysical effects are not attributed to any changes in the Cu oxidation state.

Crystalline sodium Y (NaY) zeolite has been synthesized using alternative natural source of aluminate and silicate, extracted from natural Belitung kaolin. Prior to use, the natural kaolin was pretreated to obtain fragmented metakaolin and extracted silica. Synthesis was conducted with the addition of NaY gel (two types of NaY seeds were used, prepared from colloidal sillica or sodium silica water) using hydrothermal method for 21 h at 100 °C. The characterization on the as-synthesized zeolites confirmed that the one prepared using colloidal silica-seed has closer structure similarity to NaY zeolite that was synthesized using pro analysis silicate and aluminate sources. Thus, the rest of the synthesis of NaY was carried out using colloidal silica-NaY seed. The NaY zeolites then were converted to HY, through ammonium-exchange followed by calcination, to be tested as cracking catalysts using n-hexadecane as a probe molecule. It shows that HY from metakaolin and extracted silica gives high performance, i.e., n-hexadecane conversion of 58%–64%, also C5-C12 percentage yield and selectivity of 56%–62% and 98%. This work has shown the potential to utilize kaolin as alternative silicate aluminate sources for crystalline zeolite synthesis and to obtain inexpensive and environmentally friendly catalyst materials.

The strong directing effects and difficulties in the removal of organic based surfactants makes the templated synthesis of nanoparticles in solid porous structures of defined molecular sizes such as SBA-15, without the use of surfactants, considerably attractive. However, the effects of their internal surface structures, adsorption affinities, and lattice mismatch on the particle morphology grown therein have not been fully appreciated. Here, we report the internal surface of the silica preferentially hosts isolated tetrahedrally coordinated oxidic Zn species on the molecular walls of the SBA-15 channels from wet impregnated Zn2+ and Pt2+ species. This leads to a less thermodynamically stable but kinetically controlled configuration of atomic zinc deposition on core platinum nanoparticles with unique confined lattice changes and surface properties to both host and guest structures at the interface upon reduction of the composite. This method for the formation templated nanoparticles may generate interest in forming new tunable materials as dehydrogenation catalysts.