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Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of “reaction specific” catalysts. To achieve this, colloidal chemistry methods are combined with ab initio calculations in order to define the reaction parameters, which drive chemical reactions to the desired crystal nucleation and growth path. Key in this procedure is the experimental verification of the predicted crystal facets and their corresponding electronic structure, which in case of nanostructured materials becomes extremely difficult. Here, by employing 31 P solid-state nuclear magnetic resonance aided by advanced density functional theory calculations to obtain and assign the Knight shifts, we succeed in determining the crystal and electronic structure of the terminating surfaces of ultrafine Ni 2 P nanoparticles at atomic scale resolution. Our work highlights the potential of ssNMR nanocrystallography as a unique tool in the emerging field of facet-engineered nanocatalysts. Structural and morphological control of crystalline nanoparticles is crucial in heterogeneous catalysis. Applying DFT-assisted solid-state NMR spectroscopy, we determine the surface crystal and electronic structure of Ni 2 P nanoparticles, unveiling NMR nanocrystallography as an emerging tool in facet-engineered nanocatalysts.

Titanium dioxide (TiO2) is an excellent photocatalytic material that imparts biocidal, self-cleaning and smog-abating functionalities when added to cement-based materials. The presence of TiO2 influences the hydration process of cement and the development of its internal structure. In this article, the hydration process and development of a pore network of cement pastes containing different ratios of TiO2 were studied using two noninvasive techniques (ultrasonic and NMR). Ultrasonic results show that the addition of TiO2 enhances the mechanical properties of cement paste during early-age hydration, while an opposite behavior is observed at later hydration stages. Calorimetry and NMR spin–lattice relaxation time T1 results indicated an enhancement of the early hydration reaction. Two pore size distributions were identified to evolve separately from each other during hydration: small gel pores exhibiting short T1 values and large capillary pores with long T1 values. During early hydration times, TiO2 is shown to accelerate the formation of cement gel and reduce capillary porosity. At late hydration times, TiO2 appears to hamper hydration, presumably by hindering the transfer of water molecules to access unhydrated cement grains. The percolation thresholds were calculated from both NMR and ultrasonic data with a good agreement between both results.

One thermodynamic parameter that is crucial to heat transport within the fluidized bed inside the rotary kiln, during clinker production, is the specific heat capacity. The particular parameter is often considered constant in the open literature, while, in reality, it strongly depends on the fluidized bed’s temperature and composition, considering that the temperature inside the kiln ranges from approx. 800 K up to 2000 K. For the current study, a mixing rule reported in the literature was applied in order to calculate the Cp of the fluidized bed, utilizing temperature and composition profiles available in the literature. An in-house code was developed for the comparison of the literature-reported Cps and those resulting from the mixing rule. It was discovered that the Cp of the fluidized bed had a proportional increase with the increase in the temperature along the length of the kiln. The deviation between the two values (calculated and literature) is relatively small in some cases, whereas, in others, it is quite significant, ranging from 1.56% to 52.49%, thus making the adoption of the temperature-dependence of Cp necessary. Establishing a more accurate relation for the specific heat capacity leads to a better energy balance inside the kiln, which, along with other improvements, can lead to a decrease in the energy consumed and a significant reduction in greenhouse gas emissions.

Belite, the second most abundant mineralogical phase in Portland cement, presents five polymorphs which are formed at different temperatures. The increased interest in belite cement-based products is due to the lower environmental impact associated with the lower energy consumption. The importance of belite polymorphs formed at higher temperatures for cement industry applications is high, because they present better hydraulic properties. Thus, any study that helps to explore the structure relations of all belite polymorphs is of interest for both scientific and practical points of view. In the present work, a systematic structure–superstructure relation study is presented for all polymorphs, and it is based on the work of O’Keefe and Hyde (1985). In this pioneering work, generally, the structures of oxides are considered as having common characteristics with prototype structures of alloys. The basic result of the present work is the fact that all the polymorphs adopt a common architecture which is based on capped trigonal prisms of Ca cations, which host the Si one, and the oxygen anions occupy interstitial sites, i.e., an architecture in conformity with the model which considers the oxide structures as stuffed alloys. This result supports the displacive character of the transformation structural mechanism that links the five polymorphs based on the cation sites in their structures. However, based on the sites of oxygen anions, it could be considered as of diffusion character. The study of belite polymorphs is also of interest to products obtained by doping dicalcium silicate compounds, which present interesting luminescent properties.

The discovery of two-dimensional electron gas states with giant Rashba spin splitting (RSS) in electron-doped three-dimensional topological insulators (TIs) uncovered new fascinating physics and raised hopes for novel spintronic devices. Significant challenges, including synthetic constraints and control of the magnetic properties, must be addressed before any breakthroughs are possible. Here, we show how RSS in Bi-rich Bi 2 Se 3 nanoplatelets is responsible for the appearance of remarkable orbital magnetic properties, as observed using magnetization and conduction electron spin resonance experiments and confirmed by theoretical simulations. In view of the strong spin-orbit coupling (SOC) and the proximity to the TI surface states, this discovery enlightens fundamental aspects of SOC-based functionalities of TI materials with aims for future applications. Spin engineering: nanohexagons work their magic Plate-like bismuth nanocrystals can give physicists enriched mechanisms to control spin through unexpected, surface-localized magnetism. Topological insulators have crystal structures that make them non-conductive everywhere except for the quantized states on their surfaces. Hae Jin Kim's group at KBSI and co-workers (PI, “Demokritos”, and UoI) has now used a liquid-phase, solvothermal synthesis to turn bismuth selenide (Bi 2 Se 3 ) topological insulators into nanometre-thin platelets with unique hexagonal shapes. The team discovered that sandwiching bismuth atoms between the nanohexagons disrupts the normal coupling interactions between electron spin and orbital motion at topological insulators surface states. This splitting generates so-called Rashba states that produce a special orbital-based type of magnetism, where spin states can be flipped with help from a weak magnetic field. Further spin engineering of this system is possible by altering the degree of bismuth intercalation. Bi-layer intercalation in Bi 2 Se 3 nanoplatelets gives rise to an intriguing crystal structure comprised of randomly stacked Bi 2 Se 3 and Bi 2 Se 2 . Detailed conduction electron spin resonance (CESR) and AC/DC magnetization studies prove that controlling Bi intercalation results in fine tuning the two-dimensional electron gas parabolic Rashba states, which enables the appearance of extraordinary orbital magnetism, through the coupling of the spin and orbital degrees of freedom. The methodology presented herein provides a unique and simple way for efficient spin engineering, with important potential applications.

Open cell 3D titanium carbide/silicon carbide (TiC/SiC) composite was oxidised to titanium oxide/silicon carbide (TiO 2 /SiC) following different temperature profiles in a thermal gravimetric analysis (TGA) instrument in continuous air-flow and static air (oven) environments. The TiC oxidation to anatase, starting at temperatures over 450°C, was confirmed by Raman spectroscopy and X-Ray diffraction (XRD). By increasing the temperature, the mass fraction of anatase diminished, while the mass fraction of rutile increased. SiC oxidation started at 650°C when a mixture of TiO 2 /SiO 2 /SiC could be observed by Raman, XRD and HRTEM.

Background Molybdenum sulfide (MoS 2 ) catalysts to be used for hydrodesulfurization (HDS) processes were prepared via the reductive thermal decomposition of ammonium tetrathiomolybdate at fixed temperature (653 K) by varying decomposition times and H 2 pressures. Both parameters were found to strongly influence textural and catalytic properties of the resulting MoS 2 catalysts. Methods Nitrogen sorption, FT-IR, and XRD analyses revealed the effect of varying decomposition times (3 to 7 h) and H 2 pressure (20 to 1,000 psig) on the morphology and structure of the catalysts. Dibenzothiophene (DBT) was used to assess catalytic efficiency for HDS reactions. Results The influence of time on specific surface was minimal at low pressures but increased at higher decomposition pressures. Vibrational energies of Mo-S bonds in FT-IR indicate that MoS 2 catalysts prepared at higher pressures exhibit weaker Mo-S bonds. Analysis of XRD patterns point towards an increase in stacking and crystallite size with increasing pressure; interlayer rotation about both the a - and c -axes of the stacks was also observed. Catalytic testing results show that conversion increases at higher values of decomposition time and pressure. Partially hydrogenated products were also observed at higher pressures, and the ratio of partially to fully hydrogenated DBT was calculated as an additional measure of catalytic efficiency. Conclusions Decomposition time and H 2 pressure during ammonium tetrathiomolybdate (ATM) thermal decomposition have a significant impact on the morphological and catalytic properties of the derived MoS 2 catalysts. Samples prepared for 5 h at 1,000 psig exhibited the highest conversion of DBT and the lowest ratio of partially to fully hydrogenated products.

Belite, the second most abundant mineralogical phase in Portland cement, presents five polymorphs which are formed at different temperatures. The increased interest in belite cement-based products is due to the lower environmental impact associated with the lower energy consumption. The importance of belite polymorphs formed at higher temperatures for cement industry applications is high, because they present better hydraulic properties. Thus, any study that helps to explore the structure relations of all belite polymorphs is of interest for both scientific and practical points of view. In the present work, a systematic structure–superstructure relation study is presented for all polymorphs, and it is based on the work of O’Keefe and Hyde (1985). In this pioneering work, generally, the structures of oxides are considered as having common characteristics with prototype structures of alloys. The basic result of the present work is the fact that all the polymorphs adopt a common architecture which is based on capped trigonal prisms of Ca cations, which host the Si one, and the oxygen anions occupy interstitial sites, i.e., an architecture in conformity with the model which considers the oxide structures as stuffed alloys. This result supports the displacive character of the transformation structural mechanism that links the five polymorphs based on the cation sites in their structures. However, based on the sites of oxygen anions, it could be considered as of diffusion character. The study of belite polymorphs is also of interest to products obtained by doping dicalcium silicate compounds, which present interesting luminescent properties.

The discovery of two-dimensional electron gas states with giant Rashba spin splitting (RSS) in electron-doped three-dimensional topological insulators (TIs) uncovered new fascinating physics and raised hopes for novel spintronic devices. Significant challenges, including synthetic constraints and control of the magnetic properties, must be addressed before any breakthroughs are possible. Here, we show how RSS in Bi-rich Bi sub(2)Se sub(3) nanoplatelets is responsible for the appearance of remarkable orbital magnetic properties, as observed using magnetization and conduction electron spin resonance experiments and confirmed by theoretical simulations. In view of the strong spin-orbit coupling (SOC) and the proximity to the TI surface states, this discovery enlightens fundamental aspects of SOC-based functionalities of TI materials with aims for future applications.

Background Molybdenum sulfide (MoS^sub 2^) catalysts to be used for hydrodesulfurization (HDS) processes were prepared via the reductive thermal decomposition of ammonium tetrathiomolybdate at fixed temperature (653 K) by varying decomposition times and H2 pressures. Both parameters were found to strongly influence textural and catalytic properties of the resulting MoS^sub 2^ catalysts. Methods Nitrogen sorption, FT-IR, and XRD analyses revealed the effect of varying decomposition times (3 to 7 h) and H2 pressure (20 to 1,000 psig) on the morphology and structure of the catalysts. Dibenzothiophene (DBT) was used to assess catalytic efficiency for HDS reactions. Results The influence of time on specific surface was minimal at low pressures but increased at higher decomposition pressures. Vibrational energies of Mo-S bonds in FT-IR indicate that MoS^sub 2^ catalysts prepared at higher pressures exhibit weaker Mo-S bonds. Analysis of XRD patterns point towards an increase in stacking and crystallite size with increasing pressure; interlayer rotation about both the a- and c-axes of the stacks was also observed. Catalytic testing results show that conversion increases at higher values of decomposition time and pressure. Partially hydrogenated products were also observed at higher pressures, and the ratio of partially to fully hydrogenated DBT was calculated as an additional measure of catalytic efficiency. Conclusions Decomposition time and H2 pressure during ammonium tetrathiomolybdate (ATM) thermal decomposition have a significant impact on the morphological and catalytic properties of the derived MoS^sub 2^ catalysts. Samples prepared for 5 h at 1,000 psig exhibited the highest conversion of DBT and the lowest ratio of partially to fully hydrogenated products.