dataesr/scientific-paragraphs-categorization huggingface dataset:
Characterization The BET specific surface areas and the C BET constants of the samples were obtained from nitrogen adsorption experiments at 77 K by using a Tristar instrument (Micromeritics) for the grafted powders and a ASAP 2020 (Micromeritics) for the γ-Al 2 O 3 powders. Prior to measurements, samples were degassed under vacuum overnight at 100 ˝C for the grafted powders and 300 ˝C for the γ-Al 2 O 3 powder. The weight percentage of phosphorus in the samples was determined by EDX using a Zeiss scanning electron microscope (SEM) EVO HD15 at 10 kV equipped for EDX analysis with the AZtecEnergy analysis software (Oxford instruments. Abindong, UK). Samples were prepared as pellets for the analysis and deposited on double-sided carbon tape. FTIR spectra were obtained with a Perkin-Elmer Spectrum 2 spectrophotometer and were recorded in the 4000 to 400 cm ´1 range using 32 scans at a nominal resolution of 4 cm ´1 in ATR mode (spectrum of γ-Al 2 O 3 as a background spectrum).
This is not observed in Fig. 6 , the magnetic anisotropy of the samples is similar to the one of bulk Co and does not vary significantly with temperature. TEM size distributions. The size distribution histogram of each catalyst was counted based on more than 200 particles taken from different micrographs. For improving the statistics, the measurements were carried out with several sets of images corresponding to different regions. Data acquisition was performed by using DigitalMicrograph software and the histograms were built up after manual measurements of the particle sizes.
Acknowledgements This research is conducted within the context of the CNRS LIA 'Functional nanostructures: morphology, nanoelectronics and ultrafast optics', NANOFUNC. We also thank  SICAT Co. (www. sicatcatalyst. com)for offering SiC materials. Y. L. thanks the financial support from Internal Grant, J. L. thanks the grant form CATSYNBIOFUELS. Y. S. thanks the  Leading Foreign Research Institute Recruitment Program  through the  National Research Foundation of Korea (NRF)  funded by the  Ministry of Science, ICT & Future Planning  ( NRF-2010-00453 ). Dr Charlotte Pham  is acknowledged for helpful discussion during the SiC-based materials' preparation. Finally, we also thank  Dr P. Panissod  for scientific and technical discussions.
Computational details for surface hydroxylation as well as the force field are provided in ref. 51. Rigid armchair and zigzag-typed CNTs were considered. CNTs with radius R = 13. 5 Å (CNT (20,20) and CNT(34,0)) and R = 27 Å (CNT (40,40) were used. The length of all CNTs was set to 100 Å. A graphene-based slit pore made of two graphene sheets (100 × 102 Å) separated by 27 Å was also considered. All MD simulations were carried out with the DL_POLY package (version 4. 0) 52 using a combination of the velocity-Verlet and the SHAKE-RATTLE algorithms  53. The Nose-Hoover thermostat  54, 55  with a relaxation time of τ t = 0. 5 ps was considered. Periodic boundary conditions were applied in the three directions. MD simulations were performed in the canonical ensemble at T = 300 K and T = 400 K. MD simulations were performed using a time step of 0.
Crystal data The X-ray data for single crystals of [PdCl2(L1)2] was obtained at a temperature of 193(  2 ) K on a Bruker-AXS SMART APEX II diffractometer using the MoK radiation (λ = 0. 71073 Å). Phiand omega-scans were used. The data were integrated with SAINT [25] and an empirical absorption correction with SADABS was applied  [26]. The structure was solved by direct methods, using SHELXS-97 and refined using the leastsquares method on F 2 with SHELXL-97  [27]. All.
Experimental details 1-Fluoro-adamantane was purchased from ABCR, with a purity of 99% and used as received. To study the dynamics of the low-temperature Phase II of 1F-ada, we have combined X-ray diffraction with broadband dielectric spectroscopy. Powder X-ray diffraction data were collected by means of a horizontally mounted INEL cylindrical position-sensitive detector (CPS 120). The detector, used in Debye-Scherrer geometry, is constituted by 4096 channels, providing an angular step of 0. 0291 (2y) between 41 and 1201. Monochromatic Cu K a1 radiation (l = 1. 5406 Å) was selected with an asymmetric focusing incident-beam curved quartz monochromator. The samples were introduced into 0. 5 mmdiameter Lindemann capillaries which rotate along their longitudinal axes during data collection to prevent the effects of the preferred orientations.
Results and discussion The lattice and the possible space groups of Phases I and II were determined at 295 and 100 K, respectively, by means of X-Cell software, available in the module Powder Indexing of Materials Studio,  37  according to a reasonable density and compatibility between the volume change at the II-I transition. The Pawley refinement,  38  which minimizes the weighted R-factor, R wp , describing the agreement between the experimental and the simulated patterns, helps confirm the indexing result and the systematic absences for the space group assessment. In order to determine the structure of the two crystalline phases we have built up the molecule of 1F-ada using the parameters defining the adamantane molecule C 10 H 16 ,  39   The refined structure of the high-temperature Phase I of 1F-ada is face-centred cubic (Fm% 3m), with four molecules per unit cell and a = 9.
Results and Discussion Previously, we have reported on optical and structure properties of ALD ZnO nanolayers  [5, 23, 27]. We revealed the polycrystalline structure of 200 nm ZnO layers  [28]. The fabricated ZnO layers demonstrate a rough surface with columnar growth and an average size of the grains in the range of 5-60 nm as a function of ZnO film thickness (Figure  5 ). The surface morphology was studied by an Asylum Research MFP-3D Atomic Force Microscope, operating in tapping mode and equipped with a commercial silicon tip. The obtained image was analyzed using the free software Gwyddion. From the AFM image (Figure  5a ) it is clearly seen that ZnO nanolayers of 50 nm thickness were amorphous. In this case, agglomerates of 100-200 nm were found on the surface. On the other hand, ZnO crystallization has been improved for 100 nm layers (Figure  5b ), so the agglomerates with well defined shapes of 20-40 nm have been observed (Figure  5b ).
The inner and the outer semiangles for the dark-field detector (upper DF detector) were 100 and 170 mrad, respectively. 3D TEM tomography data were acquired using a JEOL 2100F electron microscope. The acquisition of bright field (BF) and dark field (DF) tilt series was carried out simultaneously in scanning mode (STEM). A camera length of 10 cm was chosen for this experiment. It corresponds to inner and outer semiangles of 60 and 160 mrad, respectively, for the HAADF detector. A 100 μm condenser aperture was employed, allowing one to reach a probe diameter of about 0. 12 nm with a current density of 0. 5 pA Å -2. Under these conditions, the tomography series were acquired using Digital Micrograph software (tomography plugin), giving access to an automatic increment of the tilt angles and sharp control of the specimen drift and defocusing.
57 This means that each voxel (unit fragment of the volume) is attributed to either vacuum or gold. Consequently, DART is superior to SIRT when exact particle boundaries are to be determined. 58 -ray diffraction (XRD) measurements were performed with Cu Kα radiation using a Bruker D8 Advance diffractometer equipped with a Lynx eye detector. The 2θ diffractograms were recorded between 24-50°with a step size of 0. 04°and a steep time of 20 s per step. The ICDD-PDF2 database was used to identify the crystalline phases. When possible, TiO 2 and RuO 2 XRD peaks were deconvoluted, using WinPLOTR. 59  The Scherrer equation was used to calculate the crystallite size of particles (SI-19 †). 60  X-ray photoelectron spectroscopic (XPS) analyses were performed using an SSX 100/206 photoelectron spectrometer from Surface Science Instruments (USA) equipped with a monochromatised micro focused Al X-ray Kα source (powered at 20 mA and 10 kV), a 30°solid angle acceptance lens, a hemispherical analyser and a position-sensitive detector.
Acknowledgements A. K. thanks the  European doctoral school IDS FunMat  for the PhD fellowship. The authors acknowledge  Wallonie-Bruxelles International , the  Ministère Français des Affaires étrangères et européennes and the Ministère de l'Enseignement supérieur et de la Recherche  for their financial support in the framework of the Hubert Curien partnership (Tournesol), as well as the METSA network for 3D STEM tomography. The authors also acknowledge the  Fondation Collège de France. AK and DPD thank  Dr. François Devred  for the technical and logistical support in the project.
In this context, the FUELBASE project has been initiated in 2005, which aims at providing a computational tool running thermodynamic calculations and assessing the behaviour of irradiated fuel materials (oxides, carbides, etc) containing fission products and minor actinides  [2] [3] [4]. More recently, the international TAF-ID project has started in 2013 within the OECD/NEA, whose goal is to develop a thermodynamic database for nuclear materials in cooperation between several countries (www. oecd-nea. org/science/taf-id/). The binary U-O, Pu-O and ternary U-Pu-O systems have been investigated extensively already, and thermodynamic models have been developed for these systems using the CALPHAD method  [2, 5, 6]. The data available on the Np-O system are much more limited  [7] , however, and there is no satisfactory overall description using CALPHAD.
Oxygen potential data The only experimental study available on the variation of the oxygen potential of hypostoichiometric neptunium dioxide as a function of oxygen-to-metal ratio and temperature is by Bartscher and Sari  [24]. The authors have used a gas-equilibrium method in the temperature range 1470 to 1850 K. Neptunium dioxide was heated on a thermobalance in a hydrogen-water atmosphere. The oxygen potential was subsequently derived from the known H 2 O/H 2 ratio, and the corresponding O/Np ratio was calculated from the weight change of the sample. These oxygen potential lines, about midway between those of UO 2Àx and PuO 2Àx at a given temperature  [7] , are in good agreement with the trend of decreasing stability of the actinide dioxides along their series, i. e. , from ThO 2 towards AmO 2.
The authors reported a vapour made of 93% NpO 2 (g), 6% NpO(g), and 1% Np(g) at 2260 K under vacuum, with an overall gaseous composition (O/Np) gas = 1. 939  [11]. The authors assigned the same composition to their condensed phase, supposing a congruent equilibrium was reached in their experiment, but the latter interpretation must be adjusted. The vapour composition was directly analyzed after applying a 10 K/min heating ramp, with no stabilisation time at the investigated temperature (private communication), so as to stay as close as possible from a stoichiometric composition. This means their data refer to a slightly but continuously changing O/Np ratio. The composition of their condensed phase was therefore re-evaluated in the present work as detailed in Section 5.
The data were collected by step scanning in the angle range 10 6 2h 6 120 , with an integration time of about 8 h, a count step of 0:02 ð2hÞ, and a dwell of 5 s/step. Structural analysis was performed by the Rietveld method with the Fullprof2k suite  [40]. The experimental set up used in the present work consisted of a Knudsen effusion cell coupled to a quadrupole mass spectrometer (QMG422, Pfeiffer Vacuum GmbH). The sample of interest was placed in the Knudsen cell (made either of tungsten or {ZrO 2 +Ir liner}), and heated under vacuum or in the presence of a controlled oxygen pressure, in a high temperature furnace made of tungstencoil heating elements, and surrounded by seven cylindrical thermal shields (three in tungsten, four in tantalum). The choice of the tungsten and {ZrO 2 +Ir} materials for the Knudsen cell was based on their high melting points, and low reactivity with respect to actinide materials  [41].
In the latter relation, the efficiency of the second electron multiplier can be approximated as c ik ¼ d=M 1=2 ik , where M ik is the molar mass of ion k, and d is a constant, following Grimley  [46]. The atomic ionization cross-sections of neptunium and oxygen were estimated using the program SIGMA  [42, 47, 48]  and data of Mann  [47]. The total ionization cross sections of NpO(g) and NpO 2 (g) gaseous species were calculated using the modified additivity rule, as described by Deutsch et al. [49, 50]  (rðNpOÞ ¼ 12:9 Á 10 À16 cm 2 , rðNpO 2 Þ ¼ 11:2 Á 10 À16 cm 2 at 30 eV). The ionization cross sections of WO(g), WO 2 (g), and WO 3 (g) were taken from the calculations of Deutsch et al. using the DM formalism  [51]  (rðWOÞ ¼ 6:6 Á 10 À16 cm 2 ; rðWO 2 Þ ¼ 4:5 Á 10 À16 cm 2 ; rðWO 3 Þ ¼ 3:5 Á 10 À16 cm 2 at 30 eV).
3 Pa. The higher oxygen potential allowed to re-oxidize the neptunium dioxide sample: the analysis at 2164 K (AP 4 ) showed only 1. 2% NpO(g). The total and partial vapour pressures subsequently recorded on the second temperature ramp (Ramp B ) between 2056 K (AP 5 with 100% NpO 2 (g)) and 2159 K (AP 6 with 98. 8% NpO 2 (g) and 1. 2% NpO(g)) correspond to a quasi-stoichiometric neptunium dioxide sample, with a composition very close to the stoichiometric O/Np = 2 phase boundary. These data can therefore be used to derive the sublimation enthalpy of NpO 2 (cr) with a higher degree of confidence with respect to the oxygen-to-metal ratio compared to previous measurements. The total pressure of neptunium bearing species and NpO 2 (g) partial pressure corrected for the small contribution of NpO(g) (1.
Thermodynamic modelling The PARROT module of the Thermo-Calc software (Version 2015b) was used to optimize the thermodynamic parameters of all phases in the neptunium-oxygen system  [57, 58]. The oxygen solubility in the different allotropic forms of neptunium was neglected in this work. Np 2 O 5 was treated as a stoichiometric compound. The Gibbs energy functions of all the phases are referred to the enthalpy of the pure elements in their stable state at room temperature 298. 15 K and 1 bar ( o H SER i ð298:15 KÞ).
Gas phase The gas phase was described by an ideal mixture of (Np, NpO, NpO 2 , O, O 2 , O 3 ) gaseous species. The Gibbs energy is expressed by: G u ¼ Ry o i G u i þ RTRy i ln y i þ RT ln P=P o ð34Þ where y i is the fraction of the species i in the gas phase. o G u i represents the standard Gibbs energy of the gaseous species i. P o is the standard pressure. The O, O 2 , and O 3 functions were taken from the SGTE database  [61]. The Gibbs energy function for Np(g) was taken from the recent review by  [13]. The entropy and heat capacity functions for NpO(g) and NpO 2 (g) were taken from  [14]. The enthalpies were those re-determined in this work as detailed Sections 2 and 3 (see Table  11 ).
Ackermann and Rauh have used the data of Mann at maximum of the ionization cross sections to estimate the equilibrium constants of reaction, although their measurements were done at 10. 5 eV  [37]. The authors did not report individual intensity values for the ionic vapour species unfortunately, so that a correction based on the method of Younès was not possible. Instead, the cross section values have been corrected to match an ionization energy of 10. 5 eV using the program SIGMA  [42, 47, 48]  and the additivity rule for the molecular species, yielding R A ¼ 1:02209 and R B ¼ 0:95115. Using the aforementioned corrections, the data of Ackermann and Rauh  [37]  were subsequently re-analyzed in this work by second and third law methods. The enthalpy of reaction at the median temperature was assigned an uncertainty of ðAE4 kJ Á mol À1 Þ for the second law calculation.
Acknowledgements The authors would like to express their gratitude to  D. Bouëxière  for the collection of the X-ray diffraction data. The authors also thank  Dr. C. Chatillon  for the very fruitful discussions. ALS acknowledges the  European Commission  and the  Ras al Khaimah Centre for Advanced Materials  for funding her PhD studentship. This research contributes to the joint programme on nuclear materials (JPNM) of the  European Energy Research Alliance (EERA).
For this purpose, thin slices were prepared using an ultra-microtome to study the internal structure of the catalyst. Finally, we acquired high-resolution elemental data from scanning transmission X-ray microscopy-electron energy loss spectroscopy (STEM-EELS), where we created 0. 5 nm spatial resolution maps with elemental sensitivity. We illustrate this multiple-technique characterization approach for both fresh and deactivated 15 wt% Co/TiO 2 catalysts. We will use this new approach to show that there is seemingly another, different mechanism operative that may play a role in the deactivation of Co/TiO 2 FTS catalysts, which is related to the previously reported reaction-induced spreading of metal oxides on a TiO 2 surface. 34.
) shows Catalysis Science & Technology Paper metallic Co nanoparticles of about 10 nm. This size estimation does not take into account the passivation layer around the Co nanoparticles upon exposure to air. The presence of other, amorphous Co species cannot be ruled out using this method. Hard X-ray TXM was carried out at beamline 6-2c of the Stanford Synchrotron Radiation Lightsource (SSRL). 36 Monochromatic X-rays were focused by a condenser lens onto the sample, which was mounted in a capillary on an x, y, z, θ stage. The transmitted image was formed by a Fresnel zone plate onto a CCD camera. The recorded 2D images cover a field of view of ∼25 × 25 μm at ∼30 nm 2D spatial resolution. 31 Tomographic data were obtained by rotating the sample and recording the transmission image at different angles.
30 is was done below and above the Co K-edge (7709 eV). Data pre-processing and tomographic reconstruction were performed with the TXM-Wizard software package. 37 ata visualization was done using the FEI Avizo software. 3D elemental maps were formed by subtracting the reconstructed data below the edge from the data above the edge. In situ TXM experiments were conducted using a specially designed reactor. 10, 35 The spent catalyst was crushed using a mortar and pestle and loaded into a quartz capillary. The capillary was glued to the in situ holder using hightemperature epoxy. The sample was first characterized under He atmosphere at room temperature. Next, the catalyst was reduced using H 2 at 350 °C for about 2 h. TXM XANES spectra were measured during the reduction treatment. Then, the catalyst was cooled down to 250 °C, for about 20 min.
The gas flows were then switched to 2 : 1 H 2 and CO, at a pressure of 10 bar. Continuous XANES scans were carried out for about 9 h. Soft X-ray STXM experiments were performed at beamline 10 ID-1 of the Canadian Light Source (CLS). 100 nm slices of the catalyst samples were obtained by ultramicrotomy. 38 The slices were introduced into the STXM chamber, which was then evacuated to about 0. 1 mbar and backfilled to about 0. 15 bar with He. The monochromatic X-ray beam was focused on the sample by a Fresnel zone plate to a spot size of about 30 nm. Spectral image sequences (stacks) were obtained by recording images at different photon energies around the Ti L 2,3 edges (460 eV) and Co L 2,3 edges (780 eV). Data analysis was performed with the aXis2000 software. After aligning the image sequence, elemental maps were constructed by comparing images below and above the X-ray absorption edge.
X-ray absorption spectra (XAS) were extracted from the image sequences. Single pixel spectra were fitted using reference spectra obtained from high-purity Co 3 O 4 , CoO and metallic Co. High-resolution characterization of the samples was performed using STEM-EELS in a NION USTEM 200 (probe corrected) microscope. The samples were sonicated in ethanol and a small droplet was deposited on a copper TEM grid with an amorphous carbon layer. The samples were introduced into the microscope after evaporating the ethanol. An operating voltage of 60 kV was used during the experiments. EELS data were acquired in the Spectrum Imaging mode so that a full spectrum was acquired at each position of a 2D scan. To minimize beam damage, the sample area was only measured once. Data analysis was performed using custom plugins for the Gatan DigitalMicrograph software.
Elemental maps were created by selecting three windows in the EELS spectra; two were placed before the edge of the element of interest for background correction. The other one was placed over the edge. The elemental map was then obtained as the difference between the edge and the background. Where necessary, the signal-to-noise ratio was improved by principal component analysis using the Hyperspy software (www. hyperspy. org). X-ray photoelectron spectroscopy (XPS) measurements were carried out on an Axis NOVA DlD spectrometer from Kratos Analytical Ltd. Spectra were acquired using monochromatic Al-K α radiation (photon energy of 1486. 6 eV). The X-ray source was operated at 150 W (15 kV, 10 mA). The analysis area was about 0. 3 × 0. 7 mm. The analyzer was used in FOV1 mode with a pass energy of 40 or 80 eV for the narrow scans (spectra of only Co 2p, O 1s, Ti 2p and C 1s peaks) and 160 eV for the survey scan (complete spectrum).
Acknowledgements  M. de Ridder  from  Shell  is acknowledged for performing the XPS experiments. J. den Breejen  and  S. van Bavel , both from  Shell , are thanked for fruitful discussions. O. Attila ,  H. van der Bij ,  D. Cicmil ,  S. Kalirai ,  R. Oord ,  C. van Oversteeg ,  P. Paalanen ,  Z. Ristanovic ,  M. Al Samarai  and  M. Velthoen , all from  Utrecht University , are kindly thanked for their help during data acquisition. We are grateful to  P. Munnik  from  Utrecht University  for performing the ultra-microtomy. We appreciate financial support from  Shell Global Solutions, NRSC-C  and  NWO-CW VICI. Part of this research was carried out at the  Stanford Synchrotron Radiation Lightsource , a Directorate of  SLAC National Accelerator Laboratory  and an  Office of Science User Facility  operated by the  U.
S. Department of Energy Office of Science by Stanford University. Other parts of the research described in this paper were performed at the  Canadian Light Source , which is funded by the  Canada Foundation for Innovation , the  Natural Sciences and Engineering Research Council of Canada , the  National Research Council Canada , the  Canadian Institutes of Health Research , the  Government of Saskatchewan ,  Western Economic Diversification Canada , and the  University of Saskatchewan. The research leading to these results has received funding from the  European Union Seventh Framework Programme  [FP7/2007-2013] under Grant Agreement No. 312483  ( ESTEEM2 ).
Small deformation mechanical spetroscopy Rheological testing of the solutions and gels was performed in oscillation using cone and plate geometry (4 cm diameter; 1. 581° cone angle) with an Anton Paar Physica MCR-301 rheometer. Samples were loaded with minimal disturbance at room temperature, coated around the periphery of the sample with light silicone oil to minimise the loss of water, and left unperturbed for 30 min before measurements were made. A temperature sweep was obtained by heating at 1 ºC min -1 and measurements made at a frequency of 1Hz and a strain of 0. 5 %. This ensured that data was obtained in the linear viscoelastic region.
ACKNOWLEDGMENT Part of the research leading to these results (AA) as funded by the  European Community 's  Seventh Framework Program  ( FP7/2007-2013 ) under Grant Agreement No. 214015. We would like to thank  Dr. G. Sworn ,  Mr. Emanuel Kerdavid  and  Mr. Jose Fayos  of the  Dupont Company  for preparing, characterizing and providing the xanthan samples.