dataesr/scientific-paragraphs-categorization huggingface dataset:
Yet, as can be seen by reproducing the datasets of Pochet et al. [45]  and He et al. [47]  (shown in the SM), retaining the generality feature in the whole parametric space and considering different experimental RCMs is a challenging task. In the case of Pochet et al. [45] , in lean conditions the reactivity of NH 3 /H 2 mixtures is overestimated, while in the case of He et al. [47] , previous works  [45, 47, 49]  pointed out that no kinetic mechanism is able to keep the generality feature with varying equivalence ratio and blending ratio: the considered mechanisms mostly differ by their relative reactivity, according to their core NH 3 chemistry. In this case, too, sensitivity analysis was leveraged to understand the changes in the paths controlling IDTs with the hydrogen amount. Fig. 12  shows the relevant paths in determining OH mass fraction, considered as a marker of IDT.
On the other hand, R5 act as termination reactions due to the abundance of HO 2 radicals, as already observed at lower temperatures in JSR experiments (Section 3. 2), and unlike intermediate-temperature FR datasets (Section 3. 1). Concerning NH 2 + NO x reactions, the temperature range is favorable for the competition between R11 and R12 (thermal DeNO x  [15, 20, 92] ), while the high pressures at stake favor the presence of NO 2 , thus determining the parallel competition between R13 and R14. In particular, the propagation channel R13 leads to the H 2 NO intermediate (along with R7), whose major role at low temperatures has been already pointed out in Section 3. 2, and in previous works  [20, 59]. Especially with low or no hydrogen, its oxidation to HNO is indeed one of the major reactivity enhancers.
Conclusions Unraveling the chemical interactions between ammonia and hydrogen is an essential requirement for mapping the behavior of the binary blends in the whole operating space, and allowing a flexible use for a variety of applications. In this work, light was shed on the low-and intermediate-temperature oxidation of NH 3 /H 2 mixtures with a variable blending ratio. To this purpose, an experimental and modeling study was performed, by combining new data, collected in a flow reactor at intermediate temperatures, with the most recent literature datasets. These were obtained in different devices (jet-stirred reactor, rapid compression machines, laminar flames), thus covering all the conditions of interest, as well as the major combustion features (ignition, flame propagation). At the same time, an established kinetic mechanism, previously developed for ammonia oxidation, was revised according to the recent theoretical findings, and leveraged to interpret the obtained results: rate of production, flux and sensitivity analysis were the kinetic tools to identify the binary interactions, and the role of the most critical reaction steps, deserving a deeper theoretical attention in future studies.
The newly-collected datasets, covering the whole transition from pure NH 3 to pure H 2 , were coherently reproduced by the kinetic model for what concerns the reactivity onset and water formation. When adding hydrogen, the half-conversion temperature was shown to be anticipated in a linear way with the hydrogen mole fraction, except for the smallest amounts, where the anticipation rate was faster. The kinetic analysis allowed to gain an insight in the changes occurring from pure NH 3 to binary mixtures: the opposite role played by H-abstraction by the H radical from NH 3 could be highlighted, first inhibiting then enhancing reactivity, due to the availability of H atoms from the direct oxidation of H 2. Concerning the nitrogen fate, most of it was converted to N 2 (>90%), while the rest was NO, which was found to increase monotonically with the hydrogen fraction.
On the other hand, the amounts predicted by the mechanism were i) up to a factor 2 larger than what measured (as already found in previous works with pure ammonia  [20] ), ii) converging to comparable values at high temperature for all the compositions (except for the mixture richest in H 2 ), and iii) non-monotonic with the temperature for the largest hydrogen amounts. Although the third outcome might seem counterintuitive, a deeper analysis in the conversion history within the reactor could attribute NO oscillations at high temperatures to an early mixture ignition in the pre-heating region due to the increased reactivity when hydrogen was added, such that the final results became strictly dependent on the heating history (i. e. temperature profile). The analysis was then extended to lower temperatures, considering the datasets recently collected in a Jet-Stirred Reactor at atmospheric pressure.
Raman Spectroscopy Low-frequency Raman spectroscopy (LFRS) experiments were performed on the highdispersive XY-Dilor spectrometer composed of three gratings configured with a focal length of 800 mm, and using the 660 nm line of a Cobolt laser. Opening the slits at 150 µm makes it possible to detect a Raman signal down to 5 cm -1 in high resolution configuration (lower than 1 cm -1 ). All samples were loaded in spherical Pyrex cells and hermetically sealed. The temperature of each sample was regulated using an Oxford nitrogen flux device that keeps temperature fluctuations within 0. 1 • C. Low-frequency Raman spectra were collected between 5 and 200 cm -1 in 1 min, in situ, during the heating ramp at 1 • C/min. It is well known  [29]  that the LFRS requires specific data processing because of the high sensitivity of the low frequency to thermal fluctuations through the Bose factor.
In this context, the results presented above can be discussed to better understand the stabilization mechanism of the undercooled liquid state of IBP. In a first step, menthol-ibuprofen eutectic system was carefully investigated for analyzing the stability of the undercooled liquid state of IBP within the formulation. The physical state of IBP was monitored upon two successive heating ramps at 1 • C/min of various IBP X :M (1-X) mixtures. The first heating ramp performed from the crystalline state of the mixture has provided data used for plotting the phase diagram of the binary mixture. Results are very similar to those recently published with the eutectic composition slightly below X IBP = 0. 3, and the eutectic temperature very close to 20 • C. The aim of this study focused on the thermal stability of the liquid formulation.
This stu shows that dissolving IBP in the DES composed of terpenes should be a better route f avoiding IBP recrystallization than forming eutectic mixtures (ibuprofen-menthol ibuprofen-thymol). In a second step, the stability of amorphous IBP was analyzed within co-amorphous blends prepared by cryomilling ibuprofen with amino acids. Arginine was selected because of its remarkable properties for stabilizing amorphous indomethacin (IMC). However, Tg of IBP is significantly lower than Tg of IMC (Tg(IMC)-Tg(IBP) ≈ 90 °C). Tg values of various mixtures determined from low-frequency Raman data are compared, in Figure  A9  in Appendix B, to the Tg curve calculated from the Gordon-Taylor law. This figure shows that Tg of IBP-rich mixtures (XIBP ≥ 0. 4) is below room temperature. However, no recrystallization was detected in the mixture prepared by cryomilling ARG and IBP in In a second step, the stability of amorphous IBP was analyzed within co-amorphous blends prepared by cryomilling ibuprofen with amino acids.
III. RESULTS AND DISCUSSION The results of current efficiency measurements are summarized in Figure  2  and Table  I. It can be seen that the current efficiency decreases by 1. 3 and 0. 9 pct per 1 wt pct S in prebaked and graphite anodes, respectively. Our result is similar to the 1. 5 pct loss in CE per 1 wt pct S in prebaked anodes reported by Pietrzyk and Thonstad. [19]  Their value was determined for the interval (0 to 3. 82) pct S, including data obtained with graphite anodes (as zero sulfur material) and excluding butts. As shown in Figure  2 , the CE drop for prebaked anodes is, within the interval (1. 91 to 2. 90) wt pct S, larger than that for graphite anodes. Different behaviors were expected as two different anode materials are compared. They differ in not only impurity level, porosity and homogeneity but also in the type of carbon and sulfur containing compounds.
ACKNOWLEDGMENTS This work was supported by the  Ministry of Education, Science, Research and Sport of the Slovak Republic  within the project  VEGA 1/0747/21. This work was created thanks to the support of the  Operational Program Integrated infrastructure  for the project:  Advancing University Capacity and Competence in Research, Development and Innovation ( '' AC-CORD '')  ITMS2014  +:  313021X329 , co-financed by resources of  European Regional Development Fund.
Scenarios investigated Five scenarios of production of hydrogen from woodchips are investigated in this study (Fig. 2 ). The unit size chosen is 20 MWwoodchips LHV basis to ensure a woodchips feeding with a 50 kmaverage transport distance in a 27 t-moving floor truck. They correspond to the three processes modeled in details, under Aspen Plus process modeling software, in a previous paper  (Demol et al. , 2022). The gasification conditions were chosen to maximize the production of hydrogen from wood (steam and oxygen as gasification agent). This study completes the evaluation of these processes with a techno-economic and a comparative life cycle assessment. The scenarios (Fig. 2 ) and its variations are hereafter denominated as: GR-100, GR, G, P and P-S. A common pretreatment of the woodchips consisted in drying and solid conveying.
Method and hypotheses The carbon contained in the wood before harvesting was considered carbon-neutral and the related CO 2 emissions from wood pyrogasification as biogenic emissions. The different inputs and outputs of the LCI were evaluated from Ecoinvent database. The calculations were conducted with Simapro 9 software. The method chosen for the evaluation of the impacts is the midpoint method CML-IA baseline V3. 05 (CML, 2013), a common method used for hydrogen systems  (Valente et al. , 2017a). This method evaluates the following impacts: abiotic depletion (AD), abiotic depletion of fossil fuels (ADff), global warming potential for 100 years (GWP) estimated from the IPCC guidelines (IPCC, 2013), acidification potential (AP), ozone layer depletion potential (ODP), photochemical oxidation formation potential (POFP), eutrophication potential (EP) along with impacts related to toxicity for human (HTTP), fresh water and marine aquatic ecotoxicity (FAETP, MAETP), terrestrial ecotoxicity (TETP).
0006 eV): giving an adiabatic IE of 5. 3275 eV and a vertical IE of 5. 4424 eV. 32 his high-accuracy determination of the ionization energy of cobaltocene at 0 K thus provides an excellent opportunity to thoroughly test electronic structure methods as this experimental reference is free from temperature, entropic and environmental effects and has a much lower experimental uncertainty than data for other metallocenes. In this work we systematically study the accuracy and convergence of the CCSD(T) method (in its local correlation, DLPNO-form) in calculations of adiabatic-and vertical IEs of Cp 2 Co, exploring the dependence of geometry, reference orbitals, relativistic effects, basis set, PNO thresholds, local triples approximations and core-valence correlation effects on the final result. We thoroughly analyze different reference orbitals of Cp 2 Co, in an attempt to explain why some KS-DFT reference orbitals outperform others, and to understand the failure of the HF reference orbitals.
The most accurate DLPNO-CCSD(T) protocol in this work utilized CBS(4/5) basis set extrapolation of CCSD and T 0 correlation energies, with PNO-extrapolation to the CPS limit for each correlation energy, the iterative triples T 1 contribution calculated as a correction with a smaller PNO cutoff, and a core-valence correlation correction. Combined with the SCF reference energy (with BP86 orbitals) and ZPVE correction, a final adiabatic ionization energy of 5. 258 eV was predicted in very good agreement with the 5. 328 eV from experiment. Even better agreement was found for the vertical ionization energy, 5. 414 eV vs. 5. 442 eV. Scalar relativity was found to have a nonnegligible effect (À0. 08 eV) on the cobaltocene ionization energy and was included in all calculations. Free energies of ionization of a series of first-row metallocenes were calculated and compared to experimental data (at T = 350 K) from ion cyclotron experiments.
The samples were degassed beforehand under vacuum at 200 °C for 5 h. Powder X-ray diffraction (XRD) patterns were recorded in the 10-90°range on a BRUKER D8 type apparatus. The acquisition step was set to 0. 02°and the acquisition time to 2 seconds per step. Low angle diffractions were also performed from 0 to 5°for the COK12 bare support and corresponding Mo supported catalyst, on a Bruker D8 Advance diffractometer, with the small divergence and scattering slits being 0. 02°and the acquisition time being 15 seconds per step. Phase identification was determined from ICDD database search. Raman spectroscopy was performed at room temperature on an XPlora spectrometer (Horiba) equipped with a 532 nm visible green laser operating at a power of 100 mW. An optical magnification of 50 times was used and the spectra were recorded from shifts between 200 and 1200 cm À 1.
Temperature programmed reduction (H 2 -TPR) analyses were performed on a Micrometrics AutoChem II 2920 V3. 05 instrument. The sample is first pretreated under argon at 200 °C for 1 h. After cooling down, it is subjected to a programmed temperature increase from 100 to 1000 °C (10 °C/min) under a reducing mixture of 5 vol % H 2 /Ar (50 ml/min). The composition of the gas mixture is measured at the outlet by a thermal conductivity detector (TCD). Catalysts activated under H 2 at 340 °C and 1 bar and catalysts collected after test were characterized by X-ray photoelectron spectroscopy (XPS) technique. XPS spectra were recorded on a Kratos Axis Ultra DLD spectrometer using a monochromatic Al Kα source (hn = 1486. 6 eV, 150 W) and a charge neutralization system. Data analysis was performed on the CasaXPS software (Version 2.
■ ACKNOWLEDGMENTS The authors would like to acknowledge the financial support from the  Universitat Rovira i Virgili  (Grant Marti Franques  2013PMF-PIPF-90 ), the  Spanish Ministerio de Asuntos Económicos y Transformación Digital , and the  Fondo Europeo de Desarrollo Regional FEDER  ( CTQ2014-58664-R ,  CTQ2016-75016-R ,  PID2019-104427RB-I00 ,  AEI/FEDER, UE) , grant  PID 2021-128128NB-I00  funded by  MINECO/ AEI/10. 13039/501100011033  and by " ERDF A way of making Europe ", and the  Generalitat de Catalunya  ( 2017SGR1472  and  2021SGR00110 ).
Behavior and stability of flame To evaluate the effect of dilution on the laminar burning velocity, 1D calculations of CH4-air, CH4-air-H2O and CH4-air-CO2 are performed using the COSILAB code and a GRI3. 0 mechanism  (Smith et al. ). Note that the GRI-Mech 3. 0 mechanism was validated previously in the literature for CH4-air-H2O  (Boushaki et al 2012 , Mazas et al 2011)  and CH4-air-CO2  (Wang et al. 2020)  mixtures. The laminar burning velocity is an important parameter for validating chemical kinetics, modeling of turbulent combustion and the design of practical devices  (Zachary et al. 2011). Figure  3  (left) shows the calculated laminar burning velocity with the equivalence ratio at 1 bar and 300K for CH4-air, CH4-air-10%H2O and CH4-air-10%CO2 mixtures. The flame velocity is very sensitive to the dilution percent.
Powder X-ray Diffraction (PXRD) PXRD patterns were collected with a Panalytical X-Pert diffractometer in the 3-50 • and 10-100 • 2θ range for UiO-66 and oxides samples, respectively. The crystallite size was extracted through peak shape refinement using Thompson-Cox-Hastings (TCH) function implemented in FullProf software  [52, 53].
Ambient Pressure Near-Edge X-ray Absorption Spectra (AP-NEXAFS) AP-NEXAFS spectra were measured at APE-HE beamline of the Elettra Italian Synchrotron radiation source. CeO 2 was placed in a specially designed reactor cell allowing thermal treatments in the RT-400 • C range under a gas atmosphere of 1 bar. The total electron yield (TEY) mode was used to record the experimental spectra. Ce M 5 -edge spectra were collected from 880 to 910 eV with 0. 01 eV energy resolution. The measure-ment protocol followed the same steps as described for the in situ FTIR measurements (Figure  S1 ) with N 2 replaced by He (99. 99999%) and with the maximum temperature limited to 350 • C. Spectra were energy aligned to a reference CeO 2 measured simultaneously with the MOF-derived material. Spectra were background subtracted and energy aligned with the Thorondor software  [54].
A 6th order polynomial was used for background subtraction. Ce 3+ /Ce 4+ spectral pure components and their concentration evolution were extracted using MCR-ALS implemented in MATLAB. The MCR-ALS protocol lead to lack of fit (LOF) of 3. 9% with PCA and 6. 2% with experimental spectra, with 99. 6% of variance explained  [55]. Spectra and concentration were constrained to positive values while the closure condition was applied to concentrations. Notably, to increase the variance between spectra, the H 2 -TPR was conducted until 350 • C to improve Ce 4+ /Ce 3+ spectra separation. Moreover, to guarantee reproducibility of the MCR-ALS protocol for the three samples, the collected spectra were analysed together in the same dataset. Ten replicas of CeO 2 and CeF 3 reference spectra were added at the end of the dataset to support the MCR-ALS protocol in finding Ce 4+ and Ce 3+ pure spectra components.
However, during heating under He:H 2 (Figure  S8a ), the Ce 4+ bands initially gained intensity and lost the shoulder at 891 eV. The presence of this shoulder suggested a minor contribution of Ce 3+ in C100 after oxidation. At T > 200 • C, the main edge lost intensity again, while a two-band shoulder arose at around 891 eV. These bands became structured around 300 • C, and at 350 • C they had a final shape clearly attributable to Ce 3+. As we recently reported, Ce 3+ /Ce 4+ can be quantified from M 5 -edge NEXAFS spectra with a driven MCR-ALS protocol where 10 replicas of CeO 2 and CeF 3 references spectra are added at the end of the dataset  [40]. This method allowed to improve the identification of principal components whilst simultaneously adapting the references to the dataset. The procedure identified two principal components (Figure  3b ) describing 99.
Acknowledgments: The authors are grateful to APE-HE beamline ( Elettra Synchrotron ) for beamtime allocation and the experimental support. A. Kudinov  is acknowledged for support with sample synthesis and characterization. M. Signorile  is acknowledged for support during NEXAFS measurements and further scientific discussions. A. Kudinov  and  M. R. Salazar  are acknowledged for support during NEXAFS spectra measurement. D. Simonne  is acknowledged for support with NEXAFS data analysis. Maria Carmen Valsania  is acknowledged for TEM measurements. S. Rojas-Buzo  acknowledges the  Margarita Salas grant  financed by the  Ministerio de Universidades, Spain , and also funded by the  European Union-Next Generation EU. This work has been partially performed in the framework of the  Nanoscience Foundry  and  Fine Analysis  ( NFFA-MIUR Italy Progetti Internazionali ) project.
1 kPa. The equilibrium temperature was measured by a Pt-100 platinum probe with a standard uncertainty u(T) = 0. 05 K. To check the accuracy of the apparatus, the vapor pressures of the four components involved in this study were measured from 50 kPa to 101. 3 kPa with a step of 5 kPa. Experimental vapor pressure data were then compared to previously published data and correlated with the Antoine equation. The Antoine coefficients are provided in the Supplementary Materials (Table  S2 ). Before each measurement campaign (pure compound or binary mixture), the device was rinsed and dried under vacuum (~5 kPa) for one hour to prevent contamination. For the VLE measurements of the mixtures, the compositions of the liquid and condensed vapor phases collected from the ebulliometer were obtained indirectly from density measurements at 298.
VLE Data and Consistency Checks As mentioned previously, the accuracy of the experimental apparatus used for the VLE measurements and the suitability of the protocol were verified by remeasuring the VLE of the binary mixture hexane + EA at P = 101. 3 kPa. A total of 23 VLE points were measured for this system, all of which are reported in Table  8  and plotted in Figure  2. Liquids 2023, 3, FOR PEER REVIEW In Figure  3 , it can be noted that the binary systems containing branched alkan present pronounced positive excess molar volumes, with a maximum value of V E alkane molar fraction of 0. 55. These observations are consistent with previous dealing with linear alkanes + short-chain esters  [10] [11] [12] [13] [14]  or branched alkanes + EA  [  The results obtained in this work clearly indicate that for a given sa hydrocarbon CnH2n+2 in a mixture with EA, the excess molar volume is the maximum carbon atoms are arranged in a single chain and decreases when EA is mixed w isomer.
VLE Data and Consistency Checks As mentioned previously, the accuracy of the experimental apparatus used for the VLE measurements and the suitability of the protocol were verified by remeasuring the VLE of the binary mixture hexane + EA at P = 101. 3 kPa. A total of 23 VLE points were measured for this system, all of which are reported in Table  8  and plotted in Figure  2. a Standard uncertainties u are u(T) = 0. 05 K, u(P) = 0. 1 kPa and u(x) = u(y) = 0. 001. T/K, equilibrium temperature; x 1 and y 1 , liquid phase's and vapor phase's hexane mole fractions, respectively; γ i , activity coefficient of component i; g E /RT, dimensionless Gibbs function. Taking into account the non-ideality of the vapor phase using the virial equation of state truncated after the second term, activity coefficients were calculated with γ i = y i P ϕ vap i x i P • i ϕ * i (3) giving, for a binary system containing the pure components i and j, γ i = y i P x i P • i exp B ii -v L i P -P • i + P(1 -y i ) 2 2B ij -B ii -B jj R T (4) where γ i is the activity coefficient of component i, and x i and y i are the molar compositions of component i in the liquid and vapor phases.
P is the system's total pressure, and P • i is the saturation pressure of component i. The saturated liquid molar volumes v L i of the pure compounds were estimated with the Rackett equation  [42] , whereas the second virial coefficients (B ii , B jj and B ij ) were calculated from the correlation proposed by Tsonopoulos  [43]. Using the calculated activity coefficients, the values of the excess Gibbs energy (g E ) were obtained using the following expression: g E = RT ∑ x i lnγ i (5) in which R is the universal gas constant, and T is the temperature. The binary systems 3-methylpentane + EA and 2,3-dimethylbutane + EA were investigated in the same way as the binary system hexane + EA, and the experimental data acquired were treated similarly. The VLE data for the systems 3-methylpentane + EA (20 VLE data points) and 2,3-dimethylbutane + EA (20 VLE data points) are summarized in Tables  9  and 10.
Figure1clearly illustrates good agreement between the data measured in this work and previously published data, particularly for our excess molar volumes and those published by Fernández and co-workers [10]. The isobaric VLE of the binary system hexane (1)-EA (2) at 101. 3 kPa was also measured for comparison with literature data. The experimental VLE data (T, x1, y1) measured in this work at P = 101. 3 kPa are given in the Results section and are plotted in Figure2for comparison with previously published data.