dataesr/scientific-paragraphs-categorization huggingface dataset:
The ther odynamic modeling methodology is the same used in our previous studies  [30] [31] [32] [33]  and is summarized in Section II of the Supporting Information. MD Simulations. MD simulations were performed in large-scale atomic/molecular massively parallel Simulator (LAMMPS) software using the CL&Pol polarizable force field for the ILs. 47, 50, 51 The Fgases were described using available sets of parameters  [52] [53] [54]  in compatible functional forms, that is, Lennard-Jones (LJ) sites with point charges. In the CL&Pol force field, the explicit polarization effects are represented by Drude-induced dipoles, where each atomic site holds a positively charged Drude core and a negatively charged Drude particle with mass equal to 0. 4 atomic units, attached by a harmonic spring of constant k D equal to 4184 kJ•mol -1.
Results and Discussion fac-Mn(apbpy)(CO) 3 Br was anchored to a carbon cloth (CC) electrode surface via the formation of CÀ C bonds. The presence of the aniline moiety on the bipyridyl ligand enables the grafting of the complex onto carbon surfaces via the in situ formation of the corresponding diazonium salt. This method advantageously bypasses the isolation and purification of the diazonium reactive intermediate. Electrochemical reduction is performed to trigger CÀ C bond formation and N 2 evolution. To assess the amount of electrocatalyst covalently bound on CC, a comparative ICP analysis was performed on the pristine CC starting material and on Mn/CC. A surface coverage Γ of 1. 67 × 10 À 9 mol cm ECSA À 2 was obtained, in reasonable agreement with the previously reported value (1. 4 × 10 À 9 mol cm ECSA À 2 ), determined via the indirect method of charge integration of the CV data collected from CC bonded nitroaniline.
Acknowledgements This work was supported by the  LABEX iMUST  ( ANR-10-LABX-0064 ) of  Université de Lyon , within the program " Investissements d'Avenir " operated by the  French National Research Agency (ANR) , and by the regional project  SATURNO (Bioeconomy ). A. T. and L. R. synthesized and characterized Mn/CC. F. M. S, A. T. and L. R. performed electrochemical CPE experiments. A. T. and L. R. processed the μGC data. F. M. S. studied the carbonation equilibrium of amine in methanol and performed NMR experi-ments. C. N. made DFT calculations. R. G, C. N. and J. L. designed the experiments and wrote the paper. All the authors contributed to the improvement of the manuscript. We sincerely thank  Dr. Micaela Castellino  ( Politecnico di Torino, Italy ) for XPS measurements and  Dr. Alice Barbero  ( University of Torino ) for data processing.
Characterization The morphology of TiO 2 nanostructure was investigated by scanning (SEM; JEOL JSM-6700F FEG) and transmission (TEM; JEOL 2100F TEM/STEM) electron microscopies. The Raman spectra of the samples were obtained in the spectral range of 50-3000 cm À1 using a Raman spectrometer (Horiba Jobin Yvon; Aramis) with a laser excitation wavelength of 532 nm. Fourier transform infra-red (FT-IR) spectroscopy was used to investigate the interaction between functionalized TiO 2 and the target compound. The spectra were collected using a Thermo Nicolet NEXUS 670 spectrometer equipped with a MCT detector. A Thermo VG Scientific equipment was used to conduct X-ray photo-electron spectroscopy (XPS) analysis. Recorded data were processed with CasaXPS software and the spectra were corrected using the adventitious carbon peak (284.
Acknowledgements This work was financially supported by the  ANR   Bionanodetect  project ( ANR-15-CE39-0001 ). The authors would like to thank  Thierry Dintzer  and  Dris Ihiawakrim  for SEM and TEM images. We thank  Vasiliki Papaefthymiou  for the XPS measurements. Laurent Schlur  and  Denis Spitzer  are gratefully acknowledged for their help with the resonating AFM experiment.
Acknowledgements The authors are grateful to the SOLEIL general staff for providing synchrotron beamtime on the DESIRS beamline under Proposal 20201007. This work has also received financial support from the  French "Agence Nationale de la Recherche" (ANR)  under Grant No. ANR-12-BS08-0020-02  (Project  SYNCHROKIN ). This project has received funding from the  European Research Council (ERC)  under the European Union's  Horizon 2020 research and innovation programme  (grant agreement No. 848668 ). This work was also supported by the  Israel Science Foundation (ISF) , grant No. 194/20. The work at  Argonne National Laboratory  (B. R. ) was supported by the  U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division  through.
Surely, there are interesting and "burning" questions to be addressed; the present perspective attempts to highlight some of them and suggest significant topics that could benefit from additional studies. Figure  1. The number of publications per year that report novel research studies on ammonia as a fuel that have been published in the journal Fuel (ISSN 0016-2361) since 2010. The data were gathered by searching for the keyword "ammonia" and considering only research papers that directly study ammonia as a fuel application (i. e. , not including other published works on SCR, SNCR, DeNOx, or NH3 production methods such as biomass gasification; review papers were not considered here).
Combustion theory Ammonia gas-phase kinetics has been the subject of numerous studies. The overall goal of these studies is the development of detailed kinetic models accurately representing the chemistry of intermediate species at the molecular level. These models are then useful for the development of efficient and clean technologies. Accurate computational predictions can be nowadays performed with reasonable CPU time by coupling CFD codes and detailed kinetic models as long as the number of species remains reasonable. The development of high-quality predictive detailed kinetic models relies on two pillars: the use of the most reliable thermodynamic properties and kinetic parameters and the benchmarking of the model against the updated experimental datasets obtained over a wide range of conditions (e.
g. , temperature, pressure, composition, residence time, equivalence ratio, and reactor hydrodynamics). Thermodynamic properties and kinetic rate coefficients can be obtained using experiments or can be calculated using ab initio quantum-chemical calculations. Quantumchemical calculations can also be used to explore potential energy surfaces and find new reaction pathways that are missing in detailed kinetic models. The variety of literature datasets available and the process of carefully selecting data from different sources result in a plethora of literature models, even for a simple fuel like ammonia, each with different parameters. This results in a chaotic state in the field that hampers advancement, and calls for a data-centric approach  [12].
The numerical data obtained showed that the formation of NOx in the flame zone is enhanced when ammonia is added in the fuel mixture due to fuel-bound nitrogen. After peaking in the flame front (800-1400 ppm according to the percentage of ammonia in the mixture), NO concentration dropped almost to zero and then increased slowly in the secondary and dilution regions. CFD numerical simulations were also applied to other configurations. For example, Frankl et al. [66] performed a study of the use of ammonia and hydrogen in a high-pressure-dual-fuel combustion process combining engine experiments (with one diagnostic based on OH-chemiluminescence) and CFD numerical calculations (with ammonia chemistry coming from the GRI 3. 0 model  [67] ). A good qualitative resemblance between models and chemiluminescence experiments was obtained.
Acknowledgements The authors acknowledge  Alessandro Stagni  for sharing data displayed in Figure 4. This work has been partially funded by the  GTCLC-NEG  project that has received funding from the  European Union 's  Horizon 2020 research and innovation program  under the  Marie Sklodowska-Curie  grant agreement No. 101018756. AGD acknowledges financial support from the  Stephen and Nancy Grand Technion Energy Program (GTEP).
Acknowledgements The authors would like to express their appreciation for the financial support of  Kempestiftelserna  ( SMK-1850 ) and  Bio4energy program  ( B4E3-TM-1-01 ). The authors would like to express their appreciation for the financial support of the  National Natural Science Foundation of China  ( 22078146 ), the  Natural Science Foundation of Jiangsu Province  ( BK20200091 ), the  Jiangsu Province Department of Human Resources and Social Security  ( JNHB-036 ), the  Materials-Oriented Chemical Engineering State Key Laboratory Program  ( KL19-04 ) and the  Priority Academic Program Development of Jiangsu Higher Education Institution (PAPD).
Acknowledgements We are grateful to the financial support provided by the  China Scholarship Council  ( CSC Ph. D. grant No. 201804910783  to H. L. ). We also thank  Philippe Jehan  and  Elsa Caytan  for extensive MS and NMR analyses, respectively. Part of this work has been performed using NMR spectrometers belonging to the  CRMPO (UAR ScanMAT ,  CNRS-Université de Rennes 1)  and  PRISM (UAR BIOSIT ,  CNRS-INSERM-Université de Rennes 1 ) core facilities.
Thermodynamic Measurements The esterification reaction of glycolic acid with butanol (Rxn. 1) represents six different binaries: 1-butanol-butyl glycolate (binary 1); 1-butanol-water (binary 2); butyl glycolate-water (binary 3); butyl glycolate-glycolic acid (GA) (binary 4); 1butanol-glycolic acid (binary 5); and water-glycolic acid (binary 6). Binary interaction parameters are only reported for binary 2, and the other equilibriums have not yet been assessed in the open literature. Besides, few experimental data concerning the saturated vapor pressure of butyl glycolate are available. Thus, vapor pressure of BG was determined and vapor-liquid equilibrium (VLE) was proposed for the determination of the binary interaction parameter of binary 1. Liquid-liquid equilibrium (LLE) was used for the determination of interaction parameters of binary 3, and solid-liquid equilibrium (SLE) was used for the determination of the binary interaction parameters of binaries 4, 5, and 6.
Liquid-Liquid Equilibrium LLE data for BG-W binary were determined using magnetically agitated vials of 30 ml, placed in an isothermal oil bath equipped with a temperature control system. Mixtures of different compositions were prepared and stirred at a constant temperature for 1 h. Then, the temperature of the mixture was measured, using an electronic thermocouple (± 0. 1 °C), and the samples were centrifuged for 2 min at 4000 rpm. The two liquid phases were recovered separately and weighed. The composition of the samples was measured by HPLC. Samples of 400 µl were taken and diluted in 10-ml volumetric balloons with a solution of 42%-58% volume W-CAN.
5% in moles. Acetonitrile (HPLC grade, EMD) was used in the HPLC analysis. The concentrations obtained by HPLC analysis allowed for calculating the evolution of the molar concentration. From the data obtained, conversion (X) and yield (Y) were calculated by the following equations: X n ini GA -n GA n ini GA (1) Y n BG n ini GA (2) where n ini GA and n GA represent the moles of acid at t = 0 and at the corresponding sampling time; n BG corresponds to moles of butyl glycolate produced. Due to the lack of an instrument capable to determine the water amount such as Karl Fischer, the mass balance could not be determined. However, to corroborate the reliability of the analysis method, a carbon balance was completed as illustrated by Eq. 3.
Thus, the three other transformed fractions (GA, n-butanol, and water) are calculated as below: X i x i -] i x ref (5) Y i y i -] i y ref (6) The pressure is fixed at 380 mbar, and thus, the degree of freedom of the system is equal to 2. Therefore, by choosing two independent variables X BuOH and X GA , it is possible to solve the differential equations (Nc-1) for k initial coordinate points using the MATLAB software interfaced with the Simulis ProSim software for liquid-vapor equilibrium resolution. The second one is a simulation of the RD process. To represent the continuous reactive distillation system, a model was developed with the ProSim ® Plus software. The thermodynamic data obtained in this work were implemented in the NRTL model of the software. An equilibrium stage model was considered, and the developed kinetic law was implemented via a cape open source file.
For the calculation; the melting point and enthalpy of fusion of GA were taken from the literature  (Emel'yanenko et al. , 2010) , and the heat capacities of liquid and solid were calculated using the Aspen Plus V10 estimation tool. The values and expressions are summarized in Supplementary Table  S4. The binary parameters were fitted for the NRTL model by minimizing the difference between the calculated activity coefficients using the binary NRTL parameters and the experimental values determined using Eq. 8. The minimization was performed using the MATLAB 9. 4 tool, and the results are presented in Supplementary Table  S4.
, 2003). Finally, another model also mentioned and studied in the literature is the Eley-Rideal (ER) model. This model considers that the esterification reaction occurs between the adsorbed alcohol and nonadsorbed acid to obtain the non-absorbed ester and adsorbed water molecules  (Ju et al. , 2011). The mass balance is a system of ordinary differential equations and is solved using an ordinary differential equation solver ode45 in MATLAB 9. 4 p. The fourth-order Runge-Kutta method was used to numerically integrate the kinetic model. The optimization of the kinetic parameters was performed by minimizing the residual sum of squares (SRS) between experimental (x exp ) and calculated (x cal ) species mole fractions using the following objective function, represented in a general way in the equation: SRS 1 n Nc Allsamples x exp -x cal 2 ( 16 ) Where n is the number of experimental samples taken from the batch reactors in all experiments performed, and NC is the number of components considered in each sample.
FUNDING This work was performed, in partnership with the SAS PIVERT, within the frame of the  French Institute  for the  Energy Transition Institut pour la Transition Energétique (ITE) P. I. V. E. R. T (www. institut-pivert. com)selected as an  Investment for the Future ("Investissements d'Avenir "). This work was supported, as part of the Investments for the Future, by the  French Government  under the reference  ANR-001-01.
Charge transfer absorption and energy levels First, we discuss the measurements of CT absorption features necessary to confirm the formation of EDA complexes in films containing D and A molecules. The CT absorption energies for co-deposited films of DBTTF and TCNNQ have already been reported. 32 The existence of two different polymorphs (P1, P2) was suggested based on different CT absorption energies (0. 72 eV, 0. 84 eV) and different degrees of CT. The maximum of the absorption feature related to the DBTTF:F6TCNNQ EDA complex was determined to 1. 43 eV. 32 Additionally to the EDA complex absorption feature, ICT is present for the latter D:A pair, which is neglected for the discussion of EDA complexes. Absorption data of co-deposited films of DIP:TCNNQ and DIP:F6TCNNQ are shown in Fig. 4  measured at room temperature and at 77 K.
For comparison the respective absorption data of single-component films are given. The CT absorption energy of the DIP:TCNNQ complex is 1. 29 eV and for DIP:F6TCNNQ it is 0. 97 eV, in agreement with ref. 35. Shifts of peak positions and changes of spectral features upon temperature variations are absent, indicating the absence of structural phase transitions in this temperature range. No signatures of DIP cation absorption or TCNNQ/F6TCNNQ anion absorption are present here. 32, 33 g. 3  (a) Chemical structures of donor (DBTTF, DIP) and acceptor (TCNNQ, F6TCNNQ) molecules. (b) Oxidation potentials (U ox ) of donor and reduction potentials (U red ) of acceptor materials determined by cyclic voltammetry. 15, 32, 33 The oxidation potential for DIP is increased by 350 mV as given in ref. 33 considering the change of the standard potential due to the reported follow up reaction.
The measurement for the DBTTF:TCNNQ sample where predominantly the P1 polymorph is present shows an overall 2D-texture although with rather pronounced mosaicity. Part of the Bragg intensities measured by means of XRR is present in the reciprocal space map. This data allows also for estimation of the unit cell parameters, which are given in Table  2. In Fig. 6 , Bragg peaks related to the fitted unit cell parameters are marked with crosses. The roughly doubled volume of the unit cell of the P1 polymorph in contrast to the g-polymorph of DBTTF is related mainly to the roughly doubled a-parameter and points toward the presence of two crystallographically inequivalent EDA complexes in the unit cell. Additional Bragg peaks are highlighted by circles and do not belong to polymorph P1. Therefore, they are attributed to the polymorph P2, which Table  1  Summary of electronic and optical data for EDA complexes.
The co-deposited DBTTF:F6TCNNQ film shows diffraction features being absent in the single-component films of DBTTF and F6TCNNQ (see Fig. 6 ). Comparing these results with the results presented from XRR measurements shows the presence of a mixed crystal formed by DBTTF and F6TCNNQ in agreement with conclusions from optical absorption data. A refinement of unit cell parameters is too prohibitive for this dataset. None of the reported structure of mixed crystals formed from DBTTF and FxTCNQ  45, 46  or from naphtho[1,2-b:5,6-b 0 ] dithiophene and F6TCNNQ 47 could provide a sufficient close initial guess for the fitting procedure to converge to a reasonable result. However, based on the qualitative similarity with the diffraction pattern of DBTTF:TCNNQ, here we cannot exclude the presence of two polymorphs with significantly different relative abundance.
These data are shown in Si (see Fig. S5 , ESI †). Infra-red spectroscopy measurements were additionally performed on DIP:F6TCNNQ mixed crystals using a grazing incidence geometry and polarization-modulation infrared reflection-absorption spectroscopy. 34 A new feature with an estimated degree of CT of 0. 84 was observed for DIP:F6TCNNQ complexes, which was related to a strong ground-state CT. 34  This is in contrast to Raman and infra-red spectroscopy results given in the previous paragraph. The used grazing incidence geometry used here reveals a clear spatial anisotropy in comparison to the normal detection geometry before. Anisotropy in vibrational properties were reported before for pentacene and poly[2-methoxy-5-(2 0 -ethylhexyloxy)-1,4-phenylene vinylene]. 63, 64 owever, further research is necessary on this vibrational anisotropy in EDA complexes to give full explanation in the observed behaviour.
A combination of all these aspects can explain the peaking conductivity of the equimolar DIP:F6TCNNQ codeposited film. The decrease in conductivity for molar ratios close to the equimolar ratios might be related to trapping at isolated D or A molecules. Here one must note, however, that the balance between mobility defined by the morphology and the charge carrier density defined by the electrical doping determines the detailed trend of the conductivity curve. Measurements on activation energy and electrical conductivity were performed for single-component films of DBTTF, DIP and F6CTNNQ. Furthermore, co-deposited films of various molar ratios were characterised as DBTTF:TCNNQ, DBTTF:F6TCNNQ and DIP:F6TCNNQ. The data for film compositions, electrical conductivities at room temperature and activation energies are collected in ESI † (Table  S2 ).
To characterise the underlying activation behaviour upon complex doping, the dependence of the electrical conductivity on the activation energy at room temperature is displayed in Fig. 13. The conductivity was analysed by transfer-length method to reduce influence of contact resistance. 88 The points with activation energies above 600 meV refer to the single-component films of DBTTF, DIP, F6TCNNQ and 6T together with the co-deposited film of 10% F6TCNNQ and DIP. The data points with an activation energy below 500 meV can be described by a thermally activated behaviour following the equation.
Acknowledgements The work was supported financially by  Deutsche Forschungsgemeinschaft  ( DFG -OP159/2-2 ,  SCHR700/20-2 ,  Br 1728/14-2 , project no. 239543752 ). We are grateful for beamtime at The European Synchrotron Radiation Facility (ESRF, beamlines  ID10 + ID03 ) and at the  Swiss Light Source  (SLS, beamline X04SA). G. D. gratefully acknowledges support from the  Carl-Zeiss-Stiftung. W. B. and J. P. acknowledge support by the  Bavarian State Ministry for Science  and the  Arts within the collaborative research network ''Solar Technologies go Hybrid'' (SolTech). Georg Heimel performed DFT calculations and  Jan Hagenlocher  helped during synchrotron measurements.
The Scherrer equation was applied for the Au diffraction peak at 2θ = 38. 2 • , corresponding to the (111) Au plane  [50]. Transmission electron microscopy (TEM) images were obtained using a TEM/STEM FEI TECNAI F20 microscope at 200 keV and a TEM Talos F200X instrument. Samples were suspended in ethanol and treated by ultrasound for 15 min. A drop of the suspension was deposited on "quantifoil-carbon film" supported on a Cu grid and dried before analysis. TEM images were processed by using the Digital Micrograph Software by "Gatan Inc. " and ImageJ. IA Imaging and Analysis Offline by FEI company for STEM-HAADF images were used in order to determine average particle size and particle size distribution. More than 400 NPs were measured, coming from different sites of interest, for each sample.
X-ray photoelectron spectroscopy (XPS) spectra were recorded on a physical electronic spectrometer (PHI Versa Probe II) using monochromatic Al K radiation (52. 8 W, 15 kV, 1486. 6 eV) and a dual-beam charge neutralizer for analyzing the core-level signals of the elements of interest with a hemispherical multichannel detector. The XPS spectra of the samples were recorded with a constant pass energy value at 29. 35 eV and a beam diameter of 100 µm. The energy scale was calibrated using Cu 2p 3/2 , Ag 3d 5/2 , and Au 4f 7/2 photoelectron lines at 932. 7, 368. 2, and 83. 95 eV, respectively. The X-ray photoelectron spectra obtained were analyzed using PHI SmartSoft software and processed using the MultiPak 9. 6. 0. 15 package. The binding energy values were referenced to C 1 s signal at 284. 5 eV.
Acknowledgments: The REALCAT platform benefits from a state subsidy administrated by the French National Research Agency (ANR) within the frame of the 'Investments for the Future' program (PIA), with the contractual reference 'ANR-11-EQPX-0037. The European Union, through the FEDER funding administered by the Hauts-de-France Region, has co-financed the platform. Centrale Lille, CNRS, and the University of Lille as well as the Centrale Initiatives Foundation are thanked for their financial contributions to the acquisition and implementation of the equipment of the REALCAT platform. Chevreul Institute (FR 2638), Ministère de l'Enseignement Supérieur, de la Recherche et de l'Innovation, Hauts-de-France Region, and FEDER are acknowledged for supporting and partially funding this work.