Computing Surface Reaction Rates by Adaptive Multilevel Splitting Combined with Machine Learning and Ab Initio Molecular Dynamics.

Computing accurate rate constants for catalytic events occurring at the surface of a given material represents a challenging task with multiple potential applications in chemistry. To address this question, we propose an approach based on a combination of the rare event sampling method called adaptive multilevel splitting (AMS) and ab initio molecular dynamics. The AMS method requires a one-dimensional reaction coordinate to index the progress of the transition. Identifying a good reaction coordinate is difficult, especially for high dimensional problems such as those encountered in catalysis. We probe various approaches to build reaction coordinates such as support vector machine and path collective variables. The AMS is implemented so as to communicate with a density functional theory-plane wave code. A relevant case study in catalysis, the change of conformation and the dissociation of a water molecule chemisorbed on the (100) γ-alumina surface, is used to evaluate our approach. The calculated rate constants and transition mechanisms are discussed and compared to those obtained by a conventional static approach based on the Eyring-Polanyi equation with harmonic approximation. It is revealed that the AMS method may provide rate constants that are smaller than those provided by the static approach by up to 2 orders of magnitude due to entropic effects involved in the chemisorbed water molecule.

PtOx Cly (OH)z (H2 O)n Complexes under Oxidative and Reductive Conditions: Impact of the Level of Theory on Thermodynamic Stabilities.

Platinum-based catalysts with Cl- , OH- , O2- and H2 O ligands, are involved in many industrial processes. Their final chemical properties are impacted by calcination and reduction applied during the preparation and activation steps. We investigate their stability under these reactive conditions with density functional theory (DFT). We benchmark various functionals (PBE-dDsC, optPBE, B3LYP, HSE06, PBE0, TPSS, RTPSS and SCAN) against ACFDT-RPA. PBE-dDsC is well adapted, although hybrid functionals are more accurate for redox reactions. Thermodynamic phase diagrams are determined by computing the chemical potential of the species as a function of temperature and partial pressures of H2 O, HCl, O2 and H2 . The stability and nature of the Pt species are highly sensitive to the activation conditions. Under O2 , high temperatures favour PtO2 while under H2 , platinum is easily reduced to Pt(0). Chlorine modifies the coordination sphere of platinum during calcination by stabilizing PtCl4 and shifts the reduction of platinum to higher temperatures under H2 .

Tailoring the optoelectronic properties and dielectric profiles of few-layer S-doped MoO3 and O-doped MoS2 nanosheets: a first-principles study.

To gain insights into few layer (FL) van der Waals MoO3-xSx/MoS2-xOx heterostructures for photocatalytic applications, we analyze how the concentration (x) and location of anionic isovalent atom (S or O) substitutions impact their opto-electronic properties and high frequency dielectric constant profiles. By using density functional theory (DFT) calculations within the HSE06 functional, we show that the electronic band gap of FL MoO3-xSx decreases with increasing x, while the dielectric constant profile and absorption coefficient in the UV-vis range increase. The stronger band gap reductions are obtained when S-atoms are located in the internal bulk region of FL MoO3-xSx and in interaction with O-atoms of the neighboring layer. Moreover, the conduction and valence band (CB/VB) levels are shifted to higher energy values in the case of the edge location (external surface) of these S-atoms. Thanks to the determination of the thermodynamic diagrams of 4L MoO3-xSx and 6L MoS2-xOx, we propose optimal heterojunctions made of 4L MoO3-xSx with either single-layer (SL) or FL MoS2 with CB/VB levels compatible with a Z-scheme working principle and with potentials required for photocatalysis applications such as the photolysis of water into O2 and H2. This study combined with our previous theoretical investigations on bulk materials and SL provides a thorough analysis of SL-FL MoO3-xSx/MoS2 heterojunctions where the concentration and location of S-atoms in MoO3-xSx are key to design efficient materials for water photolysis.

Evaluating acid and metallic site proximity in Pt/γ-Al2O3-Cl bifunctional catalysts through an atomic scale geometrical model.

Quantifying the distances between metallic sites and acid sites is crucial for tuning the catalytic activity and selectivity of bifunctional catalysts involving sub-nanometric platinum (Pt) nano-particles (NP) highly dispersed on a chlorinated alumina support. Thanks to the quantitative use of high resolution scanning transmission electron microscopy in the high angle annular dark field mode, we first highlight the presence of few Pt NP together with Pt single atoms (SA) on γ-alumina supports exhibiting various morphologies (flat-like or egg-like), and chlorine (Cl) and Pt loadings. We demonstrate that increasing the Pt loading does not impact the NP sizes but only the Pt NP inter-distances, whereas the Cl loading influences the SA/NP proportion. Then, we establish a thorough geometrical model which accounts for the way in which the global average metallic - acid inter-site distances evolve from 1 nm to 6 nm as a function of three key physico-chemical descriptors: alumina morphologies, chlorine contents and size factor of alumina particles (directly linked to specific surface area). Considering that Cl is predominantly located at alumina crystallite edges, the morphology strongly impacts the Cl edge saturation: 0.4% for flat-like, and 1.2% for egg-like alumina at fixed specific surface area (∼200 m2 g-1). At Cl edge saturation, the inter-site distance is found to be 3 nm for flat-like, and 1 nm for egg-like alumina. However, for fixed Cl loading, the inter-site distance is less discriminated by the morphology. We discuss these trends in the case of naphtha reforming catalysts and thanks to the as-obtained geometrical model, we identify the key alumina descriptors to tune the inter-site distance.

Electronic structures of the MoS2/TiO2 (anatase) heterojunction: influence of physical and chemical modifications at the 2D- or 1D-interfaces.

To tackle the challenge of CO2 photoreduction, semiconducting layered transition metal dichalcogenides like MoS2 have attracted much attention due to their tunable 2D nano-structures. By using advanced periodic density functional theory calculations (HSE06 functional), we provide a systematic quantification of the optoelectronic properties of various interfacial heterostructures composed of 2H-MoS2 and anatase TiO2. We systematically determine the band gaps, and conduction band (CB) and valence band (VB) positions to figure out the nature of the heterojunction. Two main surface orientations of anatase TiO2 particles, (101) and (001), are considered with 2D-MoS2 nanosheets or nanoribbons forming either a 2D physical (van der Waals) or through a 1D chemical interface. The possibility to chemically modify the MoS2/TiO2 interface, either by sulfidation or hydration, and its effect on the electronic structure are deeply investigated. These modifications in the heterostructure lead to important changes in the electronic properties and charge transfer between the two materials which impact both photon absorption properties and charge carrier dynamics suspected to influence in turn the photocatalytic activity. While a type I hetrojunction is found for the 1D chemical interface, a type II heterojunction with appropriate CB/VB positions for CO2 reduction and H2O oxidation is identified for the 2D physical interface which could lead to the targeted Z-scheme mechanism with strong potential interest in photocatalysis applications.

2D MoO3-xSx/MoS2 van der Waals Assembly: A Tunable Heterojunction with Attractive Properties for Photocatalysis.

Two-dimensional (2D) van der Waals (vdW) heterostructures currently have attracted much attention in widespread research fields where semiconductor materials are key. With the aim of gaining insights into photocatalytic materials, we use density functional theory (DFT) calculations within the HSE06 functional to analyze the evolution of optoelectronic properties and high-frequency dielectric constant profiles of various 2D MoO3-xSx/MoS2 heterostructures modified by chemical and physical approaches. Although the MoO3/MoS2 heterostructure is a type III heterojunction associated with a metallic character, we found that exchanging the terminal oxo atoms of the MoO3-xSx single layer (SL) with sulfur enables shifting its CB position above the VB position of the MoS2 SL. This trend gives rise to a type II heterojunction where the band gap and charge transfer within the two layers are driven continuously by the S concentration in the MoO3-xSx SL. This fine-tuning leads to a versatile type II heterostructure proposed to provide a direct Z-scheme system valuable for photocatalytic water splitting.

Dynamic Features of Transition States for ß-Scission Reactions of Alkenes over Acid Zeolites Revealed by AIMD Simulations.

Zeolite-catalyzed alkene cracking is key to optimize the size of hydrocarbons. The nature and stability of intermediates and transition states (TS) are, however, still debated. We combine transition path sampling and blue moon ensemble density functional theory simulations to unravel the behavior of C7 alkenes in CHA zeolite. Free energy profiles are determined, linking π-complexes, alkoxides and carbenium ions, for B1 (secondary to tertiary) and B2 (tertiary to secondary) ß-scissions. B1 is found to be easier than B2 . The TS for B1 occurs at the breaking of the C-C bond, while for B2 it is the proton transfer from propenium to the zeolite. We highlight the dynamic behaviors of the various intermediates along both pathways, which reduce activation energies with respect to those previously evaluated by static approaches. We finally revisit the ranking of isomerization and cracking rate constants, which are crucial for future kinetic studies.

Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations.

Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively.

Tuning the metal-support interaction by structural recognition of cobalt-based catalyst precursors.

Controlling the nature and size of cobalt(II) polynuclear precursors on γ-alumina and silica-alumina supports represents a challenge for the synthesis of optimal cobalt-based heterogeneous catalysts. By density functional theory (DFT) calculations, we show how after drying the interaction of cobalt(II) precursor on γ-alumina is driven by a structural recognition phenomenon, leading to the formation of an epitaxial Co(OH)2 precipitate involving a Co-Al hydrotalcite-like interface. On a silica-alumina surface, this phenomenon is prevented due to the passivation effect of silica domains. This finding opens new routes to tune the metal-support interaction at the synthesis step of heterogeneous catalysts.

Tuning the properties of visible-light-responsive tantalum (oxy)nitride photocatalysts by non-stoichiometric compositions: a first-principles viewpoint.

Finding an ideal photocatalyst for achieving efficient overall water splitting still remains a great challenge. By applying accurate first-principles quantum calculations based on DFT with the screened non-local hybrid HSE06 functional, we bring rational insights at the atomic level into the influence of non-stoichiometric compositions on essential properties of tantalum (oxy)nitride compounds as visible-light-responsive photocatalysts for water splitting. Indeed, recent experiments show that such non-stoichiometry is inherent to the nitridation methods of tantalum oxide with unavoidable oxygen impurities. We considered here O-enriched Ta3N5 and N-enriched TaON materials. Although their structural parameters are found to be very similar to those of pure compounds and in good agreement with available experimental studies, their photocatalytic features for visible-light-driven overall water splitting reactions show different behaviors. Further partial nitration of TaON leads to a narrowed band gap, but partially oxidizing Ta3N5 causes only subtle changes in the gap. The main influence, however, is on the band edge positions relative to water redox potentials. The pure Ta3N5 is predicted to be a good candidate only for H(+) reduction and H2 evolution, while the pure TaON is predicted to be a good candidate for water oxidation and O2 evolution. Non-stoichiometry has here a positive influence, since partially oxidized tantalum nitride, Ta(3-x)N(5-5x)O5x (for x≥ 0.16) i.e. with a composition in between TaON and Ta3N5, reveals suitable band edge positions that correctly bracket the water redox potentials for visible-light-driven overall water splitting reactions. Among the various explored Ta(3-x)N(5-5x)O5x structures, a strong stabilization is obtained for the configuration displaying a strong interaction between the O-impurities and the created Ta-vacancies. In the lowest-energy structure, each created Ta-vacancy is surrounded by five O-impurity species substituting the five N sites characterizing one octahedral environment.

Monitoring morphology and hydrogen coverage of nanometric Pt/γ-Al2 O3 particles by in†situ HERFD-XANES and quantum simulations.

Platinum nanoclusters highly dispersed on γ-alumina are widely used as heterogeneous catalysts. To understand the chemical interplay between the Pt nanoparticles, the support, and the reductive atmosphere, we performed X-ray absorption near edge structure (XANES) in situ experiments recorded in high energy resolution fluorescence detection (HERFD) mode. Spectra are assigned by comparison with simulated XANES spectra on models obtained by molecular dynamics (DFT-MD). We propose platinum cluster morphologies and quantify the hydrogen coverages compatible with XANES spectra recorded at variable hydrogen pressures and temperatures. Using cutting-edge methodologies to assign XANES spectra, this work gives unequalled atomic insights into the characterization of supported nanoclusters.

Hydrogenation properties of KSi and NaSi Zintl phases.

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.

CO adsorption on amorphous silica-alumina: electrostatic or Brønsted acidity probe?

The adsorption of CO on amorphous silica-alumina (ASA) was calculated by DFT. CO appears as a probe of the electrostatic field induced by the whole surface, at the origin of a so-called vibrational Stark effect responsible for the CO frequency shifts. Brønsted acidity of the ASA sites does not directly correlate CO frequency shifts.

Potassium silanide (KSiH3): a reversible hydrogen storage material.

KSi silicide can absorb hydrogen to directly form the ternary KSiH(3) hydride. The full structure of α-KSiD(3), which has been solved by using neutron powder diffraction (NPD), shows an unusually short Si-D lengths of 1.47 Å. Through a combination of density functional theory (DFT) calculations and experimental methods, the thermodynamic and structural properties of the KSi/α-KSiH(3) system are determined. This system is able to store 4.3 wt% of hydrogen reversibly within a good P-T window; a 0.1 MPa hydrogen equilibrium pressure can be obtained at around 414 K. The DFT calculations and the measurements of hydrogen equilibrium pressures at different temperatures give similar values for the dehydrogenation enthalpy (≈23 kJ mol(-1) H(2)) and entropy (≈54 J K(-1) mol(-1) H(2)). Owing to its relatively high hydrogen storage capacity and its good thermodynamic values, this KSi/α-KSiH(3) system is a promising candidate for reversible hydrogen storage.

Growth of boehmite particles in the presence of xylitol: morphology oriented by the nest effect of hydrogen bonding.

The ability to design nanoparticles size and shape through the addition of simple and commercially available organic molecules is of particular interest in the catalytic domain because huge amounts of very fine powders are needed. The origin of this effect is all the more difficult to elucidate because the involved interactions are weak. In this paper, we have investigated the shaping of boehmite AlO(OH) nanoparticles in the presence of polyols like xylitol (C(5) alditol) by a combined experimental and theoretical approach. Experimental techniques such as XRD, TEM, IEP measurements, adsorption isotherms measurements, and (13)C MAS NMR experiments demonstrate that the effect of xylitol has a thermodynamic origin and suggest weak interactions between xylitol and the surface. Furthermore, the strongest proportion of lateral faces ((100), (001), and (101)) that of basal face would be in agreement with a preferential adsorption upon lateral surfaces. These results were refined by a computational approach. DFT calculations of surface energies (taking into account temperature and solvation effects) and of NMR shielding constants corroborate that molecular adsorption mode is preferred over all adsorption modes involving exchanges with surface OH groups. The preferred adsorption on lateral surfaces is attributed to the nest effect induced by hydroxyl groups localized on the concavities of the (001) and (101) surfaces, able to stabilize the xylitol molecule by hydrogen-bonding, whereas the basal (010) surface is almost flat. This combined experimental and computational approach thus provides interesting rationalization for the morphology effects observed.

Pseudo-bridging silanols as versatile Brønsted acid sites of amorphous aluminosilicate surfaces.

Amorphization tunes acidity: Pseudo-bridging silanols, suggested as versatile Brønsted acid groups by molecular modeling studies, are obtained by shifted hydrolysis of Si-O-Al bridges formed by the thermal treatment of silica deposited on gamma-Al(2)O(3) (100), and appear under given pretreatment conditions. Demixing of part of the silica from the aluminosilicate phase is predicted upon excess water adsorption.

Topological Analysis of the Interactions between Organic Molecules and Co(Ni)MoS Catalytic Active Phases.

The adsorption modes of toluene, 2,3-dimethylbut-1-ene, and 2-methylthiophene on the edges of Co(Ni)MoS nanocrystallites has been investigated with the ELF topological approach of chemical bonding. The chemisorbed modes are characterized by the formation of bonding basins linking the substrate to the catalytic sites. The electronic rearrangements within the substrate are discussed. It is shown that a unique electronic descriptor, namely the metallic atomic basin contribution to the substrate ELF basins, provides a sizable correlation with the interaction energy.

Atomic scale insights on chlorinated gamma-alumina surfaces.

The thermochemistry of chlorinated gamma-alumina surfaces is explored by means of density functional calculations as a function of relevant reaction conditions used in experiments and in high-octane fuel production in the refining industry such as hydrocarbon isomerization and reforming. The role of chlorine as a dope of the Brønsted acidity of gamma-alumina surfaces is investigated at an atomic scale. Combining infrared spectroscopy and density functional theory calculations, the most favorable location of chlorine atoms on the (110), (100) and (111) surfaces of gamma-alumina is found to result either from direct adsorption or from the exchange of basic hydroxyl groups. Moreover, the modification of the hydrogen bond network upon chlorine adsorption is put forward as a key parameter for changing the Brønsted acidity. In a second step, we use a thermodynamic approach based on DFT total energy calculations corrected by the chemical potentials of HCl and H2O to determine the adsorption isotherms of chlorine and the relative surface concentration of hydroxyl groups and chlorine species on the gamma-alumina surfaces. The determination of chlorine content as a function of temperature and partial pressures of H2O and HCl offers new quantitative data required for optimizing the state of the support surface in industrial conditions. The mechanisms of chlorination are also discussed as a function of reaction conditions.

Quantum chemical and vibrational investigation of sodium exchanged gamma-alumina surfaces.

The sodium cation is well known as an efficient poison of gamma-alumina surface acidity. This poisoning effect has been revealed both by characterization methods and catalytic tests. In this work, we propose an accurate model of sodium exchanged gamma-alumina surfaces. On realistic models of hydroxylated gamma-alumina surfaces, the location of sodium cation is determined by the use of density functional theory (DFT) methods. For the (100) and (110) surfaces of gamma-alumina, the sodium cation is found in a solvated state within an inner solvation sphere complex. Its coordination sphere is constituted by O-mu(2), O-mu(3) and HO-mu(1) surface groups. The stretching frequency of these HO-mu(1) groups is shifted, leading to the appearance of a new band predicted and observed at about 3754 cm(-1) on the IR spectrum.