Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors

Circular economy emphasizes the idea of transforming products involving economic growth and improving the ecological system to reduce the negative consequences caused by the excessive use of raw materials. This can be achieved with the use of second-generation biomass that converts industrial and agricultural wastes into bulk chemicals. The use of catalytic processes is essential to achieve a viable upgrade of biofuels from the lignocellulosic biomass. We carried out density functional theory calculations to explore the relationship between 13 transition metals (TMs) properties, as catalysts, and their affinity for hydrogen and oxygen, as key species in the valourization of biomass. The relation of these parameters will define the trends of the hydrodeoxygenation (HDO) process on biomass-derived compounds. We found the hydrogen and oxygen adsorption energies in the most stable site have a linear relation with electronic properties of these metals that will rationalize the surface's ability to bind the biomass-derived compounds and break the C–O bonds. This will accelerate the catalyst innovation for low temperature and efficient HDO processes on biomass derivates, e.g. guaiacol and anisole, among others. Among the monometallic catalysts explored, the scaling relationship pointed out that Ni has a promising balance between hydrogen and oxygen affinities according to the d-band centre and d-band width models. The comparison of the calculated descriptors to the adsorption strength of guaiacol on the investigated surfaces indicates that the d-band properties alone are not best suited to describe the trend. Instead, we found that a linear combination of work function and d-band properties gives significantly better correlation

Ensemble inequivalence in random graphs

We present a complete analytical solution of a system of Potts spins on a random k-regular graph in both the canonical and microcanonical ensembles, using the Large Deviation Cavity Method (LDCM). The solution is shown to be composed of three different branches, resulting in an non-concave entropy function.The analytical solution is confirmed with numerical Metropolis and Creutz simulations and our results clearly demonstrate the presence of a region with negative specific heat and, consequently, ensemble inequivalence between the canonical and microcanonical ensembles.Comment: 9 pages, 3 figure

The influence of support materials on the structural and electronic properties of gold nanoparticles - a DFT study

Supported gold nanoparticles are used for a wide range of catalytic processes. In this work, we use dispersion corrected density functional theory (DFT-D) to study the effect of commonly used support materials (MgO, C, CeO2) on small gold particles with up to 19 atoms. Our results show that the preferred cluster shape and morphology is highly dependent on the support material due to different adsorption strength and structural mismatch between the cluster and the surface material. We developed an algorithm to measure the mismatch between the cluster interface and the support surface. Moreover, depending on the support material, the gold clusters exhibit a positive or negative polarisation, which ultimately has strong implications on the catalytic activity of such particles. This behaviour is rationalised by an analysis of the electronic structure of the metal particles and support materials

The influence of oxygen vacancy position and Ce3+ ion localisation on the properties of small gold clusters supported on CeO2-x(111)

We study the influence of oxygen vacancies on small Au clusters supported on CeO2 using dispersion-corrected density functional theory (DFT-D). Our results show that the effect of oxygen vacancies on Au clusters is highly dependent on the cluster size and the relative position of the cluster to the vacancy. We found that the Au particles are only affected by the vacancies if they are located directly within the cluster perimeter. Using Crystal Orbital Hamilton Population (COHP) analysis, we show that the oxygen vacancy can lead to the formation of Au-Ce bonds under destabilisation of the bonds to the Au atom at the vacancy site and subsequent distortion of the cluster structure. However, we found that such Au-Ce bond formation only occurs when the interactions between the Au atom at the vacancy site and the surround Au atoms are not critical for the overall cluster stability as, for example, in the case of the central atom in a planar Au7 cluster. The formation of an oxygen vacancy can change the charge of the supported gold cluster from positive (on stoichiometric CeO2) to neutral or negative on defective CeO2-X. Interestingly, the additional electron density is located only at the Au atom at the vacancy site and is not redistributed throughout the cluster. Investigation of the electrostatic potential of the cluster surface did not show any significant changes compared to the stoichiometric surface, which is not caused by structural changes of the Au cluster

Limiting absorption principle for the dissipative Helmholtz equation

Adapting Mourre's commutator method to the dissipative setting, we prove a limiting absorption principle for a class of abstract dissipative operators. A consequence is the resolvent estimates for the high frequency Helmholtz equation when trapped trajectories meet the set where the imaginary part of the potential is non-zero. We also give the resolvent estimates in Besov spaces

SLC37A4-CDG : mislocalization of the glucose-6-phosphate transporter to the Golgi causes a new congenital disorder of glycosylation

Loss-of-function of the glucose-6-phosphate transporter is caused by biallelic mutations in SLC37A4 and leads to glycogen storage disease Ib. Here we describe a second disease caused by a single dominant mutation in the same gene. The mutation abolishes the ER retention signal of the transporter and generates a weak Golgi retention signal. Intracellular mislocalization of the transporter leads to a congenital disorder of glycosylation instead of glycogen storage disease

Density functional theory study of the partial oxidation of methane to methanol on Au and Pd surfaces

The partial oxidation of methane to methanol has been a goal of heterogeneous catalysis for many years. Recent experimental investigations have shown how AuPd nanoparticle catalysts can give good selectivity to methanol with only limited total oxidation of CH4 using hydrogen peroxide as an oxidant in aqueous media. Interestingly, the use of colloidal nanoparticles alone, without a support material, leads to efficient use of the oxidant and the possibility of introducing oxygen from O2(g) into the CH3O2H primary product. This observation indicates that a radical mechanism is being initiated by H2O2 but then the oxygen addition step, catalyzed by these nanoparticles, can incorporate O2(ads). In this contribution, we use density functional theory (DFT) to study the elementary steps in the partial oxidation of methane to methanol using H2O2 as a radical initiator and molecular oxygen as an oxidant over the low index surfaces of Pd and Au. We are able to show that pure Pd nanoparticles are prone to oxidation by O2(g), whereas the competitive adsorption of water on Au surfaces limits the availability of O2(ads). Calculations with Au added to Pd or vice versa show that both effects can be alleviated by using mixed metal surfaces. This provides a rationalization of the need to use alloy nanoparticles experimentally, and the insights from these results will aid future catalyst development

A parameterization of flow separation over subaqueous dunes

Flow separation plays a key role in the development of dunes, and modeling the complicated flow behavior inside the flow separation zone requires much computational effort. To make a first step toward modeling dune development at reasonable temporal and spatial scales, a parameterization of the shape of the flow separation zone over two-dimensional dunes is proposed herein, in order to avoid modeling the complex flow inside the flow separation zone. Flow separation behind dunes, with an angle-of-repose slip face, is characterized by a large circulating leeside eddy, where a separation streamline forms the upper boundary of the recirculating eddy. Experimental data of turbulent flow over two-dimensional subaqueous bed forms are used to parameterize this separation streamline. The bed forms have various heights and height to length ratios, and a wide range of flow conditions is analyzed. This paper shows that the shape of the flow separation zone can be approximated by a third-order polynomial as a function of the distance away from the flow separation point. The coefficients of the polynomial can be estimated, independent of flow conditions, on the basis of bed form shape at the flow separation point and a constant angle of the separation streamline at the flow reattachment point. \ud \u

Coordinated community structure among trees, fungi and invertebrate groups in Amazonian rainforests

Little is known regarding how trophic interactions shape community assembly in tropical forests. Here we assess multi-taxonomic community assembly rules using a rare standardized coordinated inventory comprising exhaustive surveys of five highly-diverse taxonomic groups exerting key ecological functions: trees, fungi, earthworms, ants and spiders. We sampled 36 1.9-ha plots from four remote locations in French Guiana including precise soil measurements, and we tested whether species turnover was coordinated among groups across geographic and edaphic gradients. All species group pairs exhibited significant compositional associations that were independent from soil conditions. For some of the pairs, associations were also partly explained by soil properties, especially soil phosphorus availability. Our study provides evidence for coordinated turnover among taxonomic groups beyond simple relationships with environmental factors, thereby refining our understanding regarding the nature of interactions occurring among these ecologically important groups