Unraveling the Role of Metal-Support Interactions on the Structure Sensitivity of Fischer-Tropsch Synthesis

Structure sensitivity plays a pivotal role in heterogeneous catalysis and the Fischer-Tropsch reaction is one of the prime examples of such a structure-sensitive reaction. The activity and selectivity of this reaction depend on the size of the nanoparticle and this trend is observed for a whole range of support materials. To understand why metal-support interactions do not affect this trend, a ReaxFF force field is developed that effectively mimics the broad variety of support materials and captures the metal-support interaction strength into a single structural parameter. Particles of 1-9 nm embedded on support materials are sampled using simulated annealing molecular dynamics and the effect of the metal-support interaction on the active site distribution is studied. It is found that although the size-dependency profile of various active site topologies depends on the interaction strength of the nanoparticle with the support, step-edge sites with an FCC(110) motif remain insensitive to the type of support. Based on microkinetic simulations, it is established that these sites are predominantly responsible for the observed atom-based FTS activity rationalizing why Fischer-Tropsch synthesis is structure-sensitive but support-insensitive.</p

Significant non-linearity in nitrous oxide chamber data and its effect on calculated annual emissions

Chambers are widely used to measure surface fluxes of nitrous oxide (N2O). Usually linear regression is used to calculate the fluxes from the chamber data. Non-linearity in the chamber data can result in an underestimation of the flux. Non-linear regression models are available for these data, but are not commonly used. In this study we compared the fit of linear and non-linear regression models to determine significant non-linearity in the chamber data. We assessed the influence of this significant non-linearity on the annual fluxes. For a two year dataset from an automatic chamber we calculated the fluxes with linear and non-linear regression methods. Based on the fit of the methods 32% of the data was defined significant non-linear. Significant non-linearity was not recognized by the goodness of fit of the linear regression alone. Using non-linear regression for these data and linear regression for the rest, increases the annual flux with 21% to 53% compared to the flux determined from linear regression alone. We suggest that differences this large are due to leakage through the soil. Macropores or a coarse textured soil can add to fast leakage from the chamber. Yet, also for chambers without leakage non-linearity in the chamber data is unavoidable, due to feedback from the increasing concentration in the chamber. To prevent a possibly small, but systematic underestimation of the flux, we recommend comparing the fit of a linear regression model with a non-linear regression model. The non-linear regression model should be used if the fit is significantly better. Open questions are how macropores affect chamber measurements and how optimization of chamber design can prevent this

Enumerating active sites on metal nanoparticles: Understanding the size dependence of cobalt particles for CO dissociation

Detailed understanding of structure sensitivity, a central theme in heterogeneous catalysis, is important to guide the synthesis of improved catalysts. Progress is hampered by our inability to accurately enumerate specific active sites on ubiquitous metal nanoparticle catalysts. We employ herein atomistic simulations based on a force field trained with quantumchemical data to sample the shape of cobalt particles as a function of their size. Algorithms rooted in pattern recognition are used to identify surface atom arrangements relevant to CO dissociation, the key step in the Fischer- Tropsch (FT) reaction. The number of step-edge sites that can catalyze C-O bond scission with a low barrier strongly increases for larger nanoparticles in the range of 1-6 nm. Combined with microkinetics of the FT reaction, we can reproduce experimental FT activity trends. The stabilization of step-edge sites correlates with increasing stability of terrace nanoislands on larger nanoparticles

Characterization of Ga/HZSM-5 and Ga/HMOR synthesized by chemical vapor deposition of trimethylgallium

Chemical vapor deposition (CVD) of trimethylgallium (TMG) has been studied as a method to disperse extraframework Ga in acidic ZSM-5 and mordenite zeolite. Various samples were extensively characterized by ICP, XPS, NMR, and FTIR. Silylation with tetramethyldisilazane is explored as a method for deactivating the external zeolite surface. The deposition of TMG in silylated ZSM-5 results in a gallium-to-aluminum ratio close to unity, which indicates a homogeneous metal distribution in the micropore space. However, pore blockage in the one-dimensional channels of mordenite results in a inhomogeneous distribution and a low Ga loading. Upon exposure to moistened air, the adsorbed methylgallium species decompose and alkoxy groups are formed. Subsequent oxidation or reduction leads to the complete removal of methyl groups. The reductive route is the preferred one resulting in a better dispersion of Ga, since oxidation of the methyl groups leads to water formation and hydrolysis of cationic Ga species

Beïnvloeden van landgebonden broeikasgasemissies : Naar een klimaatneutrale(re) inrichting van het landelijke gebied

Onderzocht is of mitigatie mogelijk terug te dringen is in de veenweidegebieden en of het door de vastlegging van koolstof in bossen te verhogen is. Daarnaast is bepaald wat de effecten zijn van het Nederlandse landgebruik in de toekomst (scenario's) op de broeikasemissie

Bramble: adaptive common neighbor analysis (CNA) for the recognition of surface topologies in nanoparticles

In heterogeneous catalysis, the active site is the specific region on the catalyst surface where the chemical reaction occurs. It plays a vital role in facilitating reactions by providing a unique arrangement of atoms and chemical properties to promote the conversion of reactants into products. Identifying these atomic motifs is crucial towards the atom-scale understanding of catalysis. Towards this aim, the common neighbor analysis (CNA) procedure acts as a powerful computational method used to analyze and classify atomic structures in materials. It involves examining the local environment of each atom to identify and quantify the types of atomic coordination and bonding, providing insights into the structural properties and behavior of materials at the atomic scale. Bramble is an efficient C++-based command-line tool to perform the CNA analysis. Uniquely, it is coupled to a pattern identification library for facile identification of the CNA fingerprints. Furthermore, for unknown fingerprint it offers the option to perform a similarity analysis based on the minimization of the Hilbert-Schmidt norm

Fire safety assessment in semi-open car parks

Guidelines for the safe design of semi-open car parks require a minimum amount of open façade in order to ensure an effective removal of heat and smoke during a car fire. In this study the fire safety level is assessed by the use of validated Computational Fluid Dynamics (CFD) simulations of different design variants. The fire safety is assessed using temperature and sight length criteria for safe deployment of the fire department. Results show that 3 out of 7 studied variants did not meet these criteria. It is therefore concluded that it is possible to design semi-open car parks which comply with current Dutch guidelines, yet when assessed with criteria for safe deployment of the fire brigade have an insufficient fire safety level

Método de utilização do programa Energyplus para verificação de desempenho térmico de ambientes com fachadas duplas

A fachada dupla consiste de duas camadas, em geral envidraçadas, colocadas a certa distância, formando uma cavidade intermediária por onde o ar circula. Essas camadas abrangem fenômenos físicos complexos, como a ventilação por efeito chaminé e as trocas térmicas radiantes. Este trabalho apresenta um método de simulação com o programa EnergyPlus para análise do desempenho de um ambiente com fachada dupla. As camadas da fachada dupla estão submetidas às trocas radiantes e convectivas na cavidade intermediária devido ao efeito da ventilação provocado pela chaminé térmica. O método empregado considera a cavidade (entre camadas) como um microclima, cujas condições climáticas foram usadas para gerar um arquivo climático específico dessa zona. Esse arquivo foi posteriormente usado em outra simulação, que considerou apenas a camada interna da fachada, com foco na radiação solar. São apresentados dados que validam o processo de simulação, em vista das variáveis disponíveis pelo programa. Os resultados foram comparados a um caso-base sem fachada dupla. Os ganhos de calor pela fachada e as temperaturas operativas internas foram usados para verificação do desempenho térmico do ambiente com a fachada dupla. Esse processo fornece subsídios para análise de modelos mais complexos