Effects of Metal Promoters (M = Fe, Co, and Cu) in Pt/M x Zr y O z Catalysts and Influence of CO2 and H2O on the CO Oxidation Activity (PROX): Analysis of Surface Properties After Reaction.

In the present paper, the effects of metal promoters (M = Fe, Co, and Cu) in Pt/M x Zr y O z catalysts and the influence of CO2 and H2O on the CO oxidation activity (PROX) were investigated. To do that, characterizations of catalyst structures and surfaces were performed and reported here. The catalyst Pt/Fe x Zr y O z (PFeZ) was the most active at low temperatures among the analyzed ones. The addition of platinum caused strong interaction with the mixed oxide, affecting the structure and the surface composition, blocking basic sites, and thus preventing catalyst deactivation. Particularly, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results evidenced the formation of carboxylate and carbonate species. Besides, the addition of CO2 and H2O in the gas feed stream affected the observed CO oxidation results, showing that CO2 competes with O2 on metallic sites. Moreover, DRIFTS and temperature-programmed desorption (TPD) analyses suggested the occurrence of OH- oxidation by CO, leading to the formation of highly reactive compounds that can be easily oxidized.

Investigating the stability of Ni and Fe nanoparticle distribution and the MWCNT structure in the dry reforming of methane.

Catalysts based on Ni and Fe nanoparticles deposited selectively on carbon nanotubes were investigated before and after the dry methane reforming. Three catalysts were synthesized and evaluated, varying the concentration of Ni inside and Fe outside the carbon tubes. BET analysis revealed that the acid treatment opened the ends of the nanotubes and resulted in a higher surface area. Transmission electron microscopy (TEM) showed 24 layers with inner diameter ranging from 4 to 6 nm and outer diameter ranging from 16 to 22 nm. Raman spectroscopy confirmed that after calcination at high temperature the structure of the nanotubes was maintained. X-ray diffraction (XRD) analysis of the catalysts confirmed the presence of NiO (2.6-3.2 nm) and Fe2O3 (4.3 nm) crystallites. The catalytic tests presented high activity in dry methane reform (DRM). The catalysts 10Ni@CNT and 10Ni@CNT/5Fe presented conversions of CH4 (63 and 67%) and CO2 (72 and 88%), respectively, at 800 °C, under atmospheric pressure. Analysis after the reaction showed an increasing ratio of ID/IG, which indicates the formation of defects. The Raman analysis showed that even after calcination at high temperatures the structures of the nanotubes were mostly preserved, and TEM images showed that during the reaction, there were formation of nanotubes occurring randomly.

The effect of carbon dioxide in the feed stream of tri-reforming of methane process compared to the partial oxidation of methane.

In this work, we studied the effect of CO2 in the feed stream of the TRM process performance of nickel supported on LaFeO3 perovskite for hydrogen production compared to the POM reaction. The perovskite and nickel supported on LaFeO3 were synthesized and characterized by thermogravimetric analysis (TGA/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and programmed reduction temperature (TPR). The catalytic tests were carried out in temperatures varying from 700 to 800 °C with feed flow of 350 cm3/min and 200 cm3/min for TRM and POM, respectively. The hydrogen selectivity for the tri-reforming was 78%, while for the partial oxidation reaction, only 55% H2 at 700 °C. Results showed that the hydrogen selectivity for the Ni/LaFeO3 catalyst is significantly higher for the tri-reforming process, suggesting that CO2 enhanced the hydrogen selectivity compared to the partial oxidation of methane. Analyses by Raman spectroscopy and thermogravimetric calculations showed structural modifications of the catalysts after the reaction. The Raman spectrum showed segregated NiO and Fe3O4 and low carbon formation at 700 °C. The proposed mechanism suggests methane and oxygen adsorption, lattice oxygen and CO2 on surface active sites, and vacancies for both reactions.

Synthesis of Reduced Graphene Oxide as a Support for Nano Copper and Palladium/Copper Catalysts for Selective NO Reduction by CO.

Copper and palladium/copper nanoparticles supported on reduced graphene oxide catalysts were synthesized and evaluated for the selective NO reduction by CO. The catalysts were characterized by XRD, nitrogen adsorption-desorption, TGA, XPS, TPR, in situ XRD, STEM, and HRTEM. The STEM and HRTEM results showed high metal oxide dispersions on the rGO. XPS results showed the presence of Cu and Pd oxide species. The reduction of copper supported on the rGO occurred in two steps for CuO x /rGOc, while that for CuO x -PdO y /rGOc occurred in one step for temperatures lower than 350 °C. Noteworthy is that the in situ XRD results showed that the rGO structure was not affected after reduction at 350 °C. The in situ XRD of reduction revealed the appearance of new phases for copper during the reduction. The catalysts were evaluated in NO reduction by CO. The tests showed that the reduced catalysts presented high performance with NO conversions and N2 selectivity above 85% at 350 °C.

A catalyst selection method for hydrogen production through Water-Gas Shift Reaction using artificial neural networks.

Hydrogen (H2) is considered a clean valuable energy source and its worldwide demand has increased in recent years. The Water-Gas Shift (WGS) Reaction is one of the major routes for hydrogen production and uses different catalysts depending on the operating process conditions. A catalyst is usually composed of an active phase and a support for its dispersion. There are currently an increasing number of researches on catalytic field focusing on transition metals nanoparticles supported on different compounds. In order to predict optimal catalyst compositions for the WGS reaction, Artificial Neural Networks (ANNs) were used to build a model from the literature catalytic data. A three-layer feedforward neural network was employed with active phase composition and support type as some of the input variables, and Carbon Monoxide (CO) conversion as output variable. The insertion of properties such as surface area, calcination temperature and time allowed predicting the reaction performance based on intrinsic catalyst variables not commonly used in phenomenological kinetic models. Also, unlike previous studies, a detailed sensitivity analysis was carried out to observe useful trends. An important outcome of this work is the proposition of ceria-supported catalysts for the WGS reaction that present larger surface areas, with Ru, Ni or Cu as active phases conducted at moderate temperatures (≈300 °C) and with reasonable space velocities (2000-6000 h-1). In addition, it was possible to predict the most relevant variables for the process: the temperature and the surface area. Thus, the results show the power of ANNs for predicting better catalysts and conditions for this important process in the environmental field.

Towards an atomic level understanding of niobia based catalysts and catalysis by combining the science of catalysis with surface science

The science of catalysis and surface science have developed, independently, key information for understanding catalytic processes. One might argue: is there anything fundamental to be discovered through the interplay between catalysis and surface science? Real catalysts of monometallic and bimetallic Co/Nb2O5 and Pd-Co/Nb2O5 catalysts showed interesting selectivity results on the Fischer-Tropsch synthesis (Noronha et al. 1996, Rosenir et al. 1993). The presence of a noble metal increased the C+5 selectivity and decreased the methane formation depending of the reduction temperature. Model catalyst of Co-Pd supported on niobia and alumina were prepared and characterized at the atomic level, thus forming the basis for a comparison with "real" support materials. Growth, morphology and structure of both pure metal and alloy particles were studied. It is possible to support the strong metal support interaction suggested by studies on real catalysts via the investigation of model systems for niobia in comparison to alumina support in which this effect does not occur. Formation of Co2+ penetration into the niobia lattice was suggested on the basis of powder studies and can be fully supported on the basis of model studies. It is shown for both real catalysts and model systems that oxidation state of Co plays a key role in controlling the reactivity in Fischer-Tropsch reactions systems and that the addition of Pd is a determining factor for the stability of the catalyst. It is demonstrated that the interaction with unsaturated hydrocarbons depends strongly on the state of oxidation.

As ciências da catálise e da superfície têm desenvolvido independentemente temas básicos para o entendimento de processos catalíticos. Pode-se até questionar se há ainda algo fundamental para ser descoberto através da interface entre catálise eciência da superfície? Catalisadores mono e bimetálicos de Co/Nb2O5 e Pd-Co/ Nb2O5 apresentaram resultados interessantes de seletividade na síntese de Fischer-Tropsch (Noronha et al. 1996, Roseniret al. 1993). A presença de metal nobre aumentou a seletividade de C+5 e diminuiu a formação de metano dependendo da temperatura de redução. Catalisadores modelo de Co-Pdsuportados em nióbia e alumina foram preparados e caracterizados a nível atômico, servindo de base para comparação do catalisador "real". Foram estudados o crescimento de partículas, bem como a morfologia e a estrutura de partículas de ambos, metal puro e ligas. É possível suportar as propostas que sugerem uma forte interação metal suporte em catalisadores reais através das pesquisas em sistemas modelos para nióbia quando comparadas com suportes de alumina onde estes efeitos não aparecem. A formação de Co2+ penetrando na rededa nióbia, sugerida para catalisadores em forma de pó, foi totalmente confirmada pelos estudos em catalisadores modelo. Mostrou-se ainda que para ambos os sistemas reais e modelos, que o estado oxidado do Co tem papel fundamental na reatividade das reações de Fischer-Tropsch e que a adição de Pd é um fator determinante para a estabilidade do catalisador. Demonstrou-se que a interação com hidrocarbonetos insaturados depende fortemente do estado oxidado do metal.