Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory

Dry reforming is a promising reaction to utilise the greenhouse gases CO2 and CH4. Nickel-based catalysts are the most popular catalysts for the reaction, and the coke formation on the catalysts is the main obstacle to the commercialisation of dry reforming. In this study, the whole reaction network of dry reformation on both flat and stepped nickel catalysts (Ni(111) and Ni(211)) as well as nickel carbide (flat: Ni3C(001); stepped: Ni3C(111)) is investigated using density functional theory calculations. The overall reaction energy profiles in the free energy landscape are obtained, and kinetic analyses are utilised to evaluate the activity of the four surfaces. By careful examination of our results, we find the following regarding the activity: (i) flat surfaces are more active than stepped surfaces for the dry reforming and (ii) metallic nickel catalysts are more active than those of nickel carbide, and therefore, the phase transformation from nickel to nickel carbide will reduce the activity. With respect to the coke formation, the following is found: (i) the coke formation probability can be measured by the rate ratio of CH oxidation pathway to C oxidation pathway (r(CH)/r(C)) and the barrier of CO dissociation, (ii) on Ni(111), the coke is unlikely to form, and (iii) the coke formations on the stepped surfaces of both nickel and nickel carbide can readily occur. A deactivation scheme, using which experimental results can be rationalised, is proposed. 

Origin of the Increase of Activity and Selectivity of Nickel Doped by Au, Ag, and Cu for Acetylene Hydrogenation

Activity and selectivity are both important issues in heterogeneous catalysis and recent experimental results have shown that Ni catalysts doped by gold exhibit high activity for the hydrogenation of acetylene with good selectivity of ethylene formation. To unravel the underlying mechanism for this observation, the general trend of activity and selectivity of Ni surfaces doped by Au, Ag, and Cu has been investigated using density functional theory calculations. Complete energy profiles from C2H2 to C2H4 on Ni(111), Au/Ni(111), Ag/Ni(111) and Cu/Ni(111) are obtained and their turnover frequencies (TOFs) are computed. The results show that acetylene adsorption on Ni catalyst is strong which leads to the low activity while the doping of Au, Ag, and Cu on the Ni catalyst weakens the acetylene adsorption, giving rise to the increase of activity. The selectivity of ethylene formation is also quantified by using the energy difference between the hydrogenation barriers and the absolute value of the adsorption energies of ethylene. It is found that the selectivity of ethylene formation increases by doping Au and Ag, while those of Cu/Ni and Ni are similar.

Self-cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Mechanochemical synthesis of TiO2/NiFe2O4 magnetic catalysts for operation under RF field

Composite NiFe2O4–TiO2 magnetic catalysts were prepared by mechanochemical synthesis from a mixture of titania supported nickel ferrite nanoparticles and P25 titania (Evonic). The former provides fast and efficient heating under radiofrequency field, while the latter serves as an active catalyst or catalyst support. The highest heating rate was observed over a catalyst prepared for a milling time of 30 min. The catalytic activity was measured over the sulfated composite catalysts in the condensation of aniline and 3-phenylbutyric acid in a stirred tank reactor and in a continuous RF heated flow reactor in the 140–170 °C range. The product yield of 47% was obtained over the sulfated P25 titania catalyst in the flow reactor.

Measurement of oxygen storage capacity in automotive catalysts

There is considerable disagreement in the literature on available oxygen storage capacity, and on the reaction rates associated with the storage process, for three-way automotive catalysts. This paper seeks to address the issue of oxygen storage capacity in a clear and precise manner. The work described involved a detailed investigation of oxygen storage capacity in typical samples of automotive catalysts. The capacity has also been precisely defined and estimates have been made of the specific capacity based on catalyst dimensions. A purpose-built miniature catalyst test rig has been assembled to allow measurement of the capacity and the experimental procedure has been developed to ensure accurate measurement. The measurements from the first series of experiments have been compared with the theoretical calculations and good agreement is seen. A second series of experiments allowed the effect of temperature on oxygen storage capacity to be investigated. This work shows very clearly the large variation of the capacity with temperature.

Deactivation of Oxidation Catalysts by Oil-Derived Sulphur

The most common mode of deactivation suffered by catalysts fitted to two-stroke engines has traditionally been thermal degradation, or even meltdown, of the washcoat and substrate. The high temperatures experienced by these catalysts are caused by excessively high concentrations of HC and CO in the exhaust gas which are, in turn, caused by a rich AFR and the loss of neat fuel to the exhaust during the scavenging period. The effects of catalyst poisoning due to additives in the oil is often regarded as a secondary, or even negligible, deactivating mechanism in two-stroke catalysts and has therefore received little attention. However, with the introduction of direct in-cylinder fuel injection to some larger versions of this engine, the quantities of HC escaping to the exhaust can be reduced to levels similar to those found on four-stroke gasoline engines. Under these conditions, the effects of poisoning are much more significant to catalyst durability, particularly for crankcase scavenged derivatives which allow considerable quantities of oil to escape into the exhaust in a neat, or partially burned form. In this paper the effects of oil-derived sulphur on catalyst performance are examined using specialised test apparatus. The oil used throughout the study was formulated specifically for a two-stroke engine fitted with direct in-cylinder fuel injection. The sulphur content of this oil was 0.21% by mass and particular attention was paid to the role of this element in the resulting deactivation. The catalyst was also designed for two-stroke applications and contained a high palladium loading of 300g/ft3 (28g/l) to prolong the life of the catalyst. It was found that the sulphur caused permanent deactivation of the CO reaction and increased the light-off temperature by around 40oC after oiling for 60 hours. This deactivation was progressive and led to a reduction in surface area of the washcoat, particularly in the micropores of around 5Å diameter. By using a validated catalyst model the change in surface area of the precious metal was estimated. It was found that the simulated palladium surface area had to be reduced by a factor of around 7.5 to produce the light-off temperature of the deactivated catalyst. Conversely, the light-off temperature of the C3H6 reaction was barely affected by the deactivation.