Sulphur Poisoning, Water Vapour and Nitrogen Dilution Effects on Copper-based Catalyst Dynamics, Stability and Deactivation during CO2 Reduction Reactions to Methanol

To reduce CO2 emissions, a flexible process operation for chemical methanol synthesis may be required as the supply of renewable energy-based feedstocks fluctuates. Determining the changing conditions’ analysis for the...

Competitive Adsorption of H2O and SO2 on Catalytic Platinum Surfaces: a Density Functional Theory Study

ABSTRACT Platinum has been widely used as the catalyst of choice for the production of hydrogen in the hybrid sulphur (HyS) cycle. In this cycle, water (H2O) and sulphur dioxide (SO2) react to form sulphuric acid and hydrogen. However, the surface reactivity of platinum towards H2O and SO2 is not yet fully understood, especially considering the competitive adsorption that may occur on the surface. In this study, we have carried out density functional theory calculations with long-range dispersion corrections [DFT-D3-(BJ)] to investigate the competitive effect of both H2O and SO2 on the Pt (001), (011) and (111) surfaces. Comparing the adsorption of a single H2O molecule on the various Pt surfaces, it was found that the lowest adsorption energy (Eads = -1.758 eV) was obtained for the dissociative adsorption of H2O on the (001) surface, followed by the molecular adsorption on the (011) surface (Eads = -0.699 eV) and (111) surface (Eads = -0.464 eV). For the molecular SO2 adsorption, the trend was similar, with the lowest adsorption energy (Eads = -2.471 eV) obtained on the (001) surface, followed by the (011) surface (Eads = -2.390 eV) and (111) surface (Eads = -1.852 eV). During competitive adsorption by H2O and SO2, the SO2 molecule will therefore preferentially adsorb onto the Pt surface. If the concentration of SO2 increases, self-reaction between two neighbouring SO2 molecules may occur, leading to the formation of sulphur monoxide (SO) and -trioxide (SO3) on the surface, which could lead to sulphur poisoning of the Pt catalytic surface. Keywords: Platinum, water, sulphur dioxide, hydrogen, adsorption, density functional theory.

A Mini Review on Lanthanum Ferrites-based Exsolved Perovskites as Fuel-flexible Anode for Solid Oxide Fuel Cells

Exsolved perovskites can be obtained from lanthanum ferrites, such as La0.6Sr0.4Fe0.8Co0.2O3, as result of Ni doping and thermal treatments. Ni can be simply added to the perovskite by an incipient wetness method. Thermal treatments include calcination in air (e.g., 500 °C) and subsequent reduction in diluted H2 at 800 °C to favor the exsolution process. The chemistry of the nanoparticles exsoluted on the substrate surface can be further modulated by a post treatment in air. These processes allow to produce a two-phase material consisting of a Ruddlesden-Popper type structure and a solid oxide solution e.g. α-Fe100-y-zCoyNizOx oxide. The formed electro-catalyst shows sufficient electronic conductivity under reducing environment at the SOFC anode. Outstanding catalytic properties are observed for the direct oxidation of dry fuels in SOFCs, including H2, methane, syngas, methanol, glycerol and propane. This anode electrocatalyst can be combined with full density electrolyte based on Gadolinia-doped Ceria or with La0.8Sr0.2Ga0.8Mg0.2O3 (LSGM) or BaCe0.9Y0.1O3-δ (BYCO) to form a complete perovskite structure-based cell. Moreover, the exsolved perovskite can be used as a coating layer or catalytic pre-layer of a conventional Ni-YSZ anode. Beside the excellent catalytic activity, this material also shows proper durability and tolerance to sulphur poisoning. In this mini review, preparation methods, physico-chemical characteristics, surface properties of exsoluted and core-shell nanoparticles encapsulated on the metal-depleted perovskite substrate surface, electrochemical properties for the direct oxidation of dry fuels and related electrooxidation mechanisms are examined and discussed.

Interaction of SO2 with the Platinum (001), (011), and (111) Surfaces: A DFT Study

Given the importance of SO2 as a pollutant species in the environment and its role in the hybrid sulphur (HyS) cycle for hydrogen production, we carried out a density functional theory study of its interaction with the Pt (001), (011), and (111) surfaces. First, we investigated the adsorption of a single SO2 molecule on the three Pt surfaces. On both the (001) and (111) surfaces, the SO2 had a S,O-bonded geometry, while on the (011) surface, it had a co-pyramidal and bridge geometry. The largest adsorption energy was obtained on the (001) surface (Eads = −2.47 eV), followed by the (011) surface (Eads = −2.39 and −2.28 eV for co-pyramidal and bridge geometries, respectively) and the (111) surface (Eads = −1.85 eV). When the surface coverage was increased up to a monolayer, we noted an increase of Eads/SO2 for all the surfaces, but the (001) surface remained the most favourable overall for SO2 adsorption. On the (111) surface, we found that when the surface coverage was θ > 0.78, two neighbouring SO2 molecules reacted to form SO and SO3. Considering the experimental conditions, we observed that the highest coverage in terms of the number of SO2 molecules per metal surface area was (111) > (001) > (011). As expected, when the temperature increased, the surface coverage decreased on all the surfaces, and gradual desorption of SO2 would occur above 500 K. Total desorption occurred at temperatures higher than 700 K for the (011) and (111) surfaces. It was seen that at 0 and 800 K, only the (001) and (111) surfaces were expressed in the morphology, but at 298 and 400 K, the (011) surface was present as well. Taking into account these data and those from a previous paper on water adsorption on Pt, it was evident that at temperatures between 400 and 450 K, where the HyS cycle operates, most of the water would desorb from the surface, thereby increasing the SO2 concentration, which in turn may lead to sulphur poisoning of the catalyst.

Ba-Ni-Hexaaluminate as a New Catalyst in the Steam Reforming of 1-Methyl Naphthalene and Methane

This work investigates the long-term performance of Ba-Ni-hexaaluminate, BaNixAl12−xO19 as a catalyst in reforming of 1-methyl naphthalene and/or methane in a model-gas simulating that from a circulating fluidized bed (CFB) gasifier during 23–29 h in a lab scale set-up, as well as the tendency for coke formation, sintering and sulphur poisoning. 1-Methyl naphthalene is used as a tar model substance. The Ba-Ni-hexaaluminate induces a high conversion of both compounds in the temperatures investigated (850 and 950 °C) under sulphur-free conditions. In sulphur-containing gas, the methane conversion stops at 20 ppm H2S and the reforming of 1-MNP at 850 °C is slightly reduced at 100 ppm. Graphic Abstract

Fabrication and Electrochemical Performance of Zn-Doped La0.2Sr0.25Ca0.45TiO3 Infiltrated with Nickel-CGO, Iron, and Cobalt as an Alternative Anode Material for Solid Oxide Fuel Cells

In solid oxide fuel cells, doped strontium titinates have been widely studied as anode materials due to their high n-type conductivity. They are used as current conducting backbones as an alternative to nickel-cermets, which suffer degradation due to coking, sulphur poisoning, and low tolerance to redox cycling. In this work, anode backbone materials were synthesized from La0.2Sr0.25Ca0.45TiO3−δ (LSCTA-), modified with 5 wt.% Zn, and infiltrated with nickel (Ni)/ceria gadolinium-doped cerium oxide (CGO), Fe, and Co. The electrodes were further studied for their electrochemical performance using electrochemical impedance spectroscopy (EIS) at open circuit voltage (OCV) in different hydrogen to steam ratios and at various operating temperatures (850–650 °C). Infiltration of electrocatalysts significantly reduced the polarization resistance and among the studied infiltrates, at all operating temperatures, Ni-CGO showed excellent electrode performance. The polarization resistances in 3% and 50% H2O/H2 atmosphere were found to be 0.072 and 0.025 Ω cm2, respectively, at 850 °C, and 0.091 and 0.076 Ω cm2, respectively, at 750 °C, with Ni-CGO. These values are approximately three orders of magnitude smaller than the polarization resistance (25 Ω cm2) of back bone material measured at 750 °C.