Sulfur Coverage Research Articles

Elastic Effects in Adsorbate–Adsorbate Interactions of C and S on a Stepped Ru Surface

We examine strain modification of adsorbate–adsorbate interaction in the (C*+S*)/fcc-Ru(211) system for relevance to biomass to hydrocarbon catalysis and the broader case of interaction changes under strain. Applied biaxial strains from −3% to +3% shift the C and S binding and interaction energies by ±0.3 eV for C and ±0.1 eV for S, binding and interaction being additive and leading to stronger binding with tension, creating larger total changes in binding for the covered surfaces. Changes in the near-neighbor interactions with strain are found to be primarily electronic in origin—there is little change in mechanical interaction. While mixing and thermodynamic analysis reveals that the C+S system will mix over the complete range of strains studied, the application of strain, whether tensile or compressive, may lead to reduced sulfur coverage. For biomass catalysis, the implication is that strain may be used to optimize hydrocarbon chemistry with only improvements in poisoning due to site blocking. It is a...

Mesoporous platinum as sulfur-tolerant catalyst for PEMFC cathodes

The performance of proton exchange membrane fuel cell (PEMFC) is highly influenced by its operating conditions. One of the vital parameter is the purity of feed gases. The cathode of PEMFC is normally fed with air from the atmosphere containing certain impurities like CO2, NO2, and SO2, which are the major contaminants for the electrocatalysts used in the fuel cell, causing both reversible and irreversible damages. The irreversible effect is caused due to adsorption of impurities like SO2 on the conventionally used platinum catalyst supported on carbon (Pt/C). It has been observed that carbon facilitates the absorption of SO2 on platinum. Hence, the present objective is to identify the catalysts containing no carbon and study their impurity tolerance in the fuel cell environment. In the present paper, we have attempted to synthesize unsupported mesoporous platinum by hard template method and studied its SO2 impurity tolerance at the cathode side for oxygen reduction reaction (ORR) for PEMFC application. The mesoporous platinum showed for a higher tolerance towards SO2 compared to its counterpart, viz., platinum black. Sulfur tolerance was evaluated by the sulfur coverage on the catalyst and its rate of recovery through electrochemical experiments. Mesoporous platinum has also exhibited a faster removal of adsorbed sulfur compared to the commercial microporous platinum black, revealing that the recovery is also fast comparatively for meso-structured platinum.

Reaction of aqueous ammonium sulfide on SiGe 25%

SiGe 25% substrates were treated with aqueous solutions of ammonium sulfide with and without added acid to understand the adsorption of sulfur on the surface. X-ray photoelectron spectroscopy showed no sulfide layer was deposited from aqueous (NH4)2S alone and instead both Si and Ge oxides formed during immersion in the sulfur solution. The addition of hydrofluoric and hydrochloric acids dropped the pH from 10 to 8 and deposited sulfides, yet increased the oxide coverage on the surface and preferentially formed Ge oxides. The sulfur coverage grew with increasing concentrations of acid in the aqueous (NH4)2S. The simultaneous deposition of O and S is suspected to be the result of oxidized sulfur species in solution. Metal-insulator-semiconductor capacitor (MISCAP) devices were fabricated to test the electrical consequences of aqueous ammonium sulfide wet chemistries on SiGe. MISCAPs treated with acidic ammonium sulfide solutions contained fewer interface defects in the valence band region. The defect density (Dit) was on the order of 10+12 cm–2 eV−1. The flat band voltage shift was lower after the acidic ammonium sulfide treatment, despite the presence of surface oxides. Adsorption of S and potentially O improved the stability of the surface and made it less electrically active.

Role of the Edge Properties in the Hydrogen Evolution Reaction on MoS2.

Molybdenum disulfide, in particular its edges, has attracted considerable attention as possible substitute for platinum catalysts in the hydrogen evolution reaction (HER). The complex nature of the reaction complicates its detailed experimental investigations, which are mostly indirect and sample dependent. Therefore, density functional theory calculations were employed to study how the properties of the MoS2 Mo-edge influence the thermodynamics of hydrogen adsorption onto the edge. The effect of the computational model (one-dimensional nanostripe), border symmetry imposed by its length, sulfur saturation of the edge, and dimensionality of the material are discussed. Hydrogen adsorption was found to depend critically on the coverage of extra sulfur at the Mo edge. The bare Mo-edge and fully sulfur-covered Mo-edge are catalytically inactive. The most favorable hydrogen binding towards HER was found for the Mo-edge covered by sulfur monomers. This edge provides hydrogen adsorption free energies positioned around -0.25 eV at up to 50 % hydrogen coverage, close to the experimental values of overpotential needed for the HER reaction.

Hydrogen adsorption on MoS2-surfaces: a DFT study on preferential sites and the effect of sulfur and hydrogen coverage.

We report a comprehensive computational study of the intricate structure-property relationships governing the hydrogen adsorption trends on MoS2 edges with varying S- and H-coverages, as well as provide insights into the role of individual adsorption sites. Additionally, the effect of single- and dual S-vacancies in the basal plane on the adsorption energetics is assessed, likewise with an emphasis on the H-coverage dependency. The employed edge/site-selective approach reveals significant variations in the adsorption free energies, ranging between ∼±1.0 eV for the different edges-types and S-saturations, including differences of even as much as ∼1.2 eV between sites on the same edge. The incrementally increasing hydrogen coverage is seen to mainly weaken the adsorption, but intriguingly for certain configurations a stabilizing effect is also observed. The strengthened binding is seen to be coupled with significant surface restructuring, most notably the splitting of terminal S2-dimers. Our work links the energetics of hydrogen adsorption on 2H-MoS2 to both static and dynamic geometrical features and quantifies the observed trends as a function of H-coverage, thus illustrating the complex structure/activity relationships of the MoS2 catalyst. The results of this systematical study aims to serve as guidance for experimentalists by suggesting feasible edge/S-coverage combinations, the synthesis of which would potentially yield the most optimally performing HER-catalysts.

Quantitative Differences in Sulfur Poisoning Phenomena over Ruthenium and Palladium: An Attempt To Deconvolute Geometric and Electronic Poisoning Effects Using Model Catalysts

Sulfur poisoning over noble-metal catalysts has traditionally been regarded as very complex and precluding from easy rational understanding, because of the problems of interference from using different supports, inability of controlling coverage due to nonuniform metal particle size, intrinsic size/shape effect of metal component, etc. Here, high-quality polyvinylpyrrolidone (PVP) polymer-supported ruthenium and palladium model nanocatalysts using without solid support are equivalently modified with preadsorbed mercaptoethanol over a range of surface concentrations in order to compare sulfur poisoning effects on the two important noble metals commonly used in industry. A typical consecutive hydrogenation reactions of alkyne to alkene and then to alkane is studied under mild reaction conditions in the liquid phase. The first stage alkyne hydrogenation is well-known to be surface insensitive, because of strong adsorption of alkyne on both metals. However, the second stage, surface-sensitive hydrogenation/isomerization of weakly adsorbed alkenes, is highly influenced by perturbations in metal surface electronic states induced by sulfur adsorbates. Using a combination of 13C NMR, Fourier transform infrared (FTIR) measurements of chemisorbed CO, kinetic products analysis and density functional theory (DFT) calculations, the electronic and geometric components of sulfur poisoning can be assigned in an almost-quantitative manner for the first time, over these two metal nanocatalysts. It is found that this sulfur adsorbate dwells preferentially on terrace sites for both metals at high coverage, causing deactivation by surface site blockage for the alkyne hydrogenation. The adsorbate can also deplete electron density from the metal surface (mixing with higher vacant band states of sulfur). As a result, reduction in adsorption strength for alkenes in the second-stage hydrogenation, leading to deactivation by electronic effects, is observed. This component is shown to contribute more significantly to the total deactivation for palladium (electron-rich metal) than ruthenium (electron-poor metal). At 60% sulfur coverage on Pd, the electronic contribution to surface adsorption can be totally cancelled out. This work clearly shows that the differing nature of metals can result in very different degrees of geometric and electronic deactivation upon sulfur adsorption over a size range of 2–3 nm without any interference from solid support, particle size/shape variations, giving important insights to developing more sulfur-tolerant catalysts in the future.

Thermodynamic complexity of sulfated zirconia catalysts

A series of sulfated zirconia (SZ) catalysts were synthesized by immersion of amorphous zirconium hydroxide in sulfuric acid of various concentrations (1–5N). These samples were fully characterized by X-ray diffraction (XRD), thermogravimetric analysis and mass spectrometry (TGA-MS), and aqueous sulfuric acid immersion and high temperature oxide melt solution calorimetry. We investigated the enthalpies of the complex interactions between sulfur species and the zirconia surface (ΔHSZ) for the sulfated zirconia precursor (SZP), ranging from −109.46±7.33 (1N) to −42.50±0.89 (4N) kJ/mol S. ΔHSZ appears to be a roughly exponential function of sulfuric acid concentration. On the other hand, the enthalpy of SZ formation (ΔHf), becomes more exothermic linearly as sulfur surface coverage increases, from −147.90±4.16 (2.14nm−2) to −317.03±4.20 (2.29nm−2) kJ/mol S, indicating formation of energetically more stable polysulfate ​species.

Dynamics of 2D adislands formed by sulfur adsorption on an O/Cu(110) nanotemplate: an STM study

We report on the stability of large sulfur islands, formed by exposing the nanostructured O/Cu(110) surface to H2S. We have found that these islands, composed of several hundreds of atoms, show a dynamic behavior at room temperature and undergo both Smoluchowski and Ostwald ripening. An additional decay mechanism has been observed at sub-saturation sulfur coverages. The island decay can be described by a classical power law. However, oscillatory deviations from the model have been observed and possible reasons for their occurrence are discussed. At saturation sulfur coverage, the islands are still mobile and undergo ripening, but no decay is observed. In these conditions, a new nanostructured S/Cu(110) surface is formed.

Estimating Symbiont Abundances and Gill Surface Areas in Specimens of the Hydrothermal Vent Mussel Bathymodiolus puteoserpentis Maintained in Pressure Vessels

The hydrothermal vent mussel Bathymodiolus puteoserpentis hosts gill-associated sulfur- and methane-oxidizing bacteria which sustain host nutrition and allow it to reach high densities at various sites along the northern Mid-Atlantic Ridge. Previous studies have demonstrated that in similar dual symbioses, relative abundances of each bacterial type could change following variations in symbiont substrate availabilities. In this study, pressurized recovery and incubations in pressure vessels were used to test whether B. puteoserpentis symbionts displayed similar behavior in the presence of symbiont substrates. The relative abundances of both types of symbionts were analyzed using fluorescence in situ hybridization (FISH) and group-specific gene copy numbers were assessed using qPCR. Specimens sampled using isobaric and non-isobaric recovery contained similar relative proportions (in surface coverage) of sulfur- and methane-oxidizing bacteria indicating that recovery type did not have impact on measured relative areas. Similarly, pressurized incubations with different substrates did lead to significant differences in the relative surface coverage of the two types of bacteria, although slight variations were measured with qPCR, suggesting changes in relative abundances of gene copy numbers but not in relative areas covered. Total gill surface areas and total bacterial numbers in specimens were estimated for the first time. Symbiont bearing-mussels display exchange surfaces about 20-fold higher than those found in similar-sized coastal mussels, and mean bacterial numbers of 2.5*1012 per specimen were estimated. This emphasizes that symbiotic mussels are a major reservoir of bacteria in vent ecosystems.

Evaluation of Polycrystalline Platinum and Rhodium Surfaces for the Electro-Oxidation of Aqueous Sulfur Dioxide

Polycrystalline Rh and Pt were studied to ascertain their electrocatalytic activity for the electro-oxidation of SO2, an important reaction in sulfur dioxide depolarized electrolyzers used to produce hydrogen. Cyclic voltammetry and linear polarization methods were employed to evaluate the catalytic activity of these surfaces. Rh exhibited 25-fold lower catalytic activity than Pt and was more susceptible to poisoning by adsorbed intermediate sulfur species. Koutecky-Levich analysis indicated a two-electron transfer reaction on the Pt surface, which corresponded to the most commonly accepted SO2 electro-oxidation reaction mechanism. The Tafel slopes in the low potential region (near the onset potential), in conjunction with an analysis of well-known reaction mechanisms, suggested that the step leading to the oxidation of water to form adsorbed hydroxyl species was the rate-determining step (RDS). This mechanistic model predicts a decrease in Tafel slope with increasing coverage of catalyst active surface sites by adsorbed sulfur species. For Pt, we estimate a surface sulfur coverage of 4 % based on the experimentally measured Tafel slope. In the case of Rh, the sulfur coverage was calculated to be approximately 1 %. The Tafel slopes obtained changed from 106 mV decade−1 for Rh and 80 mV decade−1 for Pt at potentials below 0.7 V vs. standard hydrogen electrode (SHE) to 210 mV decade−1 for Rh and 162 mV decade−1 for Pt at potentials above 0.7 V vs. SHE, suggesting a change in the reaction mechanism corresponding to a change in the surface of the electrocatalyst.

Long-Range Displacive Reconstruction of Au(110) Triggered by Low Coverage of Sulfur

We propose a new model for the c(4 × 2) phase of sulfur adsorbed on Au(110). This is a reconstruction achieved by short-range rearrangements of Au atoms that create a pseudo-4-fold-hollow (p4fh) site for adsorbed sulfur. The model is based partly upon the agreement between experimental STM images and those predicted from DFT, both within c(4 × 2) domains and at a boundary between two domains. It is also based on the stability of this structure in DFT, where it is not only favored over the chemisorbed phase at its ideal coverage of 0.25 ML, but also at lower coverage (at T = 0 K). This is compatible with the fact that in experiments, it coexists with 0.06 ± 0.03 ML of sulfur chemisorbed on the (1 × 2) surface. The relative stability of the c(4 × 2) phase at 0.25 ML has been verified for a variety of functionals in DFT. In the chemisorbed phase, sulfur adsorbs at a pseudo-3-fold-hollow (p3fh) site near the tops of rows in the (1 × 2) reconstruction. This is similar to the fcc site on an extended (111) surface. Sulfur causes a slight separation between the two topmost Au atoms, which is apparent both in STM images and in DFT-optimized structures. The second-most stable site is also a p3fh site, similar to an hcp site. DFT is used to construct a simple lattice gas model based on pairs of excluded sites. The set of excluded sites is in good qualitative agreement with our STM data. From DFT, the diffusion barrier of a sulfur atom is 0.61 eV parallel to the Au row, and 0.78 eV perpendicular to the Au row. For the two components of the perpendicular diffusion path, that is, crossing a trough and hopping over a row, the former is considerably more difficult than the latter.

Thermodynamics of sulfur poisoning in solid oxide fuel cells revisited: The effect of H2S concentration, temperature, current density and fuel utilization

Thermodynamics of sulfur poisoning in SOFCs is revisited in the present study, aiming at contributing to the understanding of the effects of different operating parameters on deactivation by sulfur. Ni–S Gibbs energy diagram shows that, whenever sulfur chemical potential is increased, the catalyst poisoning becomes greater, due to increase in nickel sulfide activity, which is a strictly increasing function of sulfur coverage on Ni surface. For studying current density effect, simulations are carried out in the range of 0 (OCV) – 1 A cm−2, at 1123 K, considering methane as a fuel. At 10 ppm H2S, an increase in current density from 0 (OCV) to 0.5 A cm−2 results in a slight increase in the nickel sulfide activity from 3.0 × 10−6 to 1.2 × 10−5; however, at 1 A cm−2, nickel sulfide activity is 25.000 times higher than at 0.5 A cm−2. At 1 A cm−2, H2 and CO are almost entirely converted to H2O and CO2 by electrochemical reaction. Therefore, the effect of current density becomes remarkable when fuel utilization approaches 100%. These theoretical findings are corroborated by the recent experimental evidences related to the detrimental influence of current density on SOFC performance during sulfur poisoning.

Hydrogen Activation on the Promoted and Unpromoted ReS2 (001) Surfaces under the Sulfidation Conditions: A First-Principles Study

Hydrogen activation on the promoted and promoter-free ReS2(001) surfaces under the sulfidation conditions is studied by means of periodic density function theory (DFT) calculations within the generalized gradient approximation. First, surface-phase diagrams are investigated by plotting the surface free energy as a function of the chemical potential of S (μS) on the unpromoted and promoted ReS2 (001) surfaces with different loadings of nickel, cobalt, tungsten, and tantalum. The results show that on the unpromoted surface sulfur coverage of 25% and on the promoted surfaces sulfur coverage of 25% as well as 25% promoter modification are the most stable conditions, respectively, under hydrodesulfurization (HDS) reaction conditions. Second, hydrogen adsorption and dissociation are explored on these preferred surfaces. It is found that hydrogen adsorbs weakly on all the surfaces studied. The physical adsorption character makes its diffusion favorable, resulting in various adsorption sites and dissociation path...

Lifetime and Performance Prediction of SOFC Anodes Operated with Trace Amounts of Hydrogen Sulfide

Chemical degradation of Solid Oxide Fuel Cell (SOFC) anodes can be caused by various types of impurities present in practical fuels, as e.g. sulfur, chlorine, phosphorus and siloxane. To allow for a deeper understanding of the processes leading to sulfur poisoning, this study presents a modeling work of SOFC operating on H2/H2O and CH4/H2/H2O gas mixtures with different hydrogen sulfide (H2S) concentrations. In order to interpret experimental measurements, an elementary kinetic model is developed comprising a detailed multi‐step reaction mechanism of sulfur formation and oxidation at Ni/YSZ anodes coupled with channel gas-flow, porous-media transport and elementary charge-transfer chemistry. A thermodynamic and kinetic data set of sulfur formation and oxidation is derived based upon various literature sources including a coverage-dependent description of the enthalpy of surface-adsorbed sulfur. Firstly, the developed model is validated against literature-based sulfur chemisorption isobars, and subsequently against electrochemical button-cell experiments displaying a significant influence of operation temperature and applied potential on cell performance and degradation. It is shown that sulfur surface coverage increases with increasing current density indicating a low sulfur oxidation rate. In order to gain for an advanced fundamental understanding of sulfur poisoning, sensitivity analyses towards total anode resistance and sulfur coverage for different operating conditions will be presented. Furthermore, the identified elementary sulfur poisoning reactions are used to extend an existing reaction mechanism for methane steam reforming which is then validated based upon a variety of electrochemical experiments. It is shown that atomically adsorbed sulfur significantly influences heterogeneous reforming chemistry, causing a substantial decrease in OCV. Under polarization, at constant current densities the cell voltage decreases in a non-linear way. After the removal of hydrogen sulfide from the feed gas the cell shows a faster recovery than in H2/H2O mixtures. In addition, numerical impedance simulations over a wide range of operating conditions were performed, which allows a physically-based assignment of observed gas concentration, heterogeneous chemistry and electrochemical processes.

Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

In recent years, there has been a growing interest in developing metal supported solid oxide fuel cells (MS-SOFCs). MS-SOFCs are interesting as they potentially offer some advantages compared to conventional electrode and electrolyte supported SOFCs, such as low materials cost, better thermal conductivity and ductility of the support. The two later aspects improve the shock resistance and lower internal gradients within the stacks. This enables fast start-up and provides higher tolerance towards operation under transient conditions that are particularly desirable for APU applications. Today’s commercially available and relevant SOFC fuels such as natural gas and diesel etc. contain trace amounts of sulfur. Thus, tolerance towards sulfur poisoning is desirable. Ceria and gadolinium doped ceria (GDC) have been reported in the literature to have a beneficial effect on the tolerance towards sulfur poisoning. The ceria can be incorporated as a Ni:GDC cermet anode, but also via infiltration of ceria and doped ceria into the conventional Ni:YSZ cermet anode. Both approaches have been reported to improve the tolerance towards sulfur poisoning [1-3]. In the present study we report the performance and sulfur tolerance of MS-SOFCs with two different microstructures of the support and the anode functional layer (AFL). The MS-SOFCs of the present study are based on ferritic stainless steel (FeCr) with an aimed operating temperature of 650ºC. This lower operating temperature compared to electrode and electrolyte supported SOFC (750ºC-850ºC) is expected to favor sulfur adsorption and hence increase the impact of sulfur poisoning. The AFL was infiltrated with Ni-GDC precursor solution and subsequent heat treated resulting in a nanostructured coating of the electrocatalyst. The two studied MS-SOFC single cells (active area 16 cm2) have initial area specific resistances (ASR) at 650ºC of 0.35 Ωcm2 and 0.7 Ωcm2 respectively. It was found that the porosity of the support and the AFL seems to have a pronounced effect on the resulting performance. The MS-SOFCs were subjected to technologically relevant H2S concentrations of 2, 5 and 10 ppm in hydrogen fuel, during galvanostatic operation at a current load of 0.25 Acm-2. The results are illustrated and compared with the conventional SOFC Ni:YSZ cermet anode in figure 1, where the relative increase in anode polarization resistance as a function of Ni sulfur coverage is shown. The comparison indicate the MS-SOFC anode of the present study to be more tolerant towards sulfur poisoning than the conventional Ni:YSZ cermet anode. [1] K. Sasaki et al., J. Electrochem. Soc., 153, A2023–A2029 (2006). [2] L. Zhang et al., International Journal of Hydrogen Energy, 35, 12359–12368 (2010). [3] C. Xu, P. Gansor, J. W. Zondlo, K. Sabolsky, and E. M. Sabolsky, J. Electrochem. Soc., 158, B1405–B1416 (2011). Figure 1

Lifetime and Performance Prediction of SOFC Anodes Operated with Trace Amounts of Hydrogen Sulfide

An elementary kinetic model is developed to predict the influence of sulfur on Ni/YSZ anodes of solid oxide fuel cells (SOFC) performance. A multi-step reaction mechanism describing the formation and oxidation of sulfur on the Ni surface is coupled with gas transport in the channel and porous phase, and charge-transfer processes. A thermodynamic and kinetic data set of sulfur formation and oxidation is derived based upon various literature sources including a coverage-dependent description of the enthalpy of surface-adsorbed sulfur. The validity of the model is demonstrated on two SOFC operation modes, namely H2/H2O/H2S and CH4/H2/H2O/H2S fuel mixtures, at different operating conditions using various electrochemical literature experiments. The first concern is the influence of adsorbed sulfur on charge-transfer processes and the second concern is the effect of adsorbed sulfur on complex methane reforming chemistry. The results reveal that sulfur surface coverage increases with current density demonstrating a low sulfur oxidation rate.

Adsorption and Dissociation of H2O on Monolayered MoS2 Edges: Energetics and Mechanism from ab Initio Simulations

The dissociation of water on 2D monolayer molybdenum disulfide (MoS2) edges was studied with density functional theory. The catalytically active sites for H2O, H, and OH adsorption on MoS2 edges with 0% (Mo-edge), 50% (S50-edge), and 100% (S100-edge) sulfur coverage were determined, and the Mo-edge was found to be the most favorable for adsorption of all species. The water dissociation reaction was then simulated on all edges using the climbing image nudged elastic band (CI-NEB) technique. The reaction was found to be endothermic on the S100-edge and exothermic for the S50- and Mo-edges, with the Mo-edge having the lowest activation energy barrier. Water dissociation was then explored on the Mo-edge using metadynamics biased ab initio molecular dynamics (AIMD) methods to explore the reaction mechanism at finite temperature. These simulations revealed that water dissociation can proceed by two mechanisms: the first by splitting into adsorbed OH and H species produced a particularly small activation free en...

Tuning self-organized O/Cu(110) nanostructures by co-adsorption of sulfur

Abstract A method for tuning the nanostructures formed by self-organized growth of oxygen on Cu(110) surface is proposed. It is shown that the range of possible nanostructures, consisting in alternating stripes of bare and oxidized copper, can largely be extended by the co-adsorption of sulfur. The classical Marchenko–Vanderbilt model describing the nanostructuration was generalized in order to take into account the change in the surface properties induced by the presence of sulfur. This modified model enabled us to infer the expressions of the periodicity and width of the self-organized stripes as a function of the sulfur and oxygen coverages.

Oxide incorporation into Ni-based solid oxide fuel cell anodes for enhanced sulfur tolerance during operation on hydrogen or biogas fuels: A comprehensive thermodynamic study

The effect of the incorporation of oxides (CeO2, CaO, MgO, SrO, BaO) into SOFC anodes on sulfur poisoning of Ni catalysts is investigated by means of a comprehensive thermodynamic study. The results demonstrate that sulfur chemical potential controls the value of bulk nickel sulfide activity, which, in turn, is a function of sulfur coverage on Ni surface. It is found that oxide incorporation into anodes can reduce the sulfur chemisorption on Ni by lowering the sulfur chemical potential. BaO incorporation may be the best option for IT-SOFCs. The strong affinity of BaO towards sulfur significantly reduces the sulfur coverage on Ni surface, from values in the range of 0.91–0.96 to 0.54–0.58, for wet hydrogen atmosphere, in such a way that catalyst poisoning can be completely prevented. In situ regeneration of BaO could occur by means of a local reaction between BaS and OH species that are generated by dissociative chemisorption of H2O. The highest H2S concentration allowed in a BaO-modified anode depends on fuel composition: 100 ppm for wet hydrogen (3%H2O), and 30–45 ppm for biogas, varying according to CH4/CO2 molar ratio. In the case of biogas, enhanced sulfur tolerance can be achieved provided that the BaCO3 phase cannot be formed. For modified and unmodified anodes, the degree of sulfur poisoning was found to decrease with increasing CH4/CO2 molar ratio in biogas. Although ceria can effectively suppress carbon deposition due to oxygen storage capacity, it cannot alleviate sulfur poisoning of Ni under carbon-free conditions. At carbon deposition boundary, ceria increases the tolerance toward H2S in the biogas only modestly.

Promoted RhPt bimetallic catalyst supported on δ-Al2O3 and CeO2–ZrO2 during full-scale autothermal reforming for automotive applications: Post-mortem characterization

The influence of sulfur and coke formation on the steam reforming of diesel was evaluated for two promoted RhPt bimetallic catalysts, composed of 1:1 Rh:Pt/10:10 La2O3: CeO2/ δ-Al2O3 (CAT 1) and 1:1 Rh:Pt/4:5 MgO: Y2O3/CeO2−ZrO2 (CAT 2). The intrinsic activity is related to the total Rh and Pt area observed after the exposure to sulfur. Therefore, the degree of deactivation is related to the amount of sulfur deposited on the active metal sites. Sulfur analysis on the aged catalyst washcoat showed a decreasing sulfur concentration in the axial direction of the reformer. The estimated sulfur coverage related to metal surface area after 40h on stream reached values of 0.145 in CAT 2, below the equilibrated sulfur coverage of 0.19 after tests with DIN 590. Thus, showing a partial deactivation due to sulfur poisoning. Further catalyst characterization on carbon deposits and thermal aging was performed by TPO, TGA, BET, CO chemisorption, and TEM analysis.