Correlation between CO surface coverage and selectivity/kinetics for the preferential CO oxidation over Pt/γ-Al2O3 and Au/α-Fe2O3: an in-situ DRIFTS study

We present in-situ IR (DRIFTS) measurements on CO adsorption and preferential CO oxidation (PROX) in H₂-rich gas on Pt/γ-Al₂O₃ and Au/α-Fe₂O₃ catalysts at their envisaged operating temperatures of 200°C and 80°C, respectively, which in combination with kinetic data show that the underlying reason for the very different PROX reaction kinetics on these two catalysts is the difference in steady-state CO coverage. Whereas on the platinum catalyst this is always near saturation under reaction conditions, causing a negative reaction order (−0.4) and a p_CO-independent selectivity, the amount of adsorbed CO on the gold particles (indicated by an IR band at ∼2110 cm⁻¹) strongly depends on the CO partial pressure. From the position of the IR band of CO adsorbed on Au/α-Fe₂O₃, the steady-state coverages on the Au surface are shown to be significantly below saturation, with an upper limit of approximately θ_CO=0.2. Low reactant surface concentrations on Au explain the positive reaction order with respect to p_CO (+0.55 at 80°C) as well as the observed decoupling of the CO and H₂ oxidation rates, which results in a loss of selectivity with decreasing p_CO.     

Tungsten carbide as supports for Pt electrocatalysts with improved CO tolerance in methanol oxidation

One anti-CO-poisoning Pt-WC/C catalyst for methanol electro-oxidation is prepared in this work, through depositing platinum on tungsten carbide support using an intermittent microwave heating (IMH) method. The catalyst presents an improved methanol oxidation performance evidenced by a negative shift in onset potential, and increase of peak current density, compared with a commercial Pt/C one. CO stripping experiments indicate that the adsorbed CO is able to be oxidized and removed from the Pt-WC/C catalyst more easily, attesting the enhanced capability of anti-poisoning to CO-like species. Theoretical calculation further provides evidence that the surface electronic structure in Pt-WC/C and Pt/C catalysts is likely different. WC supports could lead to much stronger negative electronic property, which is beneficial for avoiding CO adsorption on the Pt-WC/C catalyst. In the mean time, the electron donating effect generated by WC supports also promotes the ability to oxidize the adsorbed CO-like species on catalysts. In good agreement with experimental results, the theoretical calculation proves the anti-CO-poisoning nature of the Pt-WC/C catalyst, and well explains the origin of the improvement in the electrochemical catalytic performance for effectively accelerating the oxidation of CO to CO₂ in methanol oxidation.     

Cooperative effect of Pt and Cu on CeO2 for the CO-PROX reaction under CO2–H2O feed stream

Catalyst improvement for the preferential oxidation of CO (CO-PROX) is essential in developing efficient fuel cell technologies. Here, we investigate the promotion of the Cu/CeO₂ system with Pt, prepared by impregnation and alcohol-reduction methods, in the CO-PROX reaction under ideal and realistic feed compositions. The high Pt dispersion in PtCu/CeO₂ prepared by impregnation led to a CO conversion of 62% and CO₂ selectivity of 83% at 50 °C under a feed stream composed of H₂/CO/O₂, while monometallic Cu/CeO₂ and Pt/CeO₂ showed negligible activity at these conditions. By adding CO₂–H₂O to the feed stream, PtCu/CeO₂ catalysts prepared by both methods presented similar activity. The maximum CO conversion temperature was shifted to 100 °C. Under these conditions, Cu/CeO₂ was inactive, and Pt/CeO₂ showed identical conversion but lower CO₂ selectivity. In-situ XANES revealed that fast oxidation of Cu species at low temperatures is responsible for Cu/CeO₂ deactivation, while preferential adsorption of CO on Pt⁰ sites in PtCu/CeO₂ avoided deactivation. The use of deactivation-resistant Pt sites as complimentary sites for CO activation associated with improved oxygen mobility over Cu–CeO₂ surface proved to be an effective strategy for CO-PROX under H₂O/CO₂ feed stream at low temperatures.     

Biohydrogen production by gas phase reforming of glycerine and ethanol mixtures

In this paper the steam reforming of bioalcohols over Ni and Pt catalysts supported on bare Al₂O₃ and La₂O₃ and CeO₂-modified Al₂O₃ to produce H₂ was studied. Catalytic activity results showed that the glycerine and the intermediate liquid products may hinder the ethanol adsorption on metal active sites of the catalysts, especially at temperatures below 773 K. In fact, ethanol conversion was lower than glycerine conversion in the steam reforming reaction at low temperatures. H₂ chemisorption revealed that La₂O₃ doping of the Ni/Al₂O₃ catalyst improved the metal dispersion providing a better behaviour to the Ni/Al₂O₃-O2 catalyst towards H₂ production. In the case of Pt catalysts, the good reducibility and the H₂ spillover effect provided to the Pt/Al₂O₃-O1 catalyst the capacity to produce higher H₂ yields.     

Effect of CO and CO2 impurities on performance of direct hydrogen polymer-electrolyte fuel cells

Mechanisms by which trace amounts of CO and CO₂ impurities in fuel may affect the performance of direct hydrogen polymer-electrolyte fuel cell stacks have been investigated. It is found that the available data on CO-related polarization losses for Pt electrodes could be explained on the basis of CO adsorption on bridge sites, if the CO concentration is less than about 100 ppm, together with electrochemical oxidation of adsorbed CO at high overpotentials. The literature data on voltage degradation due to CO₂ is consistent with CO production by the reverse water–gas shift reaction between the gas phase CO₂ and the H₂ adsorbed on active Pt sites. The effect of oxygen crossover and air bleed in “cleaning” of poisoned sites could be modeled by considering competitive oxidation of adsorbed CO and H by gas phase O₂. A model has been developed to determine the buildup of CO and CO₂ impurities due to anode gas recycle. It indicates that depending on H₂ utilization, oxygen crossover and current density, anode gas recycle can enrich the recirculating gas with CO impurity but recycle always leads to buildup of CO₂ in the anode channels. The buildup of CO and CO₂ impurities can be controlled by purging a fraction of the spent anode gas. There is an optimum purge fraction at which the degradation in the stack efficiency is the smallest. At a purge rate higher than the optimum, the stack efficiency is reduced due to excessive loss of H₂ in purge gas. At a purge rate lower than the optimum, the stack efficiency is reduced due to the decrease in cell voltage caused by the excessive buildup of CO and CO₂. It is shown that the poisoning model can be used to determine the limits of CO and CO₂ impurities in fuel H₂ for a specified maximum acceptable degradation in cell voltage and stack efficiency. The impurity limits are functions of operating conditions, such as pressure and temperature, and stack design parameters, such as catalyst loading and membrane thickness.     

Modeling of bimetallic Pt-based electrocatalyst on extended-surface support for advanced hydrogen compression and separation

Electrochemical hydrogen compression (EHC) process can be used to purify and separate hydrogen from its mixtures. In this regards question of carbon monoxide (CO) tolerance of electrocatalyst, used in such a process (e.g., Pt), becomes extremely relevant. One of the approaches to increase CO tolerance is to add ruthenium metal to platinum electrocatalyst. Results of density functional theory modeling of CO adsorption on Pt–Ru alloy slabs and edges are presented in this paper. It was found that Pt₂Ru alloy has higher CO adsorption energy difference on Ru and Pt atoms, E_CO(Ru)–E_CO(Pt), than that of PtRu₂. Effect of contraction and stretching of support on CO adsorption was also investigated: stretching increases CO adsorption energy, while contraction has opposite effect. We also found that 110 surface and edges of electrocatalyst have higher CO adsorption energy than 111 surface. Finally, we considered an elementary nano-object of the modeled extended surface, whiskerette. Using molecular dynamics with Sutton-Chen potential, we simulated annealing of platinum whiskerette at 800 K and calculated trend of CO coverage: number of CO active sites increases with temperature, and after cooling, it does not reach the initial level.     

Effect of noble metal on oxidative steam reforming of methanol over CuO/ZnO/Al2O3 catalysts

Noble metals of Pd, Pt, Ru and Rh were introduced into the CuO/ZnO/Al₂O₃(30/60/10) catalyst via incipient impregnation and co-precipitation methods to examine their effects on the oxidative steam reforming of methanol (OSRM). No obvious effect of Pd and even a negative effect of Pt were observed by incipient impregnation method. With co-precipitation, noble metals were homogeneously dispersed in CuO/ZnO/Al₂O₃(30/60/10) and interacted with CuO and ZnO. They improved the reducibility of the catalysts and enhanced the dissociative adsorption of methanol. Introducing Pd, Rh or Ru promoted the conversion of methanol, but enhanced the formation of CO. Depositing platinum exhibited a high conversion of methanol and a low selectivity of CO in the OSRM reaction. The promoting effect of noble metals involved facilitating the split and adsorption of H atoms during the dehydrogenation of the intermediates in OSRM.     

Effect of magnesium on preferential oxidation of carbon monoxide on platinum catalyst in hydrogen-rich stream

The effects of magnesium on platinum catalyst used for the preferential oxidation of carbon monoxide for polymer electrolyte membrane fuel cell applications are investigated. The CO conversion and selectivity on Pt–Mg/Al₂O₃ for a H₂-rich stream are 93.1 and 62.0%, respectively, but only 70.2 and 46.89% on Pt/Al₂O₃. The superior activity of Pt–Mg/Al₂O₃ for the preferential oxidation of CO is due to an increase in the hydroxyl groups that results from an increase in basicity with the addition of Mg, as well as to an increase in the electron density on the surface of the Pt catalyst. Moreover, the content of hydroxyl groups on the Pt catalysts is promoted by water vapour.     

A comparative study of Ni catalysts supported on Al2O3, MgO–CaO–Al2O3 and La2O3–Al2O3 for the dry reforming of ethane

CO₂ utilization through the activation of ethane, the second largest component of natural and shale gas, to produce syngas, has garnered significant attention in recent years. This work provides a comparative study of Ni catalysts supported on alumina, alumina modified with CaO and MgO, as well as alumina modified with La₂O₃ for the reaction of dry ethane reforming. The calcined, reduced and spent catalysts were characterized employing XRD, N₂ physisorption, H₂-TPR, CO₂-TPD, TEM, XPS and TPO. The modification of the alumina support with alkaline earth oxides (MgO and CaO) and lanthanide oxides (La₂O₃), as promoters, is found to improve the dispersion of Ni, enhance the catalyst's basicity and metal-support interaction, as well as influence the nature of carbon deposition. The Ni catalyst supported on modified alumina with La₂O₃ exhibits a relatively stable syngas yield during 8 h of operation, while H₂ and CO yields decrease substantially for Ni/Al₂O₃.     

Pt-promoted α-Al2O3-supported Ni catalysts: Effect of preparation conditions on oxi-reduction and catalytic properties for hydrogen production by steam reforming of methane

The effect of Pt addition on the oxi-reduction properties of α-Al₂O₃-supported Ni catalysts, with different degrees of interaction between NiO and the α-Al₂O₃ support, was studied using atmospheres of H₂, H₂/H₂O, and CH₄/H₂O. The effect of Pt promotion on the reduction of NiO with H₂ was significant for NiO species that interacted more strongly with the alumina surface, but was much lower when a NiAl₂O₄-like bulk phase was formed. For samples activated with H₂, although metal dispersion decreased with increasing Pt content, the activity was maintained constant by the presence of Pt sites. For samples activated with a CH₄/H₂O mixture, the activity increased with increasing Pt content, due to the higher reducibility of Ni in the Pt-promoted catalysts. The Pt promotion effect was stable; there was no important decrease in the influence of Pt on NiO reduction, even after high temperature re-oxidation of the catalysts.     

Improved methane oxidation activity of P-doped γ-Al2O3 supported palladium catalysts by tailoring the oxygen mobility and electronic properties

Micro-mesoporous P-doped γ-Al₂O₃ with cluster morphology was obtained via an efficient ultrasound-assisted sol-gel process and taken as carrier to construct palladium catalysts for methane oxidation. It was revealed that the structure and properties of catalysts were significantly influenced by the phosphorus precursors with diverse valence and acidity. Dissimilar reducibility of surface hydroxyl and oxygen species is observed in the catalysts derived from different phosphorus sources, indicating the difference in the oxygen mobility and the capacity of the catalysts to convert intermediate CO. The behavior of charge-transfer transition and d-d transition, the transfer ability of electrons from palladium particles into the antibonding 2π* orbitals of CO, together with the surface acidity and electronic density of palladium species was likewise tailored, which demonstrated the metal-support interaction could be tuned, making palladium species behave with diverse status and electronic structures. The optimized properties cooperatively provided an enhancement in catalytic performance of P-containing catalysts.     

Ceria-promoted Ni@Al2O3 core-shell catalyst for steam reforming of acetic acid with enhanced activity and coke resistance

A series of Ni@Al₂O₃ core-shell catalysts with ceria added to the surface of Ni nanoparticles or inside the alumina shell were prepared, and the effect of ceria addition on the performance of the catalyst in the steam reforming of acetic acid was investigated. The prepared catalysts were characterized by BET, XRD, HRTEM, H₂-TPR and DTG. The addition of ceria to the surface of nickel nanoparticles greatly enhanced the activity of catalyst owing to the presence of the mobile oxygen, which migrated from the ceria lattice. Among the prepared catalysts, the Ni@Al10Ce catalyst showed the highest activity with a conversion of acetic acid up to 97.0% even at a low temperature (650 °C). The molar ratio of CO₂/CO was also improved due to the oxidation of CO by the mobile oxygen into CO₂. The coke formation on the core-shell catalysts was significantly inhibited by the addition of ceria to the surface of nickel nanoparticles due to the oxidation of carbon species by the mobile oxygen in the ceria lattice. However, the Ni@Al10Ce-a catalyst with ceria added to the alumina shell showed a low activity and the formation of a large amount of coke. It is suggested that only the ceria in close to the Ni surface has the promoting effect on the catalytic performance of the Ni@Al₂O₃ catalyst in the steam reforming of acetic acid.     

Carbon nanotube supported Pt-Ni catalysts for preferential oxidation of CO in hydrogen-rich gases

A series of carbon nano-tubes supported platinum-nickel catalysts were prepared and used for CO preferential oxidation in H₂-rich streams. The catalysts were characterized by using N₂-adsorption, XRD, HRTEM, H₂-TPD and H₂-TPR techniques. Effects of platinum and nickel loading amount, CO₂ and H₂O in the feed stream on the activity and selectivity over the catalysts were investigated. The results of catalytic performance tests show that the carbon nano-tubes supported Pt-Ni catalysts are very active and highly selective at low temperature for CO preferential oxidation in 1 vol. % CO, 1 vol. %O₂, 50 vol. % H₂ and N₂ gases. Adding 12.5 vol. % of CO₂ into the feed gases has slight negative influence on CO conversion. Adding 15 vol. % of H₂O leads to a little decrease of CO conversion at the temperature range of 100-120 °C, which is proposed to be caused by capillary wetting of water in the micro-pores of carbon nano-tubes. As the reaction temperature is higher, adding water can improve CO conversion. The characterization results indicate that platinum species are in nano-particles uniformly dispersed on the carbon nano-tubes surface. There are two kinds of nickel species, one is interacted with platinum and likely to form Pt-Ni alloy in reduction process, the other is much highly dispersed on carbon nano-tubes and strongly interacted with the supports. The high activity of the catalysts is attributed to the interaction between Pt and Ni with the formation of Pt-Ni alloy.     

Tuning activity of Pt/FeOx/TiO2 catalysts synthesized through selective-electrostatic adsorption for hydrogen purification by prox reaction

Hydrogen purification by removing CO traces was studied via the preferential CO oxidation (PROX) reaction using highly dispersed Pt catalysts supported on dual oxide FeO_x/TiO₂. These catalysts were prepared by the strong electrostatic adsorption (SEA) method by varying the pH of synthesis and the calcination temperature. By measuring the point of zero charge (PZC) of the support components, it was possible to determine the pH in which Pt can be selectively deposited onto one of the support components, obtaining Pt dispersion values above 90%. The selective SEA of a Pt precursor onto the co-support (FeO_x) was achieved at a synthesis pH between the PZCs of the support components (i.e., TiO₂ PZC = 5.2 and Fe₂O₃ PZC = 6.9) by using a Pt anionic complex. The catalytic activity for the PROX reaction, expressed in terms of the CO conversion, O₂ selectivity to CO₂, apparent activation energy, and turnover frequency, confirmed that the SEA prepared catalysts were active and selective for the PROX reaction. XPS and TPR results of the Pt/FeO_x/TiO₂ catalysts showed the formation of Pt-FeO_x interfaces, called as (Pt-FeO_x)_i interfacial sites, which enhanced the stability and catalytic activity for the PROX reaction. The concentration of these sites can be controlled by the synthesis conditions used, mainly pH and to a lower extent the calcination temperature.     

Catalytic behaviour of Mn2.94M0.06O4-δ (M=Pt,Ru and Pd) catalysts for low temperature water gas shift (WGS) and CO oxidation

Noble metal (Pt, Ru and Pd) substituted Mn₃O₄ catalysts have been synthesized in this work by a sonochemical route. The catalysts were characterised by XRD, XPS, TEM, H₂-TPR and BET surface area analyser and the activity of these catalysts was tested towards low temperature water gas shift reaction (WGS) and CO oxidation reaction. It was observed that these catalysts have the tetragonal crystalline structure of Mn₃O₄ and the average particle size was found in the range of 12 nm–22 nm. H₂-TPR results show that the strong metal support interaction between substituted metal and Mn₃O₄ leads to high reducibility and makes these catalysts active for WGS and CO oxidation. Pt substituted Mn₃O₄ showed higher activity towards WGS compared to other synthesized catalysts and 99.9% conversion was observed at 260 °C without methane formation. The activation energy of Mn_2.94Pt_0.06O_4-δ was found to be 59 ± 0.6 kJ/mol. DRIFTS analysis was carried out to propose the reaction mechanism for water gas shift and CO oxidation. Redox mechanism was hypothesized for WGS and used to correlate the experimental data over Pt substituted Mn₃O₄. Similarly, kinetic parameters were estimated based on Langmuir-Hinshelwood mechanism for CO oxidation over Pd substituted Mn₃O₄ which showed better activity compare to other synthesized catalysts and 99.9% conversion was observed at 175 °C. The activation energy was calculated from Arrhenius plot which was found to be 30 ± 0.4 kJ/mol.     

Electrospun nanofibrous Ni/LaAlO3 catalysts for syngas production by high temperature methane partial oxidation

Ni/Al₂O₃ catalysts have been widely used for methane reforming while the formation of NiAl₂O₄ with low reducibility reduces catalyst efficiency. La₂O₃ was used to promote the catalytic activity of Ni/Al₂O₃ catalysts through improving Ni dispersion. LaAlO₃ perovskite showed catalytic activity in methane coupling and also used as a catalyst support for methane reforming. This study systematically investigated the effect of La₂O₃ addition into Ni/Al₂O₃ catalysts and found the formation of LaAlO₃ perovskite played an important role, which requires high crystallization temperatures. The thermally-stable structure of nanofibrous catalysts was employed to develop high-performance Ni/LaAlO₃ catalysts. High calcination temperature resulted in the enhanced crystallinity of LaAlO₃ perovskite, improved Ni reducibility and strengthened catalyst/support interaction, which contributed to high catalytic performance during methane partial oxidation. The Ni/LaAlO₃ catalyst calcined at 1100 °C generated a CH₄ conversion of 91.2% during methane partial oxidation with H₂ and CO selectivities of 95.5% and 92.4%, respectively. It is because La₂O₃ addition into Ni/Al₂O₃ promoted Ni reduction via forming LaAlO₃. Therefore, an efficient and thermally-stable fibrous Ni/LaAlO₃ catalyst has been developed for high temperature methane partial oxidation.     

Methanation of CO2 over alumina supported nickel or cobalt catalysts: Effects of the coordination between metal and support on formation of the reaction intermediates

This study focused on the potential coordination between nickel or cobalt and alumina in Ni/Al₂O₃ and Co/Al₂O₃ catalysts and the impacts on their catalytic performances in methanation of CO₂. The results exhibited that Co/Al₂O₃ catalyst was far more active than Ni/Al₂O₃ catalyst, due to the varied reaction intermediates formed in methanation. The DRIFTS results of methanation of CO₂ exhibited that, over bare alumina, bicarbonate, formate and carbonate were the main intermediate species, which could be formed at even 80 °C. Over unsupported Ni catalyst, the formaldehyde species (H₂CO*) and CO* species were dominated. Over the Ni/Al₂O₃ catalyst, however, the reaction intermediates formed were determined by alumina and accumulated on surface of the catalysts. The coordination effects between nickel and alumina in Ni/Al₂O₃ were thus not remarkable in terms of enhancing catalytic activity when compared to that in Co/Al₂O₃ catalyst. Over unsupported Co catalyst and the bare alumina, the reaction intermediates formed were roughly similar. Nevertheless, the combination of Co and alumina in Co/Al₂O₃ catalyst could effectively facilitate the conversion of bicarbonate, formate and carbonate species. CO₂ could be activated over metallic cobalt sites, which could migrate and integrate with the hydroxyl group in alumina to form bicarbonate and further to formate and CO* species, and be further hydrogenated over cobalt sites to CH₄. Such a coordination between alumina and cobalt species promoted the catalytic performances.     

Low temperature CO oxidation and water gas shift reaction over Pt/Pd substituted in Fe/TiO2 catalysts

We demonstrate the activity of Ti_0.84Pt_0.01Fe_0.15O_2−δ and Ti_0.73Pd_0.02Fe_0.25O_2−δ catalysts towards the CO oxidation and water gas shift (WGS) reaction. Both the catalysts were synthesized in the nano crystalline form by a low temperature sonochemical method and characterized by different techniques such as XRD, FT-Raman, TEM, FT-IR, XPS and BET surface analyzer. H₂-TPR results corroborate the intimate contact between noble metal and Fe ions in the both catalysts that facilitates the reducibility of the support. In the absence of feed CO₂ and H₂, nearly 100% conversion of CO to CO₂ with 100% H₂ selectivity was observed at 300 °C and 260 °C respectively, for Ti_0.84Pt_0.01Fe_0.15O_2−δ and Ti_0.73Pd_0.02Fe_0.25O_2−δ catalyst. However, the catalytic performance of Ti_0.73Pd_0.02Fe_0.25O_2−δ deteriorates in the presence of feed CO₂ and H₂. The change in the support reducibility is the primary reason for the significant increase in the activity for CO oxidation and WGS reaction. The effect of Fe addition was more significant in Ti_0.73Pd_0.02Fe_0.25O_2−δ than Ti_0.84Pt_0.01Fe_0.15O_2−δ. Based on the spectroscopic evidences and surface phenomena, a hybrid reaction scheme utilizing both surface hydroxyl groups and the lattice oxygen was hypothesized over these catalysts for WGS reaction. The mechanisms based on the formate and redox pathway were used to fit the kinetic data. The analysis of experimental data shows the redox mechanism is the dominant pathway over these catalysts.     

Water–gas shift reaction over Pt and Pt–CeOx supported on CexZr1−xO2

The water–gas shift (WGS) reaction was examined over Pt and Pt–CeO_x catalysts supported on Ce_xZr_1−xO₂ (Ce_0.05Zr_0.95O₂, Ce_0.2Zr_0.8O₂, Ce_0.4Zr_0.6O₂, Ce_0.6Zr_0.4O₂, Ce_0.7Zr_0.3O₂ and Ce_0.8Zr_0.2O₂) under severe reaction conditions, viz. 6.7 mol% CO, 6.7 mol% CO₂, and 33.2 mol% H₂O in H₂. The catalysts were characterized with several techniques, including X-ray diffraction (XRD), CO chemisorption, temperature-programmed reduction (TPR) with H₂, temperature-programmed oxidation (TPO), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and bright-field transmission electron microscopy (TEM). Among the supported Pt catalysts tested, Pt/Ce_0.4Zr_0.6O₂ showed the highest WGS activity in all temperature ranges. An improvement in the WGS activity was observed when CeO_x was added with Pt on Ce_xZr_1−xO₂ supports (x = 0.05 and 0.2) due to intimate contact between Pt and CeO_x species. Based on CO chemisorptions and TPR profiles, it has been found that the interaction between Pt species and surface ceria-zirconia species is beneficial to the WGS reaction. A gradual decrease in the catalytic activity with time-on-stream was found over Pt and Pt–CeO_x catalysts supported on Ce_xZr_1−xO₂, which can be explained by a decrease in the Pt dispersion. The participation of surface carbonate species on deactivation appeared to be minor because no improvement in the catalytic activity was found after the regeneration step where the aged catalyst was calcined in 10 mol% O₂ in He at 773 K and subsequently reduced in H₂ at 673 K.