Water-gas shift reaction over magnesia-modified Pt/CeO2 catalysts

Fuel cells have risen as a clean technology for power generation and much effort has been done for converting renewable feedstock in hydrogen. The water-gas shift reaction (WGS) can be applied aiming at reducing the CO concentration in the reformate. As Pt/CeO₂ catalysts have been pointed out as an alternative to the industrial WGS catalysts, the modification of such systems with magnesium was investigated in this work. It was shown that the addition of MgO to Pt/CeO₂ increased the activity and stability of the catalyst irrespective of the preparation method used, either impregnation or co-precipitation. Based on TPR and IR spectroscopy experiments, it was seen that the presence of magnesium improved ceria reduction favoring the creation of OH groups, which are considered the active sites for the WGS reaction. The evolution of the surface species formed under reaction conditions (CO, H₂O, H₂) observed by DRIFTS evidenced that the formation of formate species and the generation of CO₂ is closely attached to each other; under a reaction stream containing hydrogen the presence of formate species showed to be more relevant while the CO₂ formation was hindered. It is suggested that the addition of MgO favors the formate decomposition and lower the carbonate concentration on the catalyst surface during WGS reaction.     

H2 production from a single stage water–gas shift reaction over Pt/CeO2, Pt/ZrO2, and Pt/Ce(1−x)Zr(x)O2 catalysts

To develop a single stage water–gas shift reaction (WGS) catalyst for compact reformers, Pt/CeO₂, Pt/ZrO₂, and Pt/Ce_(1−x)Zr_(x)O₂ catalysts have been applied for the target reaction. The CeO₂/ZrO₂ ratio was systematically varied to optimize Pt/Ce_(1−x)Zr_(x)O₂ catalysts. Pt/CeO₂ showed the highest turnover frequency (TOF) and the lowest activation energy (E_a) among the catalysts tested in this study. It has been found that the reduction property of the catalyst is more important than the dispersion for a single stage WGS. Pt/CeO₂ catalyst also showed stable catalytic performance. Thus, Pt/CeO₂ can be a promising catalyst for a single stage WGS for compact reformers.     

High stability and activity of Pt electrocatalyst on atomic layer deposited metal oxide/nitrogen-doped graphene hybrid support

A novel nanostructured support of ZrO₂/nitrogen-doped graphene nanosheets (ZrO₂/NGNs) hybrid was synthesized successfully by atomic layer deposition (ALD) technology to significantly improve the activity and stability of Pt electrocatalyst. Electrochemical test shows that Pt–ZrO₂/NGNs catalyst has 2.1 times higher activity towards methanol oxidation reaction (MOR) than Pt/NGNs catalyst, due to the promotion by ZrO₂ to the MOR on Pt surface. Pt–ZrO₂/NGNs catalyst has higher electrochemical surface area (ECSA) and better oxygen reduction reaction (ORR) activity than Pt/NGNs catalyst. Pt–ZrO₂/NGNs catalyst has also demonstrated 2.2 times higher durability than that of Pt/NGNs. The enhanced activity and durability were attributed to the unique triple-interaction of ZrO₂–Pt–NGNs. These findings indicate that metal oxide-metal-support is a promising catalyst structure for low temperature fuel cells.     

Effect of the CeO2 synthesis method on the behaviour of Pt/CeO2 catalysis for the water-gas shift reaction

A comparative study of three different ceria synthesis procedures (template- and MW- assisted hydrothermal synthesis and urea homogeneous precipitation) is reported in this paper. The obtained materials were employed as supports for Pt nanoparticles, and the Pt/CeO₂ catalysts were evaluated in the WGS reaction under model and realistic conditions. The influence of the support, e.g., its morphology and electronic properties, has been studied in detail by means of XRD, H₂-TPR, XPS, UV–Vis spectroscopy and toluene hydrogenation (for metal dispersion assessment). The catalytic performance of the samples is directly correlated with the modification of the electronic properties, as a result of the preparation method used. The conventional homogeneous precipitation method with urea resulted to be the best option, leading to enhanced ceria reducibility and adequate Pt dispersion, which in turns resulted in a very efficient WGS catalyst.     

A highly dispersed Pt/γ-Al2O3 catalyst prepared via deposition–precipitation method for preferential CO oxidation

Highly dispersed Pt/γ-Al₂O₃ catalysts were prepared by deposition–precipitation (DP) method with precursor solutions of various pH. The pH was controlled from 6.5 to 9.5 with 5 wt% NaOH solution. As the pH of precursor solution increases over pH 7.5, the metal dispersion and surface PtO_x species decrease and the Pt particle size increases. PrOx test was carried out with a space velocity of 60,000 mL/h g_cat in temperature ranges from 100 to 200 °C. The [O₂]/[CO] ratio was adjusted between 1 and 2 and the effect of H₂O and CO₂ was examined at [O₂]/[CO] = 2. It is interesting that the CO conversion has good agreement with the Pt metal dispersion. In addition, highly dispersed Pt/γ-Al₂O₃ catalyst prepared by DP with pH 7.5 exhibited good catalytic activity below 150 °C in PrOx due to the improvement of the metal dispersion and reducibility of surface PtO_x species at low temperatures compared with the catalyst prepared by impregnation method.     

The effect of impregnation strategy on methane dry reforming activity of Ce promoted Pt/ZrO2

Dry reforming of methane has been studied over Pt/ZrO₂ catalysts promoted with Ce for different temperatures and feed compositions. The influence of the impregnation strategy and the cerium amount on the activity and stability of the catalysts were investigated. The results have shown that introduction of 1 wt.% Ce to the Pt/ZrO₂ catalyst via coimpregnation method led to the highest catalytic activity and stability. 1 wt.%Ce–1 wt.%Pt/ZrO₂ catalyst prepared by sequential impregnation displayed inferior CH₄ and CO₂ conversion performances with lowest H₂/CO production ratios. 1 wt.%Ce–1 wt.%Pt/ZrO₂ catalyst prepared by coimpregnation showed the highest activity even for the feed with high CH₄/CO₂ ratio. The reason for high activity was explained by the intensive interaction between Pt and Ce phases for coimpregnated sample, which had been verified by X-ray photoelectron spectroscopy and Energy Dispersive X-Ray analyses. Strong and extensive Pt–Ce surface interaction results in an increase in the number of Ce³⁺ sites and enhances the dispersion of Pt.     

Hydrogen production by steam reforming of ethanol over mesoporous Ni–Al2O3–ZrO2 aerogel catalyst

A mesoporous Ni–Al₂O₃–ZrO₂ aerogel (Ni–AZ) catalyst was prepared by a single-step epoxide-driven sol–gel method and a subsequent supercritical CO₂ drying method. For comparison, a mesoporous Al₂O₃–ZrO₂ aerogel (AZ) support was prepared by a single-step epoxide-driven sol–gel method, and subsequently, a mesoporous Ni/Al₂O₃–ZrO₂ aerogel (Ni/AZ) catalyst was prepared by an incipient wetness impregnation method. The effect of preparation method on the physicochemical properties and catalytic activities of Ni–AZ and Ni/AZ catalysts was investigated. Although both catalysts retained a mesoporous structure, Ni/AZ catalyst showed lower surface area than Ni–AZ catalyst. From TPR, XRD, and H₂–TPD results, it was revealed that Ni–AZ catalyst retained higher reducibility and higher nickel dispersion than Ni/AZ catalyst. In the hydrogen production by steam reforming of ethanol, both catalysts showed a stable catalytic performance with complete conversion of ethanol. However, Ni–AZ catalyst showed higher hydrogen yield than Ni/AZ catalyst. Superior textural properties, high reducibility, and high nickel surface area of Ni–AZ catalyst were responsible for its enhanced catalytic performance in the steam reforming of ethanol.     

Oxidative steam reforming of methanol over CuO/ZnO/CeO2/ZrO2/Al2O3 catalysts

The composition (CuO/ZnO/Al₂O₃ = 30/60/10) of a commercial catalyst G66B was used as a reference for designing CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts for the oxidative (or combined) steam reforming of methanol (OSRM). The effects of Al₂O₃, CeO₂ and ZrO₂ on the OSRM reaction were clearly identified. CeO₂, ZrO₂ and Al₂O₃ all promoted the dispersions of CuO and ZnO in CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts. Aluminum oxide lowered the reducibility of the catalyst, and weakened the OSRM reaction. Cerium oxide increased the reducibility of the catalyst, but weakened the reaction. Zirconium oxide improved the reducibility of the catalyst, and promoted the reaction. A lower CuO/ZnO ratio of the catalyst was associated with greater promotion of ZrO₂. The critical CuO/ZnO ratio for the promotion of ZrO₂ was approximately 0.75–0.8. Introducing of ZrO₂ into CuO/ZnO/Al₂O₃ also improved the stability of the catalyst. Although Al₂O₃ inhibited the OSRM reaction, a certain amount of it was required to ensure the stability and the mechanical strength of the catalysts.     

Comparative study on the promotion effect of Mn and Zr on the stability of Ni/SiO2 catalyst for CO2 reforming of methane

The stability of Mn-promoted Ni/SiO₂ catalyst for methane CO₂ reforming was investigated comparatively to that of Zr-promoted Ni/SiO₂. The catalysts were prepared by the same impregnation method with the same controlled promoter contents and characterized by TPR, XRD, TG, SEM, XPS and Raman techniques. The addition of Mn to Ni/SiO₂ catalyst promoted the dispersion of Ni species, leading to smaller particle size of NiO on the fresh Ni–Mn/SiO₂ catalyst and the formation of NiMn₂O₄, which enhanced the interaction of the modified support with Ni species. Thus, the Ni–Mn/SiO₂ catalyst showed higher activity and better ability of restraining carbon deposition than Ni/SiO₂ catalyst. Besides, it exhibited stable activity at reaction temperatures over the range from 600 °C to 800 °C. However, the introduction of Zr increased the reducibility of Ni–Zr/SiO₂, and the catalyst deactivated much more dramatically when the reaction temperature decreased due to its poor ability of restraining carbon deposition, and its activity decreased monotonically with time on stream at 800 °C.     

Si-modified Pt/CeO2 catalyst for a single-stage water-gas shift reaction

Si-modified Pt/CeO₂ catalysts were prepared for a water-gas shift (WGS) reaction and the effects of this silica addition on the textural and structural characteristics, reducibility and WGS reaction performance of Pt/CeO₂ were investigated. The surface areas of the prepared catalysts increased and both interplanar spacing and average crystalline size of ceria gradually decreased with Si content, resulting in less crystalline and smaller particles. Si addition up to 20 wt. % facilitated the bulk reduction of ceria by inducing significant hydrogen consumption. The oxygen defects in the support, associated with lower valence state cerium, increased with the Si addition. These modifications offer a promising potential to increase the density of hydroxyl groups on the surface of the ceria and consequently increase the concentration of surface intermediate species. The addition of Si to ceria improved the catalytic performance for the WGS reaction, in spite of its irreducible nature. Pt catalysts supported on Si-modified ceria, with a Si content of 5-10 wt.%, exhibited a 2.5-fold increase in reaction rate and turnover frequency (TOF) compared to that of Pt/CeO₂.     

Synthesis, characterization and electrocatalytical behavior of Nb-TiO2/Pt nanocatalyst for oxygen reduction reaction

In order to point out the effect of the support to the catalyst for oxygen reduction reaction nano-crystalline Nb-doped TiO₂ was synthesized through a modified sol-gel route procedure. The specific surface area of the support, S_BET, and pore size distribution, were calculated from the adsorption isotherms using the gravimetric McBain method. The support was characterized by X-ray diffraction (XRD) technique.The borohydride reduction method was used to prepare Nb-TiO₂ supported Pt (20 wt.%) catalyst. The synthesized catalyst was analyzed by TEM technique.Finally, the catalytic activity of this new catalyst for oxygen reduction reaction was investigated in acid solution, in the absence and the presence of methanol, and its activity was compared towards the results on C/Pt catalysts.Kinetic analysis reveals that the oxygen reduction reaction on Nb-TiO₂/Pt catalyst follows four-electron process leading to water, as in the case of C/Pt electrode, but the Tafel plots normalized to the electrochemically active surface area show very remarkable enhancement in activity of Nb-TiO₂/Pt expressed through the value of the current density at the constant potential.Moreover, Nb-TiO₂/Pt catalyst exhibits higher methanol tolerance during the oxygen reduction reaction than the C/Pt catalyst.The enhancement in the activity of Nb-TiO₂/Pt is consequence of both: the interactions of Pt nanoparticles with the support and the energy shift of the surface d-states with respect to the Fermi level what changes the surface reactivity.     

Nitrogen-doped carbon coated ZrO2 as a support for Pt nanoparticles in the oxygen reduction reaction

A new nitrogen-doped carbon (CN_x) support for Pt electrocatalysts was prepared by carbonizing polypyrrole on the surface of ZrO₂ (ZrO₂@CN_x) at high temperature. Well-dispersed Pt nanoparticles were easily formed on the ZrO₂@CN_x. The electrocatalyst was characterized by FT-IR, XRD, TEM, XPS. The electrochemical performances indicate that the presence of ZrO₂ modified the electro-structure of Pt on the catalyst surface and that ZrO₂@CN_x had superior oxygen reduction activity compared to a nitrogen-doped carbon coated carbon (C@CN_x).     

CeO2–ZrO2-promoted CuO/ZnO catalyst for methanol steam reforming

The Cu-based catalysts with different supports (CeO₂, ZrO₂ and CeO₂–ZrO₂) for methanol steam reforming (MSR) were prepared by a co-precipitation procedure, and the effect of different supports was investigated. The catalysts were characterized by means of N₂ adsorption–desorption, X-ray diffraction, temperature-programmed reduction, oxygen storage capacity and N₂O titration. The results showed that the Cu dispersion, reducibility of catalysts and oxygen storage capacity evidently influenced the catalytic activity and CO selectivity. The introduction of ZrO₂ into the catalyst improved the Cu dispersion and catalyst reducibility, while the addition of CeO₂ mainly increased oxygen storage capacity. It was noticed that the CeO₂–ZrO₂-containing catalyst showed the best performance with lower CO concentration, which was due to the high Cu dispersion and well oxygen storage capacity. Further investigation illuminated that the formation of CO on CuO/ZnO/CeO₂–ZrO₂ catalyst mainly due to the reverse water gas shift. In addition, the CuO/ZnO/CeO₂–ZrO₂ catalyst also had excellent reforming performance with no deactivation during 360 h run time and was used successfully in a mini reformer. The maximum hydrogen production rate in the mini reformer reached to 162.8 dm³/h, which can produce 160–270 W electric energy power by different kinds of fuel cells.     

Low-temperature water–gas shift reaction over supported Cu catalysts

The low-temperature water–gas shift (WGS) reaction has been carried out at a very high gas hourly space velocity (GHSV) of 36,201 h⁻¹ over supported Cu catalysts prepared by an incipient wetness impregnation method. The preparation method was optimized to get a highly active CeO₂ supported Cu catalyst for low-temperature WGS. Co-precipitated Cu–CeO₂ exhibited excellent catalytic performance as well as 100% CO₂ selectivity. The high activity and stability of co-precipitated Cu–CeO₂ catalyst is correlated to its easier reducibility, high surface area and the nano-sized CeO₂ with CuO species interacting with the support.     

Effect of oxygen addition on the water–gas shift reaction over Pt/CeO2 catalysts in microchannels – Results from catalyst testing and reactor performance in the kW scale

Wash-coated Pt/CeO₂, Pt/CeO₂/ZrO₂ and Pt/Cu/CeO₂ and Pt/CeO₂/Al₂O₃ based formulations were tested in sandwich type microreactors for water–gas shift (WGS) activity. At low reaction temperature of 260 °C, low conversion of carbon monoxide was initially observed which increased considerably upon the addition of air, a behaviour which was observed even after multiple cycles of start-up, operation with and without air and shut-down. At a higher reaction temperature of 400 °C air addition did not further improve the performance of the catalysts, which converted the carbon monoxide already close to equilibrium. One of the catalysts was incorporated into a larger reactor of kW scale and tested for its performance under conditions of WGS and oxygen enhanced WGS. The carbon monoxide conversion was increased by the air addition also on the larger reactor.     

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.     

A study on the stability of a NiO–CaO/Al2O3 complex catalyst by La2O3 modification for hydrogen production

This paper details the study of La₂O₃ modifications and their effect on the stability of a NiO–CaO/Al₂O₃ sorption complex catalyst used in the ReSER (reactive sorption enhanced reforming) process of hydrogen production. The La₂O₃-modified NiO–CaO/Al₂O₃ sorption complex catalyst was prepared by isometric impregnation. The microstructure, morphology and reducibility of the La₂O₃-modified sorption complex catalyst were characterized by means of BET, TEM, XRD and TPR. The stability of the catalyst used in the ReSER process was evaluated on a laboratory-scale fixed-bed reactor. Our results showed that modifying the sorption complex catalyst with La₂O₃ improved its stability up to 30 cycles of the ReSER process for hydrogen production, while only seven cycles were obtained without La₂O₃ modification. We showed that the source of the stability improvement that the La₂O₃ in the catalyst not only functioned to restrain the decrease of the support surface area and reduce the sintering of nano-CaCO₃, which could limit the decay of the sorption capacity and stability of the catalyst, but also increased the interaction between nickel oxide and the support, which improved the stability of the catalyst by increasing the dispersion of nickel grains and inhibited the growth of nickel grain size.     

Excellent dispersion and electrocatalytic properties of Pt nanoparticles supported on novel porous anatase TiO2 nanorods

We synthesize, for the first time, a new Pt based catalyst for direct methanol fuel cells using homemade novel porous anatase TiO₂ nanorods as a new catalyst support. Pt nanoparticles are prepared by an improved ethylene glycol reduction method and supported on the surface of TiO₂ with excellent dispersion and without any aggregates. The structure and elemental composition of the TiO₂ and Pt/TiO₂ catalyst are characterized by transmission electron micrography (TEM), nitrogen sorption, energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The electrocatalytic properties of the Pt/TiO₂ catalyst for methanol and carbon monoxide electro-oxidation reactions are investigated by cyclic voltammetry (CV) in an acidic medium. Apparent electrocatalytic activity for methanol electro-oxidation reaction, high carbon monoxide tolerance and good stability are all observed for the Pt/TiO₂ catalyst. These may be attributed to the excellent dispersion of the Pt nanoparticles and the special properties of the TiO₂ support. These results imply that this Pt/TiO₂ catalyst has promising potential applications in direct methanol fuel cells.     

Enhanced water-gas shift reaction performance of MOF-derived Cu/CeO2 catalysts for hydrogen purification

The water-gas shift (WGS) reaction has received renewed interest because it is one of the key reactions for producing hydrogen and renewable energy in contemporary technologies like fuel cells and bio-refineries. Catalysts play an important role in WGS reaction for achieving high CO conversion and hydrogen generation activity. Thus, the performance and stability of catalysts are vital for the WGS reaction. In the present work, the CuCe metal-organic framework (MOF) is used as a template to derive the nanostructured Cu/CeO₂ catalyst. The influence of CuCe-MOF templated approach on the WGS activity of Cu/CeO₂ has been established. Different Cu doping levels had a significant impact on WGS activity. Amongst, the Ce_0.8Cu_0.2O₂ (Cu2Ce) catalyst had a highest CO conversion (96%). The long-term stability tests further prove that the Cu2Ce catalyst had maintained high CO conversion over 100 h reaction time. XRD and TEM results suggest that different loadings of Cu content have a distinct impact on the dispersion of Cu and the catalytic properties. N₂O chemisorption results suggest that 20 wt.% of Cu loading resulted in high Cu dispersion (52%) compared to other loadings. The H₂-temperature programmed reduction (TPR) revealed that the superior catalytic activity of Cu2Ce catalyst could be attributed to the strong reducibility (i.e. lower redox temperature) derived from CuCe-MOF template. It further suggests well-dispersed copper oxide species at low Cu loadings and crystalline copper oxide species at high Cu loadings. This work emphasizes the significance of Cu/CeO₂ catalysts with exceptional catalytic activity and stability for the WGS process with MOF-precursor.     

Hydrogen production by auto-thermal reforming of ethanol over nickel catalyst supported on metal oxide-stabilized zirconia

Metal oxide-stabilized mesoporous zirconia supports (M–ZrO₂) with different metal oxide stabilizer (M = Zr, Y, La, Ca, and Mg) were prepared by a templating sol–gel method. 20 wt% Ni catalysts supported on M–ZrO₂ (M = Zr, Y, La, Ca, and Mg) were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. The effect of metal oxide stabilizer (M = Zr, Y, La, Ca, and Mg) on the catalytic performance of supported nickel catalysts was investigated. Ni/M–ZrO₂ (M = Y, La, Ca, and Mg) catalysts exhibited a higher catalytic performance than Ni/Zr–ZrO₂, because surface oxygen vacancy of M–ZrO₂ (M = Y, La, Ca, and Mg) and reducibility of Ni/M–ZrO₂ (M = Y, La, Ca, and Mg) were enhanced by the addition of lower valent metal cation. Hydrogen yield over Ni/M–ZrO₂ (M = Zr, Y, La, Ca, and Mg) catalyst was monotonically increased with increasing both surface oxygen vacancy of M–ZrO₂ support and reducibility of Ni/M–ZrO₂ catalyst. Among the catalysts tested, Ni catalyst supported on yttria-stabilized mesoporous zirconia (Ni/Y–ZrO₂) showed the best catalytic performance.