Preferential oxidation of carbon monoxide over Pt, Au monometallic catalyst, and Pt–Au bimetallic catalyst supported on ceria in hydrogen-rich reformate

The objective of this paper was to study a preferential oxidation (PROX) of carbon monoxide over monometallic catalysts including Pt, Au and Pt–Au bimetallic catalyst supported on ceria in hydrogen-rich reformate. Single step sol–gel method (SSG) and impregnation on sol–gel method (ISG) were chosen for the preparation of the catalysts. The characteristics of these catalysts were investigated by X-ray diffractometer (XRD), Brunauer–Emmet–Teller (BET) method, transmission electron microscope (TEM), scanning electron microscope (SEM) and temperature-programmed reduction (TPR). The XRD patterns of the catalysts showed only the peaks of ceria crystallite and no metal peak appeared. From TEM images, the active components were seen to be dispersed throughout the ceria support. The TPR patterns of PtAu/CeO₂ catalyst prepared by SSG showed the reduction peaks were within a low temperature range and therefore, the catalysts prepared by SSG exhibited excellent catalytic activity for preferential oxidation of CO. Bimetallic Pt–Au catalyst improved the activity (90% conversion and 50% selectivity at 90 °C) because of the formation of a new phase. When the metal content of (1:1) PtAu/CeO₂ catalyst prepared by SSG was increased, the CO conversion did not change much while the selectivity decreased in the low temperature range (50–90 °C). The CO conversion increased with increasing W/F ratio. The presence of CO₂ and H₂O had a negative effect on CO conversion and selectivity due to blocking of carbonate and water on active sites.     

Preferential oxidation of carbon monoxide in simulated reformatted gas over PtAu/CexZnyO2 catalysts

A series of Pt–Au catalysts prepared by co-precipitation (CP) and single step sol-gel (SSG) methods was investigated for selective CO oxidation. The characteristics of the prepared catalysts were determined by XRD, BET surface area, SEM, H₂-TPR, chemisorption analysis, and FTIR. The simulated reformatted gas consisted of 1% CO, 1% O₂, 0% to 10% H₂O, 0–20% CO₂, and 40% H₂ in He balance. The operating temperature range was varied from 50 °C to 190 °C at atmospheric pressure. The experimental results elucidated that the catalytic preparation method had a significant effect on the catalyst characteristics and its activity. The catalytic performance over PtAu/Ce₁Zn₁O₂ prepared by co-precipitation was higher than that of PtAu/CeO₂ and PtAu/ZnO because of the incorporation of Ce⁴⁺ ions and the Zn²⁺ ions in the lattice. To encourage better catalytic performance, the catalysts should be calcined at 500 °C for 5 h and pretreated in a H₂ atmosphere. The CO conversion for the single- and double-stage reaction was reduced when adding water vapor and CO₂ to the feedstream; the water vapor and CO₂ molecules compete for the adsorption with CO on the active sites of the catalysts. During the deactivation test for 60 h, the CO conversion and selectivity are maintained.     

Applying a face-centered central composite design to optimize the preferential CO oxidation over a PtAu/CeO2–ZnO catalyst

The catalytic performance for the preferential oxidation of CO over a 1% (w/w) PtAu/CeO₂–ZnO catalyst prepared by co-precipitation was investigated using a full 2^k factorial design with three central points and a 95% confidence interval, in order to screen for the importance of the operating temperature (°C) and the H₂O and CO₂ contents (%) in the simulated reformate gas on the CO conversion and selectivity. The catalyst was characterized by TEM, BET, XRD and FTIR. The temperature and CO₂ content had a significant influence on the conversion, whilst the selectivity depended on the temperature only. A face-centered central composite design was then used to evaluate the optimal conditions by simultaneously considering the maximal conversion, selectivity and constraints of the composition of realistic reformate gas. The difference in the estimated response and the experimental one was within ±2% and ±3% for routing simulated and realistic reformate gases, respectively.     

Hydrogen production via methanol steam reforming over Au/CuO,Au/CeO2, and Au/CuO–CeO2 catalysts prepared by deposition–precipitation

The production of hydrogen (H₂) with a low concentration of carbon monoxide (CO) via steam reforming of methanol (SRM) over Au/CuO, Au/CeO₂, (50:50)CuO–CeO₂, Au/(50:50)CuO–CeO₂, and commercial MegaMax 700 catalysts were investigated over reaction temperatures between 200 °C and 300 °C at atmospheric pressure. Au loading in the catalysts was maintained at 5 wt%. Supports were prepared by co-precipitation (CP) whilst all prepared catalysts were synthesized by deposition–precipitation (DP). The catalysts were characterized by Brunauer–Emmett–Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM). Au/(50:50)CuO–CeO₂ catalysts expressed a higher methanol conversion with negligible amount of CO than the others due to the integration of CuO particles into the CeO₂ lattice, as evidenced by XRD, and a interaction of Au and CuO species, as evidenced by TPR. A 50:50 Cu:Ce atomic ratio was optimal for Au supported on CuO–CeO₂ catalysts which can then promote SRM. Increasing the reaction time, by reducing the liquid feed rate from 3 to 1.5 cm³ h^?1, resulted in a catalytic activity with complete (100%) methanol conversion, and a H₂ and CO selectivity of ～82% and ～1.3%, respectively. From stability testing, Au/(50:50)CuO–CeO₂ catalysts were still active for 540 min use even though the CuO was reduced to metallic Cu, as evidenced by XRD. Therefore, it can be concluded that metallic Cu is one of active components of the catalysts for SRM.