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The reduction of perchlorate by hydrogenation catalysts |
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| Authors: | Rovshan Mahmudov Yuying Shu Sergei Rykov Jingguang Chen Chin Pao Huang |
| Affiliation: | aDepartment of Civil and Environmental Engineering, University of Delaware, 301 DuPont Hall, Newark, DE 19702, USA bDepartment of Chemical Engineering, University of Delaware, 332 CLB 50 Academy Street, Colburn Laboratory, University of Delaware Newark, DE 19716, USA |
| Abstract: | Perchlorate competes with thyroid uptake of iodide, an essential nutrient for the production of thyroid hormones. Despite the extensive attempts to reduce perchlorate in aqueous solution, the process is slow and requires high temperatures even in the presence of catalysts. Therefore, perchlorate reduction under hydrogen atmosphere was employed. Monometallic and bimetallic Pt based catalysts (e.g., Pt/C, Ni-Pt/C, Co-Pt/C, and W-Pt/C) supported on activated carbon were prepared by successive incipient wet impregnation method and used for gas-phase reduction of perchlorate pre-adsorbed onto the activated carbon. The catalysts were characterized for hydrogen chemisorption and XPS. Hydrogen uptake was in the order: Co-Pt/C > W-Pt/C ≈ Pt/C > Ni-Pt/C. The least H2 uptake by Ni-Pt/C was likely due to lower dispersion on activated carbon surface with 11.5% vs. 36% for Pt/C. There was a good correlation between hydrogen uptake by impregnated activated carbon (IAC) and perchlorate reduction. The Co-Pt/C exhibited the highest hydrogen uptake and the best perchlorate reduction while Ni-Pt/C was the least reducing system. When Co-Pt/C was used almost 90% of perchlorate was reduced at 25 °C and initial surface concentration of perchlorate of 11.47 mg g−1 in 24 h. The reaction rate increased 10-folds when the reaction temperature was raised to 75 °C. In 24 h reaction time, increase of temperature from 25 to 75 °C resulted in additional 10% (Co-Pt/C) and 30% (Ni-Pt/C) increase in perchlorate reduction for Co-Pt/AC and Ni-Pt/AC, respectively, which brought the reduction efficiency close to 100%. The only reaction product that evolved was Cl−, indicating that the cleavage of the first oxygen atom of perchlorate was the rate-limiting step. The lowest activation energy for the reduction of perchlorate was 39.5 kJ mol−1 for Co-Pt/C. Results also showed that the activation of gaseous hydrogen molecules on metal catalysts was the major reducing step, although deposited metals also participated in the perchlorate reduction directly. Results of XPS analysis revealed that during adsorption/reduction some portion of the second metal in the bimetallic catalysts was lost due to dissolution while Pt was very stable. |
| Keywords: | Perchlorate Reduction Hydrogen Bimetallic catalyst Co-Pt/C Ni-Pt/C W-Pt/C Pt/C |
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