(472a) Hydrodechlorination of 1,2-Dichloroethane over Ag-Pd Catalysts Prepared By Controlled Surface Reactions
We present our results on the hydrodechlorination of 1,2-dichloroethane to form ethane, ethylene, and chloroethane over Pd and AgPd catalysts. These Pd and AgPd catalysts are synthesized on carbon, SiO2, and TiO2 supports, and we show that the formation of uniform bimetallic structures is most effective on the TiO2 support. The bimetallic catalysts are synthesized by depositing Pd by controlled surface reactions onto a supported Ag catalyst, as has previously been demonstrated for other metal systems13â19. UV visible spectroscopy is used to quantify the extent of interaction between the Pd precursor (cyclopentadienyl Pd allyl) and the support. We observe no interaction between the Pd precursor and the titania support, indicating that selective deposition of Pd onto Ag/TiO2 structures occurs during the synthesis process. On carbon and silica supports, some interaction between Pd precursor and support is observed, and Pd deposition onto Ag is not entirely selective. It is determined that formation of bimetallic AgPd structures is most effective for AgPd/TiO2, followed by AgPd/C and then AgPd/SiO2 catalysts.
FTIR spectra of adsorbed CO on the AgPd catalysts provide additional evidence for variations in the active site structure depending on the degree of interaction between Ag and Pd. On the TiO2-supported AgPd catalyst, CO adsorbs to Pd primarily in a linear configuration, while CO adsorbs in both linear and multifold configurations on the SiO2-supported AgPd catalyst. This difference in CO adsorption indicates that Pd is well dispersed on the Ag nanoparticles for the TiO2-supported catalyst, while a higher fraction of contiguous Pd sites is present on the SiO2-supported catalyst.
The ethylene selectivity decreases from 97% to 1% on AgPd/TiO2 catalysts as the Ag:Pd atomic ratio increases from 1:2 to 1:0.35. Similarly, an ethylene selectivity of 82% is achieved on the AgPd/C catalyst. On these catalysts, the selectivity to chloroethane is less than 1% and the balance of the selectivity is to ethane. The AgPd/SiO2 catalyst, however, is 91% selective to ethane and 9% selective to chloroethane. These results indicate that the well dispersed Pd achieved at low Pd loadings on TiO2 supported catalysts and carbon supported catalysts are selective to ethylene, while the contiguous Pd species formed at higher Pd loadings on TiO2 and on SiO2 are selective to ethane.
We have synthesized AgPd catalysts on TiO2, carbon, and SiO2 supports with various surface structures by using controlled surface reactions. The range of surface structures formed on these supports at various Pd loadings has allowed us to develop structure-selectivity relationships for the hydrodechlorination of 1,2-dichloroethane, observing high ethylene selectivity when Pd is well isolated because of intimate contact with Ag.
(1) Heinrichs, B.; Delhez, P.; Schoebrechts, J.-P.; Pirard, J.-P. J. Catal. 1997, 172, 322â335.
(2) Xu, L.; Stangland, E. E.; Mavrikakis, M. Catal. Sci. Technol. 2018, 8, 1555â1563.
(3) Heinrichs, B.; Noville, F.; Schoebrechts, J.-P.; Pirard, J.-P. J. Catal. 2000, 192, 108â118.
(4) Heinrichs, B.; Schoebrechts, J.-P.; Pirard, J.-P. J. Catal. 2001, 200, 309â320.
(5) Heinrichs, B.; Noville, F.; Schoebrechts, J. P.; Pirard, J. P. J. Catal. 2003, 220, 215â225.
(6) Lambert, S.; Ferauche, F.; Brasseur, A.; Pirard, J. P.; Heinrichs, B. Catal. Today 2005, 100, 283â289.
(7) Borovkov, V. Y.; Luebke, D. R.; Kovalchuk, V. I.; dâItri, J. L. J. Phys. Chem. B 2003, 107, 5568â5574.
(8) Han, Y.; Zhou, J.; Wang, W.; Wan, H.; Xu, Z.; Zheng, S.; Zhu, D. Appl. Catal. B Environ. 2012, 125, 172â179.
(9) Ito, L. N.; Harley, A. D.; Holbrook, M. T.; Smith, D. D.; Murchison, C. B.; Cisneros, M. D. Processes for converting chlorinated alkane byproducts or waste products to useful, less chlorinated alkenes. EP 0 662 941 B1, December 10, 1997.
(10) Han, Y.; Gu, G.; Sun, J.; Wang, W.; Wan, H.; Xu, Z.; Zheng, S. Appl. Surf. Sci. 2015, 355, 183â190.
(11) Han, Y.; Sun, J.; Fu, H.; Qu, X.; Wan, H.; Xu, Z.; Zheng, S. Appl. Catal. A Gen. 2016, 519, 1â6.
(12) Heinrichs, B.; Schoebrechts, J.-P.; Pirard, J.-P. Stud. Surf. Sci. Catal. 2000, 130 C, 2015â2020.
(13) AragÃ£o, I. B.; Ro, I.; Liu, Y.; Ball, M.; Huber, G. W.; Zanchet, D. Appl. Catal. B Environ. 2018, 222, 1â2.
(14) Alba-Rubio, A. C.; Sener, C.; Hakim, S. H.; Gostanian, T. M.; Dumesic, J. A. ChemCatChem 2015, 7, 3881â3886.
(15) Hakim, S. H.; Sener, C.; Alba-rubio, A. C.; Gostanian, T. M.; Neill, B. J. O.; Ribeiro, F. H.; Miller, J. T.; Dumesic, J. A. J. Catal. 2015, 328, 75â90.
(16) Liu, Y.; GÃ¶eltl, F.; Ro, I.; Ball, M. R.; Sener, C.; AragÃ£o, I. B.; Zanchet, D.; Huber, G. W.; Mavrikakis, M.; Dumesic, J. A. ACS Catal. 2017, 7, 4550â4563.
(17) Ro, I.; Liu, Y.; Ball, M. R.; Jackson, D. H. K.; Chada, J. P.; Sener, C.; Kuech, T. F.; Madon, R. J.; Huber, G. W.; Dumesic, J. A. ACS Catal. 2016, 6, 7040â7050.
(18) Ro, I.; Sener, C.; Stadelman, T. M.; Ball, M. R.; Venegas, J. M.; Burt, S. P.; Hermans, I.; Dumesic, J. A.; Huber, G. W. J. Catal. 2016, 344, 784â794.
(19) Sener, C.; Wesley, T. S.; Alba-Rubio, A. C.; Kumbhalkar, M. D.; Hakim, S. H.; Ribeiro, F. H.; Miller, J. T.; Dumesic, J. A. ACS Catal. 2016, 6, 1334â1344.