Synthesis of palladium-silver electrocatalyst by cyclic voltammetry on graphite substrate for electrochemical production of hydrogen in acid media

Document Type : Original Article


1 Analytical Chemistry Department, Chemistry Faculty, Iran University of Science and Technology, Tehran, Iran

2 Analytical Chemistry Research Group, Research Institute of Petroleum Industry, Tehran, Iran


Electrochemical production of hydrogen using high-efficiency catalysts is an effective way to achieve a clean and renewable energy source. Palladium as one of the best elements as a catalyst has a very high price. In the present study, the use of silver metal reduced the consumption of palladium and improved its efficiency. In this research, Pd-Ag coating was generated using the cyclic voltametric electrochemical deposition method in a deposition bath containing palladium and silver ions on the surface of graphite rods. Factors such as coating marking method, the concentration of two salts, number of cycles, and scanning speed were optimized. Various electrochemical tests were performed to measure the activity and catalytic stability of the samples in one-tenth of a molar sulfuric acid electrolyte. To study the surface characteristics of the coatings, field emission electron microscopy (FESEM) test equipped with X-ray energy diffraction (EDS) spectrometer and X-ray diffraction (XRD) tests were used. In the optimal case, the overvoltage in the current flux of -10 mA / cm2 is equal to -177.5 mV and its TOEFL slope is equal to (mV.dec-1) 120.9, which is one of the best catalytic activities. Compared to other coatings based on silver and palladium. The reasons for the high catalytic activity of the optimal sample include the synergy of silver and palladium atoms, the resulting nanocluster structure, and the high electrochemically active surface area. A very small change in the optimal potential of the electrode at a density of -100 mA / cm2 for 5 hours of electrolysis indicates the stability of the optimal electrode in working conditions and an acidic environment. The low-cost, single-step fabrication method without the use of any adhesives or binders and the very high catalyst activity and good stability of the optimal Pd-Ag sample make it possible to use this electrode commercially.


Main Subjects

This is an open access article under the CC-BY-SA 4.0 license.(

[1] Huang, D., Lu, J., Li, S., Luo, Y., Zhao, C., Hu, B., ... & Shen, Y. (2014). Fabrication of cobalt porphyrin. Electrochemically reduced graphene oxide hybrid Films for electrocatalytic hydrogen evolution in aqueous solution. Langmuir, 30(23), 6990-6998.
[2] Honarpazhouh, Y., Astaraei, F. R., Naderi, H. R., & Tavakoli, O. (2016). Electrochemical hydrogen storage in Pd-coated porous silicon/graphene oxide. International Journal of Hydrogen Energy, 41(28), 12175-12182.
[3] Hosseini, M., & Ariankhah, E. (2016). Electrochemical Evaluation of Ni/RuO2 and Ni/RuO2/Mixed-Metal Oxide Coatings Electrodes toward Hydrogen Evolution Reaction in Alkaline Medium. Applied Chemistry, 11(41), 147-164.
[4] Oberoi, A. S., Nijhawan, P., & Singh, P. (2018). A novel electrochemical hydrogen storage-based proton battery for renewable energy storage. Energies, 12(1), 82.
[5] X. Ji, B. Liu, X. Ren, X. Shi, A.M. Asiri, X. Sun, ACS Sustain. Chem. Eng. 6 (2018) 4499.
[6] Amirhosseiny, A., & Zarei, K. (2019). Electrochemical preparation of an electrocatalytical layer containing hollow platinum nanoparticles and reduced graphene oxide on the pencil graphite electrode for hydrogen evolving reaction. Applied Chemistry, 14 (51), 135-146. (in persion)
[7] Ghaffarinead, A., Tabatabaei, A., Sohrabi, B., & Salahandish, R. (2019). The effect of surfactants on electrochemical hydrogen production. Applied Chemistry, 14 (50), 25-39. (in persion)
[8] Liu, H., Shang, J., Zeng, L., Cao, B., Geng, H., Lang, J., ... & Gu, H. (2021). A setaria-shaped Pd/Ni-NC electrocatalyst for high efficient hydrogen evolution reaction. Chemical Engineering Journal Advances, 6, 100101.
[9] Nie, M., Sun, H., Liao, J., Li, Q., Xue, Z., Xue, F., ... & Teng, L. (2021). Study on the catalytic performance of Pd/TiO2 electrocatalyst for hydrogen evolution reaction. International Journal of Hydrogen Energy, 46(9), 6441-6447.
[10] Liu, Y. Y., Zhang, H. P., Zhu, B., Zhang, H. W., Fan, L. D., Chai, X. Y., ... & He, C. X. (2018). C/N-co-doped Pd coated Ag nanowires as a high-performance electrocatalyst for hydrogen evolution reaction. Electrochimica Acta, 283, 221-227.
[11] Song, C., Zhao, Z., Sun, X., Zhou, Y., Wang, Y., & Wang, D. (2019). In situ growth of Ag nanodots decorated Cu2O porous nanobelts networks on copper foam for efficient HER electrocatalysis. Small, 15(29), 1804268.
[12] Akhtar, A., Ghaffarinejad, A., Hosseini, S. M., Manteghi, F., & Maminejad, N. (2015). Electrocatalytic hydrogen production by bulk and nano Fe2O3 and carbon nanotube modified with Fe2O3. Journal of Electroanalytical Chemistry, 739, 73-83.
[13] Beshkar, F., & Salavati-Niasari, M. (2015). Facile synthesis of nickel chromite nanostructures by hydrothermal route for photocatalytic degradation of acid black 1 under visible light. Journal of Nanostructures, 5(1), 17-23.
[14] Huang, H., Yan, M., Yang, C., He, H., Jiang, Q., Yang, L., ... & Yamauchi, Y. (2019). Graphene nanoarchitectonics: recent advances in graphene‚Äźbased electrocatalysts for hydrogen evolution reaction. Advanced Materials, 31(48), 1903415.
[15] Dong, X., Liu, X., Chen, H., Xu, X., Jiang, H., Gu, C., ... & Hu, Y. (2021). Hard template-assisted N, P-doped multifunctional mesoporous carbon for supercapacitors and hydrogen evolution reaction. Journal of Materials Science, 56, 2385-2398.
[16] Pandurangan, M., & Kim, D. H. (2015). In vitro toxicity of zinc oxide nanoparticles: a review. Journal of Nanoparticle Research, 17, 1-8.
[17] Qiu, L., Jiang, L., Ye, Z., Liu, Y., Cen, T., Peng, X., & Yuan, D. (2019). Phosphorus-doped Co3Mo3C/Co/CNFs hybrid: A remarkable electrocatalyst for hydrogen evolution reaction. Electrochimica Acta, 325, 134962.
[18] Sun, Y., Liu, C., Grauer, D. C., Yano, J., Long, J. R., Yang, P., & Chang, C. J. (2013). Electrodeposited cobalt-sulfide catalyst for electrochemical and photoelectrochemical hydrogen generation from water. Journal of the American Chemical Society, 135(47), 17699-17702.
[19] Nodehi, Z., Rafati, A. A., & Ghaffarinejad, A. (2018). Palladium-silver polyaniline composite as an efficient catalyst for ethanol oxidation. Applied Catalysis A: General, 554, 24-34.
[20] Nazir, R., Fageria, P., Basu, M., & Pande, S. (2017). Decoration of carbon nitride surface with bimetallic nanoparticles (Ag/Pt, Ag/Pd, and Ag/Au) via galvanic exchange for hydrogen evolution reaction. The Journal of Physical Chemistry C, 121(36), 19548-19558.
[21] Gao, X., Yu, G., Zheng, L., Zhang, C., Li, H., Wang, T., ... & Chen, W. (2019). Strong electron coupling from the sub-nanometer Pd clusters confined in porous ceria nanorods for highly efficient electrochemical hydrogen evolution reaction. ACS Applied Energy Materials, 2(2), 966-973.
[22] Kim, J., Byun, S., Smith, A. J., Yu, J., & Huang, J. (2013). Enhanced electrocatalytic properties of transition-metal dichalcogenides sheets by spontaneous gold nanoparticle decoration. The journal of physical chemistry letters, 4(8), 1227-1232.
[23] Bhalothia, D., Wang, S. P., Lin, S., Yan, C., Wang, K. W., & Chen, P. C. (2020). Atomic Pt-Clusters Decoration Triggers a High-Rate Performance on Ni@Pd Bimetallic Nanocatalyst for Hydrogen Evolution Reaction in Both Alkaline and Acidic Medium. Applied Sciences, 10(15), 5155.