Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface
Source abstract
Abstract
A grand challenge in electrochemistry is to understand and promote electrochemical processes by exploring and exploiting the interface. Herein, we promoted the hydrogen evolution and oxidation reactions (HER/HOR) of platinum (Pt) in base by introducing N-methylimidazoles into the Pt-water interface. In situ spectroscopic characterization of the interface together with Quantum Mechanics computations showed that this promotion is caused by the N-methylimidazoles facilitating diffusion of hydroxides across the interface by holding the second layer water close to Pt surfaces. We accordingly propose that the HER/HOR kinetics of Pt in acid and base is governed by diffusion of protons and hydroxides, respectively, through the hydrogen-bond network of interfacial water by the Grotthuss mechanism, which accounts for the pH-dependent HER/HOR kinetics of platinum, a long-standing puzzle. Moreover, we demonstrated a 40% performance improvement of an anion exchange membrane electrolyzer by adding 1,2-dimethylimidazole into the alkaline solution fed into its platinum cathode.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Electrocatalysts for Energy Conversion · Electrochemical Analysis and Applications · Fuel Cells and Related Materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (62)
Show source-provided references
1. Sheng, W. et al. Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy. Nat. Commun. 6, 5848 (2015).10.1038/ncomms6848 ↗
2. Zheng, J., Sheng, W., Zhuang, Z., Xu, B. & Yan, Y. Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy. Sci. Adv. 2, e1501602 (2016).10.1126/sciadv.1501602 ↗
3. Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 7, 2255–2260 (2014).10.1039/C4EE00440J ↗
4. McCrum, I. T. & Koper, M. T. M. The role of adsorbed hydroxide in hydrogen evolution reaction kinetics on modified platinum. Nat. Energy 5, 891–899 (2020).10.1038/s41560-020-00710-8 ↗
5. Liu, E. et al. Unifying the hydrogen evolution and oxidation reactions kinetics in base by identifying the catalytic roles of hydroxyl-water-cation adducts. J. Am. Chem. Soc. 141, 3232–3239 (2019).10.1021/jacs.8b13228 ↗
6. Li, J. et al. Experimental poof of the bifunctional mechanism for the hydrogen oxidation in alkaline media. Angew. Chem. Int. Ed. 56, 15594–15598 (2017).10.1002/anie.201708484 ↗
7. Strmcnik, D. et al. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nat. Chem. 5, 300–306 (2013).10.1038/nchem.1574 ↗
8. Schwämmlein, J. N. et al. Origin of superior HOR/HER activity of bimetallic Pt-Ru catalysts in alkaline media identified via Ru@Pt core-shell nanoparticles. J. Electrochem. Soc. 165, H229–H239 (2018).10.1149/2.0791805jes ↗
9. Wang, Y. et al. Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect? Energy Environ. Sci. 8, 177–181 (2015).10.1039/C4EE02564D ↗
10. Lu, S. & Zhuang, Z. Investigating the influences of the adsorbed species on catalytic activity for hydrogen oxidation reaction in alkaline electrolyte. J. Am. Chem. Soc. 139, 5156–5163 (2017).10.1021/jacs.7b00765 ↗
11. Elbert, K. et al. Elucidating hydrogen oxidation/evolution kinetics in base and acid by enhanced activities at the optimized Pt shell thickness on the Ru core. ACS Catal. 5, 6764–6772 (2015).10.1021/acscatal.5b01670 ↗
12. Ledezma-Yanez, I. et al. Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes. Nat. Energy 2, 17031 (2017).10.1038/nenergy.2017.31 ↗
13. Intikhab, S. et al. Exploiting dynamic water structure and structural sensitivity for nanoscale electrocatalyst design. Nano Energy 64, 103963 (2019).10.1016/j.nanoen.2019.103963 ↗
14. Briega-Martos, V., Ferre-Vilaplana, A., Herrero, E. & Feliu, J. M. Why the activity of the hydrogen oxidation reaction on platinum decreases as pH increases. Electrochim. Acta 354, 136620 (2020).10.1016/j.electacta.2020.136620 ↗
15. Rebollar, L. et al. “Beyond adsorption” descriptors in hydrogen electrocatalysis. ACS Catal. 10, 14747–14762 (2020).10.1021/acscatal.0c03801 ↗
16. Rebollar, L. et al. On the relationship between potential of zero charge and solvent dynamics in the reversible hydrogen electrode. J. Catal. 398, 161–170 (2021).10.1016/j.jcat.2021.04.008 ↗
17. Liu, E. et al. Interfacial water shuffling the intermediates of hydrogen oxidation and evolution reactions in aqueous media. Energy Environ. Sci. 13, 3064–3074 (2020).10.1039/D0EE01754J ↗
18. Intikhab, S. et al. Caffeinated interfaces enhance alkaline hydrogen electrocatalysis. ACS Catal. 10, 6798–6802 (2020).10.1021/acscatal.0c01635 ↗
19. Sheng, W., Gasteiger, H. A. & Shao-Horn, Y. Hydrogen oxidation and evolution reaction kinetics on platinum: acid vs alkaline electrolytes. J. Electrochem. Soc. 157, B1529–B1536 (2010).10.1149/1.3483106 ↗
20. Alei, M. & Wageman, W. E. 15N NMR shifts for imidazole and 1-methyl imidazole in CH2Cl2 relative to aqueous solution. Tetrahedron Lett. 20, 667–670 (1979).10.1016/S0040-4039(01)93540-3 ↗
21. Zischang, J., Lee, J. J. & Suhm, M. A. Communication: where does the first water molecule go in imidazole? J. Chem. Phys. 135, 061102 (2011).10.1063/1.3624841 ↗
22. Osawa, M., Tsushima, M., Mogami, H., Samjeské, G. & Yamakata, A. Structure of water at the electrified platinum–water interface: a study by surface-enhanced infrared absorption spectroscopy. J. Phys. Chem. C 112, 4248–4256 (2008).10.1021/jp710386g ↗
23. Ataka, K.-i, Yotsuyanagi, T. & Osawa, M. Potential-dependent reorientation of water molecules at an electrode/electrolyte interface studied by surface-enhanced infrared absorption spectroscopy. J. Phys. Chem. 100, 10664–10672 (1996).10.1021/jp953636z ↗
24. Yao, Y., Zhu, S., Wang, H., Li, H. & Shao, M. A spectroscopic study on the nitrogen electrochemical reduction reaction on gold and platinum surfaces. J. Am. Chem. Soc. 140, 1496–1501 (2018).10.1021/jacs.7b12101 ↗
25. Li, C.-Y. et al. In situ probing electrified interfacial water structures at atomically flat surfaces. Nat. Mater. 18, 697–701 (2019).10.1038/s41563-019-0356-x ↗
26. Toney, M. F. et al. Voltage-dependent ordering of water molecules at an electrode–electrolyte interface. Nature 368, 444–446 (1994).10.1038/368444a0 ↗
27. Nagy, G. & Heinzinger, K. A molecular dynamics study of water monolayers on charged platinum walls. J. Electroanal. Chem. 327, 25–30 (1992).10.1016/0022-0728(92)80133-O ↗
28. Wang, S.-H. & Griffiths, P. R. Resolution enhancement of diffuse reflectance i.r. spectra of coals by Fourier self-deconvolution: 1. C–H stretching and bending modes. Fuel 64, 229–236 (1985).10.1016/0016-2361(85)90223-6 ↗
29. Lambert, D. K. Vibrational stark effect of adsorbates at electrochemical interfaces. Electrochim. Acta 41, 623–630 (1996).10.1016/0013-4686(95)00349-5 ↗
30. Teliska, M., O’Grady, W. E. & Ramaker, D. E. Determination of H adsorption sites on Pt/C electrodes in HClO4 from Pt L23 X-ray absorption spectroscopy. J. Phys. Chem. B 108, 2333–2344 (2004).10.1021/jp0356113 ↗
31. Roth, C. et al. Determination of O[H] and CO coverage and adsorption sites on PtRu electrodes in an operating PEM fuel cell. J. Am. Chem. Soc. 127, 14607–14615 (2005).10.1021/ja050139f ↗
32. Maniguet, S., Mathew, R. J. & Russell, A. E. EXAFS of carbon monoxide oxidation on supported Pt fuel cell electrocatalysts. J. Phys. Chem. B 104, 1998–2004 (2000).10.1021/jp992947x ↗
33. Carter, D. A., Pemberton, J. E. & Woelfel, K. J. Orientation of 1- and 2-methylimidazole on silver electrodes determined with surface-enhanced Raman scattering. J. Phys. Chem. B 102, 9870–9880 (1998).10.1021/jp982741g ↗
34. Papoian, G., Nørskov, J. K. & Hoffmann, R. A comparative theoretical study of the hydrogen, methyl, and ethyl chemisorption on the Pt(111) surface. J. Am. Chem. Soc. 122, 4129–4144 (2000).10.1021/ja993483j ↗
35. Cheng, T., Wang, L., Merinov, B. V. & Goddard, W. A. Explanation of dramatic pH-dependence of hydrogen binding on noble metal electrode: greatly weakened water adsorption at high pH. J. Am. Chem. Soc. 140, 7787–7790 (2018).10.1021/jacs.8b04006 ↗
36. Laio, A. & Parrinello, M. Escaping free-energy minima. Proc. Natl Acad. Sci. USA 99, 12562–12566 (2002).10.1073/pnas.202427399 ↗
37. Marx, D., Tuckerman, M. E., Hutter, J. & Parrinello, M. The nature of the hydrated excess proton in water. Nature 397, 601–604 (1999).10.1038/17579 ↗
38. Tuckerman, M. E., Marx, D. & Parrinello, M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution. Nature 417, 925–929 (2002).10.1038/nature00797 ↗
39. Dunnington, B. D. & Schmidt, J. R. Generalization of natural bond orbital analysis to periodic systems: applications to solids and surfaces via plane-wave density functional theory. J. Chem. Theory Comput. 8, 1902–1911 (2012).10.1021/ct300002t ↗
40. Ogasawara, H. et al. Structure and bonding of water on Pt(111). Phys. Rev. Lett. 89, 276102 (2002).10.1103/PhysRevLett.89.276102 ↗
41. Lam, Y.-C., Soudackov, A. V., Goldsmith, Z. K. & Hammes-Schiffer, S. Theory of proton discharge on metal electrodes: electronically adiabatic model. J. Phys. Chem. C 123, 12335–12345 (2019).10.1021/acs.jpcc.9b02148 ↗
42. Meng, S., Wang, E. G. & Gao, S. Water adsorption on metal surfaces: a general picture from density functional theory studies. Phys. Rev. B 69, 195404 (2004).10.1103/PhysRevB.69.195404 ↗
43. Rebollar, L., Intikhab, S., Snyder, J. D. & Tang, M. H. Determining the viability of hydroxide-mediated bifunctional HER/HOR mechanisms through single-crystal voltammetry and microkinetic modeling. J. Electrochem. Soc. 165, J3209–J3221 (2018).10.1149/2.0271815jes ↗
44. Intikhab, S., Snyder, J. D. & Tang, M. H. Adsorbed hydroxide does not participate in the volmer step of alkaline hydrogen electrocatalysis. ACS Catal. 7, 8314–8319 (2017).10.1021/acscatal.7b02787 ↗
45. Chen, M. et al. Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer. Nat. Chem. 10, 413–419 (2018).10.1038/s41557-018-0010-2 ↗
46. Harris, R. K., Becker, E. D., De Menezes, S. M. C., Goodfellow, R. & Granger, P. NMR nomenclature. Nuclear spin properties and conventions for chemical shifts (IUPAC Recommendations 2001). Pure Appl. Chem. 73, 1795–1818 (2001).10.1351/pac200173111795 ↗
47. Gaussian 16 Rev. C.01 (Wallingford CT, 2016).10.5965/1984723816322015001 ↗
48. Adamo, C. & Barone, V. Toward reliable density functional methods without adjustable parameters: the PBE0 model. J. Chem. Phys. 110, 6158–6170 (1999).10.1063/1.478522 ↗
49. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).10.1002/jcc.21759 ↗
50. Woon, D. E. & Dunning, T. H. Jr. Gaussian basis sets for use in correlated molecular calculations. V. Core-valence basis sets for boron through neon. J. Chem. Phys. 103, 4572–4585 (1995).10.1063/1.470645 ↗
51. Tomasi, J., Mennucci, B. & Cancès, E. The IEF version of the PCM solvation method: an overview of a new method addressed to study molecular solutes at the QM ab initio level. J. Mol. Struct. THEOCHEM 464, 211–226 (1999).10.1016/S0166-1280(98)00553-3 ↗
52. Dunnington, B. D., Schmidt, J. R., Dunnington, B. D. & Schmidt, J. R. Generalization of natural bond orbital analysis to periodic systems: applications to solids and surfaces via plane-wave density functional theory. J. Chem. Theory Comput. 8, 1902–1911 (2012).10.1021/ct300002t ↗
53. Shin, Y. K., Gai, L., Raman, S. & van Duin, A. C. T. Development of a ReaxFF reactive force field for the Pt–Ni alloy catalyst. J. Phys. Chem. A 120, 8044–8055 (2016).10.1021/acs.jpca.6b06770 ↗
54. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).10.1006/jcph.1995.1039 ↗
55. Aktulga, H. M., Fogarty, J. C., Pandit, S. A. & Grama, A. Y. Parallel reactive molecular dynamics: numerical methods and algorithmic techniques. Parallel Comput. 38, 245–259 (2012).10.1016/j.parco.2011.08.005 ↗
56. Shuichi, N. Constant temperature molecular dynamics methods. Prog. Theor. Phys. 103, 1–46 (1991).10.1143/PTPS.103.1 ↗
57. Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).10.1103/PhysRevB.49.14251 ↗
58. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).10.1103/PhysRevB.54.11169 ↗
59. Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).10.1063/1.4865107 ↗
60. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
61. Johnson, E. R. & Becke, A. D. A post-Hartree–Fock model of intermolecular interactions: inclusion of higher-order corrections. J. Chem. Phys. 124, 174104 (2006).10.1063/1.2190220 ↗
62. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).10.1103/PhysRevB.50.17953 ↗