电催化中的表面电荷效应 第2部分: 铂的过氧化氢反应

doi:10.1016/S1872-2067(22)64138-X

摘要/Abstract

摘要：

固体催化剂表面电荷会影响其电催化活性. 目前, 科研人员主要关注的是表面电荷如何影响局部反应区中电势和离子浓度. 本文以Pt(111)上的H₂O₂氧化还原反应为模型, 利用从头算分子动力学模拟研究了Pt(111)-水界面的特殊表面电荷效应. Pt(111)上的负表面电荷排斥反应物(H₂O₂)的O‒O键, 使其远离电极表面, 从而导致O‒O键断裂的活化能更高. 进一步建立了双电层微观动力学模型, 定量解释了Pt(111)上H₂O₂氧化还原反应的pH活性依赖, 尤其是电极电位降低时H₂O₂还原活性的异常抑制. 还探讨了该表面电荷效应在不同电解质阳离子、溶液pH值、催化剂晶面和模型参数等情况下的适用性, 与其他侧重于表面电荷对固定反应面上局部反应条件的影响机理研究不同, 本文给出了一个通过表面电荷调节反应面位置的实例.

关键词: 电催化, 表面电荷效应, 过氧化氢反应, Pt(111), 分子动力学模拟

Abstract:

Electrocatalytic activity is influenced by the surface charge on the solid catalyst. Conventionally, our attention has been focused on how the surface charge shapes the electric potential and concentration of ionic reactant(s) in the local reaction zone. Taking H₂O₂ redox reactions at Pt(111) as a model system, we reveal a peculiar surface charge effect using ab initio molecular dynamics simulations of electrified Pt(111)-water interfaces. In this scenario, the negative surface charge on Pt(111) repels the O-O bond of the reactant (H₂O₂) farther away from the electrode surface. This leads to a higher activation barrier for breaking the O-O bond. Incorporating this microscopic mechanism into a microkinetic-double-layer model, we are able to semi-quantitatively interpret the pH-dependent activity of H₂O₂ redox reactions at Pt(111), especially the anomalously suppressed activity of H₂O₂ reduction with decreasing electrode potential. The relevance of the present surface charge effect is also examined in wider scenarios with different electrolyte cations, solution pHs, crystal facets of the catalyst, and model parameters. In contrast with previous mechanisms focusing on how surface charge influences the local reaction condition at a fixed reaction plane, the present work gives an example in which the location of the reaction plane is adjusted by the surface charge.

Key words: Electrocatalysis, Surface charge effect, Hydrogen peroxide reaction, Pt(111)-aqueous solution interface, Microkinetic-double-layer model

Jun Huang, Victor Climent, Axel Groß, Juan M. Feliu. 电催化中的表面电荷效应第2部分: 铂的过氧化氢反应[J]. 催化学报, 2022, 43(11): 2837-2849.

Jun Huang, Victor Climent, Axel Groß, Juan M. Feliu. Understanding surface charge effects in electrocatalysis. Part 2: Hydrogen peroxide reactions at platinum[J]. Chinese Journal of Catalysis, 2022, 43(11): 2837-2849.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64138-X

https://www.cjcatal.com/CN/Y2022/V43/I11/2837

图/表 5

Fig. 1. (a) Polarization curves of hydrogen peroxide reduction and oxidation at Pt(111) [47]. J?app represents the dimensionless apparent current density normalized to the diffusional limiting current density. The electrolyte solution was prepared with NaF/HClO4 mixtures and 1.7 mmol L-1 H2O2. The scan rate is 50 mV s-1 and the rotation rate is 2500 r min-1. The polarization curves are divided into four regions with descriptions detailed in the main text. (b) The absolute intrinsic kinetic current density (|J?int|) in the region 3 as a function of the surface charge density (σM) calculated from Eq. (2) with Cdl = 0.3 Fm-2, and Epzc,SHE = 0.30 VSHE.

Fig. 2. Snapshots of the configuration of charged Pt(111) - water interfaces with one H2O2 molecule in water: (a) the negatively charged Pt(111) with one Li+ cation in water; (b) the positively charged Pt(111) with one F- anion in water; (c) variation of the total energy with the simulation step for the two cases; (d) histograms of the medium distance of the two oxygen atoms of the H2O2 molecule away from the outermost layer of Pt atoms.

Fig. 3. Flowchart of solving the microkinetic-double-layer model.

Fig. 4. Model-based analysis of hydrogen peroxide reactions at Pt(111). (a) Model-based polarization curves at four pHs, see legends in (c), and the experimental polarization curve for pH = 2, marked as circles. (b) Model-based polarization curves for the case of χ = 0. (c) Surface charging behaviors at four pHs. (d) The forward reaction constant of the step H2O2 + 2■R ↔ 2OHadR at four pHs. (e) The forward reaction constant of the step H2O2 + ■O ↔ OOHadO + H+ + e at four pHs.

Fig. 5. Parametric analysis of the present model of hydrogen peroxide reactions at Pt(111). (a) Influence of EDL parameters on model-based polarization curves at pH = 2. The base line corresponds to the set of model parameters used in Fig. 4, namely, $\delta_{\mathrm{rp}}^{0}=3 \AA, \epsilon_{\mathrm{rp}}=6 \epsilon_{0}, \chi_{\mathrm{rp}}=-5 \times 10^{-10} \mathrm{~m}^{3} \mathrm{C}^{-1}, \mathrm{G}_{\mathrm{a}, 01}^{0}=0.66 \mathrm{eV}$. Other lines are obtained by varying a parameter with the modified value marked aside. (b) Influence of EDL parameters on surface charging relation at pH = 2. (c) Influence of $G_{\mathrm{a}, 01}^{0}$ on model-based polarization curves at pH = 2. (d) Influence of χrp on the surface charging relation.

参考文献

[1]	A. Kozawa, J. Electroanal. Chem., 1964, 8, 20-39.
[2]	D. Strmcnik, K. Kodama, D. van der Vliet, J. Greeley, V. R. Stamenkovic, N. M. Marković, Nat. Chem., 2009, 1, 466-472.
[3]	A. C. Garcia, T. Touzalin, C. Nieuwland, N. Perini, M. T. M. Koper, Angew. Chem. Int. Ed., 2019, 58, 12999-13003.
[4]	S. Ringe, E. L. Clark, J. Resasco, A. Walton, B. Seger, A. T. Bell, K. Chan, Energy Environ. Sci., 2019, 12, 3001-3014.
[5]	B. Deng, M. Huang, X. Zhao, S. Mou, F. Dong, ACS Catal., 2022, 12, 331-362.
[6]	P. Sebastián-Pascual, Y. Shao-Horn, M. Escudero-Escribano, Current Opin. Electrochem., 2022, 32, 100918.
[7]	S.-J. Shin, D. H. Kim, G. Bae, S. Ringe, H. Choi, H.-K. Lim, C. H. Choi, H. Kim, Nat. Commun., 2022, 13, 174.
[8]	K. Chan, Nat. Commun., 2020, 11, 5954.
[9]	J. Huang, Current Opin. Electrochem., 2022, 100938.
[10]	A. Frumkin, Z. Phys. Chem., 1933, 164, 121-133.
[11]	L.-L. Zhang, C.-K. Li, J. Huang, J. Electrochem., 2022, 28, 2108471.
[12]	A. N. Frumkin, N. V. Nikolaeva-Fedorovich, N. P. Berezina, K. E. Keis, J. Electroanal. Chem. Interfacial Electrochem., 1975, 58, 189-201.
[13]	V. Climent, J. M. Feliu, J. Solid State Electrochem., 2011, 15, 1297.
[14]	V. Climent, J. Feliu, Annu. Rev. Anal. Chem., 2020, 13, 201-222.
[15]	J. Clavilier, J. Electroanal. Chem. Interfacial Electrochem., 1980, 107, 211-216.
[16]	J. Clavilier, R. Faure, G. Guinet, R. Durand, J. Electroanal. Chem. Interfacial Electrochem., 1980, 107, 205-209.
[17]	A. M. A. El-Halim, K. Jüttner, W. J. Lorenz, J. Electroanal. Chem. Interfacial Electrochem., 1980, 106, 193-207.
[18]	Z. Samec, A. M. Bittner, K. Doblhofer, J. Electroanal. Chem., 1996, 409, 165-173.
[19]	Z. Samec, A. M. Bittner, K. Doblhofer, J. Electroanal. Chem., 1997, 432, 205-214.
[20]	E. Lust, R. Truu, K. Lust, Russ. J. Electrochem., 2000, 36, 1195-1202.
[21]	V. Climent, M. D. Maciá, E. Herrero, J. M. Feliu, O. A. Petrii, J. Electroanal. Chem., 2008, 612, 269-276.
[22]	R. Martínez-Hincapié, V. Climent, J. M. Feliu, Electrochem. Commun., 2018, 88, 43-46.
[23]	V. Briega-Martos, E. Herrero, J. M. Feliu, Current Opin. Electrochem., 2019, 17, 97-105.
[24]	R. Martínez-Hincapié, V. Climent, J. M. Feliu, Current Opin. Electrochem., 2019, 14, 16-22.
[25]	J. Huang, J. Zhang, M. Eikerling, Phys. Chem. Chem. Phys., 2018, 20, 11776-11786.
[26]	D. Zhou, J. Wei, Z.-D. He, M.-L. Xu, Y.-X. Chen, J. Huang, J. Phys. Chem. C, 2020, 124, 13672-13678.
[27]	l. Zhang, J. Cai, Y. Chen, J. Huang, J. Phys. Condensed Matter, 2021, 33, 504002.
[28]	S. Ringe, C. G. Morales-Guio, L. D. Chen, M. Fields, T. F. Jaramillo, C. Hahn, K. Chan, Nat. Commun., 2020, 11, 33.
[29]	J. Huang, J. Chem. Phys., 2020, 153, 164707.
[30]	R. E. Bangle, J. Schneider, E. J. Piechota, L. Troian-Gautier, G. J. Meyer, J. Am. Chem. Soc., 2020, 142, 674-679.
[31]	A. M. Limaye, W. Ding, A. P. Willard, J. Chem. Phys., 2020, 152, 114706.
[32]	S. Sakong, K. Forster-Tonigold, A. Groß, J. Chem. Phys., 2016, 144, 194701.
[33]	J. Le, M. Iannuzzi, A. Cuesta, J. Cheng, Phys. Rev. Lett., 2017, 119, 016801.
[34]	S. Sakong, A. Groß, J. Chem. Phys., 2018, 149, 084705.
[35]	P. Li, J. Huang, Y. Hu, S. Chen, J. Phys. Chem. C, 2021, 125, 3972-3979.
[36]	J.-B. Le, Q.-Y. Fan, J.-Q. Li, J. Cheng, Sci. Adv., 2021, 6, eabb1219.
[37]	S. Sakong, A. Groß, Phys. Chem. Chem. Phys., 2020, 22, 10431-10437.
[38]	T. Iwasita, X. Xia, J. Electroanal. Chem., 1996, 411, 95-102.
[39]	C.-Y. Li, J.-B. Le, Y.-H. Wang, S. Chen, Z.-L. Yang, J.-F. Li, J. Cheng, Z.-Q. Tian, Nat. Mater., 2019, 18, 697-701.
[40]	I. Katsounaros, W. B. Schneider, J. C. Meier, U. Benedikt, P. U. Biedermann, A. A. Auer, K. J. J. Mayrhofer, Phys. Chem. Chem. Phys., 2012, 14, 7384-7391.
[41]	A. M. Gómez-Marín, K. J. P. Schouten, M. T. M. Koper, J. M. Feliu, Electrochem. Commun., 2012, 22, 153-156.
[42]	Y. L. Zheng, D. Mei, Y.-X. Chen, S. Ye, Electrochem. Commun., 2014, 39, 19-21.
[43]	E. Sitta, J. M. Feliu, ChemElectroChem, 2014, 1, 55-58.
[44]	R. Rizo, J. M. Feliu, E. Herrero, J. Catal., 2021, 398, 123-132.
[45]	V. Briega-Martos, E. Herrero, J. M. Feliu, Electrochim. Acta, 2020, 334, 135452.
[46]	Y. Zheng, W. Chen, X.-Q. Zuo, J. Cai, Y.-X. Chen, Electrochem. Commun., 2016, 73, 38-41.
[47]	V. Briega-Martos, E. Herrero, J. M. Feliu, Electrochem. Commun., 2017, 85, 32-35.
[48]	U. A. Paulus, T. J. Schmidt, H. A. Gasteiger, R. J. Behm, J. Electroanal. Chem., 2001, 495, 134-145.
[49]	T. Pajkossy, D. M. Kolb, Electrochem. Commun., 2007, 9, 1171-1174.
[50]	K. Ojha, N. Arulmozhi, D. Aranzales, M. T. M. Koper, Angew. Chem. Int. Ed., 2020, 59, 711-715.
[51]	R. Martínez-Hincapié, P. Sebastián-Pascual, V. Climent, J. M. Feliu, Electrochem. Commun., 2015, 58, 62-64.
[52]	J. Le, A. Cuesta, J. Cheng, J. Electroanal. Chem., 2018, 819, 87-94.
[53]	F. D. Lewis, J. Liu, W. Weigel, W. Rettig, I. V. Kurnikov, D. N. Beratan, Proc. Natl. Acad. Sci. USA, 2002, 99, 12536-12541.
[54]	A. Bruix, J. T. Margraf, M. Andersen, K. Reuter, Nat. Catal., 2019, 2, 659-670.
[55]	A. Salimi, C. E. Banks, R. G. Compton, Phys. Chem. Chem. Phys., 2003, 5, 3988-3993.
[56]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[57]	J. Huang, Electrochim. Acta, 2021, 389, 138720.
[58]	J. Huang, Current Opin. Electrochem., 2022, 33, 100938.
[59]	A. V. Usha, G. Atkinson, J. Solu. Chem., 1992, 21, 477-488.
[60]	A. Tjell, K. Almdal, Sensing Bio-Sensing Res., 2018, 21, 35-39.
[61]	J. O. M. Bockris, M. A. V. Devanathan, K. Müller, Proc. Roy. Soc. A, 1963, 274, 55-79.
[62]	M. J. Eslamibidgoli, M. H. Eikerling, ACS Catal., 2015, 5, 6090-6098.
[63]	J. Huang, A. Malek, J. Zhang, M. H. Eikerling, J. Phys. Chem. C, 2016, 120, 13587-13595.
[64]	W. Schmickler, in: Electrochemical Science for a Sustainable Society: A Tribute to John O’M Bockris, K. Uosaki (Ed.) Springer International Publishing, Cham, 2017, 95-111.
[65]	V. Briega-Martos, F. J. Sarabia, V. Climent, E. Herrero, J. M. Feliu, ACS Measur. Sci. Au, 2021, 1, 48-55.
[66]	M. M. Waegele, C. M. Gunathunge, J. Li, X. Li, J. Chem. Phys., 2019, 151, 160902.
[67]	F. J. Sarabia, P. Sebastián, V. Climent, J. M. Feliu, J. Electroanal. Chem., 2020, 872, 114068.
[68]	R. Smoluchowski, Phys. Rev., 1941, 60, 661-674.
[69]	L. Gierst, L. Vandenberghen, E. Nicolas, A. Fraboni, J. Electrochem. Soc., 1966, 113, 1025-1035.
[70]	R. Parsons, J. Electroanal. Chem. Interfacial Electrochem., 1969, 21, 35-43.
[71]	W. R. Fawcett, S. Levine, J. Electroanal. Chem. Interfacial Electrochem., 1973, 43, 175-184.
[72]	R. R. Nazmutdinov, D. V. Glukhov, O. A. Petrii, G. A. Tsirlina, G. N. Botukhova, J. Electroanal. Chem., 2003, 552, 261-278.
[73]	J. K. Nørskov, F. Studt, F. Abild-Pedersen, T. Bligaard, Poisoning and Promotion of Catalysts, Fundamental Concepts in Heterogeneous Catalysis, John Wiley & Sons, Newyork, 2014, 150-154.
[74]	V. Climent, N. García-Araez, J. M. Feliu, Electrochem. Commun., 2006, 8, 1577-1582.
[75]	G. Hussain, L. Pérez-Martínez, J.-B. Le, M. Papasizza, G. Cabello, J. Cheng, A. Cuesta, Electrochim. Acta, 2019, 327, 135055.
[76]	M. J. Weaver, Chem. Rev., 1992, 92, 463-480.
[77]	J. Huang, M. Li, M. J. Eslamibidgoli, M. Eikerling, A. Groß, JACS Au, 2021, 1, 1752-1765.
[78]	J. Resasco, L. D. Chen, E. Clark, C. Tsai, C. Hahn, T. F. Jaramillo, K. Chan, A. T. Bell, J. Am. Chem. Soc., 2017, 139, 11277-11287.