析氧反应中催化剂-电解质界面的质子动力学研究

doi:10.1016/S1872-2067(21)63909-8

催化学报 ›› 2022, Vol. 43 ›› Issue (1): 139-147.DOI: 10.1016/S1872-2067(21)63909-8

析氧反应中催化剂-电解质界面的质子动力学研究

曾辉炎^a,†, 曾衍铨^a,†, 漆俊^a, 顾龙^a, 洪恩纳^a, 司锐^a^,^b, 杨纯臻^a^,^b^,^*()

^a中山大学材料学院, 广东深圳518107
^b深圳综合粒子设施研究院, 广东深圳518107

收稿日期:2021-06-30 接受日期:2021-07-13 出版日期:2022-01-18 发布日期:2021-11-15
通讯作者: 杨纯臻
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21972172)

The role of proton dynamics on the catalyst-electrolyte interface in the oxygen evolution reaction

Huiyan Zeng^a,†, Yanquan Zeng^a,†, Jun Qi^a, Long Gu^a, Enna Hong^a, Rui Si^a^,^b, Chunzhen Yang^a^,^b^,^*()

^aSchool of Materials, Sun Yat-sen University, Shenzhen 518107, Guangdong, China
^bInstitute of Advanced Science Facilities (IASF), Shenzhen 518107, Guangdong, China

Received:2021-06-30 Accepted:2021-07-13 Online:2022-01-18 Published:2021-11-15
Contact: Chunzhen Yang
About author:* Tel: +86-13070246505; E-mail: yangchzh6@mail.sysu.edu.cn
First author contact:
^† Contributed equally to this work
Supported by:
National Natural Science Foundation of China(21972172)

摘要/Abstract

摘要：

电催化水分解是一种可持续的绿色产氢技术, 该技术在工业化的大规模应用急需开发高效稳定的非贵金属催化剂, 用于提高析氧反应(OER)的反应速率. 研究发现, 钙钛矿氧化物是优异的OER催化剂, 但是对于发生在催化剂-电解质固液界面上的反应机理仍有争论. 目前普遍认为, 在OER反应过程中, 水分子吸附在金属氧化物催化剂表面的金属活性中心上, 并进行连续四步的质子耦合电子转移步骤(PCET), 通过“吸附演化机制”(AEM)的方式氧化成氧气分子. 根据该机制, 调整钙钛矿材料的电子结构来控制表面性质已被广泛认为是提高OER活性的有效策略. 然而近期的研究发现, 一些高活性钙钛矿催化剂如La_1-_xSr_xCoO₃ (LSCO, x ≥ 0.5)在可逆氢电极(RHE)体系中的OER电催化活性表现出强烈的pH依赖性, 从而提出了一种晶格氧参与氧化的反应机制(LOM). 根据该机理, OER所产生的氧气分子不仅来自电解液中的水分子, 而且氧化物催化剂中晶格氧也可能直接参与O-O健的生成. 从传统的AEM机制到具有高活性的LOM反应机制, 速率限制步骤(RLS)由O-O键生成(O_(ads) + OH^- → OOH_(ads) + e^-)转变为-OOH_ads的脱质子步骤(OOH_(ads) + OH^- → OO_(ads) + H⁺ + e^-). 而且, RLS中涉及到质子转移, 表明解耦的PCET可能存在. 尽管一些实验和理论研究已经证实脱质子步骤对于高活性的OER电催化剂的重要性, 但需要进一步的工作来充分阐明质子动力学在催化剂-电解质界面以及RLS转变过程中的作用.
本文系统探究了催化剂表面质子动力学对于OER反应机理的影响, 提出一种研究催化剂表面质子动力学的实验方案, 揭示了钙钛矿氧化物的电子结构、质子动力学和催化剂-电解质界面上相关的OER机制之间的潜在关联. 采用固相法制备了La_0.5Sr_0.5CoO_3-_δ (LSCO), LaCoO₃, LaFeO₃和LaNiO₃等4种钙钛矿催化剂作为模型催化剂. 电化学测试表明, LSCO和LaNiO₃催化剂的OER电催化活性具有pH依赖行为, 而LaCoO₃和LaFeO₃的OER电催化活性对pH不敏感. H/D动力学同位素效应(KIE)的研究显示, D₂O电解液可以显著减缓LSCO和LaNiO₃催化剂表面的质子转移动力学, 降低其OER电催化活性. 反之, D₂O电解液对LaCoO₃和LaFeO₃的OER活性影响不大. 此外, 研究也发现, P_i基团的表面功能化可以有效地增强LSCO和LaNiO₃催化剂表面的质子转移动力学, 提高其OER电催化活性. 以上的测试结果为判别不同钙钛矿氧化物上协同和非协同PCET路径的限速步骤(RLS)提供了全面的依据. 对于电荷转移能较小的钙钛矿氧化物, 如LSCO和LaNiO₃, 其OER过程通过非协同PCET步骤进行, 其活性受催化剂表面质子动力学的影响较大, RLS为-OOH_ads的脱质子步骤, 体现出晶格氧参与水氧化的LOM机制. 而对于LaCoO₃和LaFeO₃等活性较差并且电荷转移能较大的钙钛矿催化剂, OER过程遵循经典的AEM机制, RLS由O-O键的形成来调控, OER性能受界面质子动力学的影响较小. 本文对于确定OER反应路径, 准确描述OER反应机理和动力学具有重要意义.

关键词: 电催化, 水氧化, 氧析出反应, 动力学同位素效应, 质子耦合电子转移, 反应机理

Abstract:

The development of non-precious metal catalysts that facilitate the oxygen evolution reaction (OER) is important for the widespread application of hydrogen production by water splitting. Various perovskite oxides have been employed as active OER catalysts, however, the underlying mechanism that occurs at the catalyst-electrolyte interface is still not well understood, prohibiting the design and preparation of advanced OER catalysts. Here, we report a systematic investigation into the effect of proton dynamics on the catalyst-electrolyte interfaces of four perovskite catalysts: La_0.5Sr_0.5CoO_3-δ (LSCO), LaCoO₃, LaFeO₃, and LaNiO₃. The pH-dependent OER activities, H/D kinetic isotope effect, and surface functionalization with phosphate anion groups were investigated to elucidate the role of proton dynamics in the rate-limiting steps of the OER. For oxides with small charge-transfer energies, such as LSCO and LaNiO₃, non-concerted proton-coupled electron transfer steps are involved in the OER, and the activity is strongly controlled by the proton dynamics on the catalyst surface. The results demonstrate the important role of interfacial proton transfer in the OER mechanism, and suggest that proton dynamics at the interface should carefully be considered in the design of future high-performance catalysts.

Key words: Electrocatalysis, Water oxidation, Oxygen evolution reaction, Kinetic isotope effect, Proton-coupled electron transfer, Reaction mechanism

曾辉炎, 曾衍铨, 漆俊, 顾龙, 洪恩纳, 司锐, 杨纯臻. 析氧反应中催化剂-电解质界面的质子动力学研究[J]. 催化学报, 2022, 43(1): 139-147.

Huiyan Zeng, Yanquan Zeng, Jun Qi, Long Gu, Enna Hong, Rui Si, Chunzhen Yang. The role of proton dynamics on the catalyst-electrolyte interface in the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2022, 43(1): 139-147.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63909-8

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图/表 7

Fig. 1. Powder XRD and Rietveld refinements of the as-synthesized LSCO (a), LaCoO3 (b), LaNiO3 (c), and LaFeO3 (d) samples. The insets show their crystal structures.

Table 1 Crystal structures, lattice parameters, and BET surface areas of the perovskites used in this study.

Compound	Space group	a (Å)	b (Å)	c (Å)	V_unit-cell (Å^-3)	BET (m² g^-1)
La_0.5Sr_0.5CoO_3-_δ	R -3 c H	5.423	5.423	13.250	338.58	1.2
LaCoO₃	R -3 c H	5.444	5.444	13.094	336.11	0.7
LaNiO₃	P b n m	5.556	7.855	5.561	242.76	1.4
LaFeO₃	R -3 c H	5.456	5.456	13.150	338.96	0.9

Fig. 2. OER performances of the perovskite catalysts. (a) Linear sweeping voltammograms of the as-synthesized LSCO, LaNiO3, LaCoO3, and LaFeO3 samples in 0.1 M KOH solution; (b) Tafel plots of the perovskites catalysts; (c) Comparison between the OER activities at an overpotential of 370 mV.

Fig. 3. pH dependence of the OER activities. (a) CV curves of the as-synthesized LSCO, LaNiO3, LaCoO3, and LaFeO3 samples in KOH solutions with pH values ranging from 12.5 to 14 at a scan rate of 10 mV s-1; (b) Tafel plots of the perovskites catalysts at the different pH values; (c) A comparison between the current densities measured at 1.6 V vs. RHE with an increase in the pH from 12.5 to 14.

Fig. 4. H/D isotope effect measurement. (a) The OER activities of the LSCO, LaNiO3, LaCoO3, and LaFeO3 perovskite catalysts in 0.1 M KOH dissolved in H2O or D2O; (b) Comparison between the OER activities (at 0.9 V vs. Ag/AgCl) in H2O and D2O. The insets illustrate the -OOH deprotonation and O-O bond formation processes on the catalyst-electrolyte interface of the perovskite.

Fig. 5. Enhancing the interfacial proton dynamics of the perovskite catalysts by surface functionalization with Pi groups. (a) The OER activities of the LSCO, LaNiO3, LaCoO3, and LaFeO3 perovskite catalysts in 0.1 M KOH with and without Pi functionalization; (b) Comparison between the OER activities of the different perovskite catalysts at 1.6 V vs. RHE in a pH = 13 KOH solution in the presence and absence of 0.1 M K3PO4. The insets illustrate the -OOH deprotonation process by the Pi coating and the O-O bond formation process on the catalyst-electrolyte interface of the perovskite.

Fig. 6. The effect of interfacial proton transfer on the OER activities of different perovskite catalysts. (a) The different charge-transfer energy (Δ) definitions for the perovskite oxides; (b) The concerted PCET and non-concerted PCET steps of the O-O bond formation and -OOHads deprotonation processes; (c) The experimental overpotentials obtained at 0.5 mA cm-2disk for the different perovskite oxides versus the charge transfer energies derived from DFT calculations [41]. Oxides with low charge-transfer energies, such as LSCO and LaNiO3, have high OER activities, but the RLS is determined by proton transfer, thus the OER kinetics is regulated or influenced to a large extent by the interfacial proton transfer kinetics. For LaFeO3, the charge-transfer energy is large, thus, the OER occurs through an electron-limited pathway, with the kinetics less affected by interfacial proton transfer.

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析氧反应中催化剂-电解质界面的质子动力学研究

The role of proton dynamics on the catalyst-electrolyte interface in the oxygen evolution reaction

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