揭示超薄Co-Fe层状双氢氧化物析氧反应的活性位点

doi:10.1016/S1872-2067(21)64033-0

催化学报 ›› 2022, Vol. 43 ›› Issue (8): 2240-2248.DOI: 10.1016/S1872-2067(21)64033-0

揭示超薄Co-Fe层状双氢氧化物析氧反应的活性位点

白雪^a^,^†, 段志遥^b^,^#^,^†(), 南兵^c^,^†, 王黎明^d, 唐甜蜜^a, 管景奇^a^,^*()

^a吉林大学化学学院, 物理化学研究所, 吉林长春130021
^b西北工业大学材料科学与工程学院, 凝固技术国家重点实验室, 陕西西安710072
^c中国科学院上海高等研究院, 上海同步辐射光源, 上海201210
^d中国科学院高能物理研究所, 中国科学院纳米生物效应与安全性重点实验室, 中国科学院-香港大学环境与健康金属组学联合实验室, 北京100049

收稿日期:2021-12-28 接受日期:2022-01-31 出版日期:2022-08-18 发布日期:2022-06-20
通讯作者: 段志遥,管景奇
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(22075099);吉林省教育厅(JJKH20220967KJ);中央高校基本研究经费(D5000210743)

Unveiling the active sites of ultrathin Co-Fe layered double hydroxides for the oxygen evolution reaction

Xue Bai^a^,^†, Zhiyao Duan^b^,^#^,^†(), Bing Nan^c^,^†, Liming Wang^d, Tianmi Tang^a, Jingqi Guan^a^,^*()

^aInstitute of Physical Chemistry, College of Chemistry, Jilin University, Changchun 130021, Jilin, China
^bState Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072, Shaanxi, China
^cShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210, China
^dCAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety & CAS-HKU Joint Laboratory of Metallomics on Health and Environment, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Received:2021-12-28 Accepted:2022-01-31 Online:2022-08-18 Published:2022-06-20
Contact: Zhiyao Duan, Jingqi Guan
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22075099);Education Department of Jilin Province(JJKH20220967KJ);Fundamental Research Funds for the Central Universities(D5000210743)

摘要/Abstract

摘要：

碱性条件下水分解生产高纯氢为能源的可持续发展提供了一条新途径. 然而电催化析氧反应(OER)需要克服高的能量势垒, 极大地影响了能源利用效率. Ir/Ru氧化物是一类性能优异的OER电催化剂, 但稀缺性和高成本限制了其大规模的工业化应用, 因此开发高性能且地球上资源丰富的元素来替代Ru/Ir氧化物有重要意义. 多相过渡金属氧化物、氢氧化物、碳化物、氮化物、卤化物、二卤化物、硒化物和磷化物只有高效的OER活性, 其中金属氧化物和氢氧化物的稳定性更好, 实际应用更广泛. 钴/铁基(氢)氧化物具有高的催化活性和稳定性, 可以构建成多种结构(包括纳米颗粒、纳米片、核-壳结构、介孔结构和结晶结构等)以提升其催化性能, 是一类能与贵金属氧化物相媲美的理想的OER电催化剂. 其中, 钴铁双金属氢氧化物(CoFe LDHs)由于其独特的二维结构和可调的化学组成, 在碱性介质中表现出良好的OER活性, 但其整体结构难以控制, 活性位点分布不均匀, 因此合理设计和制备具有超薄结构的CoFe LDHs, 提高电子传输速度是提高OER性能的关键.

本文采用一种简便的溶液反应制备CoFe基超薄双金属氢氧化物, 其厚度小于2 nm, 超薄的二维纳米片提供了丰富的OER活性位点和优异的电荷转移能力. 在1 mol/L KOH中, Co₁Fe_0.2 LDH仅需256 mV的过电位即可达到10 mA cm^-2的电流密度, 转化频率为0.082 s^-1, 在过电位为300 mV时, OER质量活性为277.9 A g^-1, 性能优于商用IrO₂, 也优于以往报道的大多数电催化剂. 动力学研究表明, Co位是OER的主要活性中心, 而掺杂Fe可以通过加速电荷转移过程降低反应势垒. 为了探究OER性能提高的机制, 对一元CoOOH, FeOOH和二元Fe-CoOOH上的五个不同位点进行了理论研究, 计算了它们在碱性介质中的理论OER过电位. 其中一元CoOOH中的Co位(0.95 V)的理论OER过电位比FeOOH的Fe位(0.7 V)低, 而二元Fe-CoOOH表面Fe原子附近的Co原子位点的理论OER过电位为0.61 V, 位于火山图的最顶端. 计算结果与实验相符, 表面Fe原子附近的Co位是OER的活性中心, 而次表面Fe的掺杂使OH*吸附作用过弱, 从而增加了速率决定步骤的能垒. 综上, 本文对合理设计高性能CoFe基水分解催化剂具有一定的参考意义.

关键词: 氢氧化钴, 氢氧化铁, 层状双氢氧化物, 析氧反应, 第一性原理研究

Abstract:

Two-dimensional layered double hydroxides (LDHs) have been identified as promising electrocatalysts for the oxygen evolution reaction (OER); however, the simple and effective synthesis of high-quality LDHs remains extremely challenging and the active sites have not been clarified. Herein, we report a facile solution-reaction method for preparing an ultrathin (thickness < 2 nm) nonprecious CoFe-based LDH. Co₁Fe_0.2 LDH delivers a current density of 10 mA cm^-2 and a high turnover frequency of 0.082 s^-1 per total 3d metal atoms at a low overpotential of 256 mV. Its mass activity is 277.9 A g^-1 at an overpotential of 300 mV for the OER. Kinetic studies reveal the Co site as the main active center for the OER. The doped Fe lowers the reaction barrier by accelerating the charge-transfer process. Theoretical calculations reveal that the surface Co sites adjacent to Fe atoms are the active centers for the OER and the subsurface Fe dopants excessively weaken the OH* adsorption, thus increasing the energy barrier of the rate-determining step. This study can guide the rational design of high-performance CoFe-based LDHs for water splitting.

Key words: Cobalt hydroxide, Iron hydroxide, Layered double hydroxide, Oxygen evolution reaction, First-principle study

白雪, 段志遥, 南兵, 王黎明, 唐甜蜜, 管景奇. 揭示超薄Co-Fe层状双氢氧化物析氧反应的活性位点[J]. 催化学报, 2022, 43(8): 2240-2248.

Xue Bai, Zhiyao Duan, Bing Nan, Liming Wang, Tianmi Tang, Jingqi Guan. Unveiling the active sites of ultrathin Co-Fe layered double hydroxides for the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2022, 43(8): 2240-2248.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64033-0

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图/表 5

Fig. 1. (a) Schematic of the process of synthesizing CoFe LDH; HRTEM images (b-d) and EDX mappings (e-g) of the Co1Fe0.2 LDH.

Fig. 2. (a) XPS survey spectrum of the Co1Fe0.2 LDH. (b) high-resolution Fe 2p XPS spectra. (c) high-resolution Co 2p XPS spectra. (d) high-resolution O 1s XPS spectra.

Fig. 3. (a) XANES spectra at the Fe K-edge of the Co1Fe0.2 LDH and reference samples (Fe foil, Fe3O4, and Fe2O3). (b) EXAFS spectra at the Fe K-edge of the Co1Fe0.2 LDH, Fe foil, and Fe3O4. (c) FT-EXAFS fitting spectrum at the Fe K-edge of Co1Fe0.2 LDH. (d) XANES spectra at the Co K-edge of the Co1Fe0.2 LDH and reference samples (Co foil, CoO, and Co3O4). (e) EXAFS spectra at the Co K-edge of the Co1Fe0.2 LDH, Co foil, and Co3O4. (f) FT-EXAFS fitting spectrum at the Co K-edge of Co1Fe0.2 LDH.

Fig. 4. (a) OER polarization curves of the catalysts loaded on the glassy carbon electrodes. Tafel slopes (b) and comparisons (c) of the overpotentials at 10 mA cm-2 and Tafel slopes of the catalysts. (d) Arrhenius plots of the kinetic current at η = 300 mV without iR compensation. (e) Multicurrent electrochemical process and (f) chronopotentiometric curve of the Co1Fe0.2 LDH.

Fig. 5. (a) OER mechanism over a metal-oxide surface site M in an alkaline solution. (b) Predicted overpotentials (ηOER) over various catalytic sites overlaid on a theoretical volcano plot of the OER; Free-energy diagrams (FEDs) of the OER using FeOOH (c), CoOOH (d), Fe-CoOOH Co (e), Fesub-CoOOH Co (f), and Fe-CoOOH Co (g) sites. The atomic models of OOH adsorbed on these sites are shown above their respective FEDs. The brown, blue, red/pink, and green balls represent Fe, Co, O, and H atoms, respectively.

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揭示超薄Co-Fe层状双氢氧化物析氧反应的活性位点

Unveiling the active sites of ultrathin Co-Fe layered double hydroxides for the oxygen evolution reaction

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