电化学（中英文） ›› 2022, Vol. 28 ›› Issue (3): 2108541. doi: 10.13208/j.electrochem.210854
所属专题： “表界面”专题文章； “电催化和燃料电池”专题文章
Jafar Hussain Shah1, 谢起贤2, 匡智崇1, 格日乐1, 周雯慧1, 刘朵绒1, Alexandre I. Rykov1, 李旭宁1, 罗景山2, 王军虎1,*(
)
收稿日期:2021-12-14
修回日期:2022-01-24
出版日期:2022-03-28
发布日期:2022-02-22
通讯作者:
王军虎
E-mail:wangjh@dicp.ac.cn
Jafar Hussain Shah1, Qi-Xian Xie2, Zhi-Chong Kuang1, Ri-Le Ge1, Wen-Hui Zhou1, Duo-Rong Liu1, Alexandre I. Rykov1, Xu-Ning Li1, Jing-Shan Luo2, Jun-Hu Wang1,*()
Received:2021-12-14
Revised:2022-01-24
Published:2022-03-28
Online:2022-02-22
Contact:
Jun-Hu Wang
E-mail:wangjh@dicp.ac.cn
摘要：
近年来,析氧反应（oxygen evolution reaction）中针对高效且具有成本效益的电催化剂开发一直是构筑有效利用可再生能源存储系统和水分解生产清洁氢能燃料的重大障碍。OER过程涉及四电子、四质子耦合并形成氧-氧(O-O)键,因此动力学上进程缓慢。为提升其在水分解产氢及二氧化碳还原反应中的应用,需要开发高效催化剂,降低OER过电位,以减轻能量转换过程中固有的能量损失。研究表明,IrO2和RuO2具有较低析氧过电位,但储量低、价格昂贵,大大限制了其在析氧反应中的大规模应用。而Ni-Fe基析氧催化剂在碱性水分解反应中展现了优异的性能,其在水分解过程中的催化机制仍有待进一步研究。
为了解决Ni-Fe基催化剂在析氧反应过程中反应位点及催化反应机制等关键问题,迫切需要更先进的原位技术来准确表征,原位追踪催化剂形态变化与电解质/电极之间的界面相互作用的影响。光谱与电化学结合的原位技术可以监测析氧反应过程催化剂自身的变化。目前,已有大量原位光谱技术与电化学进行结合,揭示Ni-Fe基催化剂在OER过程中的反应机理及活性位点,包括原位表面增强拉曼光谱、原位同步辐射X射线吸收光谱、原位紫外-可见光谱、原位扫描电化学显微镜及原位穆斯堡尔光谱等。其中,原位拉曼技术可以观察Ni-Fe催化剂的振动,可以在电解液中施加测试电压条件下监测电化学反应过程中的中间体,从而提供实时反应信息,有助于追踪电化学驱动反应是如何发生的。原位同步辐射技术可以研究OER过程中Ni-Fe催化剂材料的电子结构和局部几何结构的信息,但目前的研究中更多的是探究Ni的价态变化,对Fe的研究信息较少。原位紫外-可见光谱也主要是针对Ni(OH)2的变化展开研究,逐渐提高施加电位,Ni(OH)2会向着NiOOH逐渐变化,紫外-可见技术可以追踪Ni-Fe基电催化剂中的金属氧化过程。众多电化学原位光谱技术中,57Fe穆斯堡尔谱因具有超高的能量分辨率,是确定催化剂相结构、鉴定活性位点、阐明催化机理以及确定催化活性与催化剂配位结构之间关系的最佳手段。此外,原位穆斯堡尔光谱技术基于原子核和核外电子的超精细相互作用而给出的同质异能移、四极矩分裂以及有效磁场等针对催化剂中的Fe位点的氧化态、电子自旋构型、对称性和磁性信息进行研究,为Ni-Fe基催化剂在析氧反应中的应用提供强有力的支持。
1957年,德国科学家鲁道夫·路德维希·穆斯堡尔（Rudolf Ludwig Mössbauer）在其27岁时,发现作为晶格谐振子的原子在发射或吸收γ射线时以一定的概率不会改变它们的量子力学状态,而这一γ射线的核共振吸收现象于1961年获得诺贝尔物理学奖,不久后被命名为穆斯堡尔效应。穆斯堡尔效应是来自于无反冲的γ射线吸收和发射的核共振现象,能量Ee处于激发态的原子核（Z质子和N中子）通过产生能量为Eγ的γ射线跃迁到能量为Eg的基态,γ射线可能会被处于基态的另一个相同类型的原子核（相同的Z和N）吸收,从而转变为能量Ee的激发态。只有当发射线和吸收线足够重叠时,才能看到共振吸收。
原位穆斯堡尔谱在Ni-Fe催化剂析氧反应中应用,首先需要搭建57Fe穆斯堡尔谱仪与电化学工作站联用。标准的穆斯堡尔光谱仪主要由放射源（通常是57Co在Rh或Pd金属基质中用于57Fe穆斯堡尔光谱）、速度传感器、速度校准装置、波形发生器和同步器、γ射线检测系统、多通道分析仪、计算机,并且可选配低温恒温器或高温烘箱,以控制测量过程处于适宜温度。实际测试过程中,穆斯堡尔谱可以通过速度扫描方法生成,利用移动驱动器或速度传感器以特定速度重复移动源或样品（所谓的多普勒运动）,同时γ射线连续传输或发射穿过样品并计数在同步通道上。获得穆斯堡尔谱图后,基于穆斯堡尔谱数据库（https://medc.dicp.ac.cn/,由中国科学院大连化学研究所穆斯堡尔效应数据中心从全世界收集的穆斯堡尔谱样品数据）,对57Fe穆斯堡尔谱进行分析拟合,对含Fe基材料的物相、价态、自旋态和配位结构进行归因和分析。数据分析拟合主要利用MossWinn数据分析和拟合软件（http://www.mosswinn.com/）。以Ni-Fe氢氧化物催化剂为例,对于原始催化剂,其仅存在一种Fe3+物种,当该催化剂参与OER过程后,可能会存在Fe4+,在双峰基础上,拟合结果中则会出现肩峰向负侧移动现象,可以确认高价Fe的存在,例如Fe4+。为充分证明高价Fe的存在,对于Ni-Fe基催化剂的穆斯堡尔谱测试,还需在工况条件下进行原位测试。
20世纪80年代后期,非贵金属氧化物和氢氧化物代替贵金属氧化物阳极催化剂的电解水研究开始受到关注。Corrigan等通过将Fe杂质引入NiO阳极,测试过程中发现OER活性会增加,但后续的研究中对于Fe究竟如何改变Ni基催化剂的OER性能仍旧不清晰。尔后,原位穆斯堡尔谱的引入逐渐揭开Fe在Ni-Fe电催化水分解析氧反应中的作用。为提高测试准确性并保证穆斯堡尔谱信号的稳定,本实验室对原位穆斯堡尔谱装置做了开发和改进。主要包括三部分：(1) 穆斯堡尔光谱仪,(2) 电化学工作站,以及(3) 自主设计的原位OER电化学反应池。在我们的实验室中,使用了具有14.4 keV级γ射线的单线57Fe穆斯堡尔谱放射源57Co（Rh）,可以减少电解液中的信号衰减并获得令人满意的信噪比,附带CHI660E电化学工作站。对于常规的OER测试,在室温298 K条件下进行测试,测试前首先用α-Fe对穆斯堡尔谱仪进行多普勒速度校准,在进行原位穆斯堡尔谱-OER实验之前,电解液用氮气或氩气饱和以去除溶解的氧气。为了保证测试信号的准确性,实验中所使用的电解池不含任何Fe杂质,因此采用了Teflon材料。为避免测试过程中产生的O2气泡对信号产生干扰,可以采用蠕动泵循环电解液,并且保证测试过程中局部的微反应环境的一致性。对于普通OER测试,仅需要少量催化剂,但对于原位57Fe穆斯堡尔谱测试,只有保证Ni-Fe催化剂中57Fe含量充足的条件下,才可以获得高质量信号。但OER过程中,不建议催化剂载量过高,催化过程中主要是表面催化剂在反应,当样品过厚时,深层样品无法参与析氧反应过程,可能会有部分Fe仍旧维持Fe3+状态。通常,对于常规57Fe穆斯堡尔光谱测量的催化剂,若在制备中使用普通Fe源,则需要Fe含量在5 ~ 10 mg·cm-2,这其中仅有~2.2%的自然丰度57Fe同位素,需要长时间监测才可以采集到信号。为保证实验的顺利进行,可以在样品制备过程中直接使用57Fe源,方便快捷采集高质量信号。为了保证样品测试的准确性,在OER开始前,我们可以在同一电解液中,在开路电位（OCP）下,对其进行测试,这一原始样品的测试可与后续施加电位的Ni-Fe催化剂测试结果进行对比。有外加电压测试时,需要保证催化剂处于稳定状态下进行测试,整个测试过程中保持电流密度稳定,这不仅可以保证催化剂的稳定性,还有助于确定催化剂的真实结构。
利用原位57Fe穆斯堡尔谱,我们对通过Ni-Fe普鲁士蓝类似物原位拓扑转换获得的Ni-Fe羟基氧化物电催化剂进行了测试。基于原位拉曼技术,我们发现在阳极电位下,Ni-Fe催化剂中α-Ni(OH)2相会不可逆转变为γ-NiOOH。原位57Fe穆斯堡尔谱测试结果表明,在较低的施加电位（例如1.22 V 和1.32 V vs. RHE）下,Fe在NiFe0.2-OxHy中仅处于+3氧化态,其光谱结果与开路电位下NiFe0.2-OxHy谱图相似,其中只有一个双峰,两个峰的强度相等,可归因于高自旋 Fe3+物种。但随着外加电位增加并达到1.37 V,两个峰的强度开始变得不相等,开始出现一个小的肩峰,其同质异能移（δ）值约为-0.25 mm·s-1,可以归属为 Fe4+ 。随着电压的逐渐增加,催化剂中的Fe4+含量逐渐增加。在OER过程中,施加电位1.42 V vs. RHE时,Fe4+含量~ 12%。当施加的电势达到1.57 V时,催化剂中Fe4+的含量进一步增加到约40%。这一实例充分展现了原位57Fe穆斯堡尔谱与Ni-Fe催化OER过程的应用,也体现了NiFe0.2-OxHy催化剂原位产生的Fe4+物种的量与其水氧化反应性能呈正相关,进一步加深了对Ni-Fe水氧化催化机理的理解。
Ni-Fe基催化剂因其价格低廉,电催化析氧性能优异,因此成为碱性水分解析氧过程的理想候选者。虽然Ni-Fe基电催化剂表现出优异的OER活性,但缺乏长期稳定性阻碍了其在商业中的应用。因此,充分了解Ni-Fe催化剂的衰减机理,包括形态、组成、晶体结构和活性位点数量的变化,对于设计稳定和高效Ni-Fe催化材料非常重要,充分了解Ni-Fe催化剂在OER过程中的电子结构及其与析氧反应中间体的相互作用尤为重要。原位拉曼及原位紫外-可见光谱可以对Ni-Fe催化剂中的Ni(OH)2到NiOOH的变化进行深入探究,而原位57Fe穆斯堡尔谱测试则可以揭示Ni-Fe基催化剂中Fe的电子环境及其电子的、结构的和磁性的变化。穆斯堡尔光谱为研究Ni-Fe催化剂中Fe的局部电子结构、局部配位、键合和氧化态的提供了强大技术支撑。最近,穆斯堡尔光谱在电催化领域获得了越来越多的关注,它对于检测不同铁基催化材料中的主要活性位点有着重要作用。
Jafar Hussain Shah, 谢起贤, 匡智崇, 格日乐, 周雯慧, 刘朵绒, Alexandre I. Rykov, 李旭宁, 罗景山, 王军虎. 原位57Fe穆斯堡尔光谱技术及其在Ni-Fe基析氧反应电催化剂中的应用[J]. 电化学（中英文）, 2022, 28(3): 2108541.
Jafar Hussain Shah, Qi-Xian Xie, Zhi-Chong Kuang, Ri-Le Ge, Wen-Hui Zhou, Duo-Rong Liu, Alexandre I. Rykov, Xu-Ning Li, Jing-Shan Luo, Jun-Hu Wang. In-Situ/Operando 57Fe Mössbauer Spectroscopic Technique and Its Applications in NiFe-based Electrocatalysts for Oxygen Evolution Reaction[J]. Journal of Electrochemistry, 2022, 28(3): 2108541.
Figure 1
(A) Schematic of the electrochemical water splitting; (B) The reported OER mechanism for alkaline conditions[11]. Copyright@The Royal Society of Chemistry 2019. Reproduced with permission. (color on line)
Figure 2
Steady-state effective conductivity of NiOxHy on an interdigitated array (IDA) electrode as a function of Fe incorpo-ration from 1 mmol·L-1 Fe(NO3)3 in a 1 mol·L-1 aqueous KOH solution[34]. Copyright 2017 American Chemical Society. Reproduced with permission. （color on line）
Figure 3
Cyclic voltammograms were taken during the aging of films in various purities of KOH. A total of 13 CV scans are shown for each sample: one for the initial as-deposited film (the dark purple), and one additional scan after each 5 min aging period up to a total of 1 hour of aging (the dark red). The changes in the anodic and cathodic peak positions (ΔEp,a and ΔEp,c) are labeled for each set of CVs. (ΔEp,a value is shown for the Ni0.75Fe0.25(OH)2, as the oxidation peak is partially obscured by the OER current.)[36] Copyright 2014 American Chemical Society. Reproduced with permission. (color on line)
Figure 4
In-situ/operando XAS of the NiFe OER catalysts with varying catalyst composition Ni100-xFex: (A) Fe K-edges and (B) Ni K-edges[37]. Copyright 2016 American Chemical Society. Reproduced with permission. (color on line)
Figure 5
CVs of NiFe layered oxyhydroxide (blue) and hydrous Fe oxide (green) electrocatalysts used for the in-situ/operando experiments with 57Fe Mössbauer spectra collected at open circuit potential (gray), 1.49 V(purple), 1.62 V(yellow), and 1.76 V(red) vs. RHE. CV data were recorded in the Mössbauer-electrochemical cell with a scan rate of 25 mV·s-1 prior to Mössbauer measurements[47]. Copyright 2015. American Chemical Society. Reproduced with permission. (color on line)
Figure 6
Selected in-situ/operando spectroscopic characterization techniques for being available to capture the NiFe-based OER electrocatalytic intermediate species, investigating the OER pathways and mechanism[54]. Copyright 2021. Elsevier Inc. Reproduced with permission. (color on line)
Figure 7
(A) Schematic illustration for emission of specific energy γ-rays from the excited state of nucleus in the Mössbauer source and recoilless γ-rays resonant absorption of the same nucleus in the ground state in the absorber (sample). (B) Nuclear energy levels splitting in case of a transition between Ig = 1/2 and Ie = 3/2 like that of 57Fe due to electric monopole interaction, or electric quadrupole interaction or magnetic hyperfine interaction, and the corresponding 57Fe Mössbauer spectra.
Figure 8
Schematic illustration of (upper part) configuring a Mössbauer spectrometer copied with permission from webpage: http://www.wissel-instruments.de/ and (lower part) Operational modes of Mössbauer spectroscopy for observing a spectrum: Transmission mode (right) and backscattering mode (left, CEMS measurement). (color on line)
Figure 9
Different line shapes employed for approximation of practically measured 57Fe Mössbauer spectra. (color on line)
Figure 10
(A) Fabricated electrodes for in-situ/operando Mössbauer-electrochemical test. (B) A front view of self-designed Mössbauer-electrochemical reaction cell connected with electrochemical station. (C) In-situ/operando Mössbauer-electrochemical cell placed inside the Mössbauer instrument ready for coinstantaneous OER reaction and Mössbauer measurement. (D) The schematic illustration of in-situ/operando electrochemical 57Fe and 119Sn Mössbauer setup for electrochemical OER characterizations[66]. Copyright 2021. ELSEVIER B.V. Reproduced with permission. (color on line)
Figure 11
(A) A schematic diagram of self-designed in-situ/operando 57Fe and 119Sn Mössbauer electrochemical reaction cell. (B) A schematic illustration of multiple working electrodes parallel arrangement inside the reactor. (color on line)
Figure 12
(A) Linear sweep voltammetric results of NiFe-PBAs/CNTs with varying amount of CNTs. (B) Tafel slopes for NiFe-PBAs/CNTs. (C) XRD analysis showing the structures of NiFe-PBAs/CNTs, carbon paper, NiFe-PBAs/CNTs/carbon paper, and NiFe-PBAs/CNTs/carbon paper after activation through cyclic voltammetry. (D) Ex-situ 57Fe Mössbauer spectroscopic analysis of NiFe-PBAs/CNTs before and after CV activation. (E) Raman spectra for NiFe-PBAs/CNTs before and after CV activation. (F) In-situ/operando Raman spectroscopic analysis for NiFe-PBAs/CNTs at different applied potentials. (color on line)
Figure 13
(A-D) Ex-situ 57Fe Mössbauer analysis of NiFem-Fe PBAs doped with different ratios of Ni:Fe. (E-H) Ex-situ 57Fe Mössbauer analysis of NiFem-OxHy derived from the precursors NiFem-Fe PBAs by topotactic transformation. (color on line)
Table 1
Ex-situ 57Fe Mössbauer spectral parameters of NiFem-Fe PBAs at room temperature
| Sample | Valence/spin state | δ/Fe (mm·s-1) | Δ (mm·s-1) | Γexp(mm·s-1) | A (%) |
|---|---|---|---|---|---|
| NiFe0.11-Fe PBA | FeⅢ high spin | 0.44 | 0.50 | 0.43 | 14 |
| FeⅢ low spin | -0.17 | 0.50 | 0.38 | 86 | |
| NiFe0.2-Fe PBA | FeⅢ high spin | 0.40 | 0.65 | 0.38 | 19 |
| FeⅢ low spin | -0.16 | 0.59 | 0.46 | 81 | |
| NiFe0.25-Fe PBA | FeⅢ high spin | 0.37 | 0.65 | 0.34 | 21 |
| FeⅢ low spin | -0.15 | 0.62 | 0.45 | 79 | |
| NiFe0.29-Fe PBA | FeⅢ high spin | 0.37 | 0.64 | 0.36 | 24 |
| FeⅢ low spin | -0.15 | 0.57 | 0.44 | 76 |
Table 2
Ex-situ 57Fe Mössbauer spectral parameters of NiFem-OxHy at room temperature
| Sample | Valence/spin state | δ/Fe (mm·s-1) | Δ (mm·s-1) | Γexp (mm·s-1) | A (%) |
|---|---|---|---|---|---|
| NiFe0.11-OxHy | Fe3+ high spin | 0.32 | 0.44 | 0.28 | 100 |
| NiFe0.2-OxHy | Fe3+ high spin | 0.32 | 0.58 | 0.42 | 100 |
| NiFe0.25-OxHy | Fe3+ high spin | 0.34 | 0.35 | 0.36 | 100 |
| NiFe0.29-OxHy | Fe3+ high spin | 0.32 | 0.43 | 0.33 | 100 |
Figure 14
(A) Cyclic voltammetric curves of NiFe0.2-OxHy before (the black curves, α-phase Ni(OH)2 structure) and after electrochemical activation (the red curves, γ-phase NiOOH structure). (B-C) 57Fe Mössbauer spectra of NiFe0.2-OxHy before and after electrochemical activation. (D) Raman spectra of NiFe0.2-OxHy before (black) and after (red) applying anodic potential. (E) Operando Raman spectra of NiFe0.2-OxHy collected at different applied potentials (V vs. RHE). (F) The OER polarization curves with iR correction. (G) Overpotentials at 10 mA·cm-2. (H) Tafel plots of NiFem-OxHy with different molar ratios of Fe/Ni and commercial RuO2. (I) Chronopotentiometric curves of NiFe0.2-OxHy on Ni foam with different catalyst loadings at a constant current density of 100 mA·cm-2 for 100 h. The inset shows the chronopotentiometric curve of NiFe0.2-OxHy at a constant current density of 10 mA·cm-2[66]. Copyright 2021. ELSEVIER B.V. Reproduced with permission. (color on line)
Figure 15
The in-situ/operando 57Fe Mössbauer spectra of NiFe0.2-OxHy collected at (A) the open circuit voltage, (B) 1.37 V, (C) 1.42 V, (D) 1.47 V, and (E) 1.57 V (vs. RHE). (F) Ex-situ 57Fe Mössbauer spectrum of NiFe0.2-OxHy collected after OER. The unit of 57Fe Mössbauer parameter of isomer shift (δ) is mm·s-1 relative to standard α-Fe foil. (G) The current-time curves at different applied potentials obtained during the in-situ/operando measurements. (H) Cyclic voltammogram without iR correction of NiFe0.2-OxHy recorded during the in-situ/operando measurements. (I) The content of Fe4+ and corresponding electric current determined at different applied potentials[66]. Copyright 2021. ELSEVIER B.V. Reproduced with permission. (color on line)
Table 3
The content of high-valent iron in-situ produced in the NiFe0.2-OxHy electrocatalyst during the oxygen evolution reaction.
| This work[ | Previous report[ | ||||
|---|---|---|---|---|---|
| Potential (V vs. RHE) | Fe4+ | Potential (V vs. RHE) | Fe4+ | ||
| Fe4+ (%) | δ/Fe (mm·s-1) | Fe4+ (%) | δ/Fe (mm·s-1) | ||
| 1.32 | 0 | - | - | - | - |
| 1.37 | 2 | -0.25 | - | - | - |
| 1.42 (around onset) | 12 | -0.24 | 1.49 (around onset) | 0 | - |
| 1.47 | 23 | -0.25 | - | - | - |
| 1.52 | 36 | -0.24 | - | - | - |
| 1.57 | 40 | -0.25 | 1.62 | 12 | -0.27 |
| - | - | - | 1.76 | 21 | -0.25 |
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