Operando X-ray study of service behavior of catalytic materials based on synchrotron radiation
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摘要: 介紹了基于同步輻射的原位X射線吸收譜、原位X射線衍射譜和原位X射線光電子能譜的基本原理及功能，重點綜述了原位X射線技術在電解水催化材料服役行為動態研究中的應用進展，列舉了多種典型電解水催化劑在反應條件下結構動態變化的研究實例，為實現催化材料全生命周期動態構效關系的精準構建提供了技術基礎。最后，分析總結了原位X射線技術在面臨復雜電化學服役環境時所遇到的問題及挑戰，并提出了對先進同步輻射技術及原位X射線譜學的未來展望。Abstract: Considering the energy and environmental issues faced by human society, hydrogen has become increasingly important, and electrocatalytic water splitting is considered to be an ideal way to solve these energy issues. However, although most electrocatalysts will undergo a structural evolution when in service conditions, our understanding of the service behavior of catalysts is limited. To design highly active catalysts, operando characterization techniques must be used to study their dynamic structural evolution. Today, the development of synchrotron radiation devices has reached an important stage. Synchrotron-radiation-based X-ray characterization, which has high energy, large flux, and excellent collimation compared with the ordinary laboratory X-ray source, can capture the precise structure of catalytic materials. In this review, we present the development status of synchrotron radiation devices and the basic principles of operando X-ray absorption spectroscopy, X-ray diffraction spectroscopy, and X-ray photoelectron spectroscopy based on synchrotron radiation. In addition, we highlight studies related to the dynamic service behavior of water-splitting catalysts under real conditions and list a variety of operando studies of typical water-splitting catalysts, including NiFe hydroxide/(oxy)hydroxides, perovskite oxides, spinel oxides, and noble-metal-based catalysts. The use of operando X-ray techniques deepens our understanding of the catalyst reaction mechanism and provides a basis for identifying the dynamic structure–performance correlation of catalysts. We summarize the problems and challenges of operando X-ray-based techniques in complex electrochemical environments and propose the prospect of an advanced synchrotron radiation facility for operando X-ray characterization. With the development of the next-generation synchrotron radiation facility, adequately using this advanced X-ray light source to study the dynamic structure–activity correlation of catalytic materials throughout their life cycle to achieve the precise design and synthesis of complex pre-catalysts will advance the development of this field by enabling greater refinement and control.
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圖 1 （a）XAS裝置示意圖[11]；（b）原位XAS電化學反應池裝置示意圖；（c）XAS的圖譜包括吸收前峰，X射線吸收近邊結構和擴展邊X射線吸收精細結構[12]
Figure 1. (a) Schematic of a common setup for X-ray absorption spectroscopy (XAS) measurements[11]; (b) the structure of the electrochemical cell used in operando XAS setup experiments; (c) XAS spectra, including the pre-edge, XANES, and EXAFS regions[12]
圖 2 （a）Ni和Fe的原位傅里葉轉換EXAFS譜圖；（b）Fe摻雜γ-NiOOH的結構模型[15]；（c）不同Fe摻雜量下Ni和Fe位點K邊的傅里葉轉換EXAFS譜圖[18]
Figure 2. (a) Operando Fourier transform–extended X-ray absorption fine structure (FT-EXAFS) results of Fe and Ni sites; (b) structure model of Fe doped γ-NiOOH[15]; (c) Ni K-edge and Fe K-edge FT-EXAFS with different Fe contents[18]
圖 3 （a）帶有Al空位的CoFe0.25Al1.75O4結構模型；（b）CoFe0.25Al1.75O4轉變為CoOOH的過程示意圖；（c）CoFe0.25Al1.75O4中Co位點K邊原位的XANES（左）和傅里葉轉換EXAFS（右）譜圖（OCP為開路電壓）；（d）CoFe0.25Al1.75O4和CoAl2O4中Co的氧化態隨施加電壓（Eapplied）的原位變化[21]；（e, f）Co3O4和富氧空位Co3O4中Co位點K邊原位的XAFS譜圖；（g）Co位點配位數相對變化ΔN/N隨外加電勢的變化[22]
Figure 3. (a) Model of CoFe0.25Al1.75O4 after Al3+ leaching; (b) reconstruction process from spinel CoFe0.25Al1.75O4 into oxyhydroxide; (c) operando Co K-edge X-ray absorption near-edge structure (XANES) analysis (left axis) and in-situ fourier transforms of Co K-edge extended X-ray absorption fine structure (EXAFS) (right axis) of CoFe0.25Al1.75O4 (OCP is the open circuit potential); (d) operando Co oxidation state of CoFe0.25Al1.75O4 and CoAl2O4 at different potentials applied potentials (Eapplied)[21]; (e, f) operando XAFS of Co K-edge of pure Co3O4 and VO?Co3O4 from OCP to 1.75V; (g) structural coherence change in the EXAFS coordination number of Co ions (ΔN/N) under an applied potential[22]
圖 4 （a）形成(Co/Fe)O(OH)過程示意圖；（b, c）LaCo0.8Fe0.2O3-δ中Co位點K邊原位的XANES圖譜和傅里葉轉換EXAFS譜圖[26]；（d）Ba0.5Sr0.5Co0.8Fe0.2O3?δ催化劑中Co位點K邊原位的傅里葉轉換EXAFS譜圖；（e, f）催化劑Ba0.5Sr0.5Co0.8Fe0.2O3?δ中Co位點K邊原位的XANES譜圖[28]
Figure 4. (a) Schematic of the formation process of (Co/Fe)O(OH); (b, c) operando Co K-edge X-ray absorption near-edge structure (XANES) and Fourier transform–extended X-ray absorption fine structure (FT-EXAFS) spectra of LaCo0.8Fe0.2O3-δ[26]; (d) operando Co K-edge FT-EXAFS spectra of Ba0.5Sr0.5Co0.8Fe0.2O3?δ electrocatalyst; (e, f) operando XANES spectra recorded at the Co K-edge of the Ba0.5Sr0.5Co0.8Fe0.2O3?δ[28]
圖 5 （a）單晶Co3O4@CoO催化劑在0.5 mol·L?1 KOH（pH 13.6）和0.5 mol·L?1 Na2SO4（pH 6.5）溶液中的原位掠入射X射線衍射譜圖；（b）單晶Co3O4@CoO催化劑在OER條件下結構轉變的示意圖[29]
Figure 5. (a) Contour plots of in-situ grazing-angle X-ray diffraction signals of a Co3O4@CoO in an aqueous solution containing 0.5 mol·L?1 KOH (pH 13.6) and 0.5 mol·L?1 Na2SO4 (pH 6.5); (b) schematic representation of structural transformation within Co3O4@CoO single-crystal electrocatalysts[29]
圖 6 （a）Co3O4的原位XRD譜圖[30]；（b, c）NiFe和CoFe層狀雙氫氧化物的(003)衍射峰隨著施加電壓的變化；（d, e）NiFe和CoFe層狀雙氫氧化物的層間距隨著施加電壓的變化[31]
Figure 6. (a) Operando X-ray diffraction patterns of Co3O4[30]; (b, c) evolution of (003) peaks of NiFe LDH and CoFe LDH at different potentials; (d, e) evolution of interlayer distances in NiFe LDH and CoFe LDH at different potentials[31]
圖 7 （a）近常壓XPS裝置示意圖[40]；（b）“浸入?拉出”方法示意圖[43]；（c）Pt電極的4f信號隨著施加電壓的變化；（d）Pt電極表面結構隨施加電壓的變化；（e）K 2p信號隨著施加電壓的變化；（f, g）O 1s信號隨著施加電壓的變化及其在低結合能處的放大圖（LPW為液相水；GPW為氣相水）[44]
Figure 7. (a) Schematic of ambient pressure X-ray photoelectron spectroscopy (APXPS) device[40]; (b) illustration of the dip-and-pull operando XPS strategy[43]; (c) Pt 4f spectra as a function of the applied potential; (d) evolution of the Pt surface structure as a function of the applied potential; (e) K 2p photoelectron peak as a function of the applied potential; (f, g) O 1s photoelectron peak as a function of the applied potential and magnification of the low-binding-energy spectrum tail (LPW is the liquid phase water; GPW is the gas phase water)[44]
圖 8 （a）Ir0、IrIII和IrIV物種含量隨著電壓的變化；（b）Ir 4f 信號在不同電壓下的位置[46]；（c）分別在真空（綠）、1.3 kPa環境壓強（藍）以及OER反應下（紅）的O 1s信號（Ea是實驗時的入射X射線能量）；（d~g）IrO2納米顆粒在1.3 kPa水環境壓強下的Ir 4f XPS光譜[47]
Figure 8. (a) Evolutions of Ir0, IrIII and IrIV with the applied potential; (b) Ir 4f X-ray photoelectron spectroscopy (XPS) spectra of the IrO2 anode at different potentials (E?iR): 0 V (red), 0.7 V (orange), 1.3 V (yellow), 1.53 V (green), 1.56 V (cyan), 1.58 V (blue)[46]; (c) O 1s signal measured under vacuum (green) and under 1.3 kPa water pressure at open circuit voltage (blue) and during oxygen evolution reaction (red). The black lines below correspond to the difference spectra (Ea is the incident X-ray energy during the experiment); (d–g) Ir 4f XPS spectra of IrO2 nanoparticles under 1.3 kPa water pressure[47]
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