扫描电化学显微镜在电催化表面反应分析中的现代应用

doi:10.1016/S1872-2067(21)63948-7

摘要/Abstract

摘要：

能源和环境问题成为制约未来可持续发展的关键问题之一, 因此, 针对不同电催化反应设计电催化剂变得越来越重要. 电催化剂因其能量效率高、制备简单和易操作等优点, 而应用于可再生能源的相关反应(如水分解和人工光合作用)中. 明确不同反应电催化剂的设计原理, 深入理解其在相关反应中的催化机理, 可进一步优化催化剂性能.
本文综述了扫描电化学显微镜(SECM)应用于电催化反应的历程、关键方法以及一些代表性的工作, 阐明了电催化剂的工作机理以推进电催化剂的设计. 本文还介绍了为提高SECM的空间分辨率而尝试的纳米尺寸电极方面的新进展, 分享了纳米电极在以前研究无法涉及的单一催化实体方面的应用.

关键词: 扫描电化学显微镜, 电催化, 表面反应分析, 应用

Abstract:

Development of reaction-tailored electrocatalysts is becoming increasingly important as energy and environment are among key issues governing our sustainable future. Electrocatalysts are inherently optimized for application towards reactions of interest in renewable energy, such as those involved in water splitting and artificial photosynthesis, owing to its energy efficiency, simple fabrication, and ease of operation. In this view, it is important to secure logical design principles for the synthesis of electrocatalysts for various reactions of interest, and also understand their catalytic mechanisms in the respective reactions for improvements in further iterations. In this review, we introduce several key methods of scanning electrochemical microscopy (SECM) in its applications towards electrocatalysis. A brief history and a handful of seminal works in the SECM field is introduced in advancing the synthetic designs of electrocatalysts and elucidation of the operating mechanism. New developments in nano-sizing of the electrodes in attempts for improved spatial resolution of SECM is also introduced, and the application of nanoelectrodes towards the investigation of formerly inaccessible single catalytic entities is shared.

Key words: Scanning electrochemical microscopy, Electrocatalysis, Surface reaction, Electroanalytical chemistry, In situ electrochemical analysis, Direct quantification

C. Hyun Ryu, Yunwoo Nam, Hyun S. Ahn. 扫描电化学显微镜在电催化表面反应分析中的现代应用[J]. 催化学报, 2022, 43(1): 59-70.

C. Hyun Ryu, Yunwoo Nam, Hyun S. Ahn. Modern applications of scanning electrochemical microscopy in the analysis of electrocatalytic surface reactions[J]. Chinese Journal of Catalysis, 2022, 43(1): 59-70.

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https://www.cjcatal.com/CN/Y2022/V43/I1/59

图/表 20

Fig. 1. Schematic description of the SECM instrument.

Fig. 2. SECM feedback modes. (a) steady state current situation; (b) positive feedback; (c) negative feedback; (d) approach feedback of positive feedback and negative feedback.

Fig. 3. SECM generation/collection modes. (a) Tip generation/substrate collection (TG/SC); (b) Substrate generation/tip collection (SG/TC).

Fig. 4. Catalyst array fabrication and SECM images. (a) Schematic of the dispenser setup for the preparation of catalyst spots and sequence of steps for the deposition of catalyst precursor solutions; SEM images of typical binary (Pd-Co) (b) and ternary (c) catalyst arrays; SECM images for oxygen reduction reaction in acidic media of binary (d) and ternary (e) catalyst arrays. Adapted with permission from Ref. [19]. Copyright 2005, American Chemical Society.

Fig. 5. Nanostructured interfaces as electrocatalytic process active sites. (a) Defects such as step edges (SE) lead to nonuniform reactivity to single crystal surfaces which is nominally structurally and compositionally uniform; (b) Extended heterogeneous surfaces, such as polycrystalline metals, comprise structurally (e.g., grains and grain boundaries, GBs) and/or compositionally disparate (e.g., inclusions) sites that can possess vastly different intrinsic electrochemical activities; (c) Nanoparticles (NPs), possessing size-, shape-, and structure-dependent activity, may interact physicochemically (diffusional coupling, aggregation, sintering, etc.) during electrocatalytic turnover (i), as well as undergo dynamic interaction with the support (ii). Adapted with permission from Ref. [22]. Copyright 2019, American Chemical Society.

Fig. 6. (a) Schematic depiction of imaging ORR activities of four different types of single platinum particle by SECM; (b) Electrochemical activity map of particle array. Adapted with permission from Ref. [38]. Copyright 2010, American Chemical Society.

Fig. 7. (a) Electron transfer reactions occurring at Pt NP and HOPG; (b) SECM images for FcTMA2+/FcTMA+ coupled electron transfer reactions; (c) SECM images for H+/H2 coupled electron transfer reactions. Adapted with permission from Ref. [41]. Copyright 2016, American Chemical Society.

Fig. 8. Topographical (a) and electrochemical (b) activity map of electrochemical oxidation of [N2H5]+ on the surface of single Au nanoparticle, obtained with SECCM; (c) Normalized linear scan voltammetries at the individual active sites shown in (a). Adapted with permission from Ref. [42]. Copyright 2017, American Chemical Society.

Fig. 9. Feedback mode of oxidation/reduction of ferrocenemethanol (Fc) (a) and SG/TC of OER (c) at NiO nanosheet surface; Electrochemical activity of Fc oxidation/reduction (b) and ORR (d) map at NiO edge site. Adapted with permission from Ref. [44]. Copyright 2019, Proceedings of the National Academy of Sciences.

Fig. 10. (a,b) Electrochemical activity map of the oxidation of Fe2+ to Fe3+ at different substrate potential. Grain boundary marked with a black line shows high electrochemical activity. GB marked with a white line shows no difference compared to adjacent grains; (c) Crystal orientation map of the same area with (a,b), obtained by electron backscatter diffraction. Adapted with permission from Ref. [45]. Copyright 2013, American Chemical Society.

Fig. 11. (a,c) Schematic description of the quantification of CO2 radical dimerization and current difference according to the distance between tip and substrate. Adapted with permission from Ref. [49]. Copyright 2017, American Chemical Society. (b,d) Schematic description of the quantification of DMA radical dimerization and current plot with EC2EE model simulation. Adapted with permission from Ref. [48]. Copyright 2014, American Chemical Society.

Table 1 Applications of approach curve analysis at each case.

Case	Reaction	Application	Ref.
EC_i	Tip: O + ne^- → R Solution: $\mathrm{R} \stackrel{k}{\rightarrow} \text { Products }$ Substrate: R - ne^- → O	Dimethyl-p-phenylenediamine (DMPPD) oxidation	[50,51]
		[Cp*Re(CO)₂(p-N₂C₆H₄OME)][BF₄] reduction	[52]
		Di-tert-butyl nitroxide (DTBN) oxidation	[53]
EC_2i	Tip: O + ne^- → R Solution: $\mathrm{2R} \stackrel{k}{\rightarrow} \text { Products }$ Substrate: R - ne^- → O	Dimethyl Fumarate (DF) dimerization	[54]
		Fumaronitrile (FN) dimerization	[54]
		Acrylonitrile (AN) radical anion detection	[55]
		4-nitrophenolate (ArO^-) dimerization	[56]
		Nicotinamide adenine dinucleotide (NAD) radical detection	[57]
		Nitro radical anion dimerization	[58]
		Superoxide interaction with 1,4-dihyropyridine	[59,60]
ECE	Tip: A + ne^- → B Solution: $\mathrm{B} \stackrel{k}{\rightarrow} \text { C}$ Tip, Substrate: C + ne^- → D	Lifetime of guanosine (G) radical cation	[61]
DISP	Tip: A + ne^- → B Solution: $\mathrm{B} \stackrel{k}{\rightarrow} \text { C}$ Solution: $\mathrm{B+C} \stackrel{k}{\rightarrow} \text { A+D}$ Tip, Substrate: C + ne^- → D	Anthracene (A) reduction	[62]
DISP		Epinephrine oxidation	[63]
EC`	Tip: A + ne^- → B Solution: B + Y → A + Products	Amidopyrine oxidation	[64]
EC`	Tip: A + ne^- → B Solution: B + Y → A + Products	Aromatic Halides reduction	[65]

Fig. 12. (a-c) Schematic description of the SI-SECM processes. (d) Current response at the tip at the negative, positive, and SI-SECM conditions. Adapted with permission from Ref. [13]. Copyright 2008, American Chemical Society.

Fig. 14. (a) Diagram of the external switching device; (b) Titrations of the CoPi surface activity with switching device. Adapted with permission from Ref. [69]. Copyright 2015, American Chemical Society.

Fig. 15. (a) Coulometric titration curves of Iridium. Adapted with permission from Ref. [97]. Copyright 2015, American Chemical Society. (b) Coulometric titration curve of CoPi. Adapted with permission from Ref. [98]. Copyright 2015, American Chemical Society

Fig. 16. (a) Titration curves of Ni(OH)2 and FeOOH electrodes; (b) Time-dependent titration of Ni(OH)2 at Esubs = 0.6 V; (c) Fast and slow site rate constant and fraction of fast site at various catalysts. Adapted with permission from Ref. [112]. Copyright 2016, American Chemical Society.

Fig. 17. Reactivity of MoS2 by SI-SECM. (a) A time-dependent redox titration CAs at Esubs = -0.92 V; (b) Remaining Mo titrands as a function of tdelay; amount of HER time; (c) Same as (b) but Esubs = -1.12 V. (600 mV overpotential, 31% hydride coverage); (d) Closed up the graph during tdelay ~0.20 s and the HER rate constant of MoS2 at 31% hydride coverage (Esubs = -1.12 V) was measured at ~3.8 s-1, which is the slope of graph. Adapted with permission from Ref. [123]. Copyright 2016, American Chemical Society

Fig. 18. (a) Mechanistic study of HER on Nickel by SI-SECM. Charge density obtained from interrogation transients on Nickel surface as substrate potential increases. (b) Experimental data and Simulation data. Adapted with permission from Ref. [124]. Copyright 2017, American Chemical Society.

Fig. 19. Quantification of Hads at CuAgHg thin films compared to Cu. (a) Schematic illustration of experiment; (b) Charge density versus Esubs at Cu and CuAgHg thin films; (c) Surface redox titration curves of Cu10Ag14Hg0.6 electrode at various Esubs; (d) Linear sweep voltammograms of the hydrogen evolution reaction at each catalyst deposited on a carbon UME. Adapted with permission from Ref. [125]. Copyright 2020, American Chemical Society.

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