Advanced in-situ electrochemical scanning probe microscopies in electrocatalysis

doi:10.1016/S1872-2067(23)64396-7

Abstract

Abstract:

Electrocatalysis is critical in improving the energy conversion efficiency, decreasing carbon emissions, and promoting the development of the green energy industry. A deep understanding of the electrocatalytic processes at nanostructured electrochemical interfaces (electrodes) is required to elucidate the electrocatalytic mechanism and facilitate the rational design of electrocatalysts. Electrocatalytic surfaces, which are structurally and compositionally heterogeneous, are usually analyzed using classical macroscopic electrochemical methods that lack the high spatial resolution and temporal sensitivity required for localized electrochemical measurements. In this regard, advances in electrochemical scanning probe microscopy, including electrochemical scanning tunneling, electrochemical atomic force, scanning electrochemical, and scanning electrochemical cell microscopies, offer significant opportunities to study electrocatalytic phenomena at nanometer and ultimately atomic scales during the reaction process. In this review, we first introduce the basic principles, features, and advantages and disadvantages of each technique of these scanning probe microscopies and outline the key advancements of each technique, particularly in investigating electrocatalysis. Subsequently, hybrid techniques of probe microscopy with synergistic effects are introduced. Then, we summarize the recent progress in the application of in-situ characterization methods in electrocatalysis, including hydrogen evolution/oxidation, oxygen evolution, and CO₂ reduction reactions, focusing on the structure-activity correlation, structure evolution/stability, adsorption of the reactants or intermediates, preferred reaction pathways, and selectivity. Finally, the challenges and future developments of in-situ scanning probe microscopy in electrocatalysis are discussed.

Key words: Electrochemical scanning probe, microscopies, Electrocatalysis, Reaction mechanism, Structure-activity relationship, Interface

Dan-Qing Liu, Bingxing Zhang, Guoqiang Zhao, Jian Chen, Hongge Pan, Wenping Sun. Advanced in-situ electrochemical scanning probe microscopies in electrocatalysis[J]. Chinese Journal of Catalysis, 2023, 47: 93-120.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64396-7

https://www.cjcatal.com/EN/Y2023/V47/I4/93

Figures/Tables 14

Fig. 1. Advanced in-situ/operando electrochemical scanning probe microscopies applied in electrocatalysis.

Table 1 Comparison of in-situ EC-SPMs for electrocatalysis.

Name	Detected signal	Advantages	Disadvantages	Scope of applications	Ref.
EC-STM	tunneling current, surface current	atomic resolution	disruptive faradic current at the tip; tip potential region limited to electrolyte stability window or the stability of the tip material	nanoscale characterization of electrocatalytic processes associated with reactants adsorption/desorption and surface transformation under electrochemical reactions	[48, 49, 59,65, 69, 70]
EC-AFM	physical force, surface current	a wide range of materials including semiconductor and soft electrode materials	lower lateral resolution (typically 1‒20 nm) compared with EC-STM	morphological and mechanical changes in the interface between electrolyte and electrode with nanoscale resolution	[91, 94-97]
SECM	Faradic current	electrochemical images at the nanoscale	electrochemical activity and topography are not easily separated, diffusional broadening effect	extracting kinetics information quantitatively, resolving electrochemical activity over nanoscale systems	[98, 104, 108]
SECCM	ion current, surface current	the electrochemical properties of a surface are probed directly locally with integrated positional feedback, high mass transfer rates	resolution is limited by tip size	combined with other structural characterizing techniques, enabling high resolution correlative structure-activity investigations	[13, 41, 122, 128, 129]
SECM-AFM	physical force, faradic current	simultaneously acquiring topography, mechanical, electrical, and electrochemical map	difficulties in dual probe fabrication and theoretical consideration	imaging composite surfaces exhibiting electrochemical active sites in materials, biological and chemical sciences	[13, 137, 138, 141, 144]
SECM-STM	tunneling current, faradic current	separating topographical effects from surface electrochemical information	difficulties in elucidating precise geometry of the nanoelectrode, lack of electrochemical map with high resolution	resolving local electrochemistry at conducting surfaces	[116, 147]
SECM-SICM	ion current, faradic current	allowing for simultaneous topography and electrochemical map, generally noncontact topography and can be applied in biological materials	its resolution is usually lower than that of SECM-AFM	generating submicrometer resolution images based on topography, electrochemical and bioelectrochemical signals for local electrochemistry measurement, local pH measurement, as well as detections of enzymatic activity, cellular activity and cell membrane permeability	[119, 135, 172, 173, 176]
SECM-SECCM	ion current, faradic current	enabling high resolution electrochemical imaging with integrated positional feedback	spatial resolution is defined by the meniscus contact area, which is limited by tip size	enabling electrochemical measurements in non-aqueous environments and transient current measurements on insulating and reactive surfaces	[120]

Table 1 Comparison of in-situ EC-SPMs for electrocatalysis.

Name	Detected signal	Advantages	Disadvantages	Scope of applications	Ref.
EC-STM	tunneling current, surface current	atomic resolution	disruptive faradic current at the tip; tip potential region limited to electrolyte stability window or the stability of the tip material	nanoscale characterization of electrocatalytic processes associated with reactants adsorption/desorption and surface transformation under electrochemical reactions	[48, 49, 59,65, 69, 70]
EC-AFM	physical force, surface current	a wide range of materials including semiconductor and soft electrode materials	lower lateral resolution (typically 1‒20 nm) compared with EC-STM	morphological and mechanical changes in the interface between electrolyte and electrode with nanoscale resolution	[91, 94-97]
SECM	Faradic current	electrochemical images at the nanoscale	electrochemical activity and topography are not easily separated, diffusional broadening effect	extracting kinetics information quantitatively, resolving electrochemical activity over nanoscale systems	[98, 104, 108]
SECCM	ion current, surface current	the electrochemical properties of a surface are probed directly locally with integrated positional feedback, high mass transfer rates	resolution is limited by tip size	combined with other structural characterizing techniques, enabling high resolution correlative structure-activity investigations	[13, 41, 122, 128, 129]
SECM-AFM	physical force, faradic current	simultaneously acquiring topography, mechanical, electrical, and electrochemical map	difficulties in dual probe fabrication and theoretical consideration	imaging composite surfaces exhibiting electrochemical active sites in materials, biological and chemical sciences	[13, 137, 138, 141, 144]
SECM-STM	tunneling current, faradic current	separating topographical effects from surface electrochemical information	difficulties in elucidating precise geometry of the nanoelectrode, lack of electrochemical map with high resolution	resolving local electrochemistry at conducting surfaces	[116, 147]
SECM-SICM	ion current, faradic current	allowing for simultaneous topography and electrochemical map, generally noncontact topography and can be applied in biological materials	its resolution is usually lower than that of SECM-AFM	generating submicrometer resolution images based on topography, electrochemical and bioelectrochemical signals for local electrochemistry measurement, local pH measurement, as well as detections of enzymatic activity, cellular activity and cell membrane permeability	[119, 135, 172, 173, 176]
SECM-SECCM	ion current, faradic current	enabling high resolution electrochemical imaging with integrated positional feedback	spatial resolution is defined by the meniscus contact area, which is limited by tip size	enabling electrochemical measurements in non-aqueous environments and transient current measurements on insulating and reactive surfaces	[120]

Fig. 2. Schematic of EC-STM setup (iT: tunneling current; iS: electrochemical current).

Fig. 3. Illustration of an electrochemical cell configuration of EC-AFM.

Fig. 4. Schematic of SECM scanning modes. (a?c) Feedback mode. (d) Tip generation/substrate collection mode. (e) Substrate generation/tip collection mode. (f) Redox competitive mode.

Fig. 5. Schematic illustrating SECCM setups. (a) Double-barrel SECCM. (b) Single-barrel SECCM setups.

Fig. 6. EC-STM revealing catalytic activity with high resolution under HER conditions. (a?c) A scheme illustrating the STM tip is over the terrace (a) or over the step (b). The tunneling-current noise is likely increased when the tip is over a step edge. (c) STM line scans (constant-current mode) over Pt(111) surface in 0.1 mol L?1 HClO4 under different potentials to drive HER. (d?f) STM characterization of Pd islands on an Au(111) substrate under HER conditions. (d) STM image in air. (e) STM image in 0.1 mol L?1 sulfuric acid (constant-height mode). The inset indicates an atomically resolved image of the Au(111) substrate. (f) Line scans obtained from the experiment in Fig. 6(e). Reprinted with permission from Ref. [21]. Copyright 2017, Springer Nature.

Fig. 7. High-resolution SECM characterization of mixed-phase MoS2 under HER conditions. Feedback mode image of the sample on ITO substrate obtained with Fc redox mediator (a) and its corresponding 2D current map (b). (c) SECM image of a zoom-in area. (d) Line scans of HER activity using SG/TC mode across the same area in (c). Reprinted with permission from Ref. [209]. Copyright 2019, The Royal Society of Chemistry.

Fig. 8. SECCM mapping of HER activities on MoS2 and MoS2-WS2 heterostructure. (a) Illustration of SECCM HER measurement over MoS2 surface in 0.5 mol L?1 H2SO4. Pd-H2 was used as a quasi-reference electrode. (b) SECCM current image of 1H MoS2 nanosheets on HOPG substrate. Scan size was 15 × 15 μm2, scan rate was 130 V s?1. Applied voltage was ?1.3 V vs. RHE. Overpotential (c) and Tafel slope plot (d) of the 1H MoS2 edge (red line), terrace (green line), and HOPG edge (gray line). High-resolution SECCM current image of MoS2-WS2 heterostructure at a potential of ?1.1 V vs. RHE (e) and its illustration (f). Scan size was 5 × 5 μm2. Reproduced with permission from Ref. [213]. Copyright 2020, John Wiley and Sons.

Fig. 9. Nanoscale active sites on low carbon steel for HER revealed by SECCM. (a) EBSD map of an SECCM scanned area of the low carbon steel surface. (b) SECCM isurf map of the corresponding area shown in a. Scan area was 40 × 40 μm2. (c) Histogram of the averaged isurf measured from 7.2 to 9.8 ms from each probe landing on low index grains that have a crystal orientation within 10° of (100), (101) and (111). (d) EBSD map of one area showing a HER active grain boundary and the misorientations of the two grains were labeled. (e) The corresponding SECCM map of the averaged current from 7.2 to 9.8 ms during a pulse at a potential of ?1.337 V vs. Ag/AgCl. (f) Enhanced HER activity on local MnS inclusions. (i) SEM, (ii) EDS Sulfur map and (iii) SECCM current map. Reproduced with permission from Ref. [211]. Copyright 2019, American Chemical Society.

Fig. 10. EC-STM study of cobalt porphyrin catalyzed OER activity. Low magnification (a) and higher magnification (b) STM images of CoTPP adlayer on Au(111) substrate in 1 mol L?1 HClO4. STM measurements of CoTPP adlayer on Au(111) in 0.1 mol L?1 KOH (c) and 0.1 mol L?1 NaClO4 (d). (e) Cross section profiles along the white lines in b to d (from top to bottom). (f) Structure model for the CoTPP adlayer. (g) UV-vis spectra of CoTPP adlayer in DFM/H2O solution with KOH, NaClO4 and HClO4 electrolyte; STM images of CoTPP adlayer on Au(111) in 0.1 mol L?1 KOH at a potential of 1.30 V vs. Pt (Ebias = ?200.0 mV, It = 3.5 nA) (h) and 1.80 V vs. Pt (Ebias = ?685.0 mV, It = 3.5 nA) (i). (j,k) Cross section profiles along the white line in (h) and (i). Reproduced with permission from Ref. [75]. Copyright 2019, American Chemical Society.

Fig. 11. Correlative operando microscopy of OER electrocatalyst. (a) SECCM current density line scans of OER activity over β-Co(OH)2 particles as shown in the corresponding SEM images using scanning constant height mode (constant lateral scanning rate: 30 nm s?1). The scan direction is indicated by dotted yellow arrows. Scale bars, 1 μm. (b) Topography graph and local current density maps at increasing applied potential using hopping scanning mode (scan rate: 1 V s?1). Scale bar, 5 μm. (c) Differential height operando EC-AFM maps at different applied voltages compared to the particle morphology at 0.96 V (open circuit-voltage). Scale bar, 500 nm. (d) Line scan of change in particle height as a function of voltage over β-Co(OH)2 particle. (e) EC-AFM current (indicated by red line) and EQCM isothermal (T = 25 °C) mass change with increasing voltage (indicated by blue line). Scan rate of EC-AFM and EQCM, 5 mV min?1. (f) Operando STXM line scan of Co oxidation state at different applied voltage. (g) OER Tafel slope obtained from the STXM cell versus that taken in a macroscopic RDE cell at a scan rate of 10 mV s?1. Reproduced with permission from Ref. [130]. Copyright 2021, Springer Nature.

Fig. 12. Visualizing ORR electrocatalytic performance on individual carbon nanotubes. (a) Illustration of SECCM setup of a nanopipette scanning over an individual SWNT, where dmeniscus and dSWNT correspond to meniscus and SWNT diameter, respectively. (b) ORR activity at a pristine SWNT studied by cyclic voltammograms. Scan rate: 100 mV s?1. (c) SECCM current map of a pristine SWNT. Inset demonstrates a line scan profile of ORR current across the SWNT. (d) SECCM current map of a pristine SWNT containing a kinked region. (e) Zoom-in map of D. The corresponding line scan profiles of a kinked region (red dashed line in (e)) and a selected pristine site (black dashed line in (e)). SECCM maps and line scans of a pristine SWNT before (f) and after (g) electrochemical oxidation. Scan rate: 50 mV s?1. SECCM maps of (c), (d), (e) and (f), (g) obtained at ?1.0 and ?0.75 V vs. Ag/AgCl QRCE, respectively. All measurements performed in aerated PBS (pH 7.2) with 25 mmol L?1 KCl. Reproduced with permission from Ref. [264]. Copyright 2014, American Chemical Society.

Fig. 13. Microstructure dependence investigations of HER and CO2RR activities. (a) EBSD map along the z direction. The white box indicates the SECCM scanning area in Ar atmosphere. (b) SEM image of the scanned SECCM region. (c) SECCM current density map at ?1.05 V vs. Ag/AgCl QRCE. (d) Histogram of current densities from the SECCM scanned area. The scale bars in (b) and (c) are 5 μm. Microstructure dependence investigation of CO2 electroreduction activity. (e) EBSD map of sample A along the z direction. The white box indicates the SECCM scanning area in CO2 atmosphere. (f) SEM image of the SECCM scanned area. (g) SECCM map at ?1.05 V vs. Ag/AgCl. Scale bars in f and g are 5 μm. (h) Histogram of current densities from all the pixels marked in (f). (i) EBSD map of a highly deformed region in sample B along the z direction. (j) The corresponding SECCM map at ?1.05 V vs. Ag/AgCl. Scale bars in (i) and (j) are 5 μm. Reproduced with permission from Ref. [123]. Copyright 2021 Springer Nature.

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