Modelling the real behavior of technologically relevant materials at typical laboratory environmental conditions is a longstanding challenge. Not only classical pressure conditions are generally far from usual industrial environments (pressure gap) but also heterogeneous materials are very different from those often used to simplify the modelling strategies (material gap). For instance to monitor in-situ/operando the lateral distribution of the chemical state of surfaces and interfaces during a catalytic or electrochemical reaction at sub-micron level at environmental conditions as close as possible to the operational ones is of crucial importance to shed light on the running processes. But the possibility to investigate chemical reactions with X-ray photoelectron spectro-microscopies by overcoming material and pressure gaps is still a challenge also for modern experimental setups.

The Escamicroscopy team of Elettra which operates a Scanning Photoemission Microscope (SPEM) has recently developed novel concepts for a new generation of SPEM working under more realistic pressure conditions. The graphene sealed cells, combined for the first time with XPS by A. Kolmakov [1], allow the possibility to investigate systems which require an ambient pressure regime (e.g. liquid/solid interfaces). Despite the huge ongoing progress in the development and performance of these cells several crucial issues are unsolved and will be addressed by this presentation.

Transition metals in aqueous solution have been investigated by a multitude of techniques and are a cornerstone of many aspects of chemistry. Recently, the atmospheric chemistry community has begun to shift their attention to iron, manganese and copper containing aqueous solutions due to their propensity to generate hydroxyl radicals at the air/water interface through a Fenton mechanism. Understanding the chemical state of the transition metal present at the air/water interface, in addition to the distribution as a function of depth, would provide critical insight to the active species of hydroxyl generation. Solvation effects have been shown to significantly affect the distribution of small ions as a function of depth from the vacuum/water interface; first through molecular dynamics (MD) simulations then corroborated by liquid – jet X – ray photoelectron spectroscopy (LJ-XPS). Solvation of transition metals in aqueous solution have added complexity compared to small ions because of complexation of ligands and equilibria with the surrounding solvent.

Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and synchrotron X-ray microscopy (XRM) are powerful characterization tools and are routinely used to study a wide range of material-systems at the nanoscale. This has generated strong interests in acquiring more reliable quantitative in-situ and operando measurements in realistic reaction environments, as is possible with liquid environmental cells. This approach has already started to produce new insights on the dynamics and structural changes during electrochemical processes as lithium ion insertion/extraction, dendrite formation, metal nucleation and corrosion. However, practical aspects of replicating representative electrochemical data reminiscent of bulk behavior are still a challenge in these systems.

Here, we will discuss practical aspects of conducting operando liquid cell microscopy experiments relating to the typical geometry of these liquid-cell microscopy systems as well as artifacts coming from the microscope during operando experiments. We will also present a TEM/SEM/XRM microscopy platform that enables true electroanalytical measurements mimicking bulk behavior of the material system.

The example study shown here is performed using electrochemical cells, which consist of two microfabricated chips sandwiched with transparent SiNx membranes for encapsulating liquid and viewing in the microscope. A newly developed hardware system and specially optimized electrochemistry chips with a custom configuration for working electrode (WE), counter electrode (CE) and reference electrode (RE) allows quantitative measurements of electrochemical processes with details resembling the complete cycle of the bulk. As illustrations, we present cyclic voltammetry (CV) studies of some model compounds such as 01.M CuSO₄ and 20 mM K₃Fe(CN)₆/20 mM K₄Fe(CN)₆ in 0.1M KCl solutions. In the former case, the copper deposition and stripping occurs at the working electrode at distinct redox peaks in liquid cell and the result mimics the bulk electrochemical cells with large electrode areas and larger volume of electrolyte solution. This work highlights the fact that with suitable hardware systems and with knowledge and correction of microscope-induced artifacts, bulk behavior of the electrochemical processes can be both observed and measured quantitatively.

In this presentation, we demonstrate the feasibility of in-situ scanning electron microscopy to observe the changes in electric double layer in different electrolytes upon polarization. We designed an electrochemical liquid cell with electron transparent electrode made of bilayer graphene.^5,6. We monitored the changes in secondary electron yield from the graphene-liquid interface upon electrolyte polarization. We found that the normalized SEM image contrast is linear with the applied bias voltage and is related to the concentration and distribution of the ions at the interface. The analysis of SEM videos provide insight on long term kinetics of ionic moieties in electrolyte during polarization. This experimental methodology will be helpful for understanding the structure, property, and dynamics of the electric double layer at solid -electrolyte interfaces.

Reference

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[2]. M. Favaro, B. Jeong, P. N. Ross, J. Yano, Z. Hussain, Z. Liu and E. J. Crumlin, Nature Communications 7(2016), 12695

[3]. M. A. Brown, Z. Abbas, A. Kleibert, R. G. Green, A. Goel, S. May, and T. M. Squires, Physical Review X 6(2016), 011007

[4]. J. M. Black, M. Zhu, P. Zhang, R. R. Unocic, D. Guo, M. B. Okatan, S. Dai, P. T. Cummings, S. V. Kalinin, G. Feng, and N. Balke, Scientific Reports 6 (2016), 32389

[5]. A. Yulaev, H. Guo, E. Strelcov, L. Chen, I. Vlassiouk, A Kolmakov, ACS applied materials & interfaces 9 (2017), 26492-26502

[6]. H. Guo, E. Strelcov, A. Yulaev, J. Wang, N. Appathurai, S. Urquhart, J. Vinson, S. Sahu, M. Zwolak, and A. Kolmakov, Nano Letters,17(2017), 1034–1041