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Microfluidic Chips for In Situ Crystal X-ray Diffraction and In Situ Dynamic Light Scattering for Serial Crystallography
Published on: April 24, 2018
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Real-time observation of interfacial ions during electrocrystallization
Masashi Nakamura1, Takahiro Banzai2, Yuto Maehata2
1Department Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba, 263-8522, Japan. mnakamura@faculty.chiba-u.jp.
Scientific Reports
|April 22, 2017
Summary
Electrocrystallization mechanisms of metal cations depend on hydration energy. High hydration energy metals deposit in two steps, while low hydration energy metals adsorb rapidly on Au(111) electrodes.
Area of Science:
- Electrochemistry
- Surface Science
- Materials Science
Background:
- Electrocrystallization is crucial for industrial applications.
- Understanding metal cation deposition mechanisms is key.
- Underpotential deposition (upd) on electrode surfaces requires detailed study.
Purpose of the Study:
- To elucidate transitional structures during metal cation upd on Au(111).
- To investigate the influence of hydration energy on deposition mechanisms.
- To correlate deposition rates with cation properties and surface interactions.
Main Methods:
- Time-resolved surface X-ray diffraction (TR-SXRD).
- Step-scan infrared (IR) spectroscopy.
- Investigation of various metal cations on Au(111) electrode.
Main Results:
- A characteristic intensity transient was observed in TR-SXRD, varying with metal cations.
- Metal cations with high hydration energy undergo two-step deposition involving hydrated states.
- Thallium (Tl+) and Silver (Ag+) cations with low hydration energy adsorb rapidly without metastable states.
- Deposition rate is linked to hydration water coordination energy.
- Complex formation with coadsorbed anions (e.g., Cu2+ in sulfuric acid) slows deposition.
Conclusions:
- Hydration energy significantly dictates the electrocrystallization pathway of metal cations.
- The presence of metastable hydrated states is dependent on cation-water interactions.
- Surface interactions, including anion coadsorption, modulate deposition kinetics.
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