Oriented Thiocyanate Anions at the Air−Electrolyte Interface and Its Implications on Interfacial Water - A Vibrational Sum Frequency Spectroscopy Study

2007 ◽  
Vol 111 (12) ◽  
pp. 4484-4486 ◽  
Author(s):  
P. Viswanath ◽  
H. Motschmann
2016 ◽  
Vol 18 (27) ◽  
pp. 18424-18430 ◽  
Author(s):  
Yujin Tong ◽  
Tobias Kampfrath ◽  
R. Kramer Campen

Vibrational sum frequency spectroscopy measurements reveal that the libration frequency of interfacial water is significantly higher than bulk liquid water, suggesting that water's rotational potential stiffens on moving from the bulk liquid to the air/water interface.


Langmuir ◽  
2010 ◽  
Vol 26 (11) ◽  
pp. 8282-8288 ◽  
Author(s):  
Petru Niga ◽  
Deborah Wakeham ◽  
Andrew Nelson ◽  
Gregory G. Warr ◽  
Mark Rutland ◽  
...  

2020 ◽  
Author(s):  
Mokhtar Rashwan ◽  
Benjamin Rehl ◽  
Adrien Sthoer ◽  
Akemi Darlington ◽  
Md. Shafiul Azam ◽  
...  

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing “chemical” vs “physical” interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl<sub>2</sub> electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm<sup>-1</sup>. However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca<sup>2+</sup> ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.


2020 ◽  
Author(s):  
Mokhtar Rashwan ◽  
Benjamin Rehl ◽  
Adrien Sthoer ◽  
Akemi Darlington ◽  
Md. Shafiul Azam ◽  
...  

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing “chemical” vs “physical” interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl<sub>2</sub> electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm<sup>-1</sup>. However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca<sup>2+</sup> ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.


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