We report on a new versatile experimental setup for in situ Rutherford backscattering spectrometry at solid-liquid interfaces which enables investigations of electric double layers directly and in a quantitative manner. A liquid cell with a three-electrode arrangement is mounted in front of the beam line, and a thin window (thickness down to 150 nm) separates the vacuum of the detector chamber from the electrolyte in the cell. By minimizing the contribution of the window to the measurement, a large variety of elements at the solid-liquid interface with sensitivities far below one monolayer can be monitored. The attachment of Ba onto the surface as a function of contact time and pH value of the electrolyte solution was chosen as an example system. From our measurement, we can not only follow the evolution of the double layer but also derive limits for the point of zero charge for the surface. Our findings of are in good agreement with values found in the literature obtained by other techniques. Despite focusing on a specific system in this work, the presented setup allows for a large variety of in situ investigations at solid-liquid interfaces such as, but not limited to, tracing electrochemical reactions and monitoring segregation, adsorption, and dissolution and corrosion processes.
REFERENCES
1.
H.
von Helmholtz
, “Studien ueber electrische grenzschichten
,” Ann. Phys.
243
, 337
–382
(1879
).2.
H.
Wang
and L.
Pilon
, “Accurate simulations of electric double layer capacitance of ultramicroelectrodes
,” J. Phys. Chem. C
115
, 16711
–16719
(2011
).3.
A. J.
Bard
and L. R.
Faulkner
, Electrochemical Methods: Fundamentals and Applications
(Wiley
, New York
, 2001
), Vol. 2, p. 482
.4.
M.
Kosmulski
, “Isoelectric points and points of zero charge of metal (hydr)oxides: 50 years after Parks’ review
,” Adv. Colloid Interface Sci.
238
, 1
–61
(2016
).5.
D.
Fuerstenau
et al., “Zeta potentials in the flotation of oxide and silicate minerals
,” Adv. Colloid Interface Sci.
114
, 9
–26
(2005
).6.
X.
Cao
, D.
Jia
, D.
Li
, L.
Cui
, and J.
Liu
, “One-step co-electrodeposition of hierarchical radial NixP nanospheres on Ni foam as highly active flexible electrodes for hydrogen evolution reaction and supercapacitor
,” Chem. Eng. J.
348
, 310
–318
(2018
).7.
S.
Manne
, J.
Cleveland
, H.
Gaub
, G.
Stucky
, and P.
Hansma
, “Direct visualization of surfactant hemimicelles by force microscopy of the electrical double layer
,” Langmuir
10
, 4409
–4413
(1994
).8.
F.
Gao
, X.
Du
, X.
Hao
, S.
Li
, J.
Zheng
, Y.
Yang
, N.
Han
, and G.
Guan
, “Electrical double layer ion transport with cell voltage-pulse potential coupling circuit for separating dilute lead ions from wastewater
,” J. Membr. Sci.
535
, 20
–27
(2017
).9.
Q.
Xie
, Y.
Liu
, J.
Wu
, and Q.
Liu
, “Ions tuning water flooding experiments and interpretation by thermodynamics of wettability
,” J. Pet. Sci. Eng.
124
, 350
–358
(2014
).10.
T. G.
Drummond
, M. G.
Hill
, and J. K.
Barton
, “Electrochemical DNA sensors
,” Nat. Biotechnol.
21
, 1192
(2003
).11.
R. D.
Munje
, S.
Muthukumar
, A. P.
Selvam
, and S.
Prasad
, “Flexible nanoporous tunable electrical double layer biosensors for sweat diagnostics
,” Sci. Rep.
5
, 14586
(2015
).12.
D.
Spitzner
, U.
Bergmann
, S.
Apelt
, R. A.
Boucher
, and H.-P.
Wiesmann
, “Reversible switching of icing properties on pyroelectric polyvenylidene fluoride thin film coatings
,” Coatings
5
, 724
–736
(2015
).13.
P.
Simon
and Y.
Gogotsi
, “Materials for electrochemical capacitors
,” Nat. Mater.
7
, 845
–854
(2008
).14.
P.
Sharma
and T.
Bhatti
, “A review on electrochemical double-layer capacitors
,” Energy Convers. Manage.
51
, 2901
–2912
(2010
).15.
J.
Lyklema
, “Interfacial potentials: Measuring the immeasurable?
,” Substantia
1
, 75
–93
(2017
).16.
M. T.
Alam
, M. M.
Islam
, T.
Okajima
, and T.
Ohsaka
, “Measurements of differential capacitance in room temperature ionic liquid at mercury, glassy carbon and gold electrode interfaces
,” Electrochem. Commun.
9
, 2370
–2374
(2007
).17.
H.-J.
Butt
and M.
Kappl
, Surface and Interfacial Forces
(John Wiley & Sons
, 2018
).18.
L.
Bergström
and R. J.
Pugh
, “Interfacial characterization of silicon nitride powders
,” J. Am. Ceram. Soc.
72
, 103
–109
(1989
).19.
J.
Sonnefeld
, “Determination of surface charge density parameters of silicon nitride
,” Colloids Surf., A
108
, 27
–31
(1996
).20.
H.
Catalette
, J.
Dumonceau
, and P.
Ollar
, “Sorption of cesium, barium and europium on magnetite
,” J. Contam. Hydrol.
35
, 151
–159
(1998
).21.
D.
Macdonald
, “Some advantages and pitfalls of electrochemical impedance spectroscopy
,” Corrosion
46
, 229
–242
(1990
).22.
A.
Sacco
, “Electrochemical impedance spectroscopy: Fundamentals and application in dye-sensitized solar cells
,” Renewable Sustainable Energy Rev.
79
, 814
–829
(2017
).23.
D.
Ende
and K.
Mangold
, “Impedance spectroscopy
,” Chem. Unserer Zeit
27
, 134
–140
(1993
).24.
R.
Sprycha
, “Electrical double layer at alumina/electrolyte interface: I. Surface charge and zeta potential
,” J. Colloid Interface Sci.
127
, 1
–11
(1989
).25.
A. V.
Delgado
, F.
González-Caballero
, R. J.
Hunter
, L. K.
Koopal
, and J.
Lyklema
, “Measurement and interpretation of electrokinetic phenomena
,” Technical Report 10, International Union of Pure and Applied Chemistry
, 2005
.26.
S.
Shiraishi
, M.
Kibe
, T.
Yokoyama
, H.
Kurihara
, N.
Patel
, A.
Oya
, Y.
Kaburagi
, and Y.
Hishiyama
, “Electric double layer capacitance of multi-walled carbon nanotubes and B-doping effect
,” Appl. Phys. A
82
, 585
–591
(2006
).27.
S.
Axnanda
, E. J.
Crumlin
, B.
Mao
, S.
Rani
, R.
Chang
, P. G.
Karlsson
, M. O.
Edwards
, M.
Lundqvist
, R.
Moberg
, P.
Ross
et al., “Using ‘tender’ x-ray ambient pressure x-ray photoelectron spectroscopy as a direct probe of solid-liquid interface
,” Sci. Rep.
5
, 9788
(2015
).28.
M. A.
Brown
, Z.
Abbas
, A.
Kleibert
, R. G.
Green
, A.
Goel
, S.
May
, and T. M.
Squires
, “Determination of surface potential and electrical double-layer structure at the aqueous electrolyte-nanoparticle interface
,” Phys. Rev. X
6
, 011007
(2016
).29.
G.
Andersson
and H.
Morgner
, “Investigations on solutions of tetrabutylonium salts in formamide with NICISS and ICISS: Concentration depth profiles and composition of the outermost layer
,” Surf. Sci.
445
, 89
–99
(2000
).30.
M. J.
Bedzyk
, G. M.
Bommarito
, M.
Caffrey
, and T. L.
Penner
, “Diffuse-double layer at a membrane-aqueous interface measured with x-ray standing waves
,” Science
248
, 52
–56
(1990
).31.
O.
Magnussen
, J.
Hotlos
, R.
Nichols
, D.
Kolb
, and R.
Behm
, “Atomic structure of Cu adlayers on Au (100) and Au (111) electrodes observed by in situ scanning tunneling microscopy
,” Phys. Rev. Lett.
64
, 2929
(1990
).32.
R.
Raiteri
, B.
Margesin
, and M.
Grattarola
, “An atomic force microscope estimation of the point of zero charge of silicon insulators
,” Sens. Actuators, B
46
, 126
(1998
).33.
I.
Siretanu
, D.
Ebeling
, M. P.
Andersson
, S. S.
Stipp
, A.
Philipse
, M. C.
Stuart
, D.
Van Den Ende
, and F.
Mugele
, “Direct observation of ionic structure at solid-liquid interfaces: A deep look into the Stern layer
,” Sci. Rep.
4
, 4956
(2014
).34.
C. D.
Bain
, “Sum-frequency vibrational spectroscopy of the solid/liquid interface
,” J. Chem. Soc., Faraday Trans.
91
, 1281
–1296
(1995
).35.
A.
Ghaemi
, M.
Torab-Mostaedi
, and M.
Ghannadi-Maragheh
, “Characterizations of strontium(II) and barium(II) adsorption from aqueous solutions using dolomite powder
,” J. Hazard. Mater.
190
, 916
–921
(2011
).36.
S. P.
Mishra
and V. K.
Singh
, “Radiotracer technique in adsorption study—XIII. Adsorption of barium and strontium ions on chromium(IV) oxide powder
,” Appl. Radiat. Isot.
46
, 847
–853
(1995
).37.
L.
Alessio
, A.
Berlin
, R.
Roi
, and T.
van der Venne
, “Biological indicators for the assessment of human exposure to industrial chemicals. Antimony, soluble barium compounds, hexane and methyl ethyl ketone, thallium and tin. Industrial health and safety
,” EUR 14815 EN, EU
, 1994
.38.
M.
Torab-Mostaedi
, A.
Ghaemi
, H.
Ghassabzadeh
, and M.
Ghannadi-Maragheh
, “Removal of strontium and barium from aqueous solutions by adsorption onto expanded Perlite
,” Can. J. Chem. Eng.
89
, 1247
–1254
(2011
).39.
U. K.
Krieger
, T.
Huthwelker
, C.
Daniel
, U.
Weers
, T.
Peter
, and W. A.
Lanford
, “Rutherford backscattering to study the near-surface region of volatile liquids and solids
,” Science
295
, 1048
–1050
(2002
).40.
K.
Nakajima
, E.
Zolboo
, T.
Ohashi
, M.
Lisal
, and K.
Kimura
, “Perfect composition depth profiling of ionic liquid surfaces using high-resolution RBS/ERDA
,” Anal. Sci.
32
, 1089
–1094
(2016
).41.
R.
Kötz
, J.
Gobrecht
, S.
Stucki
, and R.
Pixley
, “In situ Rutherford backscattering spectroscopy for electrochemical interphase analysis
,” Electrochim. Acta
31
, 169
–172
(1986
).42.
K.
Padmanabhan
, P.
Drallos
, R.
Alexander
, and J.
Buchholz
, “Ion channeling through a thin Si-liquid interface
,” Appl. Phys. Lett.
48
, 578
–580
(1986
).43.
J.
Forster
, D.
Phillips
, J.
Gulens
, D.
Harrington
, and R.
Tapping
, “Ion backscattering studies of the liquid-solid interface
,” Nucl. Instrum. Methods Phys. Res., Sect. B
28
, 385
–390
(1987
).44.
J.
Forster
, D.
Phillips
, J.
Gulens
, R.
Tapping
, T.
Alexander
, J.
Leslie
, and J.
Davies
, “Anomalous penetration of Cs, Ba and Tl through thin Si films
,” Nucl. Instrum. Methods Phys. Res., Sect. B
44
, 195
–198
(1989
).45.
A.
Hightower
, B.
Koel
, and T.
Felter
, “A study of iodine adlayers on polycrystalline gold electrodes by in situ electrochemical Rutherford backscattering (ECRBS)
,” Electrochim. Acta
54
, 1777
–1783
(2009
).46.
K.
Morita
, J.
Yuhara
, R.
Ishigami
, B.
Tsuchiya
, K.
Soda
, K.
Saitoh
, S.
Yamamoto
, P.
Goppelt-Langer
, Y.
Aoki
, H.
Takeshita
et al., “An in situ RBS system for measuring nuclides adsorbed at the liquid-solid interface
,” Radiat. Phys. Chem.
49
, 603
–608
(1997
).47.
N.
De Jonge
and F. M.
Ross
, “Electron microscopy of specimens in liquid
,” Nat. Nanotechnol.
6
, 695
(2011
).48.
M.
Herrmann
, J.
Schilm
, G.
Michael
, J.
Meinhardt
, and R.
Flegler
, “Corrosion of silicon nitride materials in acidic and basic solutions and under hydrothermal conditions
,” J. Eur. Ceram. Soc.
23
, 585
–594
(2003
).49.
M.
Herrmann
, “Corrosion of silicon nitride materials in aqueous solutions
,” J. Am. Ceram. Soc.
96
, 3009
–3022
(2013
).50.
M.
Mayer
, “SIMNRA, a simulation program for the analysis of NRA, RBS and ERDA
,” AIP Conf. Proc.
475
, 541
(1999
).51.
L. S.
Čerović
, S. K.
Milonjić
, D.
Bahloul-Hourlier
, and B.
Doucey
, “Surface properties of silicon nitride powders
,” Colloids Surf., A
197
, 147
–156
(2002
).52.
V. A.
Hackley
and S. G.
Malghan
, “The surface chemistry of silicon nitride powder in the presence of dissolved ions
,” J. Mater. Sci.
29
, 4420
–4430
(1994
).53.
R.
Raiteri
, S.
Martinola
, and M.
Grattarola
, “pH-dependent charge density at the insulator-electrolyte interface probed by a scanning force microscope
,” Biosens. Bioelectron.
11
, 1009
–1017
(1996
).54.
S.-H.
Loh
and S. P.
Jarvis
, “Visualization of ion distribution at the mica-electrolyte interface
,” Langmuir
26
, 9176
–9178
(2010
).55.
T.
Baimpos
, B. R.
Shrestha
, S.
Raman
, and M.
Valtiner
, “Effect of interfacial ion structuring on range and magnitude of electric double layer, hydration, and adhesive interactions between mica surfaces in 0.05-3M and electrolyte solutions
,” Langmuir
30
, 4322
–4332
(2014
).56.
C.
Park
, P. A.
Fenter
, K. L.
Nagy
, and N. C.
Sturchio
, “Hydration and distribution of ions at the mica-water interface
,” Phys. Rev. Lett.
97
, 016101
(2006
).57.
K. A.
Lovering
, A. K.
Bertram
, and K. C.
Chou
, “New information on the ion-identity-dependent structure of Stern layer revealed by sum frequency generation vibrational spectroscopy
,” J. Phys. Chem. C
120
, 18099
–18104
(2016
).© 2019 Author(s).
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