This work is devoted to the study of adsorption properties and adsorption mechanisms of the original (I6), modified (I6COOH) nanodiamonds and charcoal dispersed in water, with respect to dissolved ions (Cu2 +, Pb2 +, NO3 –, CH3COO –) using optical spectroscopy methods: Raman and IR spectroscopies, absorption, dynamic light scattering. Mechanisms of anions and cations adsorption were studied.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3365

Burikov, S.A.

Dolenko, T.A.

Laptinskaya, T.V.

Laptinskiy, K.A.

Rosenholm, J.M.

Shenderova, O.A.

Vlasov, I.I.

SocioEconomic Challenges Journal (Sumy State University)

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ 
Vol. 5 No 4, 04031(3pp) (2013) Том 5 № 4, 04031(3cc) (2013) 
 
 
The article was reported at the International Conference «Physics and Technology of Nanomaterials and Structures», Kursk, 21-22 November, 2013 
2077-6772/2013/5(4)04031(3) 04031-1  2013 Sumy State University 
Short Communication 
 
Mechanisms of Ions Adsorption by Nanodiamonds in Aqueous Suspensions 
 
K.A. Laptinskiy1, S.A. Burikov1, T.V. Laptinskaya1, J.M. Rosenholm2, O.A. Shenderova3,  
I.I. Vlasov4, T.A. Dolenko1 
 
1 Physical Department, Moscow State University, 1/2, Leninskie gory, 119991 Moscow, Russia 
2 Center of Functional Materials, Laboratory of Physical Chemistry, Department of Natural Sciences, Abo Akadmi 
University, 20500 Turku, Finland 
3 International Technology Center, Raleigh, North Carolina 27617, United States 
4 General Physics Institute, Russian Academy of Sciences, 119991 Moscow, Russia 
 
(Received 30 September 2013; published online 10 December 2013) 
 
This work is devoted to the study of adsorption properties and adsorption mechanisms of the original 
(I6), modified (I6COOH) nanodiamonds and charcoal dispersed in water, with respect to dissolved ions 
(Cu2 +, Pb2 +, NO3 –, CH3COO –) using optical spectroscopy methods: Raman and IR spectroscopies, absorp-
tion, dynamic light scattering. Mechanisms of anions and cations adsorption were studied. 
 
Keywords: Nanodiamonds, Adsorption mechanisms, Dynamic light scattering, Raman spectroscopy,  
IR spectroscopy. 
 
 PACS numbers: 68.43. – h, 78.30. – j 
 
 
1. INTRODUCTION 
 
New efficient sorbents of inorganic and organic ions 
are very important for impurities removal from liquids 
and gases, for production of high-purity materials and 
drugs, and for biomedicine. It was shown that due to 
large specific surface, multi-functionality of surface 
groups, possibility of targeted modification of the sur-
face, adsorption properties of nanodiamond (ND) parti-
cles exceed adsorption capacity of many carbon 
sorbents. Adsorption properties of powdered detonation 
nanodiamonds are described in many papers [1, 2, 3]. It 
is obvious that in many applied problems (especially in 
biomedicine) it is advisable to use NDs dispersed in 
water. It is very important to understand mechanisms 
of adsorption in order to make targeted modifications of 
ND surface for increasing its adsorption efficiency.  
This work presents the results of a study of adsorp-
tion properties and adsorption mechanisms of the orig-
inal and modified NDs dispersed in aqueous solutions, 
with respect to dissolved ions Cu2 +, Pb2 +, NO3 –, 
CH3COO – using several complementary spectroscopic 
methods – photon correlation, absorption, Raman and 
IR spectroscopies. Parallel experiments were carried 
out with charcoal in order to compare efficiency of ad-
sorbents. 
 
2. OBJECTS AND METHODS 
 
Adsorption properties of initial (I6) and modified 
(I6СOOH) nanodiamonds in aqueous solutions of 
Cu(NO3)2, Pb(NO3)2, Cu(CH3COO)2 and Pb(CH3COO)2 
were investigated. Characterization of the ND samples 
is presented in [4, 5, 6] and in the Table 1. 
Initial solutions of copper and lead salts with con-
centrations 0.5 and 0.75 M (for nitrates), 0.2 and 0.4 M 
(for acetates) and initial suspensions of NDs with con-
centration 0.5 mg/ml were prepared in deionized 
bidistilled water. The aqua NDs suspensions were 
treated in ultrasonic bath during 3 hours. The obtained 
solutions and suspensions were characterized by differ-
ent methods (titration, dynamic light scattering (DLS), 
electron microscopy (Table 1, Fig. 1). Measured param-
eters have shown stability of aqua suspensions of NDs. 
Then NDs suspensions and salts solutions were mixed 
and were characterized by the same methods.  
Concentrations of ions before and after adsorption 
by NDs were estimated by absorption spectroscopy. The 
second approach is based on concentration dependence 
of the own Raman lines intensity of NO3 – (1045 cm – 1) 
and CH3COO – (898 cm – 1, 2950 cm – 1) [7]. Results of 
absorption spectroscopy and Raman spectroscopy are in 
good accordance. 
Adsorption efficiency of ND is determined by the 
amount of ions adsorbed on the surface unit area of 
ND. In this work it is assumed that ions concentration 
in solution changes due to sorption by NDs only, and 
the efficiency was calculated from the ratio of ions con-
centration in initial solution and in supernatant. . Cal-
culations demonstrated that ratio of areas of the total 
adsorbing surface of the aggregates was SI6/SI6COOH ~ 3, 
thus explaining 3 times higher adsorption efficiency of  
 
 
 
Fig. 1 – HRTEM image of I6 (International Technological 
Center, USA) 
 
 K.A. LAPTINSKIY, S.A. BURIKOV, T.V. LAPTINSKAYA, ET. AL J. NANO- ELECTRON. PHYS. 5, 04031 (2013) 
 
 
04031-2 
I6COOH relative to I6 (under approximately the equal 
change of Cu2+ and of the both anions concentrations). 
Ions Pb2 + are adsorbed by the modified ND slightly 
better than Cu2 + yielding 4 times higher sorption effi-
ciency of I6COOH for Pb2 +. In compare with charcoal, 
NDs adsorption efficiency didn’t show essential  
advantage (Fig. 2). Despite of this fact, the study of 
NDs adsorption properties is very important to solve 
the problem of elaboration of a multifunctional biosen-
sor on the base of NDs. Such biosensors can be used as 
sorbent, drug delivery and fluorescent marker simulta-
neously. 
 
 
 
Fig. 2 – Adsorption activity of I6, I6COOH and charcoal:  
1 – Cu2 + in Cu(CH3COO)2, 2 – CH3COO – in Cu(CH3COO)2,   
3 – CH3COO – in Pb(CH3COO)2) 
 
In order to clarify mechanisms of ion adsorption on 
ND surfaces, IR spectra of powders I6, I6COOH and 
powders, extracted from the aqueous mixtures-
suspensions (adsorbent + adsorbate) were obtained 
(Fig. 3, 4) using confocal FTIR spectrometer (Perkin 
Elmer Spectrum One).  
Presence of great amount of OH groups in IR absorp-
tion spectrum of powders (adsorbent + adsorbate) ex-
tracted from the aqueous mixtures-suspensions and ab-
sence of the valence band of Cu-O (640 cm – 1) show that 
a physical adsorption of Cu2 + ions plays a dominant role. 
A cation forms a solid hydration shell in water, and it 
moves in the solution together with this shell. We sup-
pose that adsorption of copper cations on the sur- 
 
 
Fig. 3 – IR absorption spectra of nanodiamonds I6 and I6 with 
adsorbed ions 
 
 
 
Fig. 4 – IR absorption spectra of nanodiamonds I6COOH with 
adsorbed ions 
 
face of NDs occurs without destruction of their hydra-
tion shells (Fig. 5). As both NDs have many oxygen-
containing surface functional groups, both NDs actively 
adsorb copper on their surface by hydrogen bonding. 
I6COOH (its surface was modified by oxygen-
containing groups) adsorbs copper more actively in 
comparison with I6. 
Appearance of vibrational lines of N-O and NO 
bounds in compare with IR spectra of initial NDs shows 
formation of the new bonds between nitrates anions 
and NDs surface.  
 
Table 1 – Characterization of aqueous suspensions of NDs 
 
Sample  Methods of synthe-
sis and treatment 
of studied samples 
Size  
of crystal-
lites*, [nm]  
ζ-potential [mV] @pH 
5.7, sizes of ND dis-
persions#, [nm]  
 
рН  
value  
Production 
I6  
 
Wet synthesis; 
CrO3 in H2SO4; 
NaOH + H2O2;  
fractionated 
6-10 nm 19.6  3.4 mV 
64.5 nm 
5.57 Chelyabinsk (Rus-
sia) 
I6COOH  
 
Sample I6 treated 
in air at 420 °C 
- – 27.6  17 mV 
190 nm 
3.5 The modification 
was performed in 
the International 
Technology Centre, 
Raleigh (USA)  
Chacoal   75nm, 385 nm  Russia 
 
* Size was determined by Small Angle X-ray Scattering (SAXS),  # Size was determined by DLS measurements. 
 
 MECHANISMS OF IONS ADSORPTION BY NANODIAMONDS IN… J. NANO- ELECTRON. PHYS. 5, 04031 (2013) 
 
 
04031-3 
 
 
 
Fig. 5 – Scheme of adsorption of copper ions on ND surface 
 
That means that chemical adsorption of nitrates an-
ions plays a dominant role. Observed changes of IR 
spectrum of all powders (adsorbent + adsorbate)  
extracted from the aqueous mixtures-suspensions of 
Cu(CH3COO)2 allow to say that chemical adsorption is 
the main mechanism of acetate ions adsorption by 
NDs. 
 
3. CONCLUSIONS 
 
In this research it was found that in nitrates salts 
solutions both NDs and charcoal actively adsorb nitrate 
ions and metal cations, and the adsorption efficiency of 
modified ND is about 3 times higher than that of I6 in 
respect to the ions. In acetates salts solutions both NDs 
and charcoal don’t adsorb Cu2 + and adsorb acetate ions 
weekly. The adsorption efficiency of I6, I6COOH and 
charcoal in respect to all ions in acetate salt solutions is 
practically equal. On the basis of the IR and Raman  spec-
troscopy results, we propose a hypothesis about adsorp-
tion mechanisms of nitrate and acetates anions and 
cooper cations on the surface of the NDs. According to this 
hypothesis the main mechanism of adsorption of Cu2 + 
cations is a physical adsorption, and the main mechanism 
of nitrates and acetates anions is a chemical adsorption. 
 
ACKNOWLEDGEMENTS 
 
Authors of this paper thank A.A. Shiryaev  from 
Institute of Geology of Ore Deposits, Petrography, Min-
eralogy and Geochemistry, RAS (Moscow, Russia) for 
IR spectra registration. This work was supported in 
part by RFBR grants no.12-01-31523-mol_a, 
CBP.EAP.CLG. 984276, the grant of RAS program no. 
24, the grant of President of the Russian Federation for 
leading scientific schools no 3076.2012. 
 
 
REFERENCES 
 
1. A.M. Schrand, S.A. Ciftan Hens, O.A. Shenderova, Critical 
Rev. Solid State Mater. Sci. 34, 18 (2009). 
2. V.N. Mochalin, O. Shenderova, D.Ho.Y. Gogotsi, Nat. 
Nanotechnol. 7, 11 (2012). 
3. B.V. Spitsyn, S.A. Denisov, N.A. Skorik, A.G. Chopurova, 
S.A. Parkaeva, L.D. Belyakova, O.G. Larionov, Diamond 
Related Mater. 19, 123 (2010). 
4. T.A. Dolenko, S.A. Burikov, K.A. Laptinskiy, 
T.V. Laptinskaya, J.M. Rosenholm, A.A. Shiryaev, 
A.R. Sabirov, I.I. Vlasov, J. Alloy. Compd. 586, S436 (2014). 
5. O. Shenderova, A.M. Panich, S. Moseenkov, S.C. Hens, 
V. Kuznetsov, H.M. Vieth, J. Phys. Chem. C 115, 19005 
(2011). 
6. T.A. Dolenko, S.A. Burikov, J.M. Rosenholm, 
O.A. Shenderova, I.I. Vlasov,. J. Phys. Chem. С 116, 24314 
(2012). 
7. S.A. Dolenko, S.A. Burikov, T.A. Dolenko, I.G. Persiantsev, 
Pattern Recognition and Image Analysis 22 No4, 550 
(2012). 
 


English

Mechanisms of Ions Adsorption by Nanodiamonds in Aqueous Suspensions

Electronic Sumy State University Institutional Repository

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ Vol. 5 No 4, 04031(3pp) (2013) Том 5 № 4, 04031(3cc) (2013)   The article was reported at the International Conference «Physics and Technology of Nanomaterials and Structures», Kursk, 21-22 November, 2013 2077-6772/2013/5(4)04031(3) 04031-1  2013 Sumy State University Short Communication  Mechanisms of Ions Adsorption by Nanodiamonds in Aqueous Suspensions  K.A. Laptinskiy1, S.A. Burikov1, T.V. Laptinskaya1, J.M. Rosenholm2, O.A. Shenderova3,  I.I. Vlasov4, T.A. Dolenko1  1 Physical Department, Moscow State University, 1/2, Leninskie gory, 119991 Moscow, Russia 2 Center of Functional Materials, Laboratory of Physical Chemistry, Department of Natural Sciences, Abo Akadmi University, 20500 Turku, Finland 3 International Technology Center, Raleigh, North Carolina 27617, United States 4 General Physics Institute, Russian Academy of Sciences, 119991 Moscow, Russia  (Received 30 September 2013; published online 10 December 2013)  This work is devoted to the study of adsorption properties and adsorption mechanisms of the original (I6), modified (I6COOH) nanodiamonds and charcoal dispersed in water, with respect to dissolved ions (Cu2 +, Pb2 +, NO3 –, CH3COO –) using optical spectroscopy methods: Raman and IR spectroscopies, absorp-tion, dynamic light scattering. Mechanisms of anions and cations adsorption were studied.  Keywords: Nanodiamonds, Adsorption mechanisms, Dynamic light scattering, Raman spectroscopy,  IR spectroscopy.   PACS numbers: 68.43. – h, 78.30. – j   1. INTRODUCTION  New efficient sorbents of inorganic and organic ions are very important for impurities removal from liquids and gases, for production of high-purity materials and drugs, and for biomedicine. It was shown that due to large specific surface, multi-functionality of surface groups, possibility of targeted modification of the sur-face, adsorption properties of nanodiamond (ND) parti-cles exceed adsorption capacity of many carbon sorbents. Adsorption properties of powdered detonation nanodiamonds are described in many papers [1, 2, 3]. It is obvious that in many applied problems (especially in biomedicine) it is advisable to use NDs dispersed in water. It is very important to understand mechanisms of adsorption in order to make targeted modifications of ND surface for increasing its adsorption efficiency.  This work presents the results of a study of adsorp-tion properties and adsorption mechanisms of the orig-inal and modified NDs dispersed in aqueous solutions, with respect to dissolved ions Cu2 +, Pb2 +, NO3 –, CH3COO – using several complementary spectroscopic methods – photon correlation, absorption, Raman and IR spectroscopies. Parallel experiments were carried out with charcoal in order to compare efficiency of ad-sorbents.  2. OBJECTS AND METHODS  Adsorption properties of initial (I6) and modified (I6СOOH) nanodiamonds in aqueous solutions of Cu(NO3)2, Pb(NO3)2, Cu(CH3COO)2 and Pb(CH3COO)2 were investigated. Characterization of the ND samples is presented in [4, 5, 6] and in the Table 1. Initial solutions of copper and lead salts with con-centrations 0.5 and 0.75 M (for nitrates), 0.2 and 0.4 M (for acetates) and initial suspensions of NDs with con-centration 0.5 mg/ml were prepared in deionized bidistilled water. The aqua NDs suspensions were treated in ultrasonic bath during 3 hours. The obtained solutions and suspensions were characterized by differ-ent methods (titration, dynamic light scattering (DLS), electron microscopy (Table 1, Fig. 1). Measured param-eters have shown stability of aqua suspensions of NDs. Then NDs suspensions and salts solutions were mixed and were characterized by the same methods.  Concentrations of ions before and after adsorption by NDs were estimated by absorption spectroscopy. The second approach is based on concentration dependence of the own Raman lines intensity of NO3 – (1045 cm – 1) and CH3COO – (898 cm – 1, 2950 cm – 1) [7]. Results of absorption spectroscopy and Raman spectroscopy are in good accordance. Adsorption efficiency of ND is determined by the amount of ions adsorbed on the surface unit area of ND. In this work it is assumed that ions concentration in solution changes due to sorption by NDs only, and the efficiency was calculated from the ratio of ions con-centration in initial solution and in supernatant. . Cal-culations demonstrated that ratio of areas of the total adsorbing surface of the aggregates was SI6/SI6COOH ~ 3, thus explaining 3 times higher adsorption efficiency of     Fig. 1 – HRTEM image of I6 (International Technological Center, USA)   K.A. LAPTINSKIY, S.A. BURIKOV, T.V. LAPTINSKAYA, ET. AL J. NANO- ELECTRON. PHYS. 5, 04031 (2013)   04031-2 I6COOH relative to I6 (under approximately the equal change of Cu2+ and of the both anions concentrations). Ions Pb2 + are adsorbed by the modified ND slightly better than Cu2 + yielding 4 times higher sorption effi-ciency of I6COOH for Pb2 +. In compare with charcoal, NDs adsorption efficiency didn’t show essential  advantage (Fig. 2). Despite of this fact, the study of NDs adsorption properties is very important to solve the problem of elaboration of a multifunctional biosen-sor on the base of NDs. Such biosensors can be used as sorbent, drug delivery and fluorescent marker simulta-neously.    Fig. 2 – Adsorption activity of I6, I6COOH and charcoal:  1 – Cu2 + in Cu(CH3COO)2, 2 – CH3COO – in Cu(CH3COO)2,   3 – CH3COO – in Pb(CH3COO)2)  In order to clarify mechanisms of ion adsorption on ND surfaces, IR spectra of powders I6, I6COOH and powders, extracted from the aqueous mixtures-suspensions (adsorbent + adsorbate) were obtained (Fig. 3, 4) using confocal FTIR spectrometer (Perkin Elmer Spectrum One).  Presence of great amount of OH groups in IR absorp-tion spectrum of powders (adsorbent + adsorbate) ex-tracted from the aqueous mixtures-suspensions and ab-sence of the valence band of Cu-O (640 cm – 1) show that a physical adsorption of Cu2 + ions plays a dominant role. A cation forms a solid hydration shell in water, and it moves in the solution together with this shell. We sup-pose that adsorption of copper cations on the sur-   Fig. 3 – IR absorption spectra of nanodiamonds I6 and I6 with adsorbed ions    Fig. 4 – IR absorption spectra of nanodiamonds I6COOH with adsorbed ions  face of NDs occurs without destruction of their hydra-tion shells (Fig. 5). As both NDs have many oxygen-containing surface functional groups, both NDs actively adsorb copper on their surface by hydrogen bonding. I6COOH (its surface was modified by oxygen-containing groups) adsorbs copper more actively in comparison with I6. Appearance of vibrational lines of N-O and NO bounds in compare with IR spectra of initial NDs shows formation of the new bonds between nitrates anions and NDs surface.   Table 1 – Characterization of aqueous suspensions of NDs  Sample  Methods of synthe-sis and treatment of studied samples Size  of crystal-lites*, [nm]  ζ-potential [mV] @pH 5.7, sizes of ND dis-persions#, [nm]   рН  value  Production I6   Wet synthesis; CrO3 in H2SO4; NaOH + H2O2;  fractionated 6-10 nm 19.6  3.4 mV 64.5 nm 5.57 Chelyabinsk (Rus-sia) I6COOH   Sample I6 treated in air at 420 °C - – 27.6  17 mV 190 nm 3.5 The modification was performed in the International Technology Centre, Raleigh (USA)  Chacoal   75nm, 385 nm  Russia  * Size was determined by Small Angle X-ray Scattering (SAXS),  # Size was determined by DLS measurements.   MECHANISMS OF IONS ADSORPTION BY NANODIAMONDS IN… J. NANO- ELECTRON. PHYS. 5, 04031 (2013)   04031-3    Fig. 5 – Scheme of adsorption of copper ions on ND surface  That means that chemical adsorption of nitrates an-ions plays a dominant role. Observed changes of IR spectrum of all powders (adsorbent + adsorbate)  extracted from the aqueous mixtures-suspensions of Cu(CH3COO)2 allow to say that chemical adsorption is the main mechanism of acetate ions adsorption by NDs.  3. CONCLUSIONS  In this research it was found that in nitrates salts solutions both NDs and charcoal actively adsorb nitrate ions and metal cations, and the adsorption efficiency of modified ND is about 3 times higher than that of I6 in respect to the ions. In acetates salts solutions both NDs and charcoal don’t adsorb Cu2 + and adsorb acetate ions weekly. The adsorption efficiency of I6, I6COOH and charcoal in respect to all ions in acetate salt solutions is practically equal. On the basis of the IR and Raman  spec-troscopy results, we propose a hypothesis about adsorp-tion mechanisms of nitrate and acetates anions and cooper cations on the surface of the NDs. According to this hypothesis the main mechanism of adsorption of Cu2 + cations is a physical adsorption, and the main mechanism of nitrates and acetates anions is a chemical adsorption.  ACKNOWLEDGEMENTS  Authors of this paper thank A.A. Shiryaev  from Institute of Geology of Ore Deposits, Petrography, Min-eralogy and Geochemistry, RAS (Moscow, Russia) for IR spectra registration. This work was supported in part by RFBR grants no.12-01-31523-mol_a, CBP.EAP.CLG. 984276, the grant of RAS program no. 24, the grant of President of the Russian Federation for leading scientific schools no 3076.2012.   REFERENCES  1. A.M. Schrand, S.A. Ciftan Hens, O.A. Shenderova, Critical Rev. Solid State Mater. Sci. 34, 18 (2009). 2. V.N. Mochalin, O. Shenderova, D.Ho.Y. Gogotsi, Nat. Nanotechnol. 7, 11 (2012). 3. B.V. Spitsyn, S.A. Denisov, N.A. Skorik, A.G. Chopurova, S.A. Parkaeva, L.D. Belyakova, O.G. Larionov, Diamond Related Mater. 19, 123 (2010). 4. T.A. Dolenko, S.A. Burikov, K.A. Laptinskiy, T.V. Laptinskaya, J.M. Rosenholm, A.A. Shiryaev, A.R. Sabirov, I.I. Vlasov, J. Alloy. Compd. 586, S436 (2014). 5. O. Shenderova, A.M. Panich, S. Moseenkov, S.C. Hens, V. Kuznetsov, H.M. Vieth, J. Phys. Chem. C 115, 19005 (2011). 6. T.A. Dolenko, S.A. Burikov, J.M. Rosenholm, O.A. Shenderova, I.I. Vlasov,. J. Phys. Chem. С 116, 24314 (2012). 7. S.A. Dolenko, S.A. Burikov, T.A. Dolenko, I.G. Persiantsev, Pattern Recognition and Image Analysis 22 No4, 550 (2012).  

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Mechanisms of Ions Adsorption by Nanodiamonds in Aqueous Suspensions

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