Adsorption

https://doi.org/10.1007/s10450-019-00111-8

Adsorption behavior of oxalic acid at water–feldspar interface:

experiments and molecular simulation
Xiaopeng Xue1,2 · Wei Wang1,2 · Hao Fan1,2 · Zhonghao Xu1,2 · Israel Pedruzzi1,2 · Ping Li1,2 · Jianguo Yu1,2

Received: 10 October 2018 / Revised: 7 May 2019 / Accepted: 9 May 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
Feldspar belongs to aluminosilicate minerals with a huge reserve, accounting for at least 98% in soil minerals. Oxalic acid is
the common organic matter in the natural world, having three configurations (­ H2C2O4, ­HC2O4− and ­C2O42−) dependent on pH
value in water solution. In this work, the adsorption behavior of oxalic acid at water–feldspar interface were investigated at
the molecular level through molecular dynamic simulation and advanced characterization technologies in order to provide the
useful information for bioleaching and flotation industry. Classical molecular dynamic (MD) simulation, density functional
theory (DFT) calculation and frequency calculation were performed to analyze adsorption behavior of oxalic acid at water–
feldspar interface. Adsorption of ­H2C2O4 on feldspar surface belonged to physical outer-sphere adsorption with hydrogen
bond while adsorption of ­HC2O4− and ­C2O42− belonged to inner-sphere adsorption with Al–O bond based on the molecular
dynamic simulation results. Frequency calculation demonstrated both H ­ C2O4− and ­C2O42− complexed with Al active site
rather than Si site on feldspar surface, and the detected ATR-FTIR spectra were also in agreement with the simulated results.
Dissolution experiments of feldspar with oxalic acid and TGA–DSC analysis of feldspar after oxalic acid adsorption were
carried out to evaluate the adsorption behavior. Adsorption mechanism of oxalic acid on feldspar surface was proposed.

Keywords  Adsorption · Oxalic acid · Feldspar · Molecular simulation · Mineral dissolution

1 Introduction
Oxalic acid is the common organic matter in the natural
world, which is generated frequently from biomass degrada-
tion, microbial metabolites and industrial wastes et al. There
are three kinds of configurations (­H2C2O4, ­HC2O4− and
­C2O42−) dependent on pH value in aqueous solution. It is
found that oxalic acid, as the simplest carboxylic acid, can
adsorb on many minerals, which would promote minerals
dissolution obviously, such as feldspar, kaolinite, albite and
montmorillonite (Stillings et al. 1996, 1998; Welch and
* Ping Li
liping_2007@ecust.edu.cn
* Jianguo Yu
jgyu@ecust.edu.cn
1
State Key Laboratory of Chemical Engineering, School
of Chemical Engineering, East China University of Science
and Technology, Shanghai 200237, China
2
National Engineering Research Center for Integrated
Utilization of Salt Lake, East China University of Science
and Technology, Shanghai 200237, China
Ullman 1996; Strobel 2001; Cama and Ganor 2006; Oelkers
et al. 2011; Ramos et al. 2015; Zhang and Jun 2015). Feld-
spar (K-feldspar, Na-feldspar, Ca-feldspar) reserve is huge,
accounting for at least 98% in soil minerals. Feldspar is com-
posed of Al–O and Si–O tetrahedron structures to form the
stable framework, where Al–O tetrahedron connects with
Si–O tetrahedron resulting in extra negative charges and K ­ +
locating in the tetrahedron structures space balances nega-
tive charges to obtain the stable structure (Yang et al. 2014).
Dissolution of feldspar could increase significantly the nutri-
ent element K concentration in soil for plant growth (Ramos
et al. 2017). Moreover, feldspar belongs to aluminosilicate
mineral (Crundwell 2014), and aluminosilicate ore is also
the main impurity in the hydrometallurgy process of cop-
per, gold, zinc, phosphorus et al. So it’s meaningful to study
interactions between feldspar and organic ligands.
For adsorption behavior of organic ligands on minerals,
two types of adsorption mechanisms were reported, outer-
sphere adsorption and inner-sphere adsorption (Strawn and
Sparks 1999; Johnson et al. 2004a, b, 2005). By outer-sphere
adsorption, minerals surface was hydrated by water to pro-
mote the formation of surface hydroxyls. Organic ligands

13
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 Adsorption
were adsorbed through physical hydrogen bonds with sur-
face hydroxyls, which was relatively weaker and easier to be
desorbed. Normally, outer-sphere adsorption couldn’t pro-
mote dissolution rate of minerals as a protective layer (Duck-
worth and Martin 2001). By inner-sphere adsorption, metal
ions on the minerals surface with positive charges could con-
nect with organic ligands directly through chemical bonds,
which was relatively stronger. Inner-sphere adsorption could
lower active energy to promote dissolution rate of minerals
significantly (Johnson et al. 2004b). However, it should be
noticed that the inner-sphere adsorption could inhibit disso-
lution of minerals sometimes, since inner sphere adsorption
of organic ligands with relatively bigger volume could result
in huge space resistance (Biber et al. 1994).
To probe adsorption behavior of organic acid on min-
erals surface, some advanced analytical instruments have
been developed to help figure out adsorption mechanism.
For example, Atomic Force Microscope (AFM) could detect
organic acids on minerals surface at nano scale (Filby et al.
2012; Xian et al. 2017; Xiong et al. 2018). Normally, sur-
face of minerals was smooth before adsorption, while surface
became rough after adsorption. AFM could detect adsorption
thickness and coverage fraction on mineral surface. Electrons
of organic ligands with negative charges could transfer to
metal ions on minerals surface during chemical inner-sphere
adsorption, X-ray photoelectron spectroscopy (XPS) (War-
man et al. 2016; Feng et al. 2017) could detect the electrons
transfer at different electrons orbitals. Normally, outer-sphere
adsorption wouldn’t change Attenuated Total Reflection
Flourier Transformed Infrared Spectroscopy (ATR-FTIR
spectra), while inner-sphere adsorption could change ATR-
FTIR spectra significantly. Chemical adsorption of organic
ligands on minerals surface could produce new frequency
peaks in ATR-FTIR spectra (Kubicki et al. 1999; Duckworth
and Martin 2001; Ha et al. 2008). In addition, TGA–DSC
analysis could distinguish between outer-sphere adsorption
and inner-sphere adsorption. With temperature increasing,
outer sphere adsorption of organic acid on minerals sur-
face started to be desorbed firstly at low temperature about
100–200 °C, while inner-sphere adsorption of organic acids
was desorbed at least 400 °C due to formation of complexa-
tions between organic ligands and metal ions.
In the other side, with development of computational
chemistry (Han et al. 2012), molecular simulation could
investigate theoretically the adsorption behavior of oxalic
ligands on mineral surface at an atomic level (Rai et al.
2011; Xu et al. 2013; Xiong et al. 2018). Molecular dynamic
simulation could seek the optimum adsorption site on min-
eral surface for organic ligands to distinguish between inner-
sphere adsorption and outer-sphere adsorption. The adsorp-
tion energy of outer-sphere adsorption was obviously lower
than that of inner sphere adsorption, and hydrogen bonds
length was between 2.5 and 3.5 Å and angle was greater
13
than 120° (Yeh et al. 2015) while chemical bonds length
was often less than 2.5 Å based on molecular simulation
results. Moreover, orbitals calculation and frequency cal-
culation based on DFT method could figure out the inner-
sphere adsorption behavior, such as electrons transfer and
complexation types. Here, complexation types included
mainly mononuclear monodentate and mononuclear biden-
tate which could result in different frequency in ATR-FTIR
spectra (Kubicki et al. 1997, 1999; Zhang and Jun 2015).
To the best of our knowledges, there were no reports
about molecular simulation for oxalic adsorption on Feld-
spar. So, our objective was to investigate the adsorption
behavior of oxalic acid at water–feldspar interface from the
molecular level through advanced characterization technolo-
gies and molecular dynamic simulation. Firstly, molecular
dynamic simulation was adopted to seek and predict adsorp-
tion sites of oxalic acid on feldspar surface. And then ATR-
FTIR and TGA–DSC analysis were used to validate the
molecular prediction. In the end, the adsorption mechanism
of oxalic acid on feldspar was proposed. The research infor-
mation would provide theoretical data for the utilization of
aluminate ores and the purification of valuable minerals with
aluminate impurities.
2 Experimental and theoretical sections
2.1 Experimental section
2.1.1 Feldspar mineral
Feldspar was obtained from Hebei province, China. Minerals
were crushed and finely milled. The fine ground minerals
were sieved through 200 mesh sieve and washed by dilute
HCl (0.01 M) one time, by dilute NaOH (0.01 M) one time,
by ultra pure water three times. After this procedure, miner-
als powder were totally dried at 80 °C. And then, minerals
were characterized by X ray diffraction(XRD) and Scan-
ning electron microscope (SEM), as shown in Fig. 1. Main
component of minerals was microcline, one kind of feldspar
minerals. The strongest peak intensity corresponded to facet
(0 1 0) of feldspar, the biggest surface area of feldspar and
easier to be cleaved (Xu et al. 2017). As a result, facet (0
1 0) was mainly considered in following experiments and
theoretical calculations (calculated by Material Studio 6.1).
2.1.2 Dissolution experiment
100 mL 0.05 mol/L oxalic acid ­(C2H2O4·2H2O, AR, > 99.5%)
with different pH (pH 0.00, pH 2.76, pH 6.00) were mixed
with 5 g feldspar minerals into flasks. Because both ­Cl− and
­Na+ ions have the negligible complexation with Al and
Si sites on feldspar surface, the pH values in the aqueous
Adsorption

Fig. 1  XRD spectra and SEM

image for feldspar. a Compari-
son between experimental and
computational XRD spectra
of feldspar; b SEM image of
feldspar mineral showing main
facet (0 1 0)

solutions with 0.05 mol/L oxalic acid were adjusted through
external HCl and NaOH titration in order to keep oxalic acid
existing in the single form of ­H2C2O4 at pH 0.00, the form of
­HC2O4− at pH 2.76 and ­C2O42− at pH 6.00. And then, flasks
were put into shaker at 25 °C and 180 rpm for 2 days. 1 mL
samples taken from flasks every 12 h were centrifuged at
12000 rpm and 4 °C for 10 min to obtain supernatant that
would be analyzed by Inductively Coupled Plasma Optical
Emission Spectrometer (ICP-OES) to obtain the dissolution
amounts of Al and Si elements from feldspar mineral.
2.1.3 ATR‑FTIR detection and TGA–DSC analysis
After dissolution experiment, solid fraction from centrifuga-
tion was dried at 25 °C naturally. The dried solids were ana-
lyzed by ATR-FTIR (Nicolet 6700, USA). All spectra were
obtained using KBr pellets at 25 °C with a resolution 256
scans and 4 cm−1. At the same time, the dried solids were
analyzed by TGA–DSC (SDT/Q600, TA company, USA).
Temperature increased from room temperature to 500 °C
by 20 °C/min rate under ­N2 environment when weight loss
curves were measured.
provided more accurate charges assignments than that by
classical MD calculations. Unit cell of feldspar (volume of
802.20 Å3) imported from software library were optimized
in module ­Dmol3 on geometry and three forms of oxalic
­ 2C2O4, ­HC2O4− and C
acids including H ­ 2O42− based on pro-
tonation constant (Fig. 2) were built based on research by
Weber group (Weber et al. 2014). In this work, 0.05 mol/L
oxalic acid was selected for experimental verification, and
then based on ­pKa1 and ­pKa2, the oxalic acid forms at dif-
ferent pH value were calculated. It was found that 99.98%
of oxalic acid existed the form of ­H 2C 2O 4 at pH 0.00,
99.98% of oxalic acid exists in the form of ­HC2O4− at pH
2.76, 99.98% of oxalic acid was C ­ 2O42− at pH 6.00. For
the molecular simulation, the oxalic acid solution with
pH 0.00, 2.76 and 6.00 were selected in order to investi-
gate the interaction between feldspar and each oxalic acid

2.2 Theoretical section

Material Studio 6.0 developed by Accelrys incorporation

was adopted to carry out classical molecular dynamic (MD)
simulation in Forcite module and density functional theory
(DFT) calculations in D­ mol3 module for simulating inter-
actions between oxalic acid and feldspar. Furthermore,
frequency calculations were performed in Gaussian09 W
developed by Gaussian incorporation.

2.2.1 Molecular models of feldspar and oxalic acid

Charges assignments of atoms were extremely important Fig. 2  Three forms of oxalic acid in the aqueous solution with differ-
and critical for classical MD simulation. DFT calculations ent pH value

13
 Adsorption

2.2.2 Molecular model and method of classical molecular

dynamic simulation

Classical molecular dynamic (MD) simulation was applied

to investigate oxalic acid adsorption on feldspar surface.
Oxalic acid had three forms at different pH value, as H ­ 2C2O4,
­HC2O4− and C ­ 2O42−, respectively. Crystal facet (0 1 0) of
feldspar was most stable and had the biggest surface area. So
the adsorption of three forms of oxalic acid was considered
mainly on feldspar crystal facet (0 1 0). MD simulation of
interactions models between feldspar and oxalic acid were
built in Forcite module as following procedures. Firstly, facet
Fig. 3  Molecular models of water, feldspar and oxalic acid with three (0 1 0) was cleaved and expand to 4*2*2 super cell. Then two
configurations. Black number: charges; blue numbers: bond length; water layers were added on the super cell of feldspar. Water
green number: angles (Color figure online) layer near surface of feldspar was relaxed, while another water
layer was fixed. At the same time, first layer of feldspar surface
form, respectively. Water molecule was obtained as same was relaxed while the remained parts of feldspar were fixed.
describing method as oxalic acid molecule. Finally, three forms of oxalic acid were laid accidently close
In these geometry optimization calculations, gener- to the relaxed feldspar surface as shown in Fig. 4.
alized gradient approximation (GGA) with the Perdew- Three adsorption models (A, B and C) were optimized
Burke-Ernzerhof (PBE) parametrization of the exchange on geometry to obtain the stable initial adsorption models.
correlation functional and basis set DNP 3.5 (comparable In this step, only oxalic acid molecules, one water layer near
to Gaussian 6–31 g** method) were adopted. Convergence super cell and surface of super cell were unrestrained. At last,
criteria included energy change 1 × 10−5Ha, SCF tolerance molecular dynamics simulation of each adsorption model was
1 × 10 −6, max force 0.002 Ha/Å and max displacement performed using UFF force field. UFF force field was univer-
0.005 Å. In addition, a fermi smearing 0.005 Ha was used sal force field to describe interfacial phenomenon of organic
to improve the convergence speed (Solíscalero et al. 2013). matter-mineral. The potential parameters for UFF were:
Geometry optimization results were shown in Fig. 3 and
E = ER + E𝜃 + E𝜑 + E𝜔 + Evdw + Eel
Table 1.
1 ( )2
ER = Kij r − rij
2

Table 1  Crystal parameters of Lattice length Lattice angle

feldspar
a (Å) b (Å) c (Å) 𝛼(◦ ) 𝛽(◦ ) 𝛾(◦ )

Calculation 8.573 12.962 7.219 90.567 115.917 87.750

Experiment (Ref. 1) 8.560 12.984 7.209 90.28 116.03 89.03

Ref. 1: Negro et al. (1978)

Fig. 4  Designed adsorption
models of oxalic acid with three
forms on feldspar surface. a
­H2C2O4 on feldspar; b ­HC2O4−
on feldspar; c ­C2O42− on
feldspar

13
Adsorption

was total energy of adsorption energy of adsorption models

1
without surface of feldspar, ­E4 was total energy of two water
[ ]
E𝜃 = Kijk 1 + cos (p𝜃 + 𝜑)
2 layers, respectively. N was number of unit cells where oxalic
acids contacted. Here, N was 8.
m
∑
E𝜑 = Kijkl Cn cos n𝜑ijkl
2.2.3 Molecular model and method of DFT calculation
n=0

Based on previous reports, organic ligands were easily

( )
E𝜔 = Kijkl C0 + C1 cos 𝜔ijkl + C2 2 cos 𝜔ijkl
( [ ]6
x [ x ]12 )
Evdw = DLJ −2 LJ + −2 LJ
x x
Qi Qj
( )
Eel = 332.0637
∈ Rij
where E was total energy, ER was energy of bond stretch,
E𝜃 was energy of angle bend, E𝜑 was energy of torsion, E𝜔
was energy of inversion, Eel was energy of van der waals,
respectively.
Because the energy-minimized structure had been
obtained by geometry optimization and partial of adsorption
structures were fixed, the ensemble NPT were not applied.
Here, NVT was adopted and molecular dynamic simulation
time was 1 ns with time step 1 fs to reach equilibrium state.
In addition, the initial velocities were random, and energy
deviation was 50000.0 kcal/mol. Electrostatic was described
by Ewald method while van der waals was described by
atom based method.
Parameters ­Ead was defined to evaluate the adsorption
ability of oxalic acids on surface of feldspar in equation (Shi
et al. 2013):
E1 − E2 − E3 + E4
Ead =
N B3lyp/6–31 g* were adopted to calculate the adsorption
where E­ ad was adsorption energy of organic acids on sur-
face of feldspar, ­E1 was total energy of adsorption models
after molecular dynamics simulation, ­E2 was total energy
of adsorption models without organic acids molecules, ­E3
absorbed on mineral surface by chemical adsorption. And
our MD simulation also demonstrated that oxalic ligands
would react with Al site on feldspar surface. In order to
figure out how electrons transfer in chemical adsorption,
adsorption of ligand H­ C2O4− and ­C2O42− on feldspar was
designed by DFT calculations in ­Dmol3 module as shown
in Fig. 5. Generalized gradient approximation (GGA) with
the Perdew–Burke − Ernzerhof (PBE) parametrization of
the exchange − correlation functional and basis set DNP
3.5 was used. Convergence criteria included energy change
1 × 10−5Ha, SCF tolerance 1 × 10−6, max force 0.002Ha/Å
and max displacement 0.005 Å. In addition, a Fermi smear-
ing 0.005Ha was used to improve the convergence speed.
And then, the geometry optimization was carried out for
two models in Fig. 5. Here, water molecules weren’t con-
sidered, since the classical MD simulation results showed
that organic ligands had much stronger adsorption ability
than water.
2.2.4 Molecular model and method of frequency
calculation
Chemical adsorption of organic ligand on mineral surface
would produce new frequency peaks in ATR-FTIR spec-
tra. So theoretical calculations of frequency based on DFT
methods were carried out as shown in Fig. 6. Four methods
including HF/3–21 g*, HF/6–31 g*, B3lyp/3–21 g* and
frequency of oxalic acid on feldspar surface (Al cluster and
Si cluster). Every model was optimized on geometry. And
then, the suitable methods were picked up to predict the
adsorption frequency of oxalic acid on feldspar. Blue arrow

Fig. 5  Adsorption models of
­HC2O4− (a) and C­ 2O42− (b) on
feldspar surface facet (0 1 0) for
DFT calculations

13
 Adsorption
Fig. 6  Designed models for
bond frequency calculation
represented symmetric vibration of bond C–O (marked as
C–Os) while green arrow represented anti-symmetric vibra-
tion of bond C–O (marked as C–Oas), which were two main
adsorption frequencies of oxalic ligands, while Al–Os and
Si–Os were the typical frequencies of feldspar. As shown in
Fig. 6, four frequencies were mainly considered.
3 Results and discussions
3.1 Adsorption behavior based on classical
molecular dynamics simulation
In water solution, oxalic acid has three configurations,
­ 2C 2O 4 at pH 0.00, ­H C 2O 4− at pH 2.76 and ­C 2O 42− at
H ­( C 2O 42− and H
pH 6.0, respectively. The adsorption equilibrium states
Fig. 7  Adsorption equilibrium
states of oxalic acid with three
configurations on feldspar
surface
13
on feldspar surface for oxalic acid with three configura-
tions are shown in Fig. 7, and the relative adsorption ener-
gies are calculated through classical molecular dynamics
simulation, listed in Table 2. It is found that the adsorp-
tion energy of H ­ 2C2O4 is − 0.10 eV, which is extremely
lower. Moreover, adsorption equilibrium state of ­H2C2O4
on feldspar surface shows that the bond length between
H atom ­(H2C2O4) and O atom (feldspar) is 2.919 Å with
angle 129.4°, which belongs to the hydrogen bond. There-
fore, it’s deduced that ­H2C2O4 is adsorbed physically. The
adsorption energies of ­C2O42− and ­HC2O4− are − 1.17 eV
and − 0.68  eV, respectively, which are much higher.
Based on the adsorption equilibrium states in Fig. 7, the
bond lengths between Al atom (feldspar) and O atom
­ C 2O 4−) are 3.206 Å and 3.392 Å, which
belong to the strong electrostatic force attraction. During
Adsorption

Table 2  Adsorption energies System Energy

of oxalic acid with three
configurations on feldspar E1 eV E2 eV E3 eV E4 eV Ea eV
surface
H2C2O4-feldspar A − 4128.60 − 4129.06 − 23.98 − 25.23 − 0.10 Out-sphere adsorption
HC2O4−-feldspar B − 4117.07 − 4116.79 − 18.54 − 23.69 − 0.68 Inner-sphere adsorption
C2O42−-feldspar C − 4114.09 − 4111.56 − 12.20 − 19.03 − 1.17 Inner-sphere adsorption

Table 3  Adsorption energies of organic acids on minerals in litera-

tures

Mineral Adsorption energy (eV)

Formic acid Acetic acid

Calcite − 1.06 (Ref. 2) − 0.98 (Ref. 4)

− 0.97 (Ref. 4) − 1.23 (Ref. 2)
quartz − 0.63 (Ref. 2) − 0.67 (Ref. 2)
kaolinite − 0.76 (Ref. 2) − 0.84 (Ref. 2)
TiO2 − 1.13 (Ref. 3) − 1.18 (Ref. 5)

Ref. 2: Budi et al. (2018); Ref. 3: Nunzi et al. (2010); Ref. 4: Ataman
et al. (2016); Ref. 5: Spreafico et al. (2014)

deprotonation of H ­ 2C 2O 4, charges of O atom increase

obviously (Fig. 2), as a result, adsorption transforms from
weak hydrogen bond adsorption (system A) to strong elec-
trostatic force adsorption (System B and C).
Table 3 lists some reported data for the adsorption ener-
gies of organic acids on calcite, quartz, kaolinite and ­TiO2,
respectively. These adsorption energies from literatures
are at the ranges from − 0.63 eV to − 1.23 eV, where it
is found that formic and acetic acid are adsorbed through
the coordination bond, such as O–Ca, O–Si, O–Al and
O–Ti. In this work, the calculated adsorption energies
of ­C2O42− and H ­ C2O4− (adsorbed through Al–O coordi-
nation) are at the ranges from − 0.68 eV and − 1.17 eV,
which is in agreement with the reference values.
The characterization parameter, root mean square dis-
placement (RMSD) can be used to determine the adsorp-
tion dynamics of oxalic acid on feldspar. Higher RMSD
value means that oxalic acid is in water phase rather than
adsorbed on feldspar surface. While lower RMSD value
means that oxalic acid prefers to be adsorbed on feldspar
surface. Here, RMSD is defined as the following equation
(Teklebrhan et al. 2014):
N
√
1∑
RMSD = [ri(t) − ri(0)]2
N i
where N is total number of oxalic acid molecules, ri(t) and
ri(0) represent positions of carboxylic acid at initial and t
time. Figure 8 shows RSMD calculation results, which are in
agreement with the calculated results of adsorption energy.
Fig. 8  RMSD curves for oxalic acid with three configurations
Adsorption of ­C2O42− and H ­ C2O4− with much lower RMSD
values on feldspar are stronger than that of ­H2C2O4 with
much higher RMSD value.
There are two kinds of active sites on feldspar surface,
Al site and Si site. Which site would be coordinated with
O atom (carrying most negative charges) of oxalic acid?
Figure 9 shows the radial density functional spectra between
O and Al(Si) calculated by classical molecular dynamics
simulation method. It can be seen clearly that there are
no obvious peaks between O and Si, and there are obvi-
ous peaks between Al and O in three adsorption systems
at 3.07 Å, 2.97 Å and 3.21 Å. RDF spectra indicate that O
atom with most negative charges prefer to coordinate with
Al site rather than Si site on feldspar surface. This result cor-
responds highly with the previous experimental and theoreti-
cal analysis (Welch and Ullman 1996; Criscenti et al. 2005;
Alstadt et al. 2016).
Competitive adsorption behavior caused by water mole-
cule should be considered when adsorption of organic matter
happens at mineral–water interface. Which molecule would
prefer to coordinate with Al active site, H ­ 2O or organic
ligand? RDF spectra between O atom (water) and Al atom
(feldspar) is calculated as shown in Fig. 10. Shortest distance
between O and Al is 2.93 Å in all three systems. Coordina-
tion complexation between Al and O mainly relies on elec-
trostatic force, which could be used to evaluate coordination

13
 Adsorption

Fig. 9  RDF spectra between O atom of oxalic acid and Al, Si atoms

of feldspar Fig. 11  Electrostatic force between O atom from water, oxalic acid
and Al atom of feldspar

ability. Electrostatic force is defined as F = KQ1Q2/R2, 3.2 Adsorption behavior based on DFT calculation
where K is electrostatic constant, as 9*109N·m2/C2, ­Q1
and ­Q2 are charges of two atoms, R is distance between Based on the classical molecular dynamics results,
two atoms. Here, only O atom and Al atom are consid- ­HC2O4− and ­C2O42− would incline to go on the mononuclear
ered. It can be seen that electrostatic force between H­ 2O is monodentate chemical adsorption on feldspar surface. Here,
lower than ­C2O42− and H­ C2O4− but higher than H ­ 2C2O4 as DFT calculations in ­Dmol3 module are carried out to inves-
shown in Fig. 11. It can be deduced that water would block tigate how ­HC2O4− and ­C2O42− react with feldspar. After
­H2C2O4 to coordinate with Al active site, while C ­ 2O42− and
−
­HC2O4 would be prior to coordinate with Al active site
than water. Previous study (Alstadt et al. 2016) found water
would displace acetic molecule and prior to be absorbed on
kaolinite surface. Because mineral surface properties would
change obviously in the presence and absence of water.

Fig. 10  RDF spectra between O atom of water and Al atom of feld- HC2O4−(a) and
Fig. 12  Optimized structures for adsorption of ­
spar ­C2O42−(b) on feldspar surface

13
Adsorption
Table 4  Al–O bond length between carboxylic ligand and aluminum
This paper Ref. 6 Ref. 7
Al–O Bond length (Å) 1.840 1.851 1.880
1.842 1.857 1.819
1.835 1.903
Ref. 6: Jin et al. (2011); Ref. 7: Ramos et al. (2015); Ref. 8: Kubicki
et al. (1996)
the geometry optimization for the adsorption of C ­ 2O42− and
−
­HC2O4 on feldspar surface, the reasonable adsorption con-
figuration is obtained as shown in Fig. 12, where Al–O bond
length is 1.840 Å and 1.842 Å for system A, 1.835 Å for sys-
tem B. Compared to 1.800 Å before geometry optimization
in Fig. 5, this result is very similar to previous research as
listed in Table 4. As described on molecular dynamic simu-
lation, adsorption ability of ­HC2O4− and ­C2O42− are stronger
than that of water. So, water is not considered in these DFT
calculations. According to the literatures, Al–O bond lengths
between organic ligands and Al atom distribute from 1.800
to 1.903 Å. Calculation bond length in this work are very
close to reference values listed in Table 4, which indicate
oxalic ligands complex with Al site on feldspar surface.
Fig. 13  Partial density of state for Al, Si (feldspar) and O (oxalic ligand) before and after reactions
In order to investigate how electrons change during
Ref. 8
reaction, partial density of state for Al, Si (feldspar) and O
(oxalic ligand) before and after reactions is studied, as shown
1.800 in Fig. 13. It can be seen clearly that energy partial electrons
1.807 for Al, Si and O are very close to Fermi level, which indi-
1.874 cate these electrons are very active and easier to participate
in chemical reactions. Partial density of state (Pdos) for Si
doesn’t change obviously after reaction, which explain that
electrons of Si doesn’t participate in reactions. While Pdos
shape for Al and O change obviously after reactions, not
only many peaks move to lower energy, but also intensities
of peaks decrease or increase obviously. Especially, s orbit-
als of O from organic ligands and p, d orbitals of Al atom
overlap significantly, which demonstrate that O atom reacts
with Al atom strongly. This is another proof that organic
ligands prefer to coordinate with Al atom rather than Si
atom.
3.3 Comparison of bond frequencies
between ATR‑FTIR detection values
and calculated values
ATR-FTIR spectra is used to investigate interaction between
oxalic acid and feldspar as shown in Fig. 14. It can be found
13
 Adsorption
Fig. 14  ATR-FTIR spectra for original feldspar and feldspar after
reaction with three forms of oxalic acid
there are two new peaks (1317 cm−1 and 1620 cm−1) appear-
ing at higher pH 2.76 and 6.00 values. However, there is
not any new peak appearing at pH 0.00 value, indicating
no chemical interaction between oxalic acid and feldspar.
As listed in Table 5, based on previous reports, 1317 cm−1
and 1620 cm−1 could be ascribed as vibrations of C–Os and
C–Oas bonds, respectively.
In order to explain why there are new peaks appear-
ing, four methods including HF/3–21  g*, HF/6–31  g*,
B3lyp/3–21 g* and B3lyp/6–31 g* are adopted to calcu-
late the adsorption frequency, and the predicted results are
compared with ATR-FTIR spectra. Firstly, the four methods
are used to calculate models as follows to determine which
method is suitable for this system. C–Os and C–Oas are typi-
cal vibration frequencies of ­H2C2O4, ­HC2O4− and ­C2O42−.
While Al–O and Si–O are typical vibration frequencies of
feldspar. The four typical vibrations are used to evaluate
accuracy of four calculation methods as shown in Fig. 6.
As shown in Fig. 15, correlation coefficient of HF/6–31 g*
method is highest, but the calculated frequency value is
far higher than the observed value. Frequency calculated
by B3lyp/3–21 g* method is very close to the observed
value, but correlation coefficient is lower. Both HF/3–21 g*
and B3lyp/6–31 g* methods can predict frequency more
Table 5  ATR-FTIR frequencies of carboxylic ligand adsorption on Al-bearing minerals
Bond frequency This work exp Cal (Ref. 9)
V(C–Os)/cm−1 1317 1360
V(C–Oas)/cm−1 1619 1671
Ref. 9: Kubicki et al. (1999); Ref. 10: Alstadt et al. (2016); Ref. 11: Belber and Stumm (1994); Ref. 12: Ramos et al. (2014); Ref. 13: Pettibone
et al. (2008)
13
precisely with good correlation coefficient and error, which
will be applied to predict frequency Al–oxa model and
Si-oxamodel.
As shown in Fig. 16, slope of fit line of Si–Oxa model
is 1.51 which indicate that Si–Oxa model can’t explain
experimental frequency value though correlation coefficient
is 0.99. The frequency of Al–Oxa model is very close to
experimental frequency value with slope 1.12 and accept-
able error. This calculation results prove again that oxalic
acid would prefer to complex with Al rather than Si on the
surface of feldspar. Frequency calculation results highly cor-
respond with classical molecular dynamic simulation.
3.4 Evaluation of adsorption behavior
through dissolution experiment and TGA–DSC
analysis
The dissolution experiment of feldspar mineral with oxalic
acid is carried out to evaluate the adsorption behavior. Feld-
spar minerals are mixed with 0.05 mol/L oxalic acid with
different pH (pH 0.00, pH 2.76, pH 6.00) in plastic bottles
for 2 days reactions. Al and Si leaching results are shown in
Fig. 17. It is found that Al and Si are preferentially released
from feldspar at higher and lower pH, respectively. Usually,
the dissolution rate of mineral by organic acid is defined
as R = K1*aH+ n
 + K2*anligand (Furrer and Stumm 1986), where
the first term represents the dissolution by ­H+ attack and
the second term represents the dissolution by ligand compl-
exation. For feldspar dissolution by oxalic acid, at pH 0.00,
­H+ with extremely high reactivity attack on Si site causes
faster dissolution, so both Al and Si release amounts are
much higher. With H ­ + concentration decreasing, feldspar
dissolution is mainly controlled by H ­ C2O4− complexing
with Al site at pH 2.76, so the Al and Si release amounts
become slower than that at pH 0.00. When pH 6.00, the
Al and Si release amounts are more than that at pH 2.76
due to stronger complexation ability of ­C2O42− than that of
­HC2O4−, but Al existing in the form of Al(OH)3 results in a
lower Al concentration detection in the solution.
And then, TGA–DSC characterization is used to analyze
different feldspar samples after interaction with oxalic acid
as shown in Fig. 18. According to MD simulation and DFT
calculation results, E ­ ad value equals − 0.10 eV at pH 0.00,
which means outer-sphere adsorption (physical adsorption),
Exp (Ref. 10) Exp (Ref. 11) Exp (Ref. 12) Exp (Ref. 13)
1318 1381 1429 1300
1619 1534 1617 1695
Adsorption

Fig. 15  Comparisons between the calculated frequencies by different methods and experimental frequencies

and − 1.17 eV at pH 6.00, there are obvious decomposi-

tion peaks of chemical adsorption of oxalic acid at 450 °C,
which means inner-sphere adsorption (chemical adsorp-
tion) due to ­H C 2O 4− complexing with Al site to form
­[HC2O4Al(OH)3]− cluster at pH 2.76 and ­C2O42− complex-
ing with Al site to form [­ C2O4Al(OH)3]2− cluster at pH 6.00.

3.5 Adsorption mechanism of oxalic acid at water–

feldspar interface

According to molecular simulation, ATR-FTIR, TGA–DSC

Fig. 16  Comparison of calculated frequency between Al–oxa and Si–
oxa models
­HC2O4− or ­C2O42− in the aqueous solution. The dissolution
so TG-DSC characterization result does not show obvi-
ous decomposition peak of chemical adsorption of oxalic
acid at 450 °C. E
­ ad values equaling − 0.68 eV at pH 2.76
and dissolution experiments, the adsorption mechanism of
oxalic acid at water–feldspar interface can be predicted as
shown in Fig. 19, where the dissolution of feldspar by oxalic
acid includes two parts, one is from the contribution of H ­ +
in aqueous solution attacking Si site on the feldspar surface,
and the other part is from the contribution of the complex
reaction between Al site on the feldspar surface and ­H2O,
rate of feldspar is represented as R = K1*anH+ + K2*anligand,
where the first term is the controlling step if the oxalic acid
solution with a lower pH value, such as pH 0.00, and the

13
 Adsorption

Fig. 17  Al and Si dissolution amount from feldspar at different pH by oxalic acid

Fig. 18  TGA-DSC analysis of original feldspar and feldspar after oxalic acid adsorption at different pH value

second term is the controlling step for the oxalic acid solu-
tion with a higher pH value, such as pH 6.00. There are the
co-existing ­H+, ­H2O, ­HC2O4− ­C2O42− and ­H2C2O4 in some
scenarios, it should be mentioned that the rank of the com-
plex reaction is ­H2O–Al site < HC2O4−–Al site < C2O42−–Al
site and without complex reaction between H ­ 2C2O4–Al site.
4 Conclusion
The adsorption behavior of oxalic acid at water–feld-
spar interface can be explored from the molecular level
through molecular dynamic simulation. Although feldspar
is composed of Al–O and Si–O tetrahedron structures to

13
Adsorption
Fig. 19  Interaction mechanism between oxalic acid and feldspar at
different pH
form the stable framework, oxalic acid with three con-
figurations, ­H 2 C 2 O 4 , ­H C 2 O 4 − and C
­ 2 O 42 , can adsorb
on feldspar surface to promote the mineral dissolution.
Adsorption of H ­ 2C 2O 4 on feldspar surface belongs to
physical outer-sphere adsorption with hydrogen bond for-
mation while adsorption of ­HC2O4− and ­C2O42− belong
to inner-sphere adsorption and prefer to coordinate with
Al active site rather than Si active site on feldspar sur-
face. The rank of adsorption matter on feldspar surface is
­C2O42−>HC2O4−>H2O > H2C2O4. At lower pH 0.00, water
instead of H
­ 2C2O4 will attack Al active site to promote
Al dissolution. At higher pH 2.76 and 6.00, ­HC2O4− and
­C2O42− instead of water will attack Al active site to pro-
mote Al dissolution. At acidic conditions, ­H+ would attack
Si active site to promote Si dissolution.
Acknowledgements  The authors wish to acknowledge National Natu-
ral Science Foundation of China (No. 21776089, No. U1610102, No.
21506063) and the International S&T Cooperation Program of China
(No. 2016YFE0132500).
References
Alstadt, V.J., Kubicki, J.D., Freedman, M.A.: Competitive adsorp-
tion of acetic acid and water on kaolinite. J. Phys. Chem. A 120,
8339–8346 (2016)
Ataman, E., Andersson, M.P., Ceccato, M., Bovet, N., Stipp, S.L.S.:
Functional group adsorption on calcite: I. Oxygen containing and
nonpolar organic molecules. J. Phys. Chem. C 120, 16586–16596
(2016)
Biber, M.V., Afonso, M.D.S., Stumm, W.: The coordination chemistry
of weathering: IV. Inhibition of the dissolution of oxide minerals.
Geochim. Cosmochim. Acta 58, 1999–2010 (1994)
Biber, M.V., Stumm, W.: An in situ ATR-FTIR study: the surface
coordination of salicylic acid on aluminum and iron(III) oxides.
Environ. Sci. Technol. 28, 763–768 (1994)
Budi, A., Stipp, S.L.S., Andersson, M.P.: Calculation of entropy of
adsorption for small molecules on mineral surfaces. J. Phys.
Chem. C 122, 8236–8243 (2018)
Cama, J., Ganor, J.: The effects of organic acids on the dissolution of
silicate minerals: a case study of oxalate catalysis of kaolinite
dissolution. Geochim. Cosmochim. Acta 70, 2191–2209 (2006)
Criscenti, L.J., Brantley, S.L., Mueller, K.T., Tsomaia, N., Kubicki,
J.D.: Theoretical and 27 Al CPMASS NMR investigation of alu-
minum coordination changes during aluminosilicate dissolution.
Geochim. Cosmochim. Acta 69, 2205–2220 (2005)
Crundwell, F.K.: The mechanism of dissolution of minerals in acidic
and alkaline solutions: partII application of a new theory to sili-
cates, aluminosilicates and quartz. Hydrometallurgy 149, 265–275
(2014)
Duckworth, O.W., Martin, S.T.: Surface complexation and dissolution
of hematite by C ­ 1-C6, dicarboxylic acids at pH 5.0. Geochim.
Cosmochim. Acta 65, 4289–4301 (2001)
Feng, Q., Wen, S., Deng, J., Zhao, W.: Combined DFT and XPS inves-
tigation of enhanced adsorption of sulfide species onto cerussite
by surface modification with chloride. Appl. Surf. Sci. 425, 8–15
(2017)
Filby, A., Plaschke, M., Geckeis, H.: AFM force spectroscopy study
of carboxylated latex colloids interacting with mineral surfaces.
Colloid. Surf A 414, 400–414 (2012)
Furrer, G., Stumm, W.: The coordination chemistry of weathering: I.
Dissolution kinetics of δ-Al2O3 and BeO. Geochim. Cosmochim.
Acta. 50, 1847–1860 (1986)
Ha, J., Yoon, T.H., Wang, Y., Musgrave Jr., C.B., Brown, G.E.: Adsorp-
tion of organic matter at mineral/water interfaces: 7. ATR-FTIR
and quantum chemical study of lactate interactions with hematite
nanoparticles. Langmuir 24, 6683–6692 (2008)
Han, B., Viswanathan, V., Pitsch, H.: First-principles based analysis of
the electrocatalytic activity of the unreconstructed Pt(100) surface
for oxygen reduction reaction. J. Phys. Chem. C 116, 6174–6183
(2012)
Jin, X., Yan, Y., Shi, W., Bi, S.: Density functional theory studies on the
structures and water-exchange reactions of aqueous Al(III)–oxa-
late complexes. Environ. Sci. Technol. 45, 10082–10090 (2011)
Johnson, S.B., Yoon, T.H., Kocar Jr., B.D., Brown, G.: Adsorption
of Organic matter at mineral/water interfaces: 2. Outer-sphere
adsorption of maleate and implications for dissolution processes.
Langmuir 20, 4996–5006 (2004a)
Johnson, S.B., Yoon, T.H., Slowey Jr., A.J., Brown, G.: Adsorption
of organic matter at mineral/water interfaces: 3. Implications
of surface dissolution for adsorption of oxalate. Langmuir 20,
11480–11492 (2004b)
Johnson, S.B., Brown, G., Healy, T.W., Scales, P.J.: Adsorption of
organic matter at mineral/water interfaces: 6. effect of inner-
sphere versus outer-sphere adsorption on colloidal stability. Lang-
muir 21, 6356–6365 (2005)
Kubicki, J.D., Blake, G.A., Apitz, S.E.: Molecular orbital models of
aqueous aluminum-acetate complexes. Geochim. Cosmochim.
Acta 60, 4897–4911 (1996)
Kubicki, J.D., Itoh, M.J., And, L.M.S., Apitz, S.E.: Bonding mecha-
nisms of salicylic acid adsorbed onto illite clay: an ATR-FTIR and
molecular orbital study. Environ. Sci. Technol. 31, 1151–1156
(1997)
Kubicki, J.D., Schroeter, L.M., Itoh, M.J., Nguyen, B.N., Apitz, S.E.:
Attenuated total reflectance fourier-transform infrared spectros-
copy of carboxylic acids adsorbed onto mineral surfaces. Geo-
chim. Cosmochim. Acta 63, 2709–2725 (1999)
Negro, A.D., Pieri, R.D., Quareni, S., Taylor, W.H.: The crystal struc-
tures of nine K feldspars from the Adamello Massif (northern
Italy) addendum. Acta Cryst. 34, 3843 (1978)
13
 Adsorption
Nunzi, F., Angelis, F.D.: DFT investigations of formic acid adsorption
on single-wall T ­ iO2 nanotubes: effect of the surface curvature. J.
Phys. Chem. C 115, 2179–2186 (2010)
Oelkers, E.H., Golubev, S.V., Pokrovsky, O.S., Bénézeth, P.: Do
organic ligands affect calcite dissolution rates? Geochim. Cos-
mochim. Acta 75, 1799–1813 (2011)
Pettibone, J.M., Cwiertny, D.M., Scherer, M., Grassian, V.H.: Adsorp-
tion of organic acids on tio2 nanoparticles: effects of pH, nanopar-
ticle size, and nanoparticle aggregation. Langmuir 24, 6659–6667
(2008)
Rai, B., Sathish, P., Tanwar, J., Moon, K.S., Fuerstenau, D.W.: A
molecular dynamics study of the interaction of oleate and
dodecylammonium chloride surfactants with complex alumino-
silicate minerals. J. Colloid. Interf. Sci. 362, 510–516 (2011)
Ramos, M.E., Emiroglu, C., García, D., Sainzdiaz, C.I., Huertas, F.J.:
Modeling the adsorption of oxalate onto montmorillonite. Lang-
muir 31, 11825–11834 (2015)
Ramos, M.E., Garcia-Palma, S., Rozalen, M., Johnston, C.T., Huer-
tas, F.J.: Kinetics of montmorillonite dissolution: an experimental
study of the effect of oxalate. Chem. Geol. 363, 283–292 (2014)
Ramos, C.G., Querol, X., Dalmora, A.C., Pires, K.C.D.J., Schneider,
I.A.H., Oliveira, L.F.S.: Evaluation of the potential of volcanic
rock waste from southern brazil as a natural soil fertilizer. J.
Clean. Prod. 142, 2700–2706 (2017)
Shi, W., Xia, M., Wu, L., Wang, F.: Molecular dynamics study of
polyether polyamino methylene phosphonates as an inhibitor of
anhydrite crystal. Desalination 322, 137–143 (2013)
Solíscalero, C., Ortegacastro, J., Hernándezlaguna, A., Muñoz, F.: A
DFT study of the amadori rearrangement above a phosphatidyle-
thanolamine surface: comparison to reactions in aqueous environ-
ment. J. Phys. Chem. C 117, 8299–8309 (2013)
Spreafico, C., Schiffmann, F., Vandevondele, J.: Structure and mobility
of acetic acid at the anatase (101)/acetonitrile interface. J. Phys.
Chem. C 118, 6251–6260 (2014)
Stillings, L.L., Drever, J.I., Brantley, S.L., Sun, Y., Oxburgh, R.: Rates
of feldspar dissolution at pH 3–7 with 0–8 Mm oxalic acid. Chem.
Geol. 132, 79–89 (1996)
Stillings, L.L., And, J.I.D., Poulson, S.R.: Oxalate adsorption at a pla-
gioclase (An47) surface and models for ligand-promoted dissolu-
tion. Environ. Sci. Technol. 32, 2856–2864 (1998)
Strawn, D.G., Sparks, D.L.: The use of XAFS to distinguish between
inner- and outer-sphere lead adsorption complexes on montmoril-
lonite. J. Colloid. Interf. Sci. 216, 257–269 (1999)
Strobel, B.W.: Influence of vegetation on low-molecular-weight car-
boxylic acids in soil solution—a review. Geoderma 99, 169–198
(2001)
13
Teklebrhan, R.B., Ge, L., Bhattacharjee, S., Xu, Z., Sjöblom, J.: Initial
partition and aggregation of uncharged polyaromatic molecules at
the oil–water interface: a molecular dynamics simulation study. J.
Phys. Chem. B 118, 1040–1051 (2014)
Waiman, C.V., Arroyave, J.M., Chen, H., Tan, W., Avena, M.J., Zanini,
G.P.: The simultaneous presence of glyphosate and phosphate at
the goethite surface as seen by XPS, ATR-FTIR and competitive
adsorption isotherms. Colloid. Surf. A 498, 121–127 (2016)
Weber, K.H., Liu, Q., Tao, F.M.: Theoretical study on stable small
clusters of oxalic acid with ammonia and water. J. Phys. Chem. A
118, 1451–1468 (2014)
Welch, S.A., Ullman, W.J.: Feldspar dissolution in acidic and organic
solutions: compositional and pH dependence of dissolution rate.
Geochim. Cosmochim. Acta 96, 2939–2948 (1996)
Xian, Z., Hao, Y., Zhao, Y., Song, S.: Quantitative determination of
isomorphous substitutions on clay mineral surfaces through AFM
imaging: a case of mica. Colloid. Surf. A 533, 55–60 (2017)
Xiong, Y., Li, Z., Cao, T.T., Xu, S.M., Yuan, S.L., Sjoblom, J., Xu,
Z.H.: Synergistic adsorption of polyaromatic compounds on sil-
ica surfaces studied by molecular dynamics simulation. J. Phys.
Chem. C 122, 4290–4299 (2018)
Xu, Y., Liu, Y.L., He, D.D., Liu, G.S.: Adsorption of cationic collec-
tors and water on muscovite (001) surface: a molecular dynamics
simulation study. Miner. Eng. 53, 101–107 (2013)
Xu, L., Tian, J., Wu, H., Deng, W., Yang, Y., Sun, W.: New insights
into the oleate flotation response of feldspar particles of different
sizes: anisotropic adsorption model. J. Colloid. Interf. Sci. 505,
500–508 (2017)
Yang, Y., Min, Y., Lococo, J., Jun, Y.S.: Effects of Al/Si ordering on
feldspar dissolution: part I. Crystallographic control on the stoi-
chiometry of dissolution reaction. Geochim. Cosmochim. Acta
126, 574–594 (2014)
Yeh, I.C., Lenhart, J.L., Rinderspacher, B.C.: Molecular dynamics sim-
ulations of adsorption of catechol and related phenolic compounds
to alumina surfaces. J. Phys. Chem. C 119, 7721–7731 (2015)
Zhang, L., Jun, Y.S.: Distinctive reactivities at biotite edge and
basal planes in the presence of organic ligands: implications for
organic-rich geologic ­Co2 sequestration. Environ. Sci. Technol.
49, 10217–10225 (2015)
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