Chemical Engineering Journal 381 (2020) 122647

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Chemical Engineering Journal

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The interaction of perrhenate and acidic/basic oxygen-containing groups on T

biochar surface: A DFT study
⁎
Yongsheng Huanga, Hui Hua,
a
School of Chemical Engineering, Fuzhou University, Fuzhou 350116, Fujian, China

H I GH L IG H T S

• Density functional theory was applied to investigate the ReO −

adsorption mechanism.
4

• The interaction of ReO −

and basic oxygen-containing groups was considered firstly.
4

• Basic oxygen-containing groups possess stronger affinity toward ReO . 4

−

A R T I C LE I N FO A B S T R A C T

Keywords: Biochar has a good adsorption ability for perrhenate (ReO4−), which can be attributed to its abundant oxygen-
Perrhenate containing groups, yet the effects of oxygen-containing groups on ReO4− adsorption are still unclear. Here, the
Biochar interaction of ReO4− and acidic/basic oxygen-containing groups (hydroxyl, carboxyl, pyrone and chromene) on
Oxygen-containing groups biochar were investigated by density functional theory (DFT) calculation with conductor-like screening model
DFT
(COSMO). According to the calculated results, it was evidenced that the adsorption of oxygen-containing group
Adsorption
functionalized BC towards ReO4− was gradually strengthened as decreased pH, and the protonated positively
charged oxygen-containing groups presented stronger chemisorption to ReO4− mainly through electrostatic
interaction, complexation and atomic orbital hybridization. The protonated hydroxyl and carboxyl and the
protonated etheric oxygen of pyrone and chromene can offer favorable binding sites to ReO4−. Compared with
the acidic oxygen-containing groups, the higher adsorption energy values, and the larger Mayer bond order
indexes of interacting atoms identified that the basic oxygen-containing groups have stronger affinity with
ReO4−. Pyrone had the strongest adsorption stability toward ReO4−. Our results can provide new ideas into the
design and preparation of separation materials for ReO4− or the other anions capture from the aqueous solution.

1. Introduction due to its economic advantages, abundant surface oxygen-containing

groups and excellent adsorption performance for the low concentration
Rhenium (Re) is a rare and scattered metal with excellent physi- ReO4−. The investigation of BC as adsorbent to capture ReO4− from
cochemical properties, and it is extensively used in metallurgy, defense, aqueous solution was pioneered by our previous researches [9–11]. The
catalysts, et al. Most rhenium as by-products are derived from the results showed that the presence of BC surface oxygen-containing
molybdenite industries. Lots of routes including but not limited to groups was believed to play an important role in ReO4− adsorption.
precipitation, ion exchange and solvent extraction [1–4] have been Actually, the BC surface oxygen-containing groups include acidic and
reported for the purpose of rhenium recovery from industrial effluents, basic oxygen-containing groups, for example, hydroxyl and carboxyl
where rhenium present as perrhenate ion (ReO4−). Adsorption is a groups are acidic oxygen-containing groups, while basic oxygen-con-
promising ReO4− capture method, due to the advantages of low cost, taining groups can be pyrone and chromene type structures [12,13].
simple operation and environmentally friendly. A considerable number Although some experimental and theoretical investigations have con-
of materials like polymeric ionic liquid gel, anion resin, layered double centrated on the interaction between the ReO4− and acidic oxygen-
hydroxides, metal-organic frameworks, biochar (BC) etc. [5–9], have containing groups on carbon materials [10,14], the adsorption behavior
been widely reported as useful adsorbents for ReO4−. of ReO4− and basic oxygen-containing groups remains to be explored.
Among the numerous adsorbents, BC is a potential ReO4− sorbent Based on first principles, density functional theory (DFT)

⁎
Corresponding author.
E-mail address: [email protected] (H. Hu).

https://doi.org/10.1016/j.cej.2019.122647
Received 2 July 2019; Received in revised form 26 August 2019; Accepted 27 August 2019
Available online 28 August 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

calculations are ideally suited for the investigation of adsorption be- atoms. Therefore, three different atomic sites capable of accepting a
haviors from the atomistic and electronic scale [15–19]. DFT calcula- proton from H3O+ for the pyrone group functionalized BC were con-
tion has been widely used as an efficient method to evaluate the in- sidered [26], while two different protonated atomic sites were in-
teraction between the metal cation and surface acidic oxygen- vestigated in the chromene group functionalized BC. Hence, the pro-
containing groups on carbon materials. For example, on the basis of the tonated states for pyrone group functionalized BC are [BC-Pyr-H (a)]+,
DFT calculation, Saleh et al. proposed that the carbonyl groups possess [BC-Pyr-H (b)]+ and [BC-Pyr-H (c)]+, which are corresponding to the
stronger binding ability toward Pb2+ compared with the other func- protonation on the etheric O17, carbonylic O27 and the C8 atoms. And
tional groups [20]. Besides, Wang et al. concluded that the interaction the protonated states for chromene group functionalized BC are [BC-
between the acidic oxygen-containing groups and Co2+ is stronger than Chr-H (a)]+ and [BC-Chr-H (b)]+, which are corresponding to the
the nitrogen-containing groups by means of the DFT calculation [17]. protonation on the etheric O37 and C35 atoms, respectively. Since
On the other hand, Ai et al. explored the adsorption behavior of uranyl pyrone and chromene groups are unstable under basic pH condition,
ion on graphene oxide with various acidic oxygen-containing groups by the deprotonated states for pyrone and chromene groups functionalized
DFT method, and they found that the graphene oxide containing bi- BC have not been investigated in this paper. Seven optimized distinct
hydroxyl groups have the highest adsorption capacity towards the ur- BOBC models are shown in Fig. 2 (b).
anyl ion [21]. However, since there is short of a regulatable method for
the preparation of biochar rich in basic oxygen-containing groups, there
2.2. Calculation parameters
is still lack of systematic theoretical researches for the role of basic
oxygen-containing groups on ReO4− adsorption.
All calculations were performed by the Dmol3 program package in
In this paper, DFT calculation was utilized for investigating the
Materials Studio [27,28]. The exchange-correlation energy was calcu-
microcosmic interaction of ReO4− and different acidic/basic oxygen-
lated using Perdue-Wang functional (PW91) in the spin-unrestricted
containing groups (hydroxyl, carboxyl, pyrone and chromene) on BC
generalized gradient approximation (GGA) [29,30]. Double numerical
under various pH conditions. The coronene was selected as the pristine
basis sets with polarization functions (DNP) were used for describing
carbonaceous skeleton model of BC, and constructed functionalized BC
atomic orbitals, which was comparable with the Gaussian 6–31 G (d, p)
model modified by different acidic and basic oxygen-containing groups
basis set and exhibited a better accuracy [27,31]. The DFT semi-core
to study the interaction between ReO4− and oxygen-containing groups
pseudopotential (DSPP) [32] was used to replace core electrons as a
on BC. And the detailed interaction mechanisms were evaluated by
single effective potential. The OBS’s DFT-D approach [33] was in-
analysis of adsorption structure, adsorption energy and electronic
troduced to describe the weak interactions, such as the van der Waals
property of BC/ReO4− complexes. The information obtained from the
(vdW) interaction and hydrogen bond, to obtain more accurate results.
DFT calculations may provide new view for the design of effective BC
The smearing of electronic occupations was set to be 0.005 Ha. The
adsorbents in the recovery of ReO4− from industrial effluents.
effect of water on the adsorption was investigated with the aid of
conductor-like screening model (COSMO) as implemented in Dmol3
2. Calculation model and method
program where the solvent was treated as a dielectric continuum
(permittivity = 78.54) [34]. For geometrical optimizations and energy
2.1. Biochar model
calculation, the total energy, the maximum force and the maximum
displacement were converged to 1 × 10−5 Ha, 0.002 Ha/Å and
BC is a carbon material that is mainly composed of carbonaceous 0.005 Å, respectively.
skeleton and surface functional groups. Here, coronene was selected as
the basic model of carbonaceous skeleton of BC. This model has been
successfully employed in previous literatures [22–24]. The different 2.3. Analysis methods
acidic and basic oxygen-containing groups functionalized BC were
constructed by grafting and substituting C and H atoms at the edge of The adsorption stability of ReO4− on OBC can be evaluated by
coronene, wherein the acidic oxygen-containing functional group in- calculating the adsorption energies (Eads ), which were calculated ac-
cludes hydroxyl and carboxyl, and the basic oxygen-containing func- cording to the following equation [35]:
tional group includes pyrone and chromene. As shown in Fig. 1, due to Eads = EOBC /ReO4− − EOBC − EReO4−
the effect of the acidity and alkalinity of the solution, the above four
oxygen-containing group functionalized BC (OBC) exist in different where EOBC/ReO-4 represents the total energy of ReO4− adsorbed on OBC,
forms under different pH conditions. EOBC is the energy of isolated OBC, and EReO-4 denotes the energy of free
For acidic oxygen-containing group functionalized BC (AOBC), ReO4− anion, respectively. It is well known that the adsorption energy
under acidic pH condition, the protonated states for hydroxyl and can reflect the thermodynamic stability of the system, the more nega-
carboxyl groups functionalized BC are [BC-OH2]+ and [BC-COOH2]+, tive Eads value of the system, the stronger interaction between ReO4−
respectively. While under basic pH condition, the deprotonated states and OBC.
are [BC-O]− and [BC-COO]− for hydroxyl and carboxyl groups func- The Mulliken population analysis [36] was used to analyze the
tionalized BC, respectively. Meanwhile, [BC-OH] and [BC-COOH] are details of net charge transfer during the ReO4− adsorption process.
their neutral forms at neutral pH condition. The optimized geometries Difference in the charge of ReO4− before and after adsorption was
of six AOBC models are illustrated in Fig. 2 (a). defined as △Q = Qb − Qa, where Qb and Qa are an algebraic sum of
As to the basic oxygen-containing group functionalized BC (BOBC) charge of Re and O atoms of ReO4− before and after adsorption, re-
includes pyrone and chromene groups functionalized BC, their corre- spectively. The negative value of △Q indicates that the electronic
sponding neutral forms are [BC-Pyr] and [BC-Chr]. Under acidic pH charge is transferred from the ReO4− to the OBC.
condition, as reported in previous literatures, basic sites on carbon Bond order index as a measure of bond strength, which was calcu-
surface can undergo protonation and acquire a positive charge [25]. lated according to Mayer’s definition [37]. For two adjacent atoms, a
Meanwhile, according to the Mulliken charge distribution of [BC-Pyr] large positive value of bond order means that a strong interaction be-
and [BC-Chr] (see Fig. S1), the etheric O17, carbonylic O27 and the C8 tween them.
atoms in pyrone group of [BC-Pyr] with more negative charge than The number of electrons occupied by a system in a certain energy
other atoms, indicating they have stronger ability to bind with protons. level interval can be represented by the density of states (DOS) plot
Similarly, ether in the chromene of [BC-Chr], the etheric O37 and C35 [38]. According to the partial density of states (PDOS) of bonding
atoms possess stronger ability to bind with protons than the other atoms, the interactions and nature of bonding can be well understood.

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 1. Different exist form for OBC under various pH conditions.

3. Results and discussion the gaseous state, it can clearly be seen from Figs. 3 and 4 that the
aqueous ReO4− has a slight discrepancy in the average bond distance of
3.1. The character of ReO4− Re-O and the simulated vibrational spectra, the bond distance is re-
duced by 0.002 Å, for the simulated vibrational spectra of ReO4−, the
The optimized geometric structures of ReO4− are presented in gaseous O-Re-O degenerate bending mode and Re-O asymmetric
Fig. 3. The ground state of the ReO4− is tetrahedral, with an average stretching band shift from ~302/894 cm−1 to ~287/871 cm−1 in
Re-O bond distance of 1.765 Å in gaseous. However, as to the aqueous, aqueous. These results can be attributed to the smaller solvation energy
whether in an explicit solvent or an implicit solvent, the average bond value of ReO4− (−234 kJ/mol [41]), and the structure of ReO4− is less
distance of Re-O is 1.763 Å, which is in agreement with the results of affected by the solvent effect. Furthermore, it turned out that the DFT
Bridgeman et al (1.75–1.77 Å) [39]. The computed vibrational fre- calculation based on the COSMO model is credible.
quencies are all positive in the range of 286–921 cm−1 (see Fig. 4), it is
in accordance with the study of Thompson et al [40]. Compared with

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 2. The optimized structures of AOBC and BOBC models at different pH conditions: (a) AOBC; (b) BOBC.

Fig. 3. The optimized geometric structures of ReO4−.

3.2. The interaction of ReO4− and acidic oxygen-containing groups on BC

First of all, we studied the behavior of ReO4− interacting with acidic

oxygen-containing groups on BC. Six most favorable configuration of
ReO4− adsorption on AOBC are presented in Fig. 5. Table 1 summarizes
the calculated bond distance of interacting atom (D), adsorption en-
ergies (Eads), and amount of charge transfer (△Q) for different ad- Fig. 4. The simulated vibrational spectra of ReO4−.
sorption configurations.
As shown in Fig. 5, [BC-OH2…ReO4] and [BC-COOH2…ReO4]
COOH2…ReO4] complexes are 1.043 Å (H38-ORe) and 1.019 Å (H40-
complexes are presented for the acidic pH condition, it can be found
ORe), respectively. The bond distance of H38-ORe and H40-ORe less than
that the bond distance of interacting atom in [BC-OH2…ReO4] and [BC-
the sum of H atomic radius (0.37 Å) and O atomic radius (0.74 Å), there

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 5. The optimized adsorption configurations of ReO4− on AOBC.

Table 1 protonated positively charged AOBC and it is a nucleophilic attack

The calculated bond distance of interacting atom, adsorption energies, and process. As to the neutral pH conditions, [BC-OH…ReO4]− and [BC-
amount of charge transfer for ReO4− adsorption on AOBC. COOH…ReO4]− have weaker charge transfer (-0.055 and −0.064 e),
Complexes Interacting atoms Eads (kJ/mol) △Q (e) which may be caused by the van der Waals force and hydrogen
bonding. However, almost no charge transfer occurred (~0 e) at basic
Bond D (Å) pH condition.
An analysis of bond distance and Mayer bond order was performed
[BC-OH2…ReO4] H38-ORe 1.043 −99.784 −0.426
[BC-COOH2…ReO4] H40-ORe 1.019 −93.286 −0.481 to interpret the bonding nature for the interaction between ReO4− and
[BC-OH…ReO4]− H37-ORe 1.773 −23.870 −0.055 AOBC at acidic and neutral pH conditions, the calculated results are
[BC-COOH…ReO4]− H39-ORe 1.626 −25.359 −0.064 tabulated in Table 2, ORe represents the O atom of ReO4−. For [BC-
[BC-O…ReO4]2− O31-ORe 3.642 4.042 0.005 OH2…ReO4] and [BC-COOH2…ReO4] complexes, due to the combina-
[BC-COO…ReO4]2− O38-ORe 3.780 3.606 0.000
tion of ReO4− with [BC-OH2]+ and [BC-COOH2]+, the O31-H38 and
O38-H40 bonds are elongated, the bond distance increase from 0.988 Å
and 0.983 Å to 1.490 Å and 1.572 Å, and the Mayer bond order decrease
are chemical bonds generation between ReO4− and [BC-OH2]+/[BC-
from 0.852 and 0.868 to 0.209 and 0.157. The large Mayer bond order
COOH2]+, indicating that the protonated hydroxy H38 and carboxylic
of H38-ORe (0.617) and H40-ORe (0.685) suggest that the H38-ORe and
H40 can offer favorable binding sites to ReO4−. And the calculated
H40-ORe have strong covalent character [42], and the H-OReO3 species
adsorption energies for [BC-OH2…ReO4] and [BC-COOH2…ReO4] are
formed by ReO4− adsorption on protonated hydroxyl and carboxyl are
−99.784 kJ/mol and −93.286 kJ/mol, respectively. In contrast, for
very stable. Similarly, for [BC-OH…ReO4]− and [BC-COOH…ReO4]−
[BC-OH…ReO4]− and [BC-COOH…ReO4]− complexes, which are re-
complexes, the H37-ORe and H39-ORe bonds are weakened slightly by the
presented as the situation at neutral pH condition, ReO4− is weak
adsorption of ReO4−, the bond distance increase from 0.974 Å and
bound to [BC-OH] and [BC-COOH] with longer bond distance of
0.979 Å to 0.991 Å and 1.010 Å, the Mayer bond order decrease from
1.773 Å and 1.626 Å for H37-ORe and H39-ORe. There have lower ad-
0.896 and 0.901 to 0.815 and 0.770, the smaller Mayer bond order of
sorption energies in [BC-OH…ReO4]− and [BC-COOH…ReO4]− with
H37-ORe (0.103) and H39-ORe (0.156) indicate that the H37-ORe and H39-
–23.870 kJ/mol and −25.359 kJ/mol, respectively. Besides, [BC-O…
ReO4]2− and [BC-COO…ReO4]2− complexes are considered for basic
pH condition, the bond distance of interacting atoms are 3.642 Å (O31- Table 2
ORe) and 3.780 Å (O38-ORe), respectively, ReO4− is far away from the The bond distance and Mayer bond order analysis for the interacting atoms in
basal plane of the deprotonated hydroxyl and carboxyl groups func- [BC-OH2…ReO4], [BC-COOH2…ReO4], [BC-OH…ReO4]− and [BC-COOH…
tionalized BC. The deprotonated negatively charged hydroxyl and car- ReO4]− complexes.
boxyl groups of [BC-O]− and [BC-COO]− make them potentially re- Complexes Bond Bond distance (Å) Bond order
pulsive to the ReO4−, and the positive adsorption energies of 4.042 kJ/
mol and 3.606 kJ/mol further prove their instability. These results Before After Before After
suggest that the acidic pH condition is more favorable for the ReO4−
[BC-OH2…ReO4] O31-H38 0.988 1.490 0.852 0.209
adsorption on AOBC, and the interaction of protonated positively H38-ORe / 1.043 / 0.617
charged hydroxyl groups with ReO4− is stronger. [BC-COOH2…ReO4] O38-H40 0.983 1.572 0.868 0.157
In addition, the charge transfer of adsorbed ReO4− decreased with H40-ORe / 1.019 / 0.685
increasing pH. With significant negative charge transfer value of [BC-OH…ReO4]− O31-H37 0.974 0.991 0.896 0.815
H37-ORe / 1.773 / 0.103
−0.426 e and −0.481 e for [BC-OH2…ReO4] and [BC-COOH2…ReO4], [BC-COOH…ReO4]− O38-H39 0.979 1.010 0.901 0.770
which indicates that the electrons were transferred from ReO4− to the H39-ORe / 1.626 / 0.156

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 6. The DOS plots of [BC-OH2…ReO4], [BC-COOH2…ReO4], [BC-OH…ReO4]−and [BC-COOH…ReO4]− complexes.

ORe bonds possess minor covalent character and the hydrogen bonding given in Fig. S2.
plays a dominant role. For the [BC-OH2…ReO4] and [BC-COOH2…ReO4] complexes, after
Furthermore, the DOS analysis was performed to further clarify the adsorption, the DOS of AOBC is larger than before, the DOS peak at
interaction between ReO4− and AOBC. Fig. 6 depicts the DOS plots of −24.5 eV in [BC-OH2]+ and DOS peak at –23.3/–22.2 eV in [BC-
[BC-OH2…ReO4], [BC-COOH2…ReO4], [BC-OH…ReO4]− and [BC- COOH2]+ are clearly shifted to the high energy level. However, the
COOH…ReO4]− complexes, and the DOS plots of other complexes are DOS of ReO4− shift toward the lower energy region and become largely

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

weakened. Furthermore, there increased new DOS peaks at about H (b)]+. Meanwhile, there are obviously charge transfer from ReO4− to
−20 eV and −9 eV in the DOS plots of ReO4−, which are mainly [BC-Pyr-H (a)]+, [BC-Chr-H (a)]+ and [BC-Chr-H (b)]+, the charge
composed of the ORe-2s, 2p orbital of ReO4−. These results can be at- transfer value are −0.532 e, −0.460 e and −0.538 e, respectively. And
tributed to the protonated AOBC as an electron acceptor receives the the corresponding calculated adsorption energies for [BC-Pyr-H…ReO4
electrons from ReO4− and the strong atomic orbital hybridization be- (a)], [BC-Chr-H…ReO4 (a)] and [BC-Chr-H…ReO4 (b)] are
tween H38/H40-1s orbitals and ORe-2s, 2p orbitals. −159.208 kJ/mol, −128.074 kJ/mol and −74.921 kJ/mol, showing
As to the [BC-OH…ReO4]− and [BC-COOH…ReO4]− complexes, an strong chemisorption compared to the other complexes. For the [BC-
compared with the [BC-OH2…ReO4] and [BC-COOH2…ReO4] com- Pyr-H…ReO4 (c)], [BC-Pyr…ReO4]− and [BC-Chr…ReO4]− complexes,
plexes, due to the weak electrostatic interaction between AOBC and the amount of charge transfer is tend to zero, the big interval of in-
ReO4−, the DOS peak of [BC-OH] at −21.6 eV, and DOS peak of [BC- teracting atoms and little adsorption energies indicate a loose physical
COOH] at –22.3 and −19.9 eV have a slight shift to high energy level. interaction. Compared with the [BC-Pyr-H…ReO4 (c)], [BC-Pyr…
Except the DOS of ReO4− shifts towards the negative energy region, the ReO4]− and [BC-Chr…ReO4]− complexes, the [BC-Pyr-H…ReO4 (b)]
intensity of DOS peaks of ReO4− can be observed to have a weak ten- has shorter adsorption distance, larger adsorption energy and more
dency to decrease, the adsorption mainly causes the electron redis- obvious charge transfer, ReO4− might be adsorbed onto [BC-Pyr-H
tribution of ReO4−. And the overlapped DOS between the interacting (b)]+ by hydrogen bonding. These results are also confirmed that the
atoms (H37 and ORe, H39 and ORe) is narrow, which suggest that a interactions between ReO4− and basic oxygen-containing groups on BC
weaker orbital hybridization has occurred between the interacting at acidic pH condition are much favorable than that at neutral pH
atoms. These results further confirm that the interactions of ReO4− condition, especially for the protonation on etheric O atom of chromene
with [BC-OH2]+ and [BC-COOH2]+ are stronger than the [BC-OH] and and pyrone groups could provide the stronger chemisorption for
[BC-COOH]. Orbital hybridization between the interacting atoms plays ReO4−.
a very important role in the adsorption of ReO4− on [BC-OH2]+ and Similarly, the bond distance and Mayer bond order of interacting
[BC-COOH2]+. atoms in [BC-Pyr-H…ReO4 (a)], [BC-Pyr-H…ReO4 (b)], [BC-Chr-H…
Based on these above, the bond distances of interacting atoms are ReO4 (a)] and [BC-Chr-H…ReO4 (b)] were analyzed to clarify the
shorted with decreasing pH, which is much shorter in the protonated bonding nature of interacting atoms. As shown in Table 4, for [BC-Pyr-
AOBC/ReO4− complexes than that at neutral and basic pH conditions, H…ReO4 (a)], [BC-Chr-H…ReO4 (a)] and [BC-Chr-H…ReO4 (b)] com-
and it is consistent with the more negative adsorption energy at acidic plexes, the O17-H36, O37-H40, C35-C36 and C36-O37 bonds are weakened
pH condition. ReO4− could combined with the AOBC mainly via the H significantly by the adsorption of ReO4−, with their Mayer bond order
atoms of protonated hydroxyl and carboxyl groups, leading to the for- decreasing from 0.826, 0.834, 1.098 and 1.436 to 0, 0.119, 0.989 and
mation of H-OReO3 species, the result is agreement with our previous 0.985. The large Mayer bond order of H36-ORe (a) (0.773), H40-ORe
experimental research [10]. Furthermore, according to the calculated (0.708) and C36-ORe (0.788) suggest that the H36-ORe (a), H40-ORe and
weaker charge transfer, the van der Waals force and weak hydrogen C36-ORe have obvious covalent character, the H-OReO3 and C-OReO3
bonding play a major role at neutral pH condition. For acidic pH con- species formed by ReO4− adsorption on pyrone and chromene are very
dition, there has strong chemisorption because of the obvious charge stable. Compared with [BC-OH2…ReO4] and [BC-COOH2…ReO4]
transfer, and the binding between ReO4− and AOBC mainly depend on complexes, the larger Mayer bond order of bonding atoms (H-ORe bond)
the electrostatic interaction, complexation and atomic orbital hy- and adsorption energies, suggesting that the interactions of ReO4− with
bridization between ReO4− and protonated positively charged acidic [BC-Pyr-H (a)]+ and [BC-Chr-H (a)]+ are stronger than that in [BC-
oxygen-containing groups. In short, the lower pH value of solution, the OH2…ReO4] and [BC-COOH2…ReO4]. For [BC-Pyr-H…ReO4 (b)]
more negative adsorption energy, the stronger interaction between complexes, the O27-H36 bond is slightly weakened, which can be ob-
ReO4− and AOBC. tained by observing the bond distance and Mayer bond order before and
after adsorption. The bond distance of H36-ORe (b) is greater than the
3.3. The interaction of ReO4− and basic oxygen-containing groups on BC sum of their atomic covalent radius, and the smaller Mayer bond order
(0.188), further implying that the interaction between ReO4− and [BC-
Then, the adsorption of ReO4− on BOBC was discussed, seven op- Pyr-H (b)]+ was driving by hydrogen bonding.
timized adsorption structures of ReO4− interacting with BOBC at acidic Fig. 8 portrays the DOS plots of [BC-Pyr-H…ReO4 (a)], [BC-Pyr-H…
and neutral pH conditions are depicted in Fig. 7. In detail, the adducts ReO4 (b)], [BC-Chr-H…ReO4 (a)] and [BC-Chr-H…ReO4 (b)] com-
[BC-Pyr-H…ReO4 (a)], [BC-Pyr-H…ReO4 (b)], [BC-Pyr-H…ReO4 (c)], plexes, and the DOS plots of other complexes are given in Fig. S4. For
[BC-Chr-H…ReO4 (a)] and [BC-Chr-H…ReO4 (b)] are considered due to the [BC-Pyr-H…ReO4 (a)], [BC-Chr-H…ReO4 (a)] and [BC-Chr-H…
the protonation of pyrone and chromene groups at acidic pH condition, ReO4 (b)] complexes, after adsorption, the DOS peaks of ReO4− become
while the [BC-Pyr…ReO4]− and [BC-Chr…ReO4]− complexes are re- largely weakened because of the strong interaction with BOBC. At the
presented as the situation at neutral pH condition. Among them, there same time, the generated splitting peaks of ReO4− can be attributed to
are two oxygens in the neutral [BC-Pyr], which may be both active sites the atomic orbital hybridization between ReO4− and BOBC. According
for ReO4− adsorption. According to the DFT evaluated Fukui function to the PDOS plots of interacting atoms, including H36 atom of [BC-Pyr-
values (F+) for [BC-Pyr] (see Fig. S3), which can quantitatively eval- H…ReO4 (a)], H40 atom of [BC-Chr-H…ReO4 (a)], C36 atom of [BC-Chr-
uate the local reactivity of particular atoms in the molecule [43], the H…ReO4 (b)] and O atom of ReO4−, in which showed an obviously
carbon (C18) atom adjacent to etheric oxygen in [BC-Pyr] possesses hybridization phenomenon between H36 and ORe, H40 and ORe, C36 and
stronger eletrophilicity. Therefore, for [BC-Pyr…ReO4]−, the ReO4− is ORe at bonding region, such as the DOS peaks at −20.6 and −9.3 eV in
more prone to adsorb on the C18 atom, which is adjacent to the etheric [BC-Pyr-H…ReO4 (a)], the DOS peaks at −20.6 and −9.4 eV in [BC-
oxygen of pyrone group. Table 3 summarizes the calculated bond dis- Chr-H…ReO4 (a)], the DOS peaks at –22.6 and −20.5 eV in [BC-Chr-
tance of interacting atom (D), adsorption energies (Eads) and amount of H…ReO4 (b)], implying the formation of covalent bond between H36
charge transfer (△Q) for different adsorption configurations. and ORe, H40 and ORe, C36 and ORe. As to the [BC-Pyr-H…ReO4 (b)], it
As shown in Fig. 7, the equilibrium bond distance of interacting should be noted that the DOS peak strength of ReO4− has little change,
atoms for H36-ORe, H40-ORe and C36-ORe are about 0.987 Å, 1.006 Å and and the overlapped DOS between H36 and ORe is smaller, suggesting the
1.466 Å in [BC-Pyr-H…ReO4 (a)], [BC-Chr-H…ReO4 (a)] and [BC-Chr- protonation of carbonyl oxygen in pyrone is weak to the adsorption of
H…ReO4 (b)] complexes, respectively, which are less than the sum of ReO4−.
their atomic covalent radius. It is meant that there formed covalent Overall, the acidic pH condition is also more conducive to the ad-
bonds between ReO4− and [BC-Pyr-H (a)]+/[BC-Chr-H (a)]+/[BC-Chr- sorption of ReO4− on BOBC. Especially for the protonation on etheric O

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 7. The optimized adsorption configurations of ReO4− on BOBC.

Table 3 3.4. The interaction of ReO4− and acidic/basic oxygen-containing groups

The calculated bond distance of interacting atom, adsorption energies, and co-decorated BC
amount of charge transfer for ReO4− adsorption on BOBC.
Complexes Interacting atoms Eads (kJ/mol) △Q (e) As mentioned above, acidic pH condition is most conducive to the
adsorption of ReO4− on BC. As to the basic oxygen-containing group,
Bond D (Å) the protonated etheric oxygen of pyrone is the most favorable adsorp-
tion site for ReO4−. For more comparison, the interaction of ReO4−
[BC-Pyr-H…ReO4 (a)] H36-ORe 0.987 −159.208 −0.532
[BC-Pyr-H…ReO4 (b)] H36-ORe 1.587 −36.377 −0.088 with pyrone, hydroxyl and carboxyl groups co-decorated BC at acidic
[BC-Pyr-H…ReO4 (c)] C18-ORe 2.828 −14.547 −0.027 pH condition were investigated. The optimized BC models and inter-
[BC-Chr-H…ReO4 (a)] H40-ORe 1.006 −128.074 −0.460 action structures as shown in Fig. 9. Moreover, A, B, C and D represent
−74.921 −0.538
[BC-Chr-H…ReO4 (b)] C36-ORe 1.466
the structure of ReO4− adsorption on etheric oxygen, hydroxyl, car-
[BC-Pyr…ReO4]− C18-ORe 3.024 −7.673 −0.014
[BC-Chr…ReO4]− H39-ORe 2.491 −7.178 −0.014
boxyl and carbonyl oxygen, respectively. The calculated interaction
distance (D), adsorption energies (Eads) and amount of charge transfer
(△Q) for ReO4− adsorption on oxygen-containing groups co-decorated
Table 4 BC are listed in Table 5.
The bond distance and Mayer bond order analysis for interacting atoms in [BC- It can be found that the bond distances of O–H in protonated
Pyr-H…ReO4 (a)], [BC-Pyr-H…ReO4 (b)], [BC-Chr-H…ReO4 (a)] and [BC-Chr- oxygen-containing groups become longer as 1.826 Å in A, 1.567 Å in B
H…ReO4 (b)] complexes. and 1.622 Å in C after adsorption. The H-ORe covalent bonds are formed
Complexes Bond Bond distance (Å) Bond order
by the interaction of ReO4− with H atom of protonated oxygen-con-
taining groups, the bond distance of H-ORe bonds in A, B and C are
Before After Before After 0.986 Å, 1.018 Å and 1.010 Å, which are significantly less than the sum
of their atomic covalent radii. The calculated adsorption energies of
[BC-Pyr-H…ReO4 (a)] O17-H36 0.986 1.887 0.826 0.000
ReO4− are −192.823 kJ/mol in A, −142.407 kJ/mol in B and
H36-ORe (a) / 0.987 / 0.773
[BC-Pyr-H…ReO4 (b)] O27-H36 0.977 1.010 0.900 0.760 −124.954 kJ/mol in C. As to D, the longer adsorption distance
H36-ORe (b) / 1.587 / 0.188 (3.441 Å) and lower adsorption energy (−15.221 kJ/mol) indicate that
[BC-Chr-H…ReO4 (a)] O37-H40 0.985 1.641 0.834 0.119 ReO4− adsorption on carbonyl oxygen of pyrone is a weak physisorp-
H40-ORe / 1.006 / 0.708 tion. The larger adsorption energies of A suggest that ReO4− is more
[BC-Chr-H…ReO4 (b)] C35-C36 1.455 1.513 1.098 0.989
C36-O37 1.279 1.407 1.436 0.985
inclined to interact with the protonated etheric oxygen of pyrone
C36-ORe / 1.466 / 0.788 groups. Meanwhile, the charge transfer for the A, B, C and D are
−0.562 e, −0.490 e, −0.500 e and −0.002 e, respectively. Compared
to single oxygen-containing group functionalized BC, the larger ad-
atom in pyrone and chromene groups, the higher adsorption energies sorption energy and charge transfer imply that the more oxygen-con-
indicate that the ReO4− adsorption on [BC-Pyr-H (a)] and [BC-Chr-H taining groups and more positive charge on BC are more favorable for
(a)] are more stable than that in [BC-OH2…ReO4] and [BC-COOH2… the ReO4− adsorption, and the electrostatic interaction plays an im-
ReO4], including the other BOBC/ReO4− complexes. ReO4− can com- portant role in the binding between ReO4− and BC.
bine with the protonated pyrone and chromene by forming H-OReO3 or
C-OReO3 species. And pyrone has the strongest binding ability to
4. Conclusions
ReO4−. Compared with the acidic oxygen-containing groups, the BC
containing basic oxygen-containing groups have stronger binding
The microcosmic interaction of ReO4− adsorption on BC with dif-
ability toward ReO4−.
ferent oxygen-containing groups under different pH conditions were

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 8. The DOS plots of [BC-Pyr-H…ReO4 (a)], [BC-Pyr-H…ReO4 (b)], [BC-Chr-H…ReO4 (a)] and [BC-Chr-H…ReO4 (b)] complexes.

evaluated by means of the DFT calculation. Various interaction models adsorption energy and electronic property, the protonated positively
of oxygen-containing group functionalized BC with ReO4− were con- charged oxygen-containing groups, including protonated hydroxyl and
structed. The results manifest that the adsorption of ReO4− on oxygen- carboxyl and the protonated etheric oxygen of pyrone and chromene
containing group functionalized BC is sensitive to the pH value of the act as electron acceptors have stronger electrophilic ability toward
aqueous solution. According to the analysis of adsorption structure, ReO4−, resulting in the more charge transfer and negative adsorption

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Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

Fig. 9. The optimized protonated oxygen-containing group co-decorated BC (top) and interaction of ReO4− with protonated oxygen-containing group co-decorated
BC (bottom): A. ReO4− on etheric oxygen; B. ReO4− on hydroxyl; C. ReO4− on carboxyl; D. ReO4− on carbonyl oxygen.

Table 5 [5] D. Han, X.X. Li, Y. Cui, X. Yang, X.B. Chen, L. Xu, J. Peng, J.Q. Li, M.L. Zhai,
The calculated interaction distance, adsorption energies and amount of charge Polymeric ionic liquid gels composed of hydrophilic and hydrophobic units for high
adsorption selectivity of perrhenate, RSC Adv. 8 (2018) 9311–9319.
transfer for ReO4− adsorption on acidic/basic oxygen-containing groups co-
[6] L.F. Chen, X.B. Yin, Q. Yu, L. Siming, F.Y. Meng, S.Y. Ning, X.P. Wang, Y.Z. Wei,
decorated BC. Rapid and selective capture of perrhenate anion from simulated groundwater by a
mesoporous silica-supported anion exchanger, Micropor. Mesopor. Mat. 274 (2019)
Adsorption configuration D (Å) Eads (kJ/mol) △Q (e)
155–162.
[7] K. Tanaka, N. Kozai, T. Ohnuki, B. Grambow, Study on coordination structure of Re
A 0.986 −192.823 −0.562
adsorbed on Mg–Al layered double hydroxide using X-ray absorption fine structure,
B 1.018 −142.407 −0.490
J. Porous Mat. (2018).
C 1.010 −124.954 −0.500 [8] R.J. Drout, K. Otake, A.J. Howarth, T. Islamoglu, L. Zhu, C.L. Xiao, S.A. Wang,
D 3.441 −15.221 −0.002 O.K. Farha, Efficient capture of perrhenate and pertechnetate by a mesoporous Zr
metal–organic framework and examination of anion binding motifs, Chem. Mater.
30 (2018) 1277–1284.
energy, and the adsorption processes were mainly attributed to the [9] H. Hu, L. Sun, B. Jiang, H. Wu, Q. Huang, X. Chen, Low concentration Re(VII)
recovery from acidic solution by Cu-biochar composite prepared from bamboo
electrostatic interaction, complexation and atomic orbital hybridiza- (Acidosasa longiligula) shoot shell, Miner. Eng. 124 (2018) 123–136.
tion. Compared with the acidic oxygen-containing groups, the larger [10] H. Hu, B.Q. Jiang, J.B. Zhang, X.H. Chen, Adsorption of perrhenate ion by bio-char
adsorption energy, and Mayer bond order indexes of the interacting produced from Acidosasa edulis shoot shell in aqueous solution, RSC Adv. 5 (2015)
104769–104778.
atoms indicated that the basic oxygen-containing groups include [11] H. Hu, B.Q. Jiang, H.X. Wu, J.B. Zhang, X.H. Chen, Bamboo (Acidosasa edulis)
pyrone and chromene groups are more favorable for the adsorption of shoot shell biochar: Its potential isolation and mechanism to perrhenate as a che-
ReO4−, especially for the protonation on etheric oxygen, which could mical surrogate for pertechnetate, J. Environ. Radioact. 165 (2016) 39–46.
[12] M.A. Montes-Morán, D. Suárez, J.A. Menéndez, E. Fuente, On the nature of basic
enhance the ReO4− adsorption strength on BC. Therefore, the basic sites on carbon surfaces: an overview, Carbon 42 (2004) 1219–1225.
oxygen-containing groups are also a promising candidate, which can be [13] M. Genovese, J. Jiang, K. Lian, N. Holm, High capacitive performance of exfoliated
utilized for the modification of the adsorption materials. Consequently, biochar nanosheets from biomass waste corn cob, J. Mater. Chem. A 3 (2015)
2903–2913.
our results not only provide new insights into the adsorption me-
[14] P. Rajec, O. Rosskopfová, M. Galamboš, V. Frišták, G. Soja, A. Dafnomili, F. Noli,
chanism of ReO4− on BC, but also has significant reference value for the A. Đukić, L. Matović, Sorption and desorption of pertechnetate on biochar under
subsequent new extractant screening and resin synthesis to capture static batch and dynamic conditions, J. Radioanal. Nucl. Ch. 310 (2016) 253–261.
ReO4− and the other anions from the aqueous solution. [15] C.L. Zhang, Y. Liu, X. Li, H.X. Chen, T. Wen, Z.H. Jiang, Y.J. Ai, Y.B. Sun, T. Hayat,
X.K. Wang, Highly uranium elimination by crab shells-derived porous graphitic
carbon nitride: Batch, EXAFS and theoretical calculations, Chem. Eng. J. 346 (2018)
Appendix A. Supplementary data 406–415.
[16] Q. Chen, J.W. Zheng, J.C. Xu, Z. Dang, L.J. Zhang, Insights into sulfamethazine
adsorption interfacial interaction mechanism on mesoporous cellulose biochar:
Supplementary data to this article can be found online at https:// Coupling DFT/FOT simulations with experiments, Chem. Eng. J. 356 (2019)
doi.org/10.1016/j.cej.2019.122647. 341–349.
[17] X.X. Wang, Y. Liu, H.W. Pang, S.J. Yu, Y.J. Ai, X.Y. Ma, G. Song, T. Hayat,
A. Alsaedi, X.K. Wang, Effect of graphene oxide surface modification on the elim-
References ination of Co(II) from aqueous solutions, Chem. Eng. J. 344 (2018) 380–390.
[18] B. Padak, J. Wilcox, Understanding mercury binding on activated carbon, Carbon
[1] Z.S. Abisheva, A.N. Zagorodnyaya, N.S. Bekturganov, Review of technologies for 47 (2009) 2855–2864.
rhenium recovery from mineral raw materials in Kazakhstan, Hydrometallurgy 109 [19] L. Sellaoui, D.I. Mendoza-Castillo, H.E. Reynel-Ávila, B.A. Ávila-Camacho,
(2011) 1–8. L.L. Díaz-Muñoz, H. Ghalla, A. Bonilla-Petriciolet, A.B. Lamine, Understanding the
[2] C.D. Anderson, P.R. Taylor, C.G. Anderson, Extractive metallurgy of rhenium: a adsorption of Pb2+, Hg2+ and Zn2+ from aqueous solution on a lignocellulosic
review, Miner. Metall. Proc. 30 (2013) 59–73. biomass char using advanced statistical physics models and density functional
[3] D.W. Fang, W.J. Shan, Q. Yan, D. Li, L.X. Xia, S.L. Zang, Extraction of rhenium from theory simulations, Chem. Eng. J. 365 (2019) 305–316.
sulphuric acid solution with used amine N235, Fluid Phase Equilib. 383 (2014) 1–4. [20] T.A. Saleh, V.K. Gupta, A.A. Al-Saadi, Adsorption of lead ions from aqueous solution
[4] H.S. Kim, J.S. Park, S.Y. Seo, T. Tran, M.J. Kim, Recovery of rhenium from a mo- using porous carbon derived from rubber tires: experimental and computational
lybdenite roaster fume as high purity ammonium perrhenate, Hydrometallurgy 156 study, J. Colloid Interface Sci. 396 (2013) 264–269.
(2015) 158–164. [21] Y.J. Ai, Y. Liu, W.Y. Lan, J.R. Jin, J.L. Xing, Y.D. Zou, C.F. Zhao, X.K. Wang, The

10
Y. Huang and H. Hu Chemical Engineering Journal 381 (2020) 122647

effect of pH on the U(VI) sorption on graphene oxide (GO): A theoretical study, the density functional description of solids and molecular structures, Phys. Rev. B
Chem. Eng. J. 343 (2018) 460–466. 73 (2006).
[22] Q. Chen, J.W. Zheng, L.C. Zheng, Z. Dang, L.J. Zhang, Classical theory and electron- [34] A. Klamt, G. Schüürmann, COSMO: A new approach to dielectric screening in sol-
scale view of exceptional Cd(II) adsorption onto mesoporous cellulose biochar via ventswith explicit expressions for the screening energy and its gradient, J. Chem.
experimental analysis coupled with DFT calculations, Chem. Eng. J. 350 (2018) Soc. Perkin Trans. 2 (2) (1993) 799–805.
1000–1009. [35] X. Sun, J.Y. Hwang, S.Q. Xie, Density functional study of elemental mercury ad-
[23] K. Zhang, B.L. Chen, J.F. Mao, L.Z. Zhu, B.S. Xing, Water clusters contributed to sorption on surfactants, Fuel 90 (2011) 1061–1068.
molecular interactions of ionizable organic pollutants with aromatized biochar via [36] R.S. Mulliken, Electronic population analysis on LCAO–MO molecular wave func-
pi-PAHB: Sorption experiments and DFT calculations, Environ. Pollut. 240 (2018) tions. II. Overlap populations, bond orders, and covalent bond energies, J. Chem.
342–352. Phys. 23 (1955) 1841–1846.
[24] C. Zhang, W. Wang, A. Duan, G. Zeng, D. Huang, C. Lai, X. Tan, M. Cheng, R. Wang, [37] I. Mayer, Bond orders and valences from ab initio wave functions, Int. J. Quantum
C. Zhou, W. Xiong, Y. Yang, Adsorption behavior of engineered carbons and carbon Chem. 29 (1986) 477–483.
nanomaterials for metal endocrine disruptors: Experiments and theoretical calcu- [38] B.K. Zhang, J. Liu, C.G. Zheng, M. Chang, Theoretical study of mercury species
lation, Chemosphere 222 (2019) 184–194. adsorption mechanism on MnO2(110) surface, Chem. Eng. J. 256 (2014) 93–100.
[25] P. Francesca, M. Sara, T. Luigi, New biosorbent materials for heavy metal removal: [39] A.J. Bridgeman, G.N. Cavigliasso, Density-functional investigation of bonding in
Product development guided by active site characterization, Water Res. 42 (2008) tetrahedral MO4 anions, Polyhedron 20 (2001) 2269–2277.
2953–2962. [40] S.T. Thompson, H.H. Lamb, B. Delley, S. Franzen, Vibrational spectroscopy of the
[26] D. Suarez, J.A. Menendez, E. Fuente, Contribution of pyrone type structures to double complex salt Pd(NH3)4(ReO4)2, a bimetallic catalyst precursor, Spectrochim.
carbon basicity an ab initio study, Langmuir 15 (1999) 3897–3904. Acta A Mol. Biomol. Spectrosc. 173 (2017) 618–624.
[27] B. Delley, An all-electron numerical method for solving the local density functional [41] D. Banerjee, W.Q. Xu, Z.M. Nie, L.E. Johnson, C. Coghlan, M.L. Sushko, D. Kim,
for polyatomic molecules, J. Chem. Phys. 92 (1990) 508–517. M.J. Schweiger, A.A. Kruger, C.J. Doonan, P.K. Thallapally, Zirconium-based metal-
[28] B. Delley, From molecules to solids with the DMol3 approach, J. Chem. Phys. 113 organic framework for removal of perrhenate from water, Inorg. Chem. 55 (2016)
(2000) 7756–7764. 8241–8243.
[29] J.P. Perdew, Generalized gradient approximations for exchange and correlation: A [42] C. Huang, H. Lv, C. Zuo, Z. Yuan, W. Zheng, T. Yan, Selective extraction of pluto-
look backward and forward, Phys. B 172 (1991) 1–6. nium(IV) over uranium(VI), americium(III), europium(III) and zirconium(IV) with
[30] J.P. Perdew, Y. Wang, Accurate and simple analytic representation of the electron- bidentate O-phenoxydiamide ligands: experimental and theoretical study, J.
gas correlation energy, Phys. Rev. B 45 (1992) 13244–13249. Radioanal. Nucl. Ch. 317 (2018) 103–110.
[31] B. Delley, Fast calculation of electrostatics in crystals and large molecules, J. Phys. [43] M. Pandey, S. Muthu, N.M. Nanje Gowda, Quantum mechanical and spectroscopic
Chem. 100 (1996) 6107–6110. (FT-IR, FT-Raman, 1H, 13C NMR, UV-Vis) studies, NBO, NLO, HOMO, LUMO and
[32] B. Delley, Hardness conserving semilocal pseudopotentials, Phys. Rev. B 66 (2002). Fukui function analysis of 5-Methoxy-1H-benzo[d]imidazole-2(3H)-thione by DFT
[33] F. Ortmann, F. Bechstedt, W.G. Schmidt, Semiempirical van der Waals correction to studies, J. Mol. Struct. 1130 (2017) 511–521.

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