FARMANZADEH Davood　REZAINEJAD Hamid(Department of Physical Chemistry,Faculty of Chemistry,University of Mazandaran,Babolsar,47416－95447,I.R.Iran)

DFT Study of Adsorption of Diazinon,Hinosan,Chlorpyrifos and Parathion Pesticides on the Surface of B36N36Nanocage and Its Fe Doped Derivatives as New Adsorbents

FARMANZADEH Davood*REZAINEJAD Hamid
(Department of Physical Chemistry,Faculty of Chemistry,University of Mazandaran,Babolsar,47416－95447,I.R.Iran)

In this work,we used density functional theory with the Tkatchenko and Scheffler method to investigate the adsorption of diazinon,hinosan,chlorpyrifos,and parathion organophosphorus pesticides on the surface of B36N36nanocage and its Fe doped derivatives.The assessments revealed that van der Waals interaction is a key factor in organophosphate adsorption on the surface of these nanocages as well as overlapping.The results of Fukui indices and atomic partial charges calculations indicated that these pesticides and nanocages act as nucleophile and electrophile,respectively,and the adsorption sites of all four organophosphates on these nanocages are thiophosphate groups,as well as the aromatic ring in diazinon,and the nitro group in parathion.In addition,the calculated adsorption energies yielded the best result for diazinon, and the best Fe doped B36N36derivative for adsorbing organophosphates in aqueous solution is the one in which Fe atom is located in the boron position of the square ring of B36N36.

Organophosphate;Density functional theory;van der Waals interaction;B36N36;Adsorption

1　Introduction

The most widely used pesticides are organophosphates(OPs). These compounds are esters of phosphoric and thiophosphoric acids which have mainly been used to control pest insects in agriculture.Exposure to OPs is considered as a health problem for human communities,especially farmers in rural regions1.Large amounts of these toxins in water,soil,and even plants may remain for months or years2and are quite toxic to vertebrates3.These toxin exposure may occur by inhalation,ingestion,and dermal contact1that generates irreparable damages for human and living organisms4.

Some OPs are used to control blast of rice and rice stem borer such as diazinon and hinosan.Chlorpyrifos,parathion,and malathion are other examples that are utilized to control pest of fruit trees and crops and also to destroy livestock insects.Pesticides pollute water resources in several ways.These toxins as contaminants of water resources,particularly drinking water,can cause adverse effects on human health and the environment5,6.The primary action of organophosphate pesticides as nerve agents is irreversible inhibition of cholinesterase enzymes in both insects and humans and causes various health problems such as harmful effects on the immune system and the reproductive system7－9.OPs may be risky to the brain growth of fetuses and young children, even at very little amounts10.The harmful effects of these toxin residue in the environment excited researchers to explore methods for removing these toxins from environment,and especially surface waters.Thereby many experimental researches were performed11－15,but a few theoretical studies are conducted in this topic16.

Boron nitride fullerene,B36N36,is one of the BN nanocages which have attracted the attention of many researchers.For the first time,B36N36was manufactured by electron beam irradiation in 199817.Over the past two decades,many experimental and theoretical studies have been performed to investigate geometries, electronic structures,and probable applications of B36N36and its functionalized derivatives18－24.Some properties of BN nanostructures including structural and thermal stability,resistance in oxidation,polar nature of bonds18,etc.made them useful for several applications25－27especially in the molecular adsorption that is considered in the present work.

Among the studies of properties and applications of BN nanostructures,it was tried to find the methods which modify and amplify their capabilities for improving the efficiency of their applications.One of the appropriate methods is impurity metal atoms doping into the BN nanostructures16,19,28.Doping Fe,Co,and Was endohedral were considered to change the electronic structure of B36N3619.Doped nanocages M@B36N36with alkali metals and Ti as endohedral elements were studied as adsorbents to adsorb Hatom29.Density functional theory(DFT)based reactivity descriptor study was performed for Fe doped B36N36by B/N atom substitution that revealed Fe doping increasing local reactivity of the B36N36nanocage28.Increment of ability of the molecular adsorption by metal doping on surface of BN nanostructures may be useful for removing some contaminants of environments.Adsorption of pentachlorophenol as a pollutant on surface of pristine (8,0)boron nitride nanotube and its Fe doped derivatives was studied and results were demonstrated that pentachlorophenol adsorption by Fe doped nanotube is energetically more favorable compared to pristine nanotube16.Recent studies of BN nanostructures as molecular adsorbent motivated us to investigate the application of B36N36and Fe doped nanocages in order to introduce them as new adsorbents for adsorbing organophosphorus pesticides.

2　Computational details

In this work,four OPs including diazinon,hinosan,chlorpyrifos,and parathion and B36N36,its six Fe doped derivatives and functionalized nanocages with OPs were modeled and optimized using DFT,implemented by the DMol3program package30.All electron calculations were carried out at the generalized-gradient approximation(GGA)level of theory with the Perdew-Burke-Ernzerhof(PBE)functional to the exchange-correlation energy31. The double numerical plus polarization function(DNP)were taken as basis sets with global cutoff radius of orbitals at 0.46 nm under spin-unrestricted condition and automatic option for multiplicity.Conductor-like screening model(COSMO)32method was used to calculate the solvation energies of all chemical species at the PBE/DNP level of theory.The molecular van der Waals(vdW) interactions from ground state electron density were calculated using Tkatchenko and Scheffler(TS)method that introduces damped atom-pairwise dispersion corrections33.

3　Theoretical background

3.1Reactivity quantum descriptors

DFT based quantum reactivity descriptors such as the chemical potential(μ),the chemical hardness(η)and softness(s),etc.have provided an understanding of the behavior of many chemical species in reactions.One of the local reactivity descriptor is Fukui function that is an appropriate parameter to assess the reactivity of distinct atomic sites in molecules that is introduced as34:

where v(r),ρ(r),and N are the external potential,the electron density,and the number of electrons,respectively.The reactivity of different sites in a molecule for nucleophilic,electrophilic,and free radical attacks is simply suggested by condensed to atom Fukui functions(Fukui indices)35:

3.2van der Waals interactions

There are schemes to take DFT dispersion corrections into account that introduce damped atom-pairwise dispersion corrections as Grimme37and Tkatchenko and Scheffler33schemes.The dispersion energies are calculated by Eq.(5)within both Tkatchenko-Scheffler and Grimme methods.

here,d is damping parameter and sRis a scaling factor.The important difference between two schemes is that the dispersion coefficients and damping function are determined in an empirical manner in Grimme scheme but TS scheme has been suggested based on an accurate nonempirical method to determine molecular C6coefficients from ground-state electron density.Therefore,the contributions of atoms in vdW interactions are dependent on their local chemical environment in latter scheme.

4　Results and discussion

4.1Organophosphorus pesticides;structure and reactivity

In general,oxons are organophosphorus toxins with P＝O bond that act biologically as inhibitor of acetylcholinesterase.But thions,organophosphorus toxins with P＝S bond,are biologically activated in body after changing to oxons38,39(see Fig.1).

Of selected organophosphorus toxins in this work,diazinon, chlorpyrifos,and parathion are thions of phosphorothioates group, whereas hinosan is an oxon of phosphorodithioates group40.Optimized structures of these organophosphorus pesticides are shown in Fig.2.The calculated solvation energies in water of these compounds by COSMO method are displayed in Table 1.The solvation energies showed that this phenomenon increases the stability of OPs in aqueous solution especially for parathion.

Fig.1　Two main categories of organophosphorus toxin

Intensity of intermolecular interaction between OPs and an adsorbent surface can be originated from two effects.First,overlapping of frontier orbitals of adsorbate and adsorbent increases chemically trait of the adsorption.The overlap potency of atomic sites on OPs can be assessed by a suitable theoretical approach as Fukui indices that are obtained from DFT calculations.Secondly,van der Waals interaction of OPs with the surface of adsorbent that depends on focused partial charge on atoms. Therefore,the more the partial charge is focused on atoms,the more van der Waals interaction is caused.In this work,we used Hirshfeld atomic charges36.Hirshfeld method is based on the electronic density,but it is not a basis set based scheme41.

Fig.2　Optimized structures of considered organophosphatesCarbon atoms are colored gray,oxygen red,nitrogen blue,chlorine green,and sulfur yellow.color online

Table 1　Solvation energies of organophosphorus pesticides in water calculated by conductor-like screening model

The electronegative atoms such as oxygen,sulfur,and nitrogen in OPs structure augment nucleophilicity tendencies of these compounds.Thereby Fukui indices were calculated to determine electrophilic and nucleophilic sites on OPmolecules(see Table 2).

Table 2　Fukui indices for atoms in considered organophosphates with values over 0.03 in gaseous phase

According to calculated Fukui indices(f+,f－,and f0)for atoms of OPs,it is found that the largest fare obtained for sulfur atoms, soOPs are mainly nucleophile.The amounts of f－for sulfur atoms in diazinon,hinosan(for two sulfur atoms),chlorpyrifos and parathion are 0.354,(0.151 and 0.147),0.303,and 0.466,respectively,whereas these values for theother atoms are lessthan0.1.

Fukui indices for nucleophilicity attacks(f+)in OPs are shown that this trend for atoms in aryl groups is considerable.The f+values for C(14)and N(11)in diazinon,C(19)in Hinosan,C(4)in chlorpyrifos and C(6)in parathion are 0.123,0.106,0.061,0.122, and 0.069,respectively.Also,the f+values for chlorine atoms in chlorpyrifos(Cl(8):0.122,Cl(11):0.125)and nitro group in parathion(N(9):0.117,O(13):0.176,O(14):0.176)show that these sites are remarkably talented for nucleophilic attacks.

Investigation of partial charges on atoms of OPs shows that negative partial charges are more concentrated on atoms compared to positive partial charges.As shown in Fig.3,maximum positive partial charge is related to phosphorus atom,whereas maximum negative partial charge is possessed to solfur atom of P＝S bondin diazinon,chlorpyrifos,and parathion;and oxygen atom of P＝O bond in hinosan.Oxygen,sulfur,and nitrogen atoms have large negative partial charge(NPC),so the stronger vdW interactions are expected to be caused by these atoms.On the other hand, phosphorus atom with the largest positive partial charge is surrounded by oxygen and sulfur atoms in all OPs.Hence,opposed to oxygen and sulfur atoms,non-availability of phosphorus atom causes that it cannot make a suitable interaction.Therefore,OPs may be more reactive in side of atoms with negative partial charge for vdW interactions.

Fig.3　Partial charges(e)on atoms of Ops

4.2B36N36nanocage and its Fe doped derivatives: structure and reactivity

B36N36fullerene,one of BN nanocages with 32 hexagon and six square rings and Tdsymmetry,has six different sites for substitution.There are two groups of Fe doped B36N36(FeBNNC),depending on whether Fe atom is located instead of B atoms (FeBBNNC group)or instead of N atoms(FeNBNNC group)(see Fig.4).

As shown in Table 3,Fe atom doping into B36N36increases the solvation energy of nanocage.Also negative values of binding energies(Eb)of Fe atom demonstrated the possibility of Fe doped BN nanocages formation.The binding energies are calculated using the following equation28:

where E(FeBNNC),E(VBNNC),and E(Fe)are the calculated total energies of the Fe doped B36N36,the pristine nanocage with vacancy,and the Fe atom respectively.

According to the different possible electronic configurations for iron,there may be many different multiplicities for the Fe doped cages.The best multiplicity for system is obtained by selecting automatic option for multiplicity in input file of DMol3program. In this manner,the best determined multiplicity for all systems is S=2.Transition metal doping can affect the physical and chemical properties of B36N36.In our previous study28,it was found that Fe doping in distinct locations of B36N36remarkably increases the chemical reactivity of nanocage.This effect was studied in nucleophilic and electrophilic activity of Fe doped nanocages by using Fukui functions.Fukui indices for atoms in FeBNNCs revealed that Fe atom in diverse locations is significantly more active not only in nucleophilic attack but also in electrophilic and free radical attacks compared with the other B and N atoms(see Table 4).As shown in Table 4,Fe atom site is,however,more talented for nucleophilic attack in compared to other attacks.

Fig.4　Distinct sites of B and N atoms on B36N36nanocage

4.3Adsorption of OPs on B36N36nanocage and its Fe doped derivatives

4.3.1Appropriate orientations of OPs for adsorbing on

nanocages?

Fukui indices from Table 2 and atomic partial charge from Fig.3 help us to distinguish more appropriate orientations of OPs towards B36N36and its Fe substituted derivatives.Fe substituted derivatives of B36N36are mainly electrophile in side of Fe atom.Fe atom has the largest nucleophilic Fukui index;thereby OPs make stronger interactions with Fe atom of nanocages from their nucleophile sides with larger electrophilic Fukui index(f－).

Table 3　Binding energies of Fe atom and solvation energies(in water)of the nanocages calculated at DFT level of theory with TS method

Table 4　Fukui indices of Fe and B/N atoms of FeBNNT nanocages in gaseous and aqueous phases calculated at DFT level of theory with TS method

On the other hand,as pointed out earlier,OPs can make stronger vdW interaction from atoms with large NPC.In this sense,we selected two more proper orientations of each OP in adsorption on these nanocages.Selected orientations of OPs are shown in Fig.5.In diazinon,both NPC and f－h(huán)ave more amounts for oxygen and sulfur atoms of phosphate group and nitrogen atom of aromatic ring(Fig.5(a,b)).Electrophilic Fukui indices are maximum for sulfur atoms in hinosan.On the other hand,NPC on oxygen atoms is remarkably large.So we selected two different orientations of phosphate group in hinosan(Fig.5(c,d)).In chlorpyrifos,fis maximum for sulfur atom and notable for chlorines and some carbon atoms of ring.Also,NPC on sulfur, oxygen and nitrogen atoms appear more appropriate to make stronger van der Waals interactions(Fig.5(e,f)).Sulfur atom in parathion has also maximum f－.In addition,NPC is notable on sulfur and oxygen atoms of phosphate group and oxygen atoms of nitro group.So,two proper orientations of parathion towards Fe atom of substituted cages are phosphate and nitro group sides (Fig.5(g,h)).

Fig.5　Selected orientations of each OPduring adsorption on Fe atom of doped nanocagesCarbon atoms are colored gray,oxygen red,nitrogen blue,chlorine green,iron grayish blue,and sulfur yellow.color online

4.3.2Overlapping and van der Waals interactions

As pointed out above,owing to presence of Fe atom,FeBNNCs are mainly electrophile.Hence,it is appropriate that OPs take direction toward Fe atom of FeBNNCs from their nucleophilic sites.Average of adsorption energies(Ead)for four OP insecticides on surface of FeBBNNC and FeNBNNC groups were calculatedseparately and displayed in Table 5.Adsorption energy is included two components,overlapping energy(Eov)and vdW interaction energy(EvdW)in gaseous phase as follows:

On the other hand,in aqueous phase,adsorption energy is included three components,overlapping energy(Eov),vdW interaction energy(EvdW),and solvation energy change(ΔEsol)as follows42:

Overlapping energies are calculated by DFT and vdW interaction energies are determined by Tekatchenko and sheffler method.The results in Table 5 show that the averages of adsorption energies(ēad)for adsorbing OPs on FeBNNCs are larger than similar ones on pristine B36N36in gaseous phase. Maximum ēadfor diazinon are remarkably larger than that of other OPs and are reduced for hinosan,chlorpyrifos and parathion respectively.The averages of vdW interaction energies (ēvdW)associated with adsorption of OPs on pristine cage are remarkably larger than the averages of overlapping energies (ēov).Therefore,the intensity of the adsorption on B36N36is just controlled by ēvdW,whereas contribution of ēovin adsorption on FeBNNCs is not small and is comparable with ēvdW.For example the contribution of ēovin the adsorption of diazinon,hinosan,and parathion on FeNBNNCs group is larger than ēvdWin gaseous phase.However,solvation in water makes dissimilar effects in the adsorption energies for adsorbing on B36N36compared with FeBNNCs.

Table 5　Averages over adsorption(ēad),overlapping(ēov),and vdW interaction(ēvdW)energies(in kJ?mol－1)in addition to solvation energy change Δēsol(in kJ?mol－1)for adsorbing each OPon pristine B36N36,FeBBNNC,and FeNBNNC groups

Solvation in water increases extremely the vdW interaction energies of OPs on B36N36and that is why the adsorption energies increase two to four times,whereas this phenomenon reduces the adsorption energies of OPs on FeBNNCs that is mainly related to reducing in ēov.The effect of solvation on the adsorption energies of OPs on B36N36is so large that ēadfor diazinon and parathion is more favorable for adsorbing on pristine B36N36compared to FeBNNCs.However,the larger solvation energy of FeBNNCs in water makes them more advantage to adsorb OPs in aqueous phase.For hinosan and chlorpyrifos,ēadon FeBNNCs is larger compared to ēadon B36N36,in gaseous and aqueous phases.

Fig.6　Averages over adsorption energies(-●-,-○-),overlapping energies(-◆-,-◇-),and vdW interaction energies (-■-,-□-)for adsorbing OPs on each isomer of FeBBNNC and FeNBNNC groupsFilled and unfilled symbols are related to results in gaseous and aqueous phases respectively.

In addition to the above considerations,the average adsorption energies for adsorbing OPs from two different sides(eight different measuring)on each FeBNNC with Fe atom in locations 1, 2,or 3 were investigated.Fig.6 shows the averages over adsorption(ēad)(-●-,-○-),overlapping(ēov)(-◆-,-◇-),and vdW interaction(ēvdW)(-■-,-□-)energies for adsorbing OPs on FeBBNNC and FeNBNNC groups with Fe atom in each location for gaseous and aqueous phases.In FeBBNNC group,ēadis morefavorable for adsorbing on FeB35N36-2 in both gaseous and aqueous phases whereas the adsorption on FeB35N36-3 is remarkably weaker in both phases.However,in FeNBNNC group,ēadis more favorable for adsorbing on FeB36N35-3 compared to other isomers in both phases and weaker adsorption is related to FeB36N35-2.On the other hand,FeB35N36-1 of FeBBNNC group and FeB36N35-1 of FeNBNNC group showed the largest ēov,thereby OPs make the strongest overlapping with Fe atom in location 1.Despite of vdW interaction effects,this observation is confirmed with results of our previous work28.

5　Conclusions

We studied B36N36nanocages and its Fe doped derivatives as adsorbents for adsorbing OPs pesticides such as diazinon,hinosan, chlorpyrifos,and parathion.The adsorption energies of all OPs on B36N36and FeBNNCs were calculated using DFT method with TS dispersion correction.We considered the adsorption as a combination of overlapping and vdW interaction.Fukui indices and atomic partial charges were considered to find the best sites of OPs for adsorbing on B36N36and FeBNNC nanocages.Hence,it was turned out that thiophosphate groups in all OPs,aromatic ring in diazinon,and nitro group in parathion are more proper sites to be adsorbed on mentioned nanocages.The averages of adsorption energies revealed that Fe doping into B36N36increases the adsorption strength of all OPs on nanocages in gaseous phase. However,Fe doping increases the averages adsorption energies for adsorbing of only hinosan and chlorpyrifos on FeBNNCs in aqueous phase.Also,consideration of the averages energies for adsorbing OPs on each isomer of FeBBNNC and FeNBNNC groups demonstrated that FeB35N36-1 has the most potential to adsorb OPs. Finally,this study may be useful to find appropriate methods for removing industrial or agricultural contaminants in environment, especially,water resources.

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December 21,2015;Revised:February 29,2016;Published on Web:March 2,2016.

*Corresponding author.Email:d.farmanzad@umz.ac.ir;Tel:+98-1135302382;Fax:+98-1135302350. The project was supported by the University of Mazandaran(Islamic Republic of Iran).