MINISTRY OF EDUCATION AND TRAINING

HANOI UNIVERSITY OF EDUCATION

PHAM THI BE

STUDY ON THE ABILITY TO PROCESS DDT AND γ-HCH ON

SOME METALS AND METAL OXIDES CARRIED ON g-C3N4 BY
THE DENSITY FUNCTIONAL TIGHT BINDING METHODS

Specialization: Theoretical and Physical Chemistry

Code: 9440119

SUMMARY OF CHEMICAL PhD THESIS

HA NOI – 2022
 The thesis was completed at
Department of Chemistry – Hanoi University of Education

SCIENTIFIC INSTRUCTORS:
1. Prof. Dr. Nguyen Ngoc Ha
2. Dr. Nguyen Thi Thu Ha

Review 1: Prof. Dr. Tran Thai Hoa

Review 2: Prof. Dr. Le Thanh Son
Review 3: Prof. Dr. Tran Dai Lam

The thesis will be presented before the Board of thesis review at Hanoi
University of Education on .....h..... day..... month ... year...

The thesis can be found at: National Library, Hanoi or the library of
Hanoi National University of Education
 LIST OF PUBLISHED BY AUTHOR
1. Phạm Thị Bé (2020), “Nghiên cứu lý thuyết khả năng hấp phụ
Dichlorodiphenyltrichloroethane trên than hoạt tính và than hoạt tính biến tính bởi
sắt bằng phương pháp phiếm hàm mật độ”, Tạp chí khoa học – Trường Đại học
Tây Nguyên, số 45, Tr. 13-19.
2. Nguyễn Thị Thu Hà, Phạm Thị Bé, Phùng Thị Lan, Nguyễn Thị Mơ, Lê Minh
Cầm và Nguyễn Ngọc Hà (2021), “Whether planar or corrugated graphitic carbon
nitride combined with titanium dioxide exhibits better photocatalytic
performance?”, RSC Advances, https://doi.org/10.1039/D1RA01237A (Q1,
SCIE, IF = 3.240).
3. Nguyễn Thị Thu Hà, Phạm Thị Bé và Nguyễn Ngọc Hà (2021),
“Adsorption of lindane (g-hexachlorocyclohexane) on nickel modified
graphitic carbon nitride: a theoretical study”, RSC Advances,
https://doi.org/10.1039/D1RA03797H (Q1, SCIE, IF = 4.046).
4. Phạm Thị Bé, Nguyễn Thị Thu Hà và Nguyễn Ngọc Hà (2021), “Nghiên
cứu lý thuyết khả năng hấp phụ Dichlorodiphenyltrichloroethane (DDT) trên
Graphitic carbon nitride (g-C3N4) và g-C3N4 biến tính bởi cluster Ni2”, Tạp
chí Xúc tác và Hấp phụ, T10(3), Tr. 106-111.
5. Nguyễn Thúy Hằng, Phạm Thị Bé, Nguyễn Thị Kim Giang, Nguyễn Hoàng
Hào, Nguyễn Hồng Anh và Nguyễn Thị Thu Hà (2021), “nghiên cứu lý
thuyết khả năng hấp phụ 2,4-dichlorophenoxylacetic trên carbon hoạt tính
biến tính bởi Fe và Ag”, Tạp chí Khoa học và Công nghệ B, T63(11DB), Tr.
02-06.
6. Phạm Thị Bé, Nguyễn Thị Thu Hà và Nguyễn Ngọc Hà (2021), “Nghiên cứu
lý thuyết khả năng hấp phụ Dichlorodiphenyltrichloroethane trên Graphitic
Carbon Nitride biến tính bởi sắt bằng phương pháp phiếm hàm mật độ”, Tạp
chí khoa học – Trường Đại học Tây Nguyên, số 51, Tr. 60-66.
7. Phạm Thị Bé, Nguyễn Hoàng Hào, Nguyễn Thị Kim Giang, Nguyễn Thị Thu
Hà và Nguyễn Ngọc Hà (2022), “Theoretical insight into the adsorption of
dichlorodiphenyltrichloroethane on titanium dioxide supported on graphitic
carbon nitride”, Russian Journal of Physical Chemistry A: Focus on Chemistry,
DOI: 10.1134/S0036024422100065 (Q4, SCIE, IF = 0.697).
8. Phạm Thị Bé, Bùi Công Trình, Nguyễn Văn Thức, Nguyễn Ngọc Hà và
Nguyễn Thị Thu Hà (2022), “Electronic and optical properties of metal
decorated graphitic carbon nitride M/g-C3N4 (M = K, Ca, Ga, Ni, Cu): a
theoretical study’, Tạp chí Hóa học (review).
 1

INTRODUCTION
1. The reason for choosing topic
Environmental pollution caused by chemical agents is always a news
issue, urgent and receives the attention of the whole society. Vietnam is an
agricultural country with a very large area of rice and cash crops, which
means regular use of pesticides and growth stimulants. In addition, in many
provinces and cities in our country, there are many storages of pesticides
that have been seriously degraded. The drainage system at the warehouses
is almost nonexistent, so when heavy rains form a surface stream that
washes away residual pesticides, polluting groundwater, surface water and
soil pollution on a large scale.
Among the pesticides belonging to the POPs group,
dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH)
have been widely used in agricultural production in our country as well as in
many other countries around the world. Residues of the these substances in
soil and water are still very high and therefore need to be treated.
Among the methods used to treat POPs, advanced oxidation process
using photocatalyst systems is receiving the attention of scientists.
For the reasons mentioned above, we select the research problem:
Study on the ability to process DDT and γ-HCH on some metals and
metal oxides carried on g-C3N4 by the density functional tight binding
methods.
2. Research objective and tasks
a. Research objective
The objective of this study is use computational chemistry methodsto
study the structute, electronic properties and optical properties of g-C3N4
based photocatalysts; g-C3N4 modified by metals: Me/g-C3N4 (Me = K, Ca,
Ga, Fe, Ni và Cu); g-C3N4 modified by metal oxide MexOy/g-C3N4 (MexOy
 2

= ZnO và TiO2); study the ability of adsorption, decomposition and

metabolism of some pesticides belonging to the POPs group (DDT and
HCH) on these material systems; clarify the nature of the interaction
between POPs with metal centers, catalytic metal oxides; predict reaction
directions, preferred reaction products. Thereby contributing to the direction
of the experiment to synthesize highly effective materials in POPs treatment.
b. Research tasks
- Researching domestic and foreign documents, analyzing and
reviewing published research works closely related to the thesis topic,
presenting outstanding issues, thereby pointing out the issues that the thesis
should focus on solving research;
- Studying the theorytical basis of computational chemical methods in
thesis (density functional method GFN2-xTB, CREST method, RP transition
state determination method, dynamic method MD).
- Studying the geometric structure, electronic properties and optical
properties of g-C3N4; g-C3N4 modified by metals: Me/g-C3N4 (Me = K, Ca,
Ga, Fe, Ni và Cu); g-C3N4 modified by metal oxide MexOy/g-C3N4 (MexOy
= ZnO và TiO2);
- Study the adsorption capacity of DDT and HCH on g-C3N4, Me/g-
C3N4 (Me = Fe, Ni) and TiO2/g-C3N4.
- Study on the degradability of DDT and HCH decomposition under
photocatalytic effect.
3. Scope and object of the study
a. Research object
Research focuses on materials systems based on g-C3N4: g-C3N4
modified by some metals and: g-C3N4 modified by some metals oxides; and
POPs pesticides include: DDT and HCH.
b. Research Scope
 3

Study to clarify the molecular nature of interactions between metal

atoms, semiconductor oxide cluster with g-C3N4, to clarify the influence of
g-C3N4 modification on electronic and optical properties. And the
adsorption and degradability of this photocatalyst for pesticides belonging
to the POPs group (DDT, HCH).
4. Scientific and practical significance of the thesis
a. Scientific significance of the thesis
Theoretical calculations used in the thesis will provide necessary
information at the molecular level on the nature of interactions between
metals, semiconductor oxides and g-C3N4, electron structure of material
systems. On the basic of g-C3N4, predicting optical properties such as band
gap value, UV-Vis spectra, ... of Me, MexOy systems carried on g-C3N4.
From there, predict and explain the adsorption and hotocatalytic degradation
of DDT and HCH of these material systems. The obtained results can be
useful references for scientist, graduate student in the field of adsorption-
catalysis, computational chemistry.
b. Practical significance of the thesis
Due to the toxic nature, persistent in the environment, difficult to
biodegrade and chemically and especially dangerous to human health of
DDT and HCH, the study of material systems to decompose these
substances is very important. This has important practical significance.
Besides, with Vietnam participation in the Stockholm Convention and in the
context of widespread use of pesticides in our country, the problem of
handling POPs pesticides should be studied. The obtained results can
provide useful information in the development of adsorption-photocatalytic
technology to treat organic pesticides in the form of POPs.

5. New points of the thesis

 4

- The geometrical structures, electronic and optical properties of graphitic

carbon nitride (g-C3N4) in corrugated (cGN) and planar forms (pGN); g-
C3N4 doped with metals (K, Ca, Ga, Fe, Ni, Cu), and g-C3N4 combined with
semiconductor oxides (ZnO)3, (TiO2)7 were studied;
- The interaction energy, and electronic properties (ionization energy – IP,
electron affinity – EA, global electrophilic index – GEI, fractional occupied
density – FOD, … ) of the studied systems were calculated for clarifying the
influence of the inclusion of metal atoms and metal oxides on the structure
and properties of g-C3N4;
- It has been predicted that Fe/g-C3N4, Ni/g-C3N4, and TiO2/g-C3N4 have the
potential to be used as photocatalysts for the decomposition of DDT and
HCH;
- The adsorption of DDT and HCH on Fe/g-C3N4, Ni/g-C3N4, and TiO2/g-
C3N4 was studied in detail. The preferred adsorption sites, the structural
parameters of the adsorption configurations, the adsorption energy, as well
as population analysis were determined to figure out the nature of the
adsorption process. It has been shown that the adsorption of DDT and HCH
on modified g-C3N4 material systems is chemical in nature, while the
adsorption process on primitive g-C3N4 is physisorption. The influence of
different solvents (water solvent, ethanol, acetonitrile, and benzene) on the
adsorption process has also been studied;
- The thermal stability of the DDT, HCH adsorption configurations was
evaluated utilizing molecular dynamics method;
- A new mechanism for DDT and HCH decomposition has been proposed.
This mechanism proposes receiving electrons directly from photocatalyst
causes decomposition of DDT, HCH through cleavage of C - Cl bonds.
6. The layout of the thesis
Introducing the reasons for choosing the topic, the purpose, and scope
 5

of the research, the new points of the thesis, the scientific and practical
significance of the thesis.
Chapter 1: Introduce the theoretical basis including the problems of
quantum chemical theory.
Chapter 2: Overview of the research system and method of calculation.
Chapter 3: Research results and discussion.
Conclusion: Briefly summarize the results of the thesis.
 6

Chapter 1. THEORY BASIS

1.1. Density functional theory

DFT theory calculates electron correlations over electron density
functions. The DFT functions divide the electronenergy into parts that can
each be calculated separately such as: kinetic energy, electron-nuclear
interaction, Coulomb repulsion and some exchange correlations
calculated for the corresponding part. Remaining electron- electron
interaction (which itself is divided into two separate parts, the exchange
energy and the correlation energy).
1.2. GFN-xTB method
GFN-xTB is a semi-empirical tight binding (TB) method for the
calculation of structure, vibrational frequencies and noncovalent
interactions of large molecular systems with 1000 or more atoms. GFN
indicates the design of the approach to yield reasonable geometries,
vibrational Frequencies, and Noncovalent interactions, and “x” stands for
extensions in the AO basic set and the form of the Hamiltonian. In general,
GFN-xTB provides for molecules from the whole periodic table higher
accuracy for the target properties than existing ‘general-purpose’ semi-
empirical approaches. It is applicable to a wider range of systems and is
computationally and numerically more robust than other schemes with
comparable accuracy.
1.3. Moleculer Dynamic method (MD)
Moleculer Dynamic method are used in chemistry, for example, for
studies of the effect of tamperature on reactions, product stability with
respect to temperature, time, … which cannot be calculated. Directly from
the results of solving the Schrödinger equation. The MD method generally
revolves around the use of Newton’s second law F = ma.
 7

1.4. Reaction path Estimates

By default three runs with increasing push/pulling strengths
 -k 2 =  2 - 4  × k1 
at typical values of α = 0.5-1 are conducted. Very tight
optimization thresholds are applied in order to avoid trapping in spurious
geometries. The subsequent incomplete optimizations without the biasing
potential at every point of the path (tylically 30 -200) are limited to 2-4
geometry optimizations steps such as a fall-back to the reactant/product is
prevented. It is recommended that the use checks the resulting path for
chemical reliability.
 8

Chương 2. LITERATURE REVIEW

2.1. Dichlorodiphenyltrichloroethane (DDT)

DDT - Dichlorodiphenyltrichloroethane is a very stable and toxic
substance that takes a long time to decompose in the natural environment.
DDT has been used as a miracle drug to kill pests, asimple and cheap
solution to very effectively kill crop pets, contributing to improving
productivity and killing many harmful insects, human diseases such as lice,
mosquitoes, …
2.2. Hexachlorocyclohexane (HCH)
HCH - Hexachlorocyclohexane is toxic to humans and animals and is
also a slow decomposer. HCH is used to kill pests. Weeds, fast effects and
simple reuse.
2.3. Graphitic carbon nitride (g-C3N4)
g-C3N4 has become a hot spot in materials science thanks to its
distinctive electronstructure. With medium band gap energy as well as
thermal stability, and many valuable properties such as: low density,
noncorrosion, impremeability. g-C3N4 has become one of them.
Photocatalyst materials are the most promising and have been studied for
applications in many reactions such as water spitting, pollutant degradation
and CO2 reduction. However, in the pure from g-C3N4 has the disadvantage
of easy recombination of photogenerated electrons and holes, small specific
surface area, and poor photocatalytic ability. Therefore, there have been
many studies on modifying g-C3N4 surface by metal or metal oxide to
overcome this shortcoming.
2.4. Research in the country and in the world
Researches on the application of g-C3N4 in POPs treatment, including
 9

DDT and HCH treatment, are still limited, and if any, are maiinly
experimental studies, theoretical studies. Guide for experimental research is
quite limited.
2.5. Method of calculation
All optimization and energy calculations were performed using the semi-
empirical tight binding based quantum chemistry method (GFN2-xTB). The
preferred site was determinef by classical force firld combined molecular
method – the reaction Path method. Besides, a number of other mrthods are
used in combination to study the thermal stability of the adsorption systems
(molecular dynamics simulation-MD). These methods are all proven methods
suitable for research systems. The results obtained are reliable.
 10

Chapter 3. RESULTS AND DISCUSSION

3.1. GEOLOGICAL STRUCTURE, ELECTRON PROPERTIES AND

OPTICAL PROPERTIES OF g-C3N4
3.1.1. Geological structure of g-C3N4

Figure 3.1. Optimized structure of cGN

Figure 3.2. Optimized structure of pGN

 11

Table 3.1. The structural parameters of cGN và pGN

Calculated using the GFN2-xTB method
Parameter cGN pGN pGN [116]*
d(C-N2), Å 1,323 1,323 1,330
d(C-N1), Å 1,397 1,408 1,460

The structural parameters obtained by the GFN2-xTB method are very close
to the results calculated according to the density functional theory for the
studied system.
3.1.2. Electron properties and optical properties of g-C3N4
Table 3.2. Parameters IP, EA and GEI of cGN và pGN
IP, eV EA, eV GEI, eV
cGN 7,0856 2,2618 2,2641
pGN 6,6276 2,1531 2,1539
The IP and EA values of pGN are both lower thn that of cGN. The
GEI values of cGN and pGN are relatively high, and both indicate high
electron acceptability of pGN as well as cGN.

Figure 3.3. HOMO và LUMO of cGN depicted at an isovalue 0,03 e Å-3

 12

Figure 3.4. HOMO và LUMO of pGN depicted at an isovalue 0,03 e Å-3

Observing HOMO and LUMO images can lead to the conclusion that
N2 atoms will be chemically more reactive than N1 atoms.
An effective photocatalyst is a material that satisfies the following two
requirements: (1) the recombination rate of h+ and e* is low, (2) h+ and e*
can be generated under visible light irradiation.
Starting from the first requirement, we propose three hypotheses for
the explanation of an effective separation of h+ and e*:
(1-a) The reduction and oxidation sites are located separately to
facilitate photocatalytic reaction;
(1-b) The greater the distance between h+ and e* is, the more efficient
the separation is;
(1-c) The electron density of HOMO (where h+ is formed) as well as
LUMO (where e* is generated) in narrow space results in high densities of
h+ and e*, which would be more effective for the electron transfer process.
Observing the HOMO and LUMO images of cGN and pGN in figure 3.3
and figure 3.4, the HOMO and LUMO of cGN and pGN are distributed in
different spatial rigions and spread over many atoms, resulting in density
photogenerated electrons and holes are quite small. Hower, the
photogenerated electron and hole are far apart resulting in efficient
separation and slow recombination. The same is true for pGN. These
 13

structural features, combined with moderate band gap energies, explain the
photocatalytic activity of g-C3N4.
Table 3.3. The parameters of the first excitation of g-C3N4
Oscillator
Excitation
strength The amplitude of MO transition
energy (eV)
f x 104
0,07 (H-4 0,06 (H-4 0,06 (H-1
cGN 4,235 9,93
 L)  L+3)  L+1)
0,11 (H-1 0,08 (H 0,06 (H
pGN 3,841 7,07
L+12) L+22) L+15)

Figure 3.5. Molecular orbitals involved in the first excitation of cGN

depicted at an isovalue 0,03 e Å-3

The MOs involved in the first excited states of cGN are distributed in
a narrower space than that of pGN. Athough the excitation energy in the first
excited staten of cGN is large than that of pGN (4.235 eV and 3.841 eV).
But, according to hypothesis (1-c) proposed above: The elecron density of
H as well as L concentrated in the narrow region would be better, so cGN is
predicted to have higher photocatalytic activity than pGN. This result is
completely consistent with previously published studies on the catalytic
activities of cGN and pGN.
 14

Figure 3.6. Molecular orbitals involved in the first excitation of pGN

depicted at an isovalue 0,03 e Å-3

cGN pGN
Hình 3.7. FOD plots of cGN and pGN depicted at an isovalue 0,03 e Å-3
Observing the FOD images of cGN and pGN can once again confirm
that the N2 atoms are more chemically active than the N1 aroms.
3.2. MODIFIED g-C3N4 BY METALS (Me) AND CLUSTER OXIDE
METALS (MexOy)
3.2.1. Modified g-C3N4 by metals Me (K, Ca, Ga, Fe, Ni and Cu)

K/cGN (a) và K/pGN (b) Ca/cGN (a) và Ca/pGN (b)

Figure 3.8. Optimized structure
 15

Ga/cGN (a) và Ga/pGN (b) Fe/cGN (a) và Fe/pGN (b)

Figure 3.9. Optimized structure

Ni/cGN (a) và Ni/pGN (b) Cu/cGN (a) và Cu/pGN (b)

Figure 3.10. Optimized structure
Table 3.4. The calculated formation parameters of Me (K, Ca, Ga, Fe,
Ni và Cu) trên g-C3N4
Eint,
Total BO with N q(Me),
Configuration (kJ dmin, Å
BO atoms e
mol-1)
Me/cGN
K/cGN -209,4 2,588 0,330 0,101 + 0,627
Ca/cGN -366,3 2,703 1,594 0,752 + 0,480
 16

Ga/cGN -460,9 2,188 1,338 1,078 +0,271

Fe/cGN -1178,3 1,873 2,620 1,414 +0,023
Ni/cGN -443,8 1,957 2,611 2,184 +0,444
Cu/cGN -383,3 1,904 1,506 1,251 +0,262
Me/pGN
K/pGN -164,9 2,706 0,095 <0,05 + 0,549
Ca/pGN -293,3 2,459 1,165 0,497 + 0,431
Ga/pGN -414,5 2,212 1,345 1,076 +0,257
Fe/pGN -408,9 2,463 1,618 0,800 +0,375
Ni/pGN -312,9 2,019 1,841 1,140 +0,457
Cu/pGN -307,0 2,038 1,167 0,954 +0,383
Figure 3.11 and figure 3.12 prediced Fractional Occupation Density-
FOD of Me/cGN và Me/pGN.

Figure 3.11. FOD plots of Me/cGN(pGN) (Me = K, Ca, Ga, Cu)

depicted at an isovalue 0,03 e Å-3
 17

Fe/cGN and Ni/cGN Fe/pGN and Ni/pGN

Figure 3.12. FOD plots of Me/cGN depicted at an isovalue 0,03 e Å-3
3.2.2. Modified g-C3N4 by oxide metals MexOy (ZnO, TiO2)

ZnO/cGN ZnO/pGN
Figure 3.10. Optimized structure
Table 3.5. The calculated formation parameters of ZnO on cGN and pGN
Configuration Eint, (kJ mol-1) dmin (Å) BO
ZnO/cGN -356,6 d(Zn1-N) = BO(Zn1-N) =
1,849 0,869
d(Zn2-N) = BO(Zn2-N) =
2,071 1,054
d(Zn3-N) = BO(Zn3-N) =
1,962 0,808
ZnO/pGN -252,6 d(Zn1-N) = BO(Zn1-N) =
2,245 0,149
d(Zn2-N) = BO(Zn2-N) =
 18

2,299 0,146
d(Zn3-N) = BO(Zn3-N) =
2,281 0,158

TiO2/cGN TiO2/pGN
Figure 3.113. Optimized structure
Table 3.6. The calculated formation parameters of TiO2 on cGN and pGN
Configuration Eint, (kJ mol-1) dmin (Å) BO
TiO2/cGN -376,3 d(Ti1-N) = 2,116 BO(Ti1-N) =
d(Ti2-N) = 2,006 0,346
d(Ti3-N) = 2,439 BO(Ti2-N) =
0,540
BO(Ti3-N) =
0,256
TiO2/pGN -268,3 d(Ti1-N) = 2,718 BO(Ti1-N) =
d(Ti2-N) = 2,749 0,272
BO(Ti2-N = 0,127

3.3. ELECTRON PROPERTIES AND OPTICAL PROPERTIES OF

Me (Me = Ni, Fe)/g-C3N4, TiO2/g-C3N4
Table 3.7. The calculated IP, EA and GEI of g-C3N4, Me/g-C3N4 (Me =
(Fe, Ni), TiO2/g-C3N4
 19

IP, eV EA, eV IP-EA, eV GEI, eV

cGN and cGN modified
cGN 7,0856 2,2618 4,8238 2,2641
Fe/cGN 5,9824 2,8724 3,1100 3,1514
Ni/cGN 6,0526 2,2535 3,7991 2,2700
TiO2/cGN 7,3451 3,2069 4,1382 3,3633
pGN and pGN modified
pGN 6,6276 2,1531 4,4745 2,1539
Fe/pGN 5,8952 2,5282 3,3670 2,6342
Ni/pGN 5,6250 2,1298 3,4952 2,1506
TiO2/pGN 6,9409 3,1891 3,7518 3,4190

Table 3.8. Band gap energy (Eg), values EVB và ECB of g-C3N4, Me/g-
C3N4 (Me = Ni, Fe), TiO2/g-C3N4
χ , eV Eg, eV EVB, eV ECB, eV
cGN 4,6737 3,274 1,8107 -1,4633
Fe/cGN 4,4274 3,224 1,5394 -1,6846
Ni/cGN 4,1531 3,287 1,2966 -1,9904
TiO2/cGN 5,2760 3,160 2,3560 -0,804
pGN 4,3904 3,192 1,4864 -1,7056
Fe/pGN 4,2117 3,665 1,5442 -2,1208
Ni/pGN 3,8774 3,317 1,0359 -2,2811
TiO2/pGN 5,0650 3,246 2,1880 -1,058
 20

Systems cGN, Fe/cGN, Ni/cGN Systems pGN, Fe/pGN, Ni/pGN

and TiO2/cGN and TiO2/pGN

Figure 3.14. Graph of CB and VB energy

 21

3.4. THE ABSORPTION OF DDT AND HCH ON g-C3N4, Me/g-C3N4

(Me = Fe, Ni) AND TiO2/g-C3N4
The adsorption capacity of DDT and HCH was studied on g-C3N4,
Me/g-C3N4 (Me = Fe, Ni) and TiO2/g-C3N4 in the absence of solvents and
in 4 different solvents: Water, ethanol, acetonitrile and benzene. The
adsorption parameters are considered as adsorption energy (Eads), minimum
distance from adsorbent (dmin), BO bond order according to Wiberg scale
and charge on atoms according to Hirshfeld. The results obtained were that
DDT and HCH were physically adsorbed on the original g-C3N4 material
systems adsorb DDT and HCH better than the outstanding primitive g-C3N4.
The nature of this adsorption force is chemisorption. In the presence of
solvent, the adsorption process still occurs and there is no significant
change.
The thesis also studied the kinetics of DDT and HCH adsorption on
Me/g-C3N4 (Me = Fe, Ni) and TiO2/g-C3N4 was favorable or not by conducting
a sugar study. DDT and HCH adsorption reactions on this system are
molecular superdynamics-Reaction Path (RP) method. The results showed that
the adsorption of DDT and HCH on the systems Me/g-C3N4 (Me = Fe, Ni) and
TiO2/g-C3N4 had Ea = 0, indicating that the (chemical) adsorption stage was
does not go through the transition state. Thus, the adsorption process of DDT
and HCH on thse systems is very favorable.
The thesis conducts thermal stability analysis of the adsorption
congigurations at 298K, 323K, and also investigates at some higher
temperatures (373K, 473K, 573K, 673K) using the analysis dynamics
simulation method MD. The simulation time is 50 ps with a time step of 4
fs. The obtained results show that these adsorption configurations are stable
at the considered temperatures.
 22

3.5. PROPOSED NEW MECHANISM OF DDT AND HCH

DECLARATION UNDER THE PHOTOCATALY
In this study, the thesis proposes a photocatalyst mechanism to directly
decompose difficult to decompose organic pollutants, without requiring the
presence of dissolved oxygen. In this mechnism, electrons in the first excited
state in the photocatalyst (adsorbent) are transferred to the sorbent
(POPs).When adsorbents (POPs) gain this electron, they easily decompose
into less toxic, more environmentally friendly compounds.

a. DDT initial b. DDT after receiving 1 electron

Figure 3.125. Comparison of C-Cl bond lengths in DDT molecular

a. HCH initial b. HCH after receiving 1 electron

Hình 3.136. Comparison of C-Cl bond lengths in HCH molecular
 23

Table 3.9. The charge of the Cl atoms in the DDT moleculer

Charge DDT DDT after receiving 1
initial electron
Cl15 -0,169 -0,221
Cl16 -0,170 -0,221
Cl17 -0,124 -0,204
Cl18 -0,116 -0,208
Cl19 -0,125 -0,638
Table 3.10. The charge of the Cl atoms in the HCH moleculer
Charge HCH HCH after receiving 1
initial electron
Cl10 -0,168 -0,190
Cl11 -0,144 -0,190
Cl12 -0,144 -0,192
Cl17 -0,140 -0,632
Cl18 -0,140 -0,281
Cl19 -0,148 -0,281
Looking at figure 3.15 and figure 3.16 and table 3.9 and 3.10, it can
be seen that, when DDT and HCH molecules receive 1 electron from the
adsorbent (also a photocatalyst), the length of the C-Cl bonds in these
molecules are mostly stretched. In the DDT melecule, the C 1-C15 and C9-
Cl16 bonds are initially 1,726 Å long and after receiving 1 electron, these
two bonds are both 1,737 Å long. In the HCH molecule, the C3-Cl8, C5-Cl19
bond are both 1,786 Å long and these bonds all increase to 1,906 Å after the
HCH molecule gains 1 more electron. In particular, after the molecule
received 1 electron, the C14-Cl19 bond in the DDT and the C4-Cl17 bond in
the HCH molecule had bond lengths of 2.450 Å and 2.434 Å, respectively.
These bonds are all much longer than the sum of the convalent radii of the
 24

C atom and the Cl atom: 0.770 Å + 0.990 Å = 1.760 Å. That proves, the C14-
Cl19 bond in the DDT molecule and the C4-C17 bond in the HCH molecule
have been brocken, the Cl19 atom and the Cl17 atom have been separated
from these molecules. This is again confirmed when considering the charges
on the Cl atoms in the DDT and HCH molecules, the charges of these Cl
atoms both increase significantly (significantly more negative) compared to
the original. In particular, Cl19 atom in the DDT molecule and Cl17 in the
HCH molecule, the negative charge increased most markedly. Therefore, it
can be concluded, Cl atom separated from DDT molecule, HCH will esist
under Cl ion. On the other hand, the ability to separate the remaining Cl
atoms from these molecules will also be much easier than the original DDT
and dHCH molecules.

KẾT LUẬN

Applying the Tight Binding density functional method (GFN2-xTB) to

study the electronic and optical properties of g-C3N4 materials in both
corrugated (cGN) and planar (pGN) forms. The, 6 metals K, Ca, Ga, Fe, Ni,
Cu and 2 metal oxide clusters ZnO and TiO2 were doped into the base
material g-C3N4. Calculation results show that, out of 5 doped metals. 2
metals, Fe and Ni, create better chemical bonds and have better chemical
activity than the remaining metals; of the two metal oxides doped into g-
C3N4 the TiO2 oxide when combined with g-C3N4 gives the composite
material more negative energy, and exhibits better photocatalytic activity
than the original material. Therefore, 3 materials systems Fe/g-C3N4, Ni/g-
C3N4 và TiO2/g-C3N4 were selected to study the adsorption properties as
well as the photocatalytic decomposition ability for two pesticides, DDT
and HCH. Some conclusions drawn from the thesis are as follows:
1. The geometric structure of graphitic carbon nitride (g-C3N4) has been
 25

studied in both cGN and pGN forms. It has been calculated that the cGN
ripple pattern is more stable and stable than the plat pGN corrugated. This
result is consistent with previous experimental and theoretical studies. At
the same time, the optical properties of cGN and pGN were studied, the
results showed that cGN has higher photocatalytic activity than pGN. At the
same time, when studying the electronic properties of g-C3N4 by calculating
and analyzing the FOD value, we obtained the results that nitrogen atoms
(denoted as N2 atoms) and carbon in triazine heterocycle are active. More
active than the nitrogen atoms outside the ring (denoted as atom N1).
2. After doping metal and metal oxides on g-C3N4. The electronic end
optacal properties of the materials systems based on g-C3N4 have been
studied: Fe/g-C3N4, Ni/g-C3N4 và TiO2/g-C3N4. The results show that Fe/g-
C3N4, Ni/g-C3N4 và TiO2/g-C3N4 materials can be used as photocatalysts for
the degradation of DDT and HCH.
3. The adsorption capacity of DDT and HCH has been studied on Fe/g-
C3N4, Ni/g-C3N4 and TiO2/g-C3N4 in the absence of solvent, and in 4 different
solvents: Water solvent, ethanol solvent, acetonitrile solvent and benzene
solvent. The obtained results show that the adsorption capacity of DDT and
HCH on primitive g-C3N4 is initially physical in nature, the adsorption force
here is van der Walls force. And the adsorption of DDT and HCH on Fe/g-C3N4,
Ni/g-C3N4 and TiO2/g-C3N4 systems is chemical adsorption, the adsorption
force is the covalent bond formed. Between the adsorbent and the adsorbent. In
the presence of solvents, the adsorption still occurred and there was no
significant change.
4. Initially, the photocatalytic mechanism for direct degradation of DDT
and HCH under the effect of g-C3N4 based materials: Fe/g-C3N4, Ni/g-C3N4 and
TiO2/g-C3N4 was initially proposed.