EN S202064346-Du Wei - Modélisation Et Étude Du Mécanisme D'élimination Du Chrome Hexavalent Par Les Nanoparticules de Fer À Valence Zéro

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Chinese Book Classification Number: X523

UDC: 624.1
school School Code Code: 10005
Master's Degree
Thesis
professional masteral dissertation
op Kan sur Objective: Modeling and Mechanism

ini gxi na Study of Hexavalent Chromium Removal
on radi me by Zero-Valent Iron Nanoscale
cal Ti
118
op Kan writ By Du Wei
-I-
ini gxi ings
on radi or
cal wor
118 ks
Category/Field of
specialization: Civil
engineering and water
conservancy
Instructor Teacher
Teacher：Zhang
Yongxiang
D a t e o f s u b m i s s i o n : May 2023
- II -
-I-
UDC: 624.1 School Code: 10005
Chinese Book Classification Number: X523 Academic Number:
Classified Level: Public
Master of Engineering Thesis,

Beijing Institute of Technology
Title Modeling and Mechanism of Hexavalent Chromium

Removal by Zero-valent Iron Nanoparticles
E n g l i s h t i t l e :SYSTEMATIC STUDY OF NANO ZERO-
VALENT IRON AND A NEW METHOD FOR
CALCULATING ELECTRON EFFICIENCY
theory Essay :: Du Wei (1982-), Chinese

Writers footballer
author
science :: civil engineering and water
Subjects conservancy
Specialization
Profession
research :: Theory and Technology of
Research Healthy Cycle of Urban Water
- III -
III
Direction System
Orientation
apply for :: Master's Degree in Civil
Please Engineering and Water
Academic Resources
Degree
point (the way) :: Prof. Yongxiang Zhang
guide
Teachers
Teachers
classifier for :: Department of Urban
houses, small Construction
buildings,
hospitals and
institutions in
unit
place
reply argue :: May 2023
Date
Period
degree- :: Beijing University of Technology
granting
unit
- IV -
-V-
III
Statement of Originality
I declare that the thesis presented is my personal research work and
research results under the guidance of my supervisor. To the best of my
knowledge, the thesis does not contain research results that have been
published or written by others, nor does it contain materials that have been
used for the purpose of obtaining degrees or certificates from the Beijing
Institute of Technology or other educational institutions, except for the
places that are specifically labeled and acknowledged in the text. Any
contribution to this research by comrades working with me has been clearly
stated and acknowledged in the thesis.
Signature Name:
Date Period: May
25, 2023
Note on authorization to use the paper
I am fully aware of the regulations of Beijing Institute of Technology

concerning the retention and use of the dissertation, that is, the university
has the right to retain the copies of the dissertation sent to it, and to allow
the dissertation to be inspected and borrowed; the university may publish
the dissertation in whole or in part, and may use photocopying,
microfilming, or other means of reproduction to preserve the
dissertation. - VI -
(Confidential papers shall be subject to this provision upon declassification)
Signed: Date Period: 2023 May 25 May 2023
Signature of Mentor: Date: 2023 May 25 May 2023
- VII -
III
- VIII
-
sum
mari
es
summarize summary
Economic and industrial development inevitably has a serious
impact on environmental systems. Nano zero-valent iron
(nZVI), as one of the most commonly used nanoparticles, has carried out a lot
of research in removing pollutants from environmental waters. However,
nZVI modeling is less studied and mostly based on simple kinetic
models. In order to further explore the practicality of nZVI, it is
necessary to establish more complex models to describe the reaction
process and reaction mechanism, and then develop its practicality.
The aim of this thesis is to systematically summarize the research
content of nano zero-valent iron, as well as the opportunities and
difficulties it faces in the process of application. The synthesis and
modification methods of nano zero-valent iron and its applications are
mainly introduced, and several outlooks on nZVI are presented. In
addition, there are application-constrained problems of nano zero-valent
iron, mainly for the assessment of reactivity which needs to save time and
cost. Through the establishment of pseudo-primary kinetic models,
pseudo-secondary models, and intra-particle diffusion models, it is shown
that these computationally simple models can only partially confirm the
removal of Cr(VI) by nZVI, and that new models are needed to analyze
and quantify the individual reaction mechanisms. Summarizing the
existing studies, in order to improve the potential applicability of nZVI,
in this study, a model for the removal of Cr(VI) by nZVI was developed to
simulate the changes of various ions during the reaction process, to give
the changes of active sites, and to propose a new method for calculating
the electronic efficiency. Finally, the parameters were rate-determined by
experimental data and characterization to improve the reliability of the
model. In conjunction with the model, the specific effects of the initial
concentration of Cr(VI) and the initial pH on the electronic efficiency and
reactivity were discussed. The results show that:
Due to the influence of reaction mechanisms such as proton
content and precipitation at different pH conditions, the removal of
Cr(VI) by nZVI is more consistent with the pseudo-secondary kinetic
model under neutral conditions, whereas it is more consistent with the
-I-
Beijingin
pseudo-primary kinetic model University of Technology
other cases. In addition, only the neutral
condition reached the three stages of intraparticle diffusion at 60 min. The
failure of the acidic condition was due to the corrosion of nZVI, and the
alkaline condition was due to the elaboration of hydroxides on the
surface of nZVI.
The initial concentration and the initial pH mainly depend on
changing the utilization efficiency of the active site and the degree of
corrosion of nZVI to affect the electronic efficiency, which is directly
proportional to the pH value. At pH 3, 5, 7, 9 and 11, the electronic
efficiencies were 39.18%, 47.56%, 58.81%, 59.12% and 84.19%, respectively.
In addition, we found that both nZVI and Fe(II) played reducing roles,
but nZVI was sometimes not the main role.
Possible reaction mechanisms were analyzed by combining
experiments, modeling and characterization. The whole reaction process
was divided into three stages: pollutant adsorption, electron transfer process
and mass transfer process. Firstly, the active sites adsorb the pollutants by
electrostatic force or complexation force, secondly, the electron transfer
from nZVI enhancement to water or pollutants realizes the reduction, and
finally the mass transfer occurs, and the water produces Cr(III), Fe(II)
precipitation and co-precipitation. The detailed analysis of the three stages
further reveals the mechanism of nano zero-valent iron for the removal of Cr(VI)
in water. The modeling and calculation of the electronic efficiency provide
a new evaluation method for the application of nZVI, which further guides
the development of nZVI.
- II -
sum
mari
es
Keywords: nano zero-valent iron; hexavalent chromium removal; mechanistic
study; kinetic modeling; electronic efficiency
-I-
Beijing University of Technology
abstract
The economic and industrial development inevitably has a serious impact on environmental
systems. Nanometer zero-valent iron (nZVI), as one of the most commonly used nanoparticles,
has carried out a lot of research in the removal of pollutants from environmental waters.
Nanometer zero-valent iron (nZVI), as one of the most commonly used nanoparticles, has carried
out a lot of research in the removal of pollutants from environmental waters. However, nZVI
models have been less studied and are mostly based on simple kinetic models. In order to further
investigate the practicality of nZVI, it is necessary to develop more complex models to describe
the reaction process and the reaction time. In order to further investigate the practicality of nZVI,
it is necessary to develop more complex models to describe the reaction process and reaction
mechanism, and then develop its practicality.
The purpose of this thesis is to systematically summarize the research on nZVI, as well as
the opportunities and difficulties faced in its application. The synthesis and modification
methods of nano zero-valent iron and its applications are mainly introduced, and several
perspectives on nZVI are presented. The synthesis and modification methods of nano zero-valent
iron and its applications are mainly introduced, and several perspectives on nZVI are presented.
In addition, nZVI has application-limited problems, mainly for the assessment of reactivity
which requires time and cost saving. developing pseudo primary kinetic models, pseudo
secondary models, and intraparticle diffusion models, it is shown that these computationally
simple models can only partially confirm the removal of the reactivity. By developing pseudo
primary kinetic models, pseudo secondary models, and intraparticle diffusion models, it is shown
that these computationally simple models can only partially confirm the removal of Cr(VI) by
nZVI, and new models are needed to analyze and quantify each reaction mechanism.
Summarizing the existing studies, in order to improve the potential applicability of nZVI, in this
study, a model for Cr(VI) removal by nZVI was developed, the changes of various ions during
the reaction were simulated to give the changes of active sites, and a new method for calculating
the electronic efficiency was proposed. Finally, the parameters were rate determined by
experimental data and characterization to improve the reliability of the model. The specific
effects of the initial concentration of Cr(VI) were determined by experimental data and
characterization to improve the reliability of the model. The specific effects of the initial
concentration of Cr(VI) and the initial pH on the electron efficiency and reactivity were
discussed in conjunction with the model. The results show that.
Due to the influence of reaction mechanisms
- II - such as proton content and precipitation under
The removal of Cr(VI) by nZVI under neutral conditions is more consistent with the pseudo-
secondary kinetic model, while the other cases are more consistent with the pseudo-first-order
abstract
kinetic model. other cases are more consistent with the pseudo-first-order kinetic model.
Moreover, only the neutral condition reached the three stages of intraparticle diffusion at 60 min.
The acidic condition was not reached due to the corrosion of nZVI, and the alkaline condition
was due to the elaboration of hydroxide on the nZVI. The acidic condition was not reached due
to the corrosion of nZVI, and the alkaline condition was due to the elaboration of hydroxide on
the nZVI surface.
The initial concentration and initial pH depend mainly on changing the utilization efficiency
of the active site and the degree of corrosion of nZVI to influence the electron efficiency, which
is proportional to the pH value. The initial concentration and initial pH depend mainly on
changing the utilization efficiency of the active site and the degree of corrosion of nZVI to
influence the electron efficiency, which is proportional to the pH value. The electron efficiencies
were 39.18%, 47.56%, 58.81%, 59.12% and 84.19% at pH 3, 5, 7, 9 and 11, respectively. In
addition, we found that both nZVI and Fe(II)
- III -
nZVI played a reducing role, but nZVI was sometimes not the main role.
The possible reaction mechanism was analyzed by combining experiments, models and
characterization. The whole reaction process was divided into three stages: pollutant adsorption,
electron transfer process and mass transfer process. The whole reaction process was divided into
three stages: pollutant adsorption, electron transfer process and mass transfer process. Firstly the
active site adsorbs the pollutant by electrostatic force or complexation, secondly the electron
transfer raised by nZVI to water or pollutant realizes reduction, and finally mass transfer occurs
and Cr( III) and Fe(III) precipitates. III) and Fe(III) precipitation and co-precipitation are
produced in water. The detailed analysis of the three stages further reveals the mechanism of
hexavalent chromium removal by nZVI. The detailed analysis of the three stages further reveals
the mechanism of hexavalent chromium removal by nano-ZVI in water. The modeling and
calculation of the electron efficiency provide a new way of evaluation for the application of
nZVI and further guide the application of nano-ZVI. The modeling and calculation of the
electron efficiency provide a new way of evaluation for the application of nZVI and further
guide the development of nZVI.
Keywords: nanoscale zero-valent iron; chromium removal; mechanistic studies; kinetic model,
electron efficiency
IV
cata
logs
catalogs
summarize ............................................................................... Abstract I
Abstract........................................................................................................................ III
Introduction ............................................................................................................. - 1 -
1.1 Advances in nano-zero-valent iron remediation technology
.................................................................. - 1 -
1.1.1 Overview of nano zero-valent iron
............................................................................... - 1 -
1.1.2 Overview of zero-valent iron nanopreparation
....................................................................... - 1 -
1.1.3 Overview of zero-valent iron nanomodification
....................................................................... - 3 -
1.1.4 Field study of nano zero-valent iron
................................................................... - 6 -
1.1.5 Current status of different modeling studies
......................................................................... - 11 -
1.2 Overview of research on hexavalent chromium removal from water
........................................................................ - 12 -
1.2.1 Sources of hexavalent chromium and its hazards
................................................................. - 12 -
1.2.2 Hexavalent Chromium Treatment
............................................................................. - 12 -
1.2.3 Research key elements and technology roadmap
......................................................... - 13 -
1.3 Chapter Summary
.................................................................................................... - 13 -
Materials and methods............................................................................. 15
2.1 Test Materials and Instruments .............................................................. 15
2.2 Preparation of materials and experimental methods ...................... 15
2.2.1 Preparation of nZVI ........................................................................... 15
2.2.2 Experimental Procedures and Measurements......................... 16
2.2.3 Characterization of Cr and Fe in the solid phase.......................... 16
A study of kinetic modeling .................................................................... 19
3.1 Introduction.................................................................................................. 19
3.2 Kinetic Modeling......................................................................................... 19
3.3 Chapter Summary ...................................................................................... 23
Modeling of Cr(VI) removal ..................................................................... 25
4.1 Introduction.................................................................................................. 25
4.2 Modeling ....................................................................................................... 25
4.2.1 Kinetic Modeling.............................................................................. 25
4.2.2 Electron efficiency calculations and precipitation ratio calculations
............................................................................................................. 28
4.3 Chapter Summary ...................................................................................... 29
Study on the results of Cr(VI) removal by nano zero-valent iron.. 31
5.1 Introduction.................................................................................................. 31
5.2 Results and Discussion.............................................................................. 31
-V-
5.2.1 characterization ................................................................................ 31

5.2.2 Effect of initial concentration and electron efficiency ......... 33
5.2.3 Effect of pH and Electron Efficiency............................................ 36
5.3 Reaction Mechanism for the Removal of Cr(VI)................................. 38
5.4 Chapter Summary ...................................................................................... 39
Conclusion and Outlook........................................................................................ 41
Academic papers published during the master's degree program ........... 51
Acknowledgements.................................................................................................. 53
References .................................................................................................................. 43
Appendix.................................................................................................................... 55
VI
cata
logs
preface
1.1 Progress of nano zero-valent iron remediation technology
1.1.1 Nano Zero Valent Iron Overview
Groundwater ex situ remediation techniques and groundwater in situ
remediation techniques have been investigated. With the advantages of
removing deep contaminants, actively attacking the contaminant plume,
low site destructiveness, low cost and short time-consumption, the in situ
groundwater technology has been successfully used in the groundwater
remediation of contaminants such as organochlorine, Cr(VI), lead, and so on[1] .
Nano zero valent iron (nZVI), as an emerging nanoengineered material for
in-situ groundwater remediation, can be directly injected into aquifers
with the advantages of environmental friendliness, low cost, large specific
surface area and strong reducibility[2] . Zero-valent iron nanoparticles
have been extensively studied and show high potential for contaminant
removal. Zero-valent iron nanoparticles are defined as iron particles
with particle sizes between 1 and 100 nm, which are characterized by
large specific surface area, strong reducibility, and environmental
friendliness. Artificially prepared nano zero-valent iron forms an oxide
layer outside the iron shell due to its susceptibility to oxidation,
constituting a core-shell structure. The complex composition of the core-
shell structure includes ferrite (FeOOH), galena (FeO), magnetite (Fe3O4),
magnetohematite (gFe2O3) and hematite (a-Fe2O3) [3] . The presence of oxide
shells not only avoids corrosion of the nZVI iron core, but also transfers the
iron shell electrons to contaminants in the active site to achieve reduction.
From an engineering point of view, the direct use of nanoscale materials
in practical applications presents operational problems and poor
recyclability, which may pose a potential risk to the receiving ecosystem[4]
.
1.1.2 Overview of zero-valent iron nanopreparation
The preparation methods of nano zero-valent iron can be categorized
into two types, decomposition and synthesis, based on the morphological
changes of nZVI[5] . The decomposition method involves the conversion of
large iron particles into nanoscale particles. Synthesis, on the other hand,
-1-
converts iron at the molecular level, or even smaller, to the nanoscale. In
this paper, we will focus on the common preparation methods, and the
characteristics of nZVI prepared by different m e t h o d s are summarized
in Table 1-1. In addition to the methods described in Table 1-1, there are
many other methods for the preparation of nZVI, such as vapor deposition,
which makes it easy to adjust the morphology of the particles, and vapor
condensation, which enhances the stability of the particles, etc.[6] . From Table 1-1,
i t c a n b e seen that different methods not only affect the particle size and
surface area of nZVI, but also the final morphology of nZVI. The ball
milling method produces flaky nanoparticles due to the milling process,
which is clearly different from the other methods. The ecological safety of
nZVI prepared by the green synthesis method is more reliable, and the
prepared materials are renewable and economically sound. The laser
pyrolysis method is easy to obtain nanoparticles with smaller particle size.
In this section, the characteristics of the different methods are described one
by one.
-2-
Chapter 1
Introducti
on
Table 1-1 Summary of the characteristics of zero-valent iron nanoproduction
methods
Table 1-1 Summary of the characteristics of nZVI preparation methods
Preparat Method comple Methodol specificities parti morphol surface literat

cle area
ion Type mentary ogical ogical (m2 /g) ures
size
method method note (nm)
Compared to
liquid- Two-step co Slightly
(chem not have other methods, 10 [7]
phas reduction of agglomera
which are suitable nc
e ical) palladium ted
for laboratory-level
reduc metal is Uniformly
synthe studies, the
tion modification granular
preparation of e
sis simplicity 50
With the change
At an ultrasonic
liquid- Ultrasou significantly increased from no
(chemic intensity of 29.9 sonication to an 42 (1000W)
[8]
phas nd the effective
e al) Assist 500, 1000W also reaction surface area intensity of
reduc Original FeSO4 and stability of nZVI. 1000W, the
synthesi particle
tion
s structure
changed from a
spherical shape
to a more
spherical shape.
Plate-like, then
needle-like.
During the
mechan High reactivity, less Zero-valent iron
decomp not have grinding 29.6 [9]
ical stability and flakes broken by
process, an than micronized
ball osition flowability of
average 100 alumina action
milli particles
particle size of
ng
5 μm is added.
Aluminum
oxide abrasive
grains
Fe-Al2O3
composites Effectively prevented
mechan less Zero-valent iron
decomp not have were prepared nZVI from 116 [10]
ical by co-milling agglomerating and nanoparticl
ball osition than es are
natural pyrite forming larger 100
milli irregularly
and aluminum particles, keeping it at
ng shaped
fertilizers the nanoscale.
Ultrasound reduces
Ultrasou
electrod (chemic not have particle 1~20 nZVI appears as a 25.4 [11]
nd
agglomeration and
epositio al) Assist dispersed globule
facilitates smaller
n synthesi particles.
generation
s
ultrason Palladium-iron Uniform 444.43
electrod (chemic ibid Appr [12]
icasonic bimetallic distribution of (with stone
epositio al) wave deposition on ox. 50 particles, cut graphene
surface
n synthesi Auxiliar Graphene electrode)
y, Electrode Clean, localized
s Nitrogen agglomeration
-3-
Utilizing green Compared with other The synthesized
green plants such as nanoparticle nanoparticles are 2.42 (max)
(chemic not have Damascus rose, synthesis techniques, 100 inhomogeneous [13]
synth
esis al) thyme and two- plant extracts are and sufficiently
leafed nettle non-toxic, dispersed to
synthesi together renewable, and exhibit different
s nanoparticle environmentally shapes and voids
friendly to living spatial
organisms.
Environmentally
friendly and
ecologically
acceptable
Iron The core-shell Almost every
laser 3-7
(chemic not have pentacarbonyl morphology of iron- particle has one [14]
pyrol
(vapor) and carbon surrounded by a
ysis al)
acetylene were nanocomposites may carbon matrix
synthesi used as iron and be affected by the nucleus
carbon donor reaction zone
s Influence of air flow,
very small particle
size.
Liquid-phase reduction, due to its simplicity and ease of use, is
currently the most common method for the preparation of nZVI in
laboratory-scale studies. The reaction principle of the liquid-phase
reduction method is that the Fe2+ or Fe3+ in the reduction of BH4-
generates suspended nZVI in water, or is directly reduced on the surface of the
loaded material to realize the loading modification, and the reaction equations are shown
in (1)(2)[15] . It is worth noting that BH4- also reacts with water (3)(4)[16] ,
which affects the yield of nZVI. However, the high cost and
environmental risk constrain the large-scale production and
application. Moreover, nZVI particles are susceptible to adulteration by
impurities during the reduction process. The principle of the liquid
phase reduction method is to reduce Fe2+ or Fe3+ in water by BH4- , which
generates suspended nZVI in water or directly reduces it on the surface
of the loaded material to realize the load modification.
+ 3BH - + 9H O → 4Fe0 ↓ + 3BO- + 12H + + 6H ↑
4Fe3+
4
2
2 3
(1)
2Fe2+ - 2Fe0 +BO- +
+ BH + 3H O → ↓ + 4H + 3H ↑
4
2
2 3
(2)
BH−4 + 2H O
2 → BO +
−
2 4H
↑
2
(3)
BH−4 + 3H O
2 → H BO + 4H ↑
2
3 3 (4)
Mechanical ball milling method is in the ball mill, through the continuous
friction and collision between the grinding balls and raw materials, so as to
-4-
Chapter 1
Introducti
on
Methods to obtain smaller average particle size particles. Compared with
the liquid phase reduction method, the mechanical ball milling method is
more economical and less environmentally friendly, which is due to the
high environmental impact of the milling method due to the high energy
consumption in the production process[17] . The mechanical ball milling
method has great potential for application, mainly in facilitating the
mass production of nZVI, but as nZVI is moving towards multifunctional
materials, the difficulty of combining the mechanical ball milling
method with modification methods is a key step in limiting its
application.
The microemulsion method is a method that utilizes metal salts and
certain precipitating agents to form microemulsions, which are heat-treated
to obtain nanoparticles by controlling the nucleation and growth of
microparticles[18] . The microemulsion has a high ability to encapsulate inorganic
particles, eliminates harmful organic solvents, and forms a highly
homogeneous microstructure, and the size of the nanoparticles obtained is
close to the size of the original monomer droplets used as nanoreactors[19] .
However, the preparation process of this method is complicated and requires
certain operation.
Electrodeposition is a production method in which nZVI is deposited
at an inert cathode by electrolyzing an electrolyte containing Fe3+/Fe2+ . In this
process, the metal on the electrode surface vaporizes under the action of
an electric arc and cools on the electrode in contact with water, forming
nZVI. However, the resulting nanoscale particles tend to aggregate, and
at the electrode the nanoparticles can agglomerate in order to increase
their size and decrease their reactivity[11] .
Carbothermal reduction is a method of reducing iron-containing
compounds to nZVI at high temperatures (temperature > 600°C) using
carbon as the reducing agent[20] . One of the characteristics of this method
is that carbon is both the reducing agent and the loading material of nZVI.
Carbon is superior to other materials because of its high surface area, rich
functional groups and good chemical stability[21] . Important factors affecting
the preparation of composites include the iron-containing compounds, the
appropriate iron-carbon ratio, and the preparation temperature. Taking
Fe3O4 as an example, the reaction equation can be expressed as reaction
-5-
(7) [22]
Fe 3O
4 + 2C → 3Fe + 2CO
0
2
(5)
Green synthesis methods are mostly used to prepare nZVI by reducing

raw materials with natural compounds extracted from plants and reacting
Fe2+ or Fe3+ ions with phenolic (-OH) groups, proteins or organic acids in
the extracts. The materials prepared using these substances have certain
antioxidant properties and also provide dispersants and masking agents
for the synthesis of nZVI, preventing the aggregation and oxidation of
nZVI during the synthesis process[23] .
Ultrasound assistance is the most commonly used assistance method.
When prepared by liquid-phase reduction with increasing ultrasonic
power, the nZVI particle structure changes from spherical to plate-like and
then to needle-like[8] . The cavitation effect of ultrasound leads to the pyrolysis
of water to produce -H radicals, which can be used to generate H2S with
sulfur-containing organics.This process can be used for the preparation of
modified sulfurized zero-valent iron nanoparticles. In addition, microwave-
assisted can also be used in mechanical ball milling process, through the
synergistic effect of microwave and ball milling, a large amount of highly
active nZVI is continuously generated during collision and exfoliation; -
OH radicals and H+ generated by the coupling effect of microwave and
milling also increase the reaction rate[10] .
1.1.3 Overview of zero-valent iron nanomodification
nZVI due to its high surface energy and intrinsic magnetic interactions when in
the atmosphere and water, will be in its
-6-
Chapter 1
Introducti
on
The formation of an oxide layer on the surface leads to a decrease in
reactivity[24] , which can be optimized by means of material
modification. These include loading modification, surfactant
modification, bimetallic modification, vulcanization modification, and

so on. The various modification methods are schematically shown in
Fig. 1-2 .
Figure 1-1 nZVI Modification Map
Figure 1-1 nZVI modification method
Load modification is to load nZVI onto the surface of the material in

a uniformly dispersed manner to reduce the agglomeration of nZVI, as
shown in Figure 1-1 (a). The main function of load modification is to inhibit
the agglomeration of nanoparticles and to increase the specific surface area of
the modified material. The carrier materials with adsorption properties promote
the degradation of pollutants by adsorbing the pollutants and accelerating the
contact process between the pollutants and nZVI. Load-modified nZVI is
mostly prepared by liquid-phase reduction. As mentioned before, carbon
thermal reduction can also be used to prepare loaded nZVI materials, and
the composites prepared by carbon thermal reduction of different carbon
materials are shown in Table 1-2. The materials selected for load modification
are generally characterized by high surface area and porous structure, such as
clays and carbon materials with high surface area, etc. The 2:1 ratio in clays
can be used for the preparation of loaded nZVI materials. The 2:1 type in
clay is easily suspended in water and adsorbs cationic species due to the
negatively charged lattice substitution, and is also characterized by a
high specific surface area, good thermal stability and acceptable
mechanical strength[25] . However, the remediation efficiency of pure clay
minerals for aqueous phase micropollutants is not high. Desorption also
-7-
produces secondary pollution, and the difficulty of separating and recovering
clay from solution after adsorption reduces its use in industrial wastewater
treatment[26] . Common clay materials for modification include kaolinite,
montmorillonite, bentonite, etc. The significant advantages of carbonaceous
materials are their large specific surface area, high porosity and good adsorption
properties. Surfactants and polymers can be used to provide spatially stable
suspensions of nZVI particles to inhibit aggregation [27].
-8-
Chapter 1
Introducti
on
Table 1-2 nZVI prepared by carbothermal reduction method
Table 1-2 nZVI prepared by carbon thermal reduction method
Carbon materials Particle size after nZVI morphology Surface area/m2 -g-1 quote
used loading/nm
The appearance of spherical or

Lignin powder 12~63 ellipsoidal nanoparticles, material 433 at 900°C [28]
The surface of the material

becomes rough
rice husk Approx. Good shape Treatment [29]
100 temperature 256 at

800°C
nzvi were uniformly distributed on The treatment
Ordered mesopores 20~30 the OMC and viewed temperature at
[30]
(OMC)
900°C is
An organized mesopore
structure is detected 715.16
The composites are in the form of

iron based organic 2~20 flakes, nZVI highly loaded fractions Treatment [31]
framework temperature 800°C is

Fabricated in a carbon 423
carrier
Bimetallic modification is a modification that combines nZVI with

another metal to enhance the reactivity, so it is commonly used for
pollutants that require dehydrogenation, but the environmental
problems that may be caused by the second metal should not be ignored,
as shown in the schematic diagram in Figure 1-1 (b). The principle is that the
second metal combines with nZVI to form a primary cell, which enhances
reactivity and accelerates electron transfer[12] . The metal catalyzes the
decomposition of molecular hydrogen into atomic hydrogen, which becomes a
powerful reducing agent, see equations (6) and (7) [32] . The metals
commonly used for bimetallic modification are palladium (Pd), platinum
(Pt), nickel (Ni), copper (Cu) and silver (Ag). Of these, palladium exhibits
very high dechlorination efficiency, and almost all studies have shown
palladium to be the most effective catalyst for improving NZVI activity[33]
.
H →2 catalyst action → 2H*
(6)
(⋅OH, H* ) + organic compound →

(7)
dehydrogenation product
The potential role of sulfide nano-zero-valent iron (S-nZVI) in pollutant
-9-
remediation has attracted much attention due to its larger specific surface
area and stronger reducing ability than nZVI, and the generated iron
sulfide can be used as an electron-transferring medium, which can
efficiently transfer the electrons from the core of nZVI to the target
pollutants on its surface, as shown schematically in Fig. 1- 1 (c). It should
be added that the shell of S-nZVI is not a single iron sulfide, but a
complex composition of sulfides, and it is these sulfides that improve
the hydrophobicity, electron transfer properties of nZVI. So far, two
methods have been developed for the sulfidation of nZVI. They are the
one-step method: NaBH4 and Na2S2O4 are added to the iron solution, and the
reaction equations are shown in (8)-(11). and the two-step method: NZVI is
synthesized by NaBH4 followed by the addition of Na2S. The reaction
equations are given in (12)-(16) [34] . The actual sulfur content and
hydrophobicity of S-NZVI prepared by the one-step method were
significantly higher than those of the two-step S-NZVI method, with more
obvious selectivity. On the other hand, the two-step method can only
increase the actual sulfur content in a very limited way, whether by
increasing the sulfur dosage or prolonging the vulcanization time[35] .
2S O2− + H O → 2HSO− + S O2−
24 2 3 23 (8)
- 10 -
Chapter 1
Introducti
on
S2O
4
2− + S O2− + 2H O + H+ → H S + 3 H S O
23 2 2
− (9)
3
H2 S → 2H+ + S2− (10)
Fe2+ + S2− → FeS (11)
Fe0 + 2H 2O → Fe(OH) +2 H (12)

2
Fe(OH) →
2 Fe2+ + 2OH − (13)
Na 2S + H O → 2Na+ + HS− + OH− (14)

2
Fe2+ + 2HS− → FeS + H 2S (15)
2FeS + 2H+ → FeS +2 Fe2+ + H (16)

2
Surface modification is an effective method for the dispersion and

migration of nZVI in aqueous media due to the fact that the coating
molecules provided by the surface modifying reagents reduce the forces
between the nanoparticles through the spatial site resistance effect,
which improves the stability of the nZVI, as shown schematically in
Figure 1-1 (d). A critical micelle concentration exists in the surfactant
solution, when there is an equilibrium of colloidal plasmas and ions,
beyond which the properties of the solution such as surface tension and
interfacial tension change significantly. The surface of nZVI is modified
in such a way that the charge changes after coating and will reduce
electrostatic attraction and aggregation . At lower surfactant
[36]
concentrations, the surface coating, on the one hand, reduces contaminant

concentration by providing more available surface sites, but on the other
hand, occupies reaction sites and inhibits the mass transfer of
contaminants from water to the particle surface through electrostatic or
spatial repulsion . The disadvantages of surface modification are also
[37]
manifested in the blockage of active sites, reduction of diffusion channels,

inhibition of electron transfer from nZVI to contaminants, scavenging of
reactive radicals, and partitioning of contaminants to surfactants [15].
1.1.4 A field study of nano zero-valent iron

Zero-valent iron nanoparticles have been applied in permeable
- 11 -
reactive walls, e.g., Eijamal et al.[38] used bimetallic-modified nZVI as a

filler material, which improved the phosphorus removal performance
by a factor of 2.2 compared to nZVI. The reduced particle size of nZVI,
which is much smaller than the pore size of the aquifer, allows it to be
dispersed in cemented slurry or injected directly into the subsoil[39]
instead of being used as a filler medium for permeable reactive walls.
Most of today's nZVI research is based on short, one-factor experiments
in the laboratory, and the removal of organic contaminants by modified
materials is cost prohibitive[40] . This research system is far from practical
applications in environmental waters and can lead to an overestimation of the nZVI
removal performance [41]. And it is important to elaborate the role of
different influencing factors. Among them, Response Surface
Methodology (RSM) is a scientific and practical experimental design
method, which can avoid the shortcomings of the traditional
methods[42] ; on the other hand, conducting site studies is the most
effective means to evaluate the nZVI capacity over a long period of time.
- 12 -
Chapter 1
Introducti
on
A number of field studies have also been conducted on nZVI. The
main categories are contaminant removal and groundwater transport of
nZVI. Table 1-3 shows the field studies of different nZVI applications.
From Table 1-3, it can be seen that different modifications have been
applied in field studies, but there are still differences. The palladium-
metal modification used in Taiwan achieved a high removal of vinyl
chloride (~90%) in about 15 days, while the same percentage of
halogenated pollutant removal was achieved in about 40 days using
biochar-loaded nZVI and polyacrylic acid surface-modified nZVI. It is
evident that bimetallic modification is a rapid way to remove
contaminants, both at the laboratory level and in field studies. It is
important to note that removal efficiency studies cannot exclude the
effect of site factors, which distinguishes field studies from laboratory
studies. Load modification, which is commonly used in the laboratory,
accounts for a small percentage of field applications, most likely due to
limitations on the mobility of the loaded material. In contrast, studies
on nZVI migration and mobility have focused on sulfide modification
and surface modification, which is attributed to the fact that the
modified nano zero-valent iron is well dispersed and can migrate in
groundwater media. Therefore, the choice of modification method for
the site should be based on the actual conditions of the site.
Definition.
Table 1-3. Summary of field studies of nZVI
Table 1-3Field research on nZVI
examine polluta nZVI nZVI dosag pour into
Location Layout Resulting Literature
format nts modi (nm) e way (of life)
typology
Osan, Wonju, Korea (conc ficati (Kg) Trichloroethylene concentrations
The
monitoring entrat on were reduced by 95.7%.
wells are
located in a ion)
Pollutants going to the southwest of the Trichloroeth Polyacrylic acid gravit Monitoring of site-
industrial park ationa
[43]
2 of the ylene (1.92 surface generated chlorides

injection l
wells, modification injecti
on
30
In addition to ~38.2mg/L) The results showed that a total of 2214g of
4m on a
Gangwon-do Characteristics trichloroethylene (TCE) was treated.
Highway circle Vinyl.
Maintenance
nursing
office
A four-port multilayer monitoring well in complexes Distance to injection wells approx. Vinyl chloride (620)
Kaohsiung, Taiwan 8
0
Pollutants going to active industrial ~4562
~
- 13 -
mg/L) Bimetallic palladium
modification 60
The degradation efficiency of vinyl chloride is [44]
200m2 of the test 1m, 2m, 3m Input 50~99%.

in the debris and
inspect a 5m. Biochar-nZVI blends
Trichloroethyl promote the removal of
field 200 [45]
ene and (excluding chlorinated hydrocarbons over
trichlorome raw long pressure injection times.
Pollutants going to the Biochar Load Modification
thane Removal. Decrease in
North China Plain (0.5ug/L~) (weight
pollutant concentrations in the
Old Army Removal 21,200ug/L) of
test area
Vehicle charcoal)
90% or more
maintenance sites
One 160m3 nZVI
The contaminants went to a certain Copper- 50~150 gravita Divalent copper removal
printed circuit board reactor, a clarifier. containing tional rate of 96% or more
wastewater injectio
n
[46]
None, 55
In addition to the manufacturing (70mg/L) confirm (343 mg/g)
prepared on
plant Cleaning tanks and a site or agree
coagulation with
sedimentation tank
Two monitoring
wells were The injection fluid moves at
Pollutants to Ontario, Canada gravita
Distributed at a trichloroeth not have <200 [47]
least from the injection well
distance from ylene tional 0.8 m. Trichloroethylene in
the injection
A former soldier of the division, nZVI injectio treated areas
London.
n
Wells 0.8m, 2.4m confirm Concentration reduced by
Relocation Vehicle assembly
facility or agree
placement more than 99%
with
Osan, Wonju, The monitoring Most nZVI particles remain in the

Korea wells are injection well
distributed in
the injection
nZVI Southwest of the industrial Polyacrylic gravitational pressure
park acid surface 90~500 30.75 Within 2m of wells up to 4d [48]
mig 2, 4m into the modification strength

well not have Maximum nZVI
Gangwon-do Highway concentration reached
ratio Maintenance suffix
(math.) forming
n circle
noun
from
adjective,
correspo
nding -
ness or -
ity
nursing office
Good horizontal and
Sarnia, Ontario 8 monitoring
Vulcanization vertical distribution was
nZVI wells distributed one with 86.0±12
modification, achieved in the study
[49]
abandoned chlorine in the

mig carboxymethyl Gravity Note area, with multiple
center of a water injection
ratio not have cellulose confirm or agree with monitoring wells both
Chemical solvent production facility surface downstream and
n Well 0.91~2.70m
modification upstream of the injection
suffix forming wells.
noun from Detection. Travel
adjective, distances from 0.9m to
corresponding -
ness or -ity
Adjacent east and At least 2.7m
locations west
sides
nZVI S a r n i a , Ontario monitoring well located in water injection nZVI
sodium carboxymethylcellulose pressure injection in the presence of CMC polymer. [50]
- 14 -
Chapter 1
Introducti
on
migr One of the Within 2m of Surface modification confirm or agree Synthesized nZVI has a field-
ation contaminated the well with wide
Sandy various Some degree of mobility, at
subsurface locations least to the point of moving
Move 1m
area
As shown in Figure 1-2, the nZVI suspension is injected into the

injection well by gravity or pressure injection. The injection range of the
suspension can be controlled by the use of isolators in the injection
wells. The migration of nZVI in the groundwater over a period of time
can be detected in the monitoring wells. Therefore, to determine the
anisotropy of nZVI mobility in groundwater, it is necessary to place
monitoring wells around the injection wells. According to the summary
of this paper, the distance of the monitoring wells should not exceed 5 m.
As summarized in Table 5, the migration distance of nZVI in
groundwater was controlled to be within 3 m in several nZVI migration
studies. In addition to the determination of nZVI, the hydrodynamic
properties of the aquifer in the region can be obtained by pumping
fluorescein into the injection wells and then automatically sampling the
samples in the monitoring wells to complete the tracer test. In some
studies, observation wells are also arranged between injection wells and
monitoring wells, mainly for the purpose of extracting core data and
analyzing the geological conditions of the aquifer.
Figure 1-2 Schematic diagram of the site layout for nZVI field applications
Figure 1-2 Schematic diagram of the layout of nZVI's field application
The site study needs to consider more factors, such as the arrangement
of nZVI injection wells and indicator monitoring wells, and the distance
between injection wells and monitoring wells, all of which affect the
determination of contaminant concentration and the monitoring of the
migration distance of nZVI in groundwater. The appropriate
- 15 -
arrangement can not only accurately evaluate the mobility and stability
of nZVI, but also describe in detail the concentration change and
morphology transformation of nZVI over a long period of time. nZVI
should also be used in consideration of the geological conditions, and the
efficiency of remediation using nZVI in dense geological strata is low.[51] .
In addition, the injection method of nZVI is also an important factor
affecting the migration of nZVI. For example, in the sandbox
experiment, the first injection of modified nVZI can help the subsequent
injection of nZVI transport, which improves the total nZVI mobility, but the
plume diffusion is small[52] 实际上，由于 nZVI disadvantages of high surface energy and magnetic
interactions, and it is easy to rapidly aggregate during the reaction process, resulting in low in situ remediation efficiency
and restricting the in situ remediation effect[53]

. Therefore, avoiding nZVI agglomeration at the
site is one of the research priorities. In addition, the problems of easy
oxidation and passivation also shorten the lifespan of nZVI and inhibit
the application of nZVI in the field[28] . This also confirms the necessity of
modification in practical applications. In addition to the above problems,
it is almost impossible to remove the nZVI impurities formed during the
remediation of groundwater contamination, and the modified material
will also remain in the water and affect the groundwater environment
for a long time. The long-term success of in-situ nZVI remediation often
depends on short-term abiotic dechlorination of nZVI after the
remediation.
- 16 -
Chapter 1
Introducti
on
biotransformation, care must be taken not to inhibit the growth of healthy
microbial communities[52] . Therefore, we conclude that for any nZVI-based
groundwater remediation project, site-specific modification of nZVI is
the key to contaminant removal at the site, and investigation of the
toxicity and transformation pathways of nZVI is the key to reducing the
risk of nZVI use. Reaction mechanism of nano zero-valent iron
Most of the current applications of nZVI are based on its strong
reducing properties and large surface area. nZVI is strongly reducing due to
its electrode potential of -0.44V, which allows it to reduce substances with higher
electrode potentials. The strong reducibility is due to its electrode potential
of -0.44 V, which can reduce substances with higher electrode potentials.
nZVI has been shown to be effective in transforming a wide range of
environmental pollutants, including chlorinated solvents, organochlorine
pesticides, polychlorinated biphenyls (PCBs), organic dyes, as well as
inorganic pollutants such as perchlorate, nitrate, heavy metal ions, etc.[54] ,
and hydroxides produced during the reaction process, which have lower
toxicity and also act as a good flocculating agent[55] . In this section, the
mechanism of action of nZVI will be specified according to the pollutant
categories, and the catalytic mechanism of nZVI will also be explained.
Heavy metals are common pollutants in groundwater, which are
difficult to speak biologically and mostly exist in cationic form, while
hexavalent chromium exists in anionic form in the water body. nZVI is
more likely to adsorb anions due to its positively charged surface due to
the presence of the core-shell structure. nZVI removal mechanisms for
metallic elements include reduction, oxidation, adsorption,
precipitation, and co-precipitation, the expressions of which can be
found in (17)-(21)[6] . The removal process is not a single reaction but a
combination of the above different mechanisms and is not
simultaneous. The table shows the different points of mechanistic action
of nZVI on common metal elements.
Men+ + me− → Me(n−m)+ / Me0 (17)
Men + -me− → Me(n+m)+ (18)
Men +
+ iron oxide and hydroxide → Men + @ iron oxide and hydroxide (19)
- 17 -
Me n + + nOH− → Me(OH) n
(20)
Men+ + Iron oxides and hydroxides→ Me − Fe − OOH (21)
The most important mechanism of action of nZVI is reductive,

where the oxide shell of nZVI acts as an electron channel to transfer
electrons to the iron core for electron exchange. The core-shell structure
also provides active sites for the adsorption of pollutants by electrostatic
adsorption or complexation. However, due to the strong reducing nature of
nZVI, side reactions are always unavoidable, as in (6), which compete for the
active sites of nZVI. In addition to the active sites provided by this core-
shell structure, the iron sulfide shell of S-nZVI provides hydroxyl groups
with active sites, and functional groups such as hydroxyl, carboxyl, and
phosphoric acid groups are also present in different modified materials to
provide more active sites[56] . Precipitation and co-precipitation form
precipitates that can act as adsorbents to a certain extent, and iron oxides are
ferromagnetic, which are as easy to separate after treatment as iron,
reducing environmental risks.
- 18 -
Chapter 1
Introducti
on
Table 1-4 Removal Mechanisms of Common Metallic Elements[57]
Table 1-5 Removal mechanism of common metal elements
mechanis Cr As Cu Se Co Hg U Cd
m
restore to √ √ √ √ √ √ √
the
original
state
oxidize √ √ √
adsorptio √ √ √ √ √ √
n
precipitat √ √ √
es
coprecipi √ √ √
tation
For the removal of halogenated organic compounds, it mainly relies
on the provision of electrons to replace halogenated elements, and the
reaction equations can be found in (22)-(24) [58] . The reaction equation is
shown in (22)-(24)[[59] . It can be divided into three steps: firstly, the
organic compound combines with nZVI to form a complex; secondly, the
electrons are transferred from nZVI to the halogenated organics; and
finally, the reaction releases the reduction product . The Fe2+ produced by
the reaction or corrosion is oxidized to Fe(OH)3, which subsequently
forms iron hydrides via the forms of scheelite quartz, acicular ferrite
and magnetite [60]. While
Fe0 → Fe2+ + 2e− (22)

R - X + H+ + 2e− → R - H + (23)
X−
(24)
2H+ + 2e− → H 2
Nitrate, phosphate, bromate and other anions in water can also be

removed by nZVI, but the mechanism is not the same, the difference is
shown in Table 1-6. nZVI's active site firstly adsorbs hydrogen ions, which
show a positive charge, and then the active site binds with anions in
4
water[61] . After reduction, bromate and perchlorate are reduced to Br− and Cl−
- 19 -
by nZVI, while the reduction of nitrate by nZVI reduces nitrate to NH+ .

Although anions in water are generally not the main pollutants in water,
their presence will hinder the reduction of other pollutants by nZVI and
reduce the efficiency of nZVI. It should be added that today's
mechanistic arguments are based more on the derivation of reaction
pathways from reaction products and lack of positive arguments for the
reaction process. This situation makes it difficult to identify the main
degradation pathways as multiple pathways in the reaction process cannot
be quantified. A number of existing articles have modeled the pollutant
removal process and removal rate based on the mechanism[61, 62] . We
provide an idea. The reaction equations can be provided by modeling and
the adsorption and degradation processes can be quantified, and finally
the mechanism can be demonstrated by data such as nZVI solids that are
not involved in the calculation of changes in the model.
- 20 -
Chapter 1
Introducti
on
Table 1-5 Common Anion Removal Mechanisms [63-66]
Table 1-6 Common Anion Removal Mechanisms
mechani nitrate phosphat bromate perchlor

sm es ate
restore to √ √ √
the
original
state
adsorptio √ √ √ √
n
precipita √
tes
coprecipi √ √
tation
1.1.5 Current status of different modeling studies
T h e current research models for nZVI are dominated by kinetic
models, among which. Pseudo-primary kinetic model, pseudo-secondary
kinetic model, and intra-particle diffusion model are the commonly
used simulation models for nZVI. Their forms are simple and easy to
calculate, and they can qualitatively describe the importance and order of
the mechanism, and the specific model calculations can be found in
Chapter 3. The modeling of nZVI is based on the following principles: (1)
pseudo-primary kinetics suggests that some factors are not part of the
reactivity; (2) q u a s i - s e c o n d a r y kinetics suggests that
the adsorption process is a chemical process and that there are
influences other than pollutant concentration. Many studies have found
that the removal of Cr(VI) by modified nZVI is more consistent with the
pseudo-second order kinetic model[53, 67-69] . This confirms that the
adsorption at the active sites on the nZVI surface does not only adsorb,
but also reduces Cr(VI) during the entire removal process.
The Eley-Rideal-based model to examine the chemical reduction
kinetics of zero-valent iron to pollutants is a more accurate model. Wu[70] et
al. applied the Eley-Rideal-based model for the first time to characterize the
changes in the reaction sequence, and proposed the competitive adsorption
- 21 -
of nitrate and protons on the active sites on the iron surface, and their
study concluded that the reduction reaction step on a single site on the
iron surface controls the whole process. In other words, the adsorption of
reactants and desorption of products are very fast compared to the
reaction steps, and therefore an adsorption-desorption equilibrium can
be assumed.Yoshino et al.[71] applied the Eley-Rideal's model to phosphate
removal and introduced a mechanism for contaminant precipitation
removal, which further extends the applicability type of this
model.Guzman et al.[72] simulated based on this model Zero-valent iron
was used in the reaction process of permeable reaction barriers to
examine the kinetic study of the removal of oxidant contaminants, nitrate
to chlorinated organics. The formulation and development of the Eley-
Rideal model is described in Chapter 4.
Furthermore, although nZVI is considered to be an effective pollutant
removal material, nZVI particles rapidly aggregate due to their magnetic
properties, which results in its reduced effectiveness in water
treatment. As mentioned above, modification of nZVI is considered as a
viable approach to address the shortcomings of nZVI and to develop its
utility. The effectiveness of the modification was also mostly evaluated
under ideal conditions with the help of the demonstration of the removal
rate. This is obviously not in line with the practical application. This is
because the removal rate is not only affected by the material itself, but
also by the amount of material added. In other words, when the treatment
effect is not ideal, increasing the dosage to some extent can often improve
the removal rate. This will inevitably lead to the increase of pollutant
removal cost, and it is necessary to consider the economic benefits in the
practical application of nZVI. Liu[73] has proposed a method based on
economic
- 22 -
Chapter 1
Introducti
on
The electron efficiency of the benefit is defined as the percentage of
electrons utilized by the reduction process relative to the electrons
provided by nZVI in a given time. Here the electrons supplied by nZVI
are not all the electrons that unreacted nZVI could theoretically supply,
but rather the electrons supplied by nZVI that are consumed at the end
of the reaction, which is determined based on the morphology of the
reacted iron. Obviously, the advantage of this evaluation is to optimize the
cost and make full use of the electrons; the disadvantage is that it does not
reflect the pollutant removal rate. Following this, Zhou et al.[74] reviewed
ways to improve the electron selectivity of nZVI, arguing for the
importance of this cost-effective assessment, but indicating that more
cost-effective and rapid assessments are still needed. Electronic efficiency
is an economically important parameter considering the consumption
of nZVI and can help one to choose among the wide variety of modified
materials.
1.2 Overview of hexavalent

chromium removal studies in
water
1.2.1 Sources of hexavalent chromium
and its hazards
Chromium ions and their compounds are widely used in paper, electroplating, dye
manufacturing, leather tanning, and paint industries.
[75]. However, due to improper disposal, chromium can enter bodies of water or
and soil. Hexavalent chromium passes through the digestive and respiratory
tracts,
Skin and mucous membrane invasion into the human body, easily
absorbed by the body. It is carcinogenic in the body and may cause
hereditary genetic defects.Cr(VI) is enriched in the h u m a n b o d y
through the food chain due to its water solubility and
m o b i l i t y [76] . In addition, Cr( VI) has a long-lasting effect on the
environment. Chromium interferes with several metabolic
processes and is toxic to plants, which may lead to plant death [77]
. Due to its carcinogenicity, persistence and bioaccumulation, it can pose
- 23 -
a high risk to ecosystems and public health. Chromium is present in the aqueous
environment in two forms, Cr(III) and Cr(VI), with Cr(VI) being more mobile
and toxic than Cr(III), and highly soluble at any pH. Cr(VI) in water affects
the slow growth of crops, even stopping them in severe cases, and people
who work or live in chromate environments for long periods of time
have a higher risk of lung cancer. Cr(III), on the other hand, is not only
non-toxic, but also easily precipitates from solution as Cr(OH)3[68] .
Therefore converting toxic Cr(VI) to non-toxic Cr(III) is an important way to
control chromium pollution.
1.2.2 Hexavalent Chromium Treatment
Treatment methods for Cr(VI) include physical adsorption, chemical
treatment, and photocatalytic method. The adsorption method works on
the principle that it is a method to adsorb Cr(VI) from water by using
materials with special functional groups and high specific surface area,
and commonly used adsorbents include activated carbon, diatomaceous earth,
polymers, tree chips, microbial flocculants, etc. The main feature of the chemical
treatment method is to convert Cr(VI) into Cr(III), which can then be used to treat Cr(III).
The main feature of the chemical treatment method is the conversion of
Cr(VI) into Cr(III) to realize the reduction of toxicity. There are also new
methods such as photocatalytic method. The photocatalytic method
accelerates the reaction process by using a solid semiconductor as an oxidant
during the redox reaction, which is characterized by a high reaction rate
and high removal efficiency.
Nano zero-valent iron (nZVI) technology mainly relies on chemical
methods to remove Cr(VI) from water. The advantage of nZVI over other
materials is that there are many modification methods and more
extensive research. Modified materials can be selected to improve the
reactivity for the removal of pollutants.
- 24 -
Chapter 1
Introducti
on
1.2.3 Main content of research and technology roadmap
In this paper, we have done the following research, and the technology
roadmap is shown in Figure 1-2:
(1) Carry out an overview study of nZVI, and carry out targeted
research on the limited application of nZVI, so as to provide a theoretical
basis for subsequent research.
(2) A batch test of Cr(VI) removal by nZVI was carried out to
investigate the effects of initial concentration of Cr(VI), initial pH, and
common anions in water on the removal of Cr(VI).
(3) The products of Cr(VI) removal by nZVI were characterized by XPS to
analyze the product changes before and after the reaction and to provide a
basis for model validation.
(4) To model the removal of Cr(VI) by nZVI and provide a new
way to calculate the electron efficiency (5) To comprehensively
analyze the specific effects of reactivity under different
conditions and further elaborate the reaction mechanism.
Figure 1-7 Technology Roadmap

Figure1-7 Technology road map
1.3 Summar
y of the
chapter
Economic and industrial development inevitably has a serious
- 25 -
impact on the environmental system. nZVI, as one of the most commonly

used nanoparticles, has carried out a great deal of research on the
removal of pollutants from environmental waters. This chapter
systematically summarizes the research on nZVI, as well as the
opportunities and difficulties it faces in its application. Currently, based on
the actual environmental conditions, in addition to considering the effects of multiple
factors, the practicality and economic benefits of the materials should also be
emphasized. For example, the response surface method is a design
experiment that considers multiple factors, but it does not reflect whether
the cost of the material is reasonable in the case of maximum removal
rate. As mentioned before, a more comprehensive and quantitative
method to select the modification method of nZVI is the focus of future
development, in order to achieve the purpose of high efficiency removal
at low cost without causing secondary pollution. In addition, the current
research models are mainly focused on simple kinetic models, which are
difficult to be determined.
- 26 -
Chapter 1
Introducti
on
The percentage of different mechanisms of quantitative response. In
summary, this study hopes to establish a model for the removal of Cr(VI)
by nZVI by summarizing the research contents of nZVI. On the one hand,
it can exhaustively describe the proportion of different mechanisms
and quantitatively determine their importance, and on the other hand, it
can provide a simpler way for the calculation of the electronic efficiency
and enhance the potential application of nZVI.
- 27 -
Chapter 2
Materials and
Methods
Materials and methods
2.1 Test Materials and Instruments
The reagents and instruments used in the test are listed in Table 2-1
and Table 2-2.
Table 2-1 Main reagents
Table2-1 Primaryreagent
Reagent Name molecular formula Reagent purity manufacturer (of a product)
of a reagent
ferrous sulfate FeSO4-7H2O Tianjin Dingshengxin Chemical Co.
AR
sodium borohydride NaBH4 AR Tianjin Dingshengxin Chemical Co.
caustic soda NaOH AR Tianjin Dingshengxin Chemical Co.
hydrochloric acid HCl AR Tianjin Dingshengxin Chemical Co.
common salt NaCl AR Tianjin Fuchen Chemical Reagent

Factory
potassium KCr2O7 AR Shanghai McLean Biochemical
dichromate Technology Co.
Table 2-2 Main Instruments

Table2-2 Maininstrument
Instrumentation Equipment Model manufacturer (of a product)
Flow type peristaltic pumps BT100-1L Baoding Lange Constant

Current Pump Co.
Benchtop Thermostatic Oscillator DSHZ-300A Nanjing Xinyi Biotechnology

Co.
electronic balance FA2004 Tianjin Tianma Hengji
Instrument Co.
ultrapure water device SIM-T30UV Beijing Feixiang Seth
Technology Co.
Digital electric mixer E30-H Shanghai Ouhe Machinery
Equipment Co.
Freeze dryer FD-1A-50 Shanghai Biron Instrument
Manufacturing Co.
ultraviolet-visible 2082S UV/VIS Shanghai Unocal Instruments
spectrophotometer Co.
Zeta Potential and Particle Size 90Plus Zeta Brookhaven Instruments, USA
Analyzer
- 15 -
2.2 Preparation of materials and experimental methods
2.2.1 Preparation of nZVI
As mentioned in Chapter 1, the advantages of the liquid-phase
reduction method over other preparation methods are simplicity of
operation and homogeneity of particles. Moreover, it is currently the
most popular preparation method at the laboratory level, and the nZVI
prepared by this method is more meaningful for real and simulation
analysis. The specific experimental procedure is as follows:
In a 1000 mL three-necked flask, add a certain amount of deionized
water (continuously pass nitrogen for 15 min to ensure deoxygenation),
weighing a certain amount of ferrous sulfate (FeSO4-H2O) added to the
three-necked flask and constantly stirring to pass the nitrogen, to be FeSO4-
7H2O is completely dissolved with a peristaltic pump with a rate of 5 mL
min-1 drop 250 mL of sodium borohydride solution ( NaBH4 to Fe molar ratio
of about 2.2:1). The molar ratio of NaBH4 to Fe2+ was about 2.2:1). Nitrogen
was passed through the reaction to deoxygenate the solution, and the
drop was completed.
16
Chapter 2
Materials and
Methods
The solution was then stirred for 15 min so that the hydrogen gas could be
completely discharged. The prepared particles were filtered with a
solvent filter and washed three times with deionized water and ethanol to
remove impurity ions. To ensure that the particles were not oxidized,
nitrogen was continuously passed into the solution to deoxidize during
the filtration process, and the particles were quickly put into a freeze-
drying oven at a controlled temperature of 50°C for 720 min after the
completion of the filtration process, and then dried for spare parts.
2.2.2 Experimental Procedures and Measurement Methods
In order to obtain the model parameters, three sets of removal experiments
with parallel samples were set up. First, 500 mL of water samples were taken and
nitrogen was used to remove oxygen from the water. The removal experiments
were conducted at the initial pollutant concentrations of 100 mg/L, 50 mg/L, and
10 mg/L (Cr/Fe=1:10) and pH 3, 5, 7, 9, and 11. When the experiment was
conducted at 0, 5, 15, 30,
Cr(VI), total chromium, total iron and Fe(II) were measured at 45 and 60
min. The Cr and Fe in the samples were determined by UV-Vis
spectrophotometer. For the determination of Cr(VI), dibenzoyl
dihydrazide spectrophotometry (GB7467-1987) was used, and in order to
avoid possible Fe(III) interference, phosphoric acid was used instead of
sulfuric acid before adding dibenzoyl dihydrazide solution[18] ; potassium
permanganate oxidized dibenzoyl dihydrazide spectrophotometry
(GB7466-1987) was used for t h e determination of total Cr in water. The
determination of Fe in water was carried out by o-phenanthroline
spectrophotometry (HJ-T345-2007). The calibration curve was plotted
according to the method as shown in Figure 2-1:
0.10 0.40
y=0.4989x-0.0006 y=0.2500x-0.0005
R=0.999 0.35 R=0.999
0.08
0.30
0.06 0.25
absorb
absorb
ance
ance
0.20
0.04 0.15
0.10
0.02
0.05
0.00 0.00
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
(a) Concentra (b) Concentration (mg/L)
tion (mg/L)
- 15 -
Figure 2-1 Calibration curve (R in the figure
represents the correlation
coefficient r2) Figure2-1 Calibration

curve
2.2.3 Characterization and analysis of Cr and Fe in the solid phase

In order to combine the simulation and experimental analysis and
further describe the reaction mechanism, the samples were freeze-dried
anaerobically after the experiment and analyzed by X-ray photoelectron
spectroscopy (XPS, ThermoEscalAB250Xi; ThermoFisher). The elemental
composition and compound structure of the sample surface were
obtained from the peak positions, peak shapes and intensities of the
characteristic peaks in the XPS spectra. The full spectrum of the sample
and the narrow spectrum of Cr2p, Ols, Fe2p and C1s orbitals were
obtained by XPS. The spectra were finally processed by Avantage
and CasaXPS software, and calibrated at a binding energy of 284.6 eV
(C1s peak) to eliminate the influence of charge effect. The atomic
concentration was determined from the size of the peak area, and the
shift of the peak position was used to determine the change in the valence
state of the element.
In addition, an X-ray diffractometer (XRD) (D8Advance, Bruker) was used to measure
the diffraction angle and diffraction peaks by varying the diffraction angle and the
diffraction peaks.
18
Chapter 2
Materials and
Methods
The relative intensity of nZVI was used to examine the phase composition
of the samples to investigate the correlation between the crystal structure,
chemical composition and macroscopic properties of the materials. In order
to further confirm the results of the XPS analysis and to provide possible
reaction products, the nZVI before and after the reaction should be
analyzed accordingly.
The nZVI was suspended in 0.1 mM NaCl solution, the pH of the
solution was adjusted with NaOH or HCl, and sonicated in an ultrasonic
cell grinder (BILON-650Y) for 30 min. nZVI was also measured using a Zeta
potential and particle size analyzer (90Plus Zeta) over the pH range of 3 to 10.
The electrophoretic mobility of nZVI was measured using a Zeta potential and
particle size analyzer (90Plus Zeta) over a pH range of 3 to 10. Zeta potential
was calculated by the Smoluchowski equation.
17
18
Chapter 3: Results of Cr(VI) Removal
by Zero-valent Iron Nanoparticles
Study of kinetic modeling

3.1 introductory
The studies on nZVI have mainly focused on the mechanism and
reactivity of modified nZVI to Cr(VI) [3, 10]. In the related reports on
modification, when the reaction mechanisms of nZVI are discussed, the
importance and order of some mechanisms are described qualitatively
based on experimental results and characterization, and the various
reactions are seldom discussed quantitatively. Meanwhile, in the existing
articles, reaction kinetics and adsorption isotherms are usually used to
describe the reaction processes and understand the reaction mechanisms.
Pseudo-primary kinetic model and pseudo-secondary kinetic model are
commonly used simulation models for nZVI, which are simple in form
and easy to calculate. In order to investigate the kinetic mechanism of
Cr(VI) r e m o v a l b y m o d i f i e d nZVI, these methods are also used in this
chapter.
3.2 kinetic model

The pseudo-primary kinetic model, the pseudo-secondary kinetic model,
and the intraparticle diffusion model are the classical models for studying
adsorption kinetics with the aim of observing the rate-controlling steps of
substance changes and physicochemical reactions during adsorption. The
magnitude of the constant k of the kinetic model represents the speed
of the reaction rate; this paper focuses on the reactivity issue, so the
reaction constant k is not discussed in this section.
Pseudo-primary reaction kinetics modeling[78] :
ln C0 = -
C Kobst (25)
Where, C: concentration of Cr(Ⅵ) at

time t, mg/L; C0: initial concentration
of Cr(Ⅵ), mg/L; t: reaction time, min;
kobs: apparent rate constant, min -1
Pseudo-secondary adsorption kinetic modeling [42]:
t q
= t k
- 19 -
1 t
+ 2
s ( qe ) qe
(
2
6
)
kobs: pseudo-primary reaction kinetics, g-mg-1 -min -1;

qt is the adsorption capacity at time, mg/g;
qe is the equilibrium capacity at equilibrium time, mg/g;
The correlation coefficients R2 were calculated using two kinetic
models at different pH and are shown in Table 3-1.
20
Table 3-1 Statistics of correlation coefficients of kinetic models

Table3-1 Kinetic model correlation coefficient statistics
pH 3 5 7 9 11 Average
r2
pseudo first- 0.993 0.977 0.856 0.973 0.999 0.959
order kinetics
pseudo- 0.908 0.989 0.999 0.973 0.614 0.897
secondary
dynamics
(math.)
The reduction of Cr(VI) by nZVI is not a one-factor process, and the
pseudo-primary kinetics suggests that some factors are not part of the
reactivity under some conditions; the quasi-secondary kinetics suggests
that the adsorption process is a chemical process, and that there are
other influences besides the concentration of pollutants. Combined
with this table, the removal of Cr(VI) by nZVI is more consistent with the
pseudo-primary kinetic model. However, no matter which model is
used, the variation of R2 is large. As shown in Figures 3-1(a) and 3-1(b),
the whole process at pH 7 is more consistent with the pseudo-secondary
kinetic process. This suggests that the Cr(VI) removal process is a
chemisorption process as well as a monolayer coverage of limited active
sites on a homogeneous surface[79] . The removal of Cr(IV) by modified
nZVI is more in line with the pseudo-second-order kinetic model, as
mentioned above. However, in this study, this pattern was shown when
the pH was near neutral. In contrast, the pseudo-first-order kinetic
model has a higher R2 as the pH value increases, see Fig. 3-1(c) and Fig. 3-
1(d). This situation may be due to the alkaline condition, the content of
- 19 -
H+ is less and it is difficult to realize chemical reduction. Moreover, the
Cr(III) and Fe(III) in the water at this time indicate the formation of
precipitation at nZVI, which physically adsorbs the pollutants in the
water.
3.50
Raw data
Pseudo-
secondary
simulation
3.25
R=0.614
t/qt(min-g/mg)
3.00
2.75
2.50
0 15 30 45 60
(d) pH 11 Time (min)
22
Fig. 3-1 Pseudo-primary and pseudo-secondary kinetic fitting plots (R in the plots indicates the
correlation coefficient r )2
Figure 3-1 Pseudo first-order model and Pseudo second-order model
The prerequisite assumptions for applying the model of intra-particle

diffusion are: during adsorption, the resistance to diffusion through the liquid film
is so small that it is negligible, or the resistance to diffusion through the
liquid film acts only for a short period of time; the direction of diffusion of
the particles is stochastic, and the concentration of adsorbate is fixed; and
the coefficient of internal diffusion is a constant, and does not vary with
the time of adsorption and the location of the adsorption. The adsorption
of metal ions from the liquid phase to the interior of a solid material requires
three processes. The first process is the diffusion of metal ions, i.e.,
chromium ions diffuse from the liquid phase to the outer surface of the
particles through the fluid-mediated membrane on the surface of the
material, and this stage is usually called the membrane diffusion stage; the
second stage is that chromium ions enter into the pores of nZVI from the
outer surface of nZVI and diffuse to the inner surface of the particles, and
this stage is usually called the intra-particle diffusion stage. The third
stage is the diffusion of chromium ions within the nZVI. This stage is the
elemental exchange or chemical reaction of chromium ions on the active
sites within the nZVI, which is usually called the adsorption reaction
stage. The rate of adsorption reaction of metal ions by solid materials
depends on the above three reaction stages. In general, the intra-particle
diffusion stage progresses slowly and has a greater influence on the
adsorption process. On the contrary, the membrane diffusion phase and
the adsorption reaction phase proceed relatively fast and have a negligible
effect on the adsorption rate. In order to better investigate the diffusion
mechanism within the material, an intra-particle diffusion model was fitted and its
equation is given in Eq. (27).
Intraparticle diffusion modeling:
1
qt = KF t + c
2 (27)
where KF represents the rate constant for the

intraparticle diffusion model, g-mg-1 -min -1 ;
Combined with the formula, the first stage simulation, second stage
21
simulation and third stage simulation of the installation were plotted at pH=7,
for example.
The fitted plots of the intra-particle diffusion model for the stage
simulations are shown in Fig. The maximum correlation coefficient of the
three-stage simulation shows that the intra-particle diffusion model is a
three-stage nonlinear plot at pH 7, which indicates that the adsorption at
this time is a continuous segmented process. The first stage of linear
adsorption is related to surface diffusion, the second stage is an
intraparticle diffusion process, and the third stage is an equilibrium
dynamic process of adsorption and desorption.
25
raw data raw data
Intraparticle 20 Intraparticle
diffusion diffusion
20 fitting fitting
15
15
qt(mg/g)
qt(mg/g)
10
10
5
5 R1=0.978
R=0.901 0 R2=0.983
0
0 2 4 6 0 2 4 6 8
8
(a) first (b) secon

t1/2 (min1/2) t1/2 (min1/2)
stage d
phase
22
25
raw data
Intraparticle
diffusion
20 fitting
15
qt(mg/g)
10
r1=0.983
5 r2=1.000
r3=0.983
0
0 2 4 6 8
(c) three- t1/2 (min1/2)
stage
Fig. 3-2 Three stages of the intraparticle diffusion model (R in the figure denotes the correlation
coefficient r2)
Figure 3-2 Three stages of intraparticle diffusion model
The simulated correlation coefficients for other pH conditions are
shown in Tables 3-2, 3-3, and 3-4, and it can be seen that pH=3, 5 is a one-
stage equation. This is due to the fact that under acidic condition, the nZVI
was corroded and the surface layer of the particles was peeled off, which
prevented the adsorbed particles from entering into the internal
diffusion stage. pH=9, 11 is two-stage, i.e., the diffusion stage has
reached the period of internal diffusion, when the particles in the water
were adsorbed on the surface of nZVI, and the formation of hydroxide on
the surface under alkaline condition provided more channels for the
internal diffusion of particles, thus the balance between adsorption and
desorption was not achieved temporarily. Therefore, the equilibrium
between adsorption and desorption could not be realized for the time
being.
Table 3-2 Statistics of correlation coefficients for intra-particle
diffusion fitting (one-paragraph)
Table3-2 Statistical table of correlation coefficients for the intraparticle diffusion fit (One-part)
pH pH3 pH5 pH7 pH9 pH11
Intra-particle 0.996 0.990 0.901 0.971 0.980

diffusion model

diffusion fits (bipartite)
Table3-3 Statistical table of correlation coefficients for intraparticle diffusion fitting (Two-stage)
pH pH7-1 pH7-2 Average r2 pH9-1 pH9-2 Average r2
23
Intra-particle 0.978 0.983 0.980 0.984 0.997 0.991

diffusion model
pH pH11-1 pH11-2 Average r2
Intra-particle 1 0.997 0.998

diffusion model

diffusion fits (three bands)
Table3-4 Statistical table of correlation coefficients for intraparticle diffusion fitting (Three-stage)
pH pH7-1 pH7-2 pH7-2 Average
r2
Intra-particle 0.994 1 0.983 0.992
diffusion model
As can be seen from the above, these kinetic models, while

computationally simple, are relatively simplified and cannot describe the
role of different reaction mechanisms (e.g., precipitation and co-
precipitation) in Cr(VI) removal, making it difficult to elucidate the reaction
process in detail. With the change of pH, the reaction mechanism is more
replicated, and more specific models are needed to describe the reaction
process and to elaborate the
24
The specific role of mechanisms such as reduction and precipitation.
3.3 Summary of the chapter

In this chapter, pseudo-primary and pseudo-secondary kinetics as
well as intra-particle diffusion were modeled. It was found that under
neutral conditions, the whole removal process was more consistent with
the pseudo-secondary kinetic model, while other cases were more
consistent with the pseudo-primary kinetic model. This is due to the
influence of reaction mechanisms such as proton content and
precipitation under different pH conditions. Intra-particle diffusion in
three stages can describe the reaction process more accurately, but the
third stage was reached only at pH=7 at 60 min, acidic conditions due to
the corrosion of nZVI, and alkaline conditions due to the production of
hydroxides on the surface of nZVI. To further elaborate the mechanism
of Cr(VI) removal by nZVI, a more complex model is needed to quantify
the mechanism.
25
26
Chapter 4 Modeling of Cr(VI)
Removal
Modeling of Cr(VI) removal

4.1 introductory
The removal mechanism of Cr(VI) is now generally recognized to
include reduction, adsorption, precipitation, and co-precipitation[19-21] .
Among them, nZVI plays the most important role in reduction, i.e., the
conversion of Cr(VI) to Cr(III) by electron transfer. Therefore, most of the
modification of nZVI is to avoid the agglomeration of nZVI, reduce the
mass transfer resistance, and give full play to the reactivity of nZVI in
redox. The modified materials can not only directly adsorb Cr(VI) in
water, but also have certain adsorption effect on the products of
different mechanisms. In addition to this, the modified materials can
also improve the crystallinity o f nZVI and reduce the nZVI adsorption
performance to improve the reactivity[80] . However, the presence of the
modification obviously complicates the removal mechanism, and in view
of these effects, the present study does not intend to introduce the
modifying materials, and aims to optimize the model parameters to
reveal the mechanism of nZVI action under the premise of fully
considering the mechanism of nZVI action itself. Meanwhile, although
there are other forms of Cr(VI) in aqueous solution such as HCrO4-CrO42-
, and
so on[ 8 1 ] with the change of pH, the different forms do not affect the
modeling, and we will use CrO42- to build the model. This is because no
matter which form of Cr(VI), the stoichiometric relationship of its reaction
with Fe0 , Fe2+ remains the same, and the number of electrons involved in
redox in the reaction remains the same.
4.2 model building

4.2.1 Kinetic modeling
The reduction reaction of dichromate follows a surface-controlled
reaction, i.e., the smaller the size of the iron nanoparticles or the larger the
number of iron nanoparticles, the larger the surface area of the iron
nanoparticles, and the higher the removal of dichromate[82] . nZVI first
adsorbs dichromate through the active sites and then reacts with the
dichromate on the active sites. The active sites are not only provided by
nZVI, but also by the oxide layer including Fe2O3,Fe3O4,FeOOH, etc.[64] . Based on
- 25 -
this, the model assumes that an equilibrium exists prior to adsorption
desorption and that the adsorption of dichromate by nZVI is based on a
proton on the active site. The kinetic and equilibrium expressions are
shown below:
Adsorption of protons in water is present at the active site (S) on nZVI[64] :
H+ + S k1
() S ⋅ H +
, r = k ⎡H + ⎤θ - k θ
k-1 ads 1 1 ⎣ ⎦S -1 SH
(28)
where θS denotes the proportion of uncovered active sites, θSH denotes

the proportion of active sites covered with protons, and k1 and k-1 denote
the reaction rate constants for the forward and reverse reactions,
respectively, of the proton adsorption reaction at the active site. The
active site (S) adsorbs protons and exhibits a positive charge, and the
dichromate, which exhibits a negative charge, adsorbs to the active site with
protons by electrostatic adsorption:
k21
Cr2O7 2− + (S ⋅ H+ ( S⋅ + ⋅ Cr O2−
ads 27 ads
)
k-21
H ) (29)
26
Removal
And the active sites without adsorbed protons can adsorb hexavalent
chromium in water by complexation:
k22
Cr2 O 2− + S k-22 (S ⋅ Cr O2 ) 2 7
−
7 ads (30)
However, regardless of the adsorption, the pollutant is adsorbed onto the

surface of the core-shell structure and participates in the reduction reaction.
Theoretically, it is difficult to distinguish between the two. Therefore, for
the convenience of calculation, we consider the two adsorption modes as
the same (either electrostatic adsorption or complex adsorption), i.e., k21
and k22 are unified as k2, while k-21 and k-22 are unified as k-2. The reaction
rate of adsorption can be expressed as (34) or (35).
r2 = k 2 ⎡⎣Cr O2− - k -2θSHCr

(34)
⎤⎦θ 2SH 7
r2 = k 2 ⎡⎣Cr O2− -k- SCr

(35)
⎤⎦θ 2
S
7 2θ
where θSHCr denotes the proportion of active sites that have adsorbed
dichromate by electrostatic interaction and θSCr denotes the proportion
of 2active
7
sites that have adsorbed dichromate by complexation. k2 and k-2
denote the reaction rate constants for the forward and reverse reactions of
adsorption of Cr O2- at the active site, respectively. In this paper, we adopt
the method of considering both ways as electrostatic adsorption. In
addition, there is a secondary adsorption of protons at the active site
(S)[61] :
H+ + (S ⋅ H+ ⋅ H+ ) ,r =k [H+ ]θ -k θ
) k3
( S⋅ +
SH-3
ads ads 3 3
k-3
H SHH
(36)
where θSHH denotes the ratio of active sites for secondary adsorbed
protons. When the active site (S) binds dichromate, the iron core will
provide electrons through the oxide shell to reduce dichromate to
Cr(III):
3Fe0 + (�⋅ H+ ⋅ Cr O2− ) +13H ⎡H+ ⎤
k4
+ → 3Fe2+ + 2Cr3+ + 7H O+S, r = k θ
2 7 ads 2 4 4 SHCr ⎣
(37)
⎦
As we stated above, nZVI that is not involved in the reaction will be
- 27 -
)
corroded by water (not considering oxygen corrosion under aerobic

conditions) to produce Fe(II) and hydrogen. Although the reaction allows
the active sites of nZVI to be re-released, the reaction of nZVI with water
is still an important factor affecting the rate of the reaction, as shown in
the following equation:
k5
(S ⋅ H +
⋅ H+
ads
0
+ Fe →
Fe2+
+ H2 ↑ +S, r5 = k5θSHH (38)
Fe(II) from redox and corrosion can also react with dichromate:
k6
6Fe2+ + (�⋅ H ⋅ Cr2 7

+ O2− )
ads
+13H → 6Fe3+ + 2Cr3+ + 7H O+S
+
2
⎡⎣H+ ⎡⎣Fe2+
r6=k θ6 SHCr ⎤⎦ ⎤⎦ (39)
Although precipitation is included in the Cr(III) removal mechanism,
no clear boundaries for precipitation and co-precipitation can be given
based on the limited experimental results parameters. In other words,
the reaction-calculation relationship for the co-precipitation reaction is
not clear, and the precipitation reaction can be combined as part of the co-
precipitation in the model. Therefore, we describe precipitation and
coprecipitation together as:
28
Removal
xCr3+ + yFe3+ + 3( x + y)OH− = xCr(OH)

3 ⋅ yFe(OH)
3
(40)
↓
The values of x and y in the reaction process are not fixed, and
the ratio of Cr and Fe in the co-precipitation has not been addressed in
the current study on the mechanism of Cr removal. The ratio of Cr and Fe
in the co-precipitation is not addressed in the current study of the
mechanism of Cr removal, and it is different under different pH
conditions. Therefore, we would like to describe the precipitation
process of Cr and Fe separately by splitting the reaction equations. This
has the advantage of avoiding the need to give x and y directly in the
model, and fitting the ratios to some extent by changing the k values.
The total precipitation process is then described as:
Fe3+ + 3H 2O = Fe(OH) ↓ +3H+ , r ⎡⎣Fe3+⎤⎦
3 =k (41)
7
7
Cr3+ + 3H 2O = Cr(OH) ⎡⎣Cr 3+
3 ↓ +3H+ , r8 (42)
⎤⎦
=k 8
Some studies have considered that nZVI undergoes redox on the iron
surface, thus adding the adsorption of iron ions at the active site[27] . The
co-precipitation reaction of Cr(III) also occurs on the surface of nZVI, and
the resulting precipitates are attached to the surface of nZVI in a large
proportion[28] , thus neglecting the adsorption of ferric ions on the
surface of nZVI.
Assuming that the adsorption of different species on the active site is
rapid and that the adsorption equilibrium is reached instantaneously, the
fraction of the active site covered by dichromate and proton can be
expressed as a function of their adsorption equilibrium constants (K1,K2,
and K3) and their aqueous solution concentrations[61] :
k1 = ⎡HθSH k2 θSHCr θSHH
⎤θ , = k = ⎡Cr O2− ⎤θ = k3 ⎡H ⎤θ
+ +
K1 = k K2 , K3
k
-1 ⎣ ⎦S -2 2 7 ⎦ SH -3 ⎣ ⎦ SH (43)
⎣
From this, the relationship between the active sites with adsorbed
chromium and those with secondary adsorption of hydrogen to hydrogen
and dichromate ions in aqueous solution can be deduced:
K K ⎡⎣Cr O2− ⎤⎦ ⎡⎣H+ ⎤⎦
θSHCr 1 22
⎤2 7
=1+ ⎡H+ ⎤ + K K ⎡H+ + K K ⎡Cr O2− ⎤ ⎡H+ ⎤
K
K +K⎤2
1⎣ ⎦ 13 ⎣ ⎦ ⎡H 12 ⎣
27
27 ⎦⎣ ⎦ (
4
4
)
θSHH = 1 + K ⎡H+ ⎤ + K K ⎡H+⎣ ⎤2 + K⎦ K ⎡Cr O2− ⎤ ⎡H+ ⎤
13
1⎣ ⎦ 13 ⎣ 12 ⎣ 27 ⎦ ⎣
(45)
⎦ ⎦
It should be noted that the fractions of adsorptionactive-sites
released by the reactions (37),(38) are not utilized twice. This is
because the reduction process of nZVI is not a single electron transfer
process, but is accompanied by a mass transfer process, which results in
a limited number of active sites. Based on the above equations, the
differential equations for different species over time can be derived,
where the reduction rate of dichromate is expressed as:
d ⎡⎣Cr2 7O2- ⎤⎦ = r + r = k θ ⎣⎡H+⎤⎦+kθ ⎡⎣H+ ⎡⎣Fe2+

- 4 6 4 SHBr 6 SHBr
⎤⎦ ⎤⎦
dt (46)
Similarly, the rate of change of trivalent chromium ion can be expressed

as:
28
Removal
d ⎡⎣Cr3+ ⎤⎦ = 2r + 2r - r = 2k θ ⎡⎣H+ ⎤⎦ +2k θ ⎡⎣H+ ⎤⎦ ⎡⎣Fe2+ ⎤⎦ - k ⎡⎣Cr3+ ⎤⎦

4 6 8 4 SHCr 6 SHCr 8
dt (47)
The rate of change

of divalent iron is: d ⎡⎣Fe 2 +
= 3r4 +r5 -6r6
⎤⎦
dt
= 3k4θ SHCr ⎡⎣H + ⎤⎦ + k SHH - SHCr ⎡⎣H + ⎤⎦

(48)
6k6θ
θ 5 ⎡⎣Fe2+⎤⎦
Rate of change of trivalent iron:

d ⎡⎣Fe3+ ⎤⎦
= 6r-r = k θ ⎡⎣H+ ⎤⎦ ⎡⎣Fe2+ ⎤⎦ - k ⎡⎣Fe3+ ⎤⎦
67 6 SHCr 7
dt (49)
In summary, the relationship between the content of different

species in the water with time can be rescued by applying the fourth-
order Lungkuta method for solving the equations based on several
differential equations.
4.2.2 Electron efficiency calculations and precipitation ratio calculations
The concept of e-efficiency, which is actually the efficiency of a
pollutant in utilizing electrons, has been introduced above and can be
expressed as equation (50) [73] .
EE = Ne × 100%
Nt (50)
Ne denotes the total number of electrons transferred to the

pollutant, i.e., the number of electrons that play a role in the redox
process of Cr(VI); Nt denotes the total number of electrons supplied by
the reacted nZVI, i.e., this fraction does not include the electrons
supplied by the nZVI that does not react but is converted to Fe(II) and
Fe(III). In this paper Ne is the amount of electrons consumed by the
reduced Cr(III) in the solid and liquid phases at the end of the reaction,
which can be expressed as reaction equation (51) [83]:
L S
N e= 3n Cr
+ Cr (III) (51)
(III) 3n
Cr (III)
whe L
re n 29
denotes the Cr(III) denotes the amount of

content in the liquid Cr(III) in the solid phase,
phase; nS i.e. Cr (III)
The amount of Cr(III) in the precipitation or co-precipitation product

loaded on the surface of nZVI at the end of the reaction. the total
amount of electrons supplied by nZVI can be calculated using Equation
(52):
L L S
N t = 2n + Fe(III)
+ Fe(III) (52)
Fe(II) 3n 3n
n LFe(II) n L
Fe(III)
n S
Fe(III) The content of Fe(II) in the liquid phase, the content of
Fe(III) in the liquid phase, and the content of Fe(III) in the
liquid phase, respectively, are shown.
The amount of Fe(III) in the solid phase can be expressed as the amount of Fe(III) in the
solid phase. In summary, the amount of Fe(III) in the solid phase is required to calculate
the electron efficiency,
30
Removal
Cr(III) content. They can be calculated as in equation (53) below:

S S
d Cr (III) ⎤⎦ d ⎤⎦
= r = k ⎡⎣Cr ⎤⎦ ⎣⎡Fe
3+ 3+
Fe (III) (53)
⎡⎣n = ⎡⎣n ⎤⎦
7
dt dt 7
It should be noted here that the reaction equation is built in

equation (36) with x, y both taken as 1. When x and y are taken different
values, the reaction equation has different forms. Combined with the
experimental results, the electronic efficiency is calculated by modeling
according to (50)-(53). In this study, the electronic efficiency was
calculated by modeling. In addition, in order to elucidate the co-
precipitation mechanism and determine the precipitation rate, Fe(III) and
Cr(III) in the solid phase. The calibration of the model parameters depends on
the experimental Cr(VI),Cr(III), and Fe(III).

In this section, the specific mechanism of Cr(VI) removal by nZVI
is described and a new model for Cr(VI) removal by nZVI is developed based
on the reaction mechanism. The model can calculate the proportions of
different reaction mechanisms by testing and characterizing the rate-
setting parameters. On this basis, the model provides a way to calculate
the electronic efficiency. Finally, the whole simulation process is realized
by writing Python code.
31
32
Study on the results of Cr(VI) removal by nano zero-valent iron

5.1 introductory
The previous chapter modeled the removal of Cr(VI) by nZVI and
provided a new method for calculating the electron efficiency. In this chapter,
the occupancy of different mechanisms is provided based on the rate-
determined model parameters, and the reduction process is refined and
the corresponding electron efficiencies are provided. In order to further reveal
the law, the characterization analysis, such as XPS and XRD, is combined to
explore the material change rule on the nZVI surface, which lays the
foundation for summarizing the nZVI removal mechanism.
5.2 Results and discussion

5.2.1 characterization
Figure 5-1 XPS analysis of nZVI before and after the reaction
Figure 5-1 XPS analysis of nZVI before and after the reaction
Figure 1 shows the XRD analysis of nZVI before and after the
experiment. From Fig. 5-1 (a), we can see that the c o n t e n t o f Fe0
31
(B.E=706.0eV) o n t h e s u r f a c e o f nZVI b e f o r e t h e r e a c t i o n i s
not high, and the surface is dominated by Fe(III)
(B.E=710.7eV) and Fe(II) (B.E=713.2eV), and the satellite peaks of Fe2p3/2
confirm the aging of nZVI in the a i r and the generation of two different
valence states. Figure 5-1 (b) shows that Cr has been attached to the surface of
nZVI in various ways. Specifically, in Fig. 5-1 (c), the combination of
Fe2.4Cr0.6O4,Cr(OH)3,Cr(III) is 576.6 eV, and the combination of Fe2.4Cr0.6O4,Cr(OH)3,C
)r(Iis
576.6 eV, and the combination of Fe2.4Cr0.6O4,Cr(OH)3is576.6
,Cr(I) eV.
32
577.4 eV and 578.2 eV. In addition, although some studies have suggested
that the peaks with binding energies in the vicinity of 579 to 580 eV are
produced by hexavalent chromium -[8486 ], at this point in time the
chromium is in the form of CrO3. We are therefore inclined to think that the
peaks are produced by Cr2O3 (B.E = 580.1 eV) with a much higher binding
energy, or by Fe(III) and Cr(III) co-precipitation products. In FIG. 5-1 (d), the
photoelectron peaks are in the range of 711 to 730 eV, which corresponds to
the binding energies of 2p3/2 and 2p1/2 for Fe2+ and Fe3+ . The peak with a
binding energy of 710.6 eV is thought to be produced by FeCr2O4. The
peak binding energy of 710.6 eV is believed to be produced by FeCr2O4.
The peak at 711.8 eV is produced by Fe(OH)O. In addition, we only observe
the guard star peak of Fe(III) after fitting, while the guard star peak of
Fe(II) at Fe2p3/2 is not significant. In addition, after fitting, we only
observe the guard star peak of Fe(III), while the guard star peak of Fe(II)
a t Fe2p3/2 is not significant, thus Fe(III) (B.E = 712.6 eV) is the main component of
(110)
the reacted nZVI surface.

(311)
(440)
(220)
(511)
(221)
♦ Fe0 -Fe3O4 -Fe2O3 -FeOOH

• ♦
(chemistry
)
-
- ♦
- - ♦
(c (c
ocia
tion
diss
h h
e e
m m
i i
s s
t t
r r
y) y)
Angle (2θ)
Figure 5-2 XRD analysis of nZVI before and after the reaction
Figure 5-2 XRD analysis of nZVI before and after the reaction
The XRD pattern of nZVI is given in Fig. 5-2. The diffraction peak at
2θ=44.7° confirms the presence of Fe0 . The diffraction intensity indicates
the content of the particles, and the intensity of the characteristic peak of
Fe0 is higher after the reaction than before. It is inferred that there is a
substance transfer process during the reaction, and the oxidized shells
formed may be dislodged during the reaction, resulting in the r e c o v e r y
33
o f t h e a c t i v e s i t e s used for decontamination. S e v e r a l o t h e r
c r y s t a l f o r m s r e l a t e d t o i r o n i n c l u d e m a g n e t i t e (Fe3O4 , 2θ =
30.00° (220), 56.96° (511) and 62.60° (440)), magnetic hematite (γ-Fe2O3 , 2θ =
35.49° (311))
and goethite (α-FeOOH, 2θ = 53.17° (221)) [28] . These results indicate that
Cr(VI) is reduced and Fe0 is consumed to form iron oxides that are deposited on the
surface of the nanoparticles, hindering the contact between the particles and the
pollutants.
34
40
20
Zeta Potential
0
(mV)
-20
-40
3 4 5 6 7 8 9 10 11
pH
Figure 5-3 Zeta potential of

nZVI Figure 5-3 Zeta potential of
nZVI
As shown in Figure 5-3, nZVI has a positive zeta potential under acidic
conditions and a negative zeta potential under alkaline conditions, with
an isoelectric point near pH 7.0, where the electrostatic force on the
particle surface is low and the repulsive force is weak. Since the pH
range of the groundwater is usually between 6.5 and 8.5, the nZVI colloids
agglomerate faster and are more likely to destabilize and settle in this
environment.
5.2.2 Effect of initial concentration and electron efficiency
35
Figure 5-4 Effect of Different Initial Concentrations of Cr(VI)

Figure 5-4 Effect of different initial concentrations of Cr(VI)
The pH and Cr(VI) concentration in water are the key factors

affecting the electronic efficiency of nZVI [25]. Therefore, three
different initial concentrations (100 mg/L, 50 mg/L, 10 mg/L) were used to
simulate the reaction process under the condition of 1:10 Cr/nZVI mass
ratio. The parameters used in the model are shown in Table 5-1. It
should be noted that the model parameters were not chosen to maximize
the correlation coefficient. Since the solution of the reaction process is
an integral of the reaction equation, according to the Newtonian Leibniz
formula, we made sure that the parameters at the end of the simulation
were closer to the monitored values in order to improve the accuracy of
the calculation of the electronic efficiency. The modeling is done in such
a way that the reaction equation (9) controls the Fe(II) content, but this
process is subject to the concentration of Fe(II) in the water itself, so
that there is always an abrupt change in Fe2+ at the beginning of the
simulation.
Figures 4(a)-(c) show the variation of Cr(VI), Cr(III), Fe(III) and Fe(II)
in water over a period of 60 min. The concentration of Cr(VI) decreased
continuously under all the three conditions with removal rates of
27.49%, 44.32% and 28.74%, respectively. Among them, the reduction was
faster when the initial concentration was 50 mg/L, especially in the first
15 m i n . At the end of the test, the utilization rate of the adsorbed active
site θSHCr was 47.45%. Compared with the other two cases (15.94% at 100
mg/L and 17.30% at 10 mg/L), this suggests that the concentration
dependence of Cr(VI) removal may be caused by the different reactivity
36
of the active site. Combined with the XRD analysis in Fig. 2, we deduced
that due to the effect of concentration, the active sites were more
reactive at an initial concentration of 50 mg/L compared to 10 mg/L.
More. However, at 100 mg/L, due to the higher concentration, the
hydroxide precipitates from the reaction were more likely to come into
contact with nZVI, covering the active sites to a greater extent. Although
the reduction of Cr(VI) occurs mainly at the solid-liquid interface, the
large number of active sites does not mean that the pollutant is more
reactive[87] . In Fig. 4(a), the initial dosage of Cr(VI) and nZVI was higher,
but the concentration of ions produced by redox was similar to that of
the 50 mg/L condition. This implies that the decrease in active site
utilization at 100 mg/L was affected by the solid precipitation process. The
reason for this is that precipitation and co-precipitation prevented the
contact of Cr(VI) with NZVI and hindered electron transfer[88] .
Regardless of the initial concentration, the Fe(II) content starts to
decrease after 15 min due to the fact that the corrosion reaction
produces Fe(II) faster than the oxidation of Fe(II). At this stage, due to
the precipitation of Fe(III) and the
37
The formation rate is similar and the concentration of Fe(III) does not
fluctuate much. In addition, the adsorption of nZVI on solids occurred
simultaneously with the reduction process, but nZVI preferred to
adsorb precipitates when both the concentration of pollutants and
precipitated solids were high. In Fig. 4(c), the reduction effect was not
obvious at 10 mg/L due to the low content of nZVI, and it was difficult to
analyze the changes of Cr(III), Fe(III), and Fe(II) because of the low
content (<0.2 mg/L).
Figure 5-4(d) also shows the proportion of the reaction equation (7),
(9) in the reduction process. From this we can see that at an initial
concentration of 100 mg/L (nZVI dosing of 1g/L), a large amount of nZVI is
corroded by the water without Cr oxidation, and the electron transfer
efficiency is low, which produces more Fe2+ in the water. At this time,
the reduction of Cr(VI) mainly relies on the corrosion-produced Fe2+
rather than nZVI, which results in the depletion of more Fe2+ and the
production of more Fe3+ . The amount of Fe precipitation increases as a
result. As a result the amount of Fe3+ precipitation increases. At lower
concentrations, the reduction of nZVI itself dominates. Figure 5-4(d) also
shows the percentage of reaction (10), (11) in the total precipitation
process.
Ratio. Due to the loss of electrons, the reduction of a given amount of
Cr(VI) requires a greater amount of nZVI, which also leads to the fact that
the amount of iron precipitated in the water is always higher than the
amount of chromium precipitated, especially when the corrosion is
more severe. Finally, depending on the parameters employed for the
reaction, we calculated the electronic efficiencies of 49.60%, 58.81%, and
48.08% for the three cases, respectively. Some studies [8,20,25] have
shown that the bare nZVI vs. Cr(VI) is about 10% or even lower, which is
very different from the present study electron efficiency. This is partly
due to the fact that in this study, the reaction environment is anaerobic,
and only the corrosion of nZVI by water exists, without the oxidation of
nZVI by dissolved oxygen in water. On the other hand, it is because part of
the nZVI was corroded by water and precipitated, but the experimental
sampling was not monitored in real time so that this process would not
be observed. Nevertheless, the calculated electronic efficiencies reflect
38
the ability of Cr(VI) to utilize the electrons provided by nZVI. There is a
positive correlation between the electron efficiency and the active site,
and we are inclined to believe that the active site is responsible for the
transfer of electrons to Cr(VI) as a whole, i.e., the contaminant is
transferred to the active site and then obtains electrons from the iron
core.
Table 5-1 Model Calculation Parameters
K1 K2 K3 k4 k5 k6 k7 k8
mM-1 mM-1 mM-1

mM - mM-1 -min-1
min-1 min-1 min-1
min-1
100mg/L 200 294180 1000 235000 800 5026050 8.376 80.594
50mg/L 2000 294180 1000 4256500 310 50818950 2.792 77.994
10mg/L 1000 294180 1000 70,000 95 22338000 83.767 77.994
pH3 100 588.36 1000 400 200 2513.025 5.026 10.919
pH5 1000 20 2E+5 108750 156 36000 4.420 20.104
pH9 10000 10000 100 5.655E+8 295 895600000 93.593 78.183
39
pH11 10000 294180 1000 3.25E+8 60 4.8305E+11 6.701 29.326
Table 5-1 Table of model calculation parameters
5.2.3 Effect of pH and Electronic Efficiency
Figure 5-5 Effect of Different Initial pH

Figure 5-5 Effect of different initial pH
Figure 5-5 shows the experimental and simulation results for

different pH conditions. The simulation results for pH 7 are from Fig.
2(b), and the data are from the 50 mg/L section in Table 1. From Fig. 5-5 (a),
it can be seen that the removal of Cr(VI) was enhanced (53.20%) under
36
acidic condition. Andbythe content
Zero-valent ofNanoparticles
Iron other ions in the water was also
significantly elevated. This
37
This is due to the increased corrosion of nZVI and the dissolution of the
surface passivation layer under acidic conditions. However, the
utilization rate of the active site is only 21.62% compared to the pH 5 case.
Considered in conjunction with Fig. 5-1(e), this situation indicates that
although the strong acidic condition reduces the reactivity of the active
site, more Fe(II) is produced by the nZVI corrosion, which leads to the
reduction of Cr(VI). Regarding the reduction of the active site, this may
be due to the fact that the acidic condition (pH=3) destroys the nZVI shell
that provides the active site and dissolves the nZVI[89] . Thus, in Fig. 3(b), the
active site utilization is 44.87%, which is slightly lower than the pH 7 case.
Comparing Fig. 5-5 (c) and Fig. 5-5 (d), we find that at pH 9 there is a
sudden change in some of the ions in the water, whereas at pH 11 there is
very little change in these ions. We tend to think that at pH 9, the corrosive
effect is stronger and the precipitation rate is slower, so more active sites are
available for the reaction at the beginning. However, as the reaction
proceeds, as the pH rises, it reduces the nZVI reactivity and accelerates
the formation of hydroxides, preventing the contaminants from
approaching the nZVI surface. This view is confirmed by Fig. 3(f), where
the total number of active sites used for reduction decreases under
alkaline conditions and intensifies with decreasing pH. As in the case of
pH 11, the total active sites available for reduction were about 33.33%,
while the active site utilization was only 4.28% and the removal rate was
19.84%, which was much less than the other cases. Fig.
3(f) describes the theoretically available active sites for reduction, which
can be categorized into those that have been used and those that remain
unused. The percentage of used active sites decreases with increasing and
decreasing pH. pH > 7, the solid products of the reaction process, the
passivation of the nZVI surface, and the low proton content of the water
prevent the active sites from functioning, resulting in a high content of
unused active sites. pH < 7, the acidic conditions accelerate the solubilization
of the nZVI and destroy the surface active sites, in spite of the high proton
content. The unused active sites may be permanent. Unused active sites
may be permanently lost.
Figure 5-5 (e) shows that the amount of Cr(III), Fe(III) precipitated and
the ratio of the two ions are similar at pH 3 and 11. However, the key to
38
controlling the amount of precipitation under acidic conditions is the Fe(II)
produced by corrosion, whereas the key under alkaline conditions is the
lower Fe(III),Cr(III) concentration in the precipitation equilibrium. The
maximum precipitation occurred at pH 5. The increase in precipitation is
mainly due to the precipitation of Cr(III). The composition of the
precipitated solid product is mainly the hydroxide of Fe(III)_. In addition,
as can be seen from Fig. 5-5 (e), the ratio of nZVI to Fe(II) reduction
decreases with decreasing pH. This is apparently due to the fact that low
pH increases the corrosion rate of nZVI and electrons are captured by
water. It is noteworthy that a change in pH always reduces the Cr(VI)
capacity of nZVI itself.
Finally, according to the parameters provided by the model, the
electron efficiencies were 39.18%, 47.56%, 58.81%, 59.12%, and 84.19% at
five pH conditions. nZVI's outer shell efficiently transfers electrons from
the core to its surface while protecting the core from corrosion[90] .
However, under acidic conditions, the shell is dissolved and more
electrons are transferred to the protons in the water. Therefore, as the pH
decreases, the electron efficiency decreases. Combined with the above
analysis, we can conclude that pH affects the electronic efficiency by
influencing corrosion, and pH can change the reducibility of nZVI. At pH
11, although the loss of material is small, the content of each ion in water
is also
39
is not high, but the removal rate is very low and there are few active sites
available for reduction. At pH 3, the electronic efficiency is lowest and the
increase in removal rate comes at the cost of materials. In this study, we
favored the use of nZVI in neutral waters because at pH 7, the reaction rate
was slow, but the removal rate was high, and the material still had
potential (a large percentage of the unused active sites were not
destroyed). How to balance the electronic efficiency and the removal rate
is also one of the issues to be faced in future studies.
5.3 Reaction Mechanism for Cr(VI) Removal
Figure 6-1 Mechanism of Cr(VI) removal by nZVI

Figure 6-1 Mechanism of Cr(VI) removal by nZVI
As shown in Figure 6-1, we divide the whole reaction process into

three stages. The first stage is the adsorption stage, in which the active
site adsorbs the pollutant by electrostatic force or complexation force.
Through these two adsorption methods, the pollutant is bound to the
active site, and the protons on the active site can participate in the
subsequent reduction reaction. Specifically, Cr(VI) is first adsorbed by
anaerobic nZVI particles, and then Cr(VI) is reduced to Cr(III) [91] . As can
be seen above, this ratio is very low under acidic and neutral conditions.
However, at pH11, about 60% of the active sites were not used for oxidative
reduction due to severe inhibition of electrostatic adsorption. The second
stage is the most important stage for Cr(VI) removal: the electron transfer
stage[53] . The effective electron transfer consists of two main parts. One
38
part is the transfer of electrons from the iron core through the nZVI shell;
the other part is the electron transfer process of Fe(II), which comes from
the corrosion of nZVI by water and the reduction of Cr(VI) by nZVI. In
general, the action of nZVI is the main mode of reduction of Cr(VI) (non-
acidic conditions). A t p H 3, the action of Fe(II) exceeded the reduction of
nZVI (22.18%:31.02%). This is due to the fact that at pH 3, more electrons
supplied by nZVI are consumed by protons rather than Cr(VI)[92] .
Moreover, we observed that Fe(II) always acts at a very fast rate under non-
acidic conditions. This leads to the fact that after Cr(VI) is partially reduced
(>10 mg/L), Fe(II) in water
39
and Fe(III) always remained low (<3 mg/L). Furthermore, the ineffective
electron transfer is mainly due to the transfer of electrons from nZVI to
hydrogen ions. As we stated above, this process is affected by pH. Under
acidic conditions, the ineffective electron transfer was exacerbated. But
this process also reduces the surface passivation of nZVI and enhances
the reactivity[93] . The last stage is the stage of mass transfer. In this stage,
Cr(III) and Fe(III) are released into the water to form precipitates, co-
precipitate, and transfer to the particle surface. Our XPS analysis
revealed the presence of the coprecipitation product. Its composition is
complex, formed mainly by species such as FeCr2O4,CrxFe1-xOOH and CrxFe1-
x(OH)3
[69, 94, 95] . Whereas, XRD analysis showed the transfer of these
precipitates and retention of hydroxides during the reaction of nZVI. In
this step, the solid product transferred to the surface undergoes a mass
transformation process. In Fig. 1(c)-(d) and Fig. 2, we observed the
precipitation products Fe(OH)3, Cr(OH)3 and the produced Fe3O4, Cr2O3, etc.
This confirms the existence of mass transfer. Also, in the model, we
calculated the ratio of total precipitation to be between 1.38 and 4.00
(molar ratio of Fe to Cr) under several conditions. In practical
experiments, this ratio is smaller, taking into account the removal of the
precipitated fraction.

In this chapter, we developed a Cr(VI) removal model and verified the
accuracy of the model experimentally and through characterization. The
model innovatively combines precipitation and co-precipitation analyses
to simulate the reaction process under different initial pollutant
concentrations and different pH conditions. We quantified the reduction
capacities of nZVI and Fe(II) during the reduction process, calculated the
molar ratio of Fe/Cr in the solid products, and analyzed the reaction
process in conjunction with the change of active sites. For the limited
economic evaluation of nZVI, this study introduced the electronic
efficiency calculation, which can only be performed by characterization
analysis (XAFS analysis), into the model, thus providing a simple and
inexpensive evaluation method for nZVI. However, the increase in electron
efficiency is accompanied by a decrease in the removal rate. The use of
40
modified methods may be the key to solving this problem. p H increases or
decreases always diminish the reduction capacity of nZVI. The
difference in the removal rate at different pH values is due to the
reducing ability of Fe(II). In other words, under acidic conditions, Fe(II)
produced by corrosion is more effective in increasing the removal rate; under
alkaline conditions, the reactivity of nZVI is suppressed, while the function
of Fe(II) is stabilized (compared to neutral conditions).
41
42
Conclusion
s and
outlook
Conclusions and outlook

Conclusion:
As one of the most commonly used nanoparticles, nZVI has become
one of the research hotspots due to its strong reducibility,
environmental friendliness, and large surface area. This study
systematically summarizes the research on nZVI, focusing on the
opportunities and difficulties facing the current development. The current
research on nZVI focuses on the exploration of multiple influencing factors.
The main reason for the limited application of nZVI is that it is difficult
to comprehensively evaluate the reactivity of nZVI in a cost-effective
way. On the basis of fully utilizing the performance of nZVI, the
comprehensive evaluation of nZVI is the focus of future development,
so as to achieve the purpose of efficient removal at low cost.
In this study, the reaction mechanism of nZVI is further
analyzed by establishing pseudo-primary and pseudo-secondary
kinetics as well as intraparticle diffusion models. Its simple form
and easy calculation can determine the order of importance of the
mechanism to some extent. The main conclusion is that the reduction
process of nZVI under neutral conditions is more consistent with the
pseudo-secondary kinetic model, while the pseudo-primary kinetic
model is more applicable under acidic and alkaline conditions, which is
caused by the reaction mechanisms such as proton content and
precipitation under different pH conditions. Although these models are
useful, they are unable to reflect the proportion of different mechanisms
and maintain a high correlation between pH changes, which may lead to
misjudgment of the pollutant removal mode. Therefore, in this study,
we summarized the Cr(VI) removal studies of nZVI and the related
mechanisms, and developed a model of Cr(VI) removal by nZVI, which
would also provide a simpler way for the calculation of the electronic
efficiency. The model is realized by writing Python code to realize the
whole simulation process through experiments and characterization of
rate-setting parameters.
Model simulations and related calculations were carried out to obtain
the changes of active site usage, mechanism ratio, and electron efficiency
- 41 -
under different conditions, and the experimental process was analyzed by
XRD, XPS, and zeta potential characterization. The main conclusions are
that the increase of the electronic efficiency is accompanied by the
decrease of the removal rate; the increase or decrease of the pH value
always weakens the reduction ability of nZVI, and the difference of the
removal rate under different pH values is due to the reduction ability of
Fe(II). Under acidic conditions, Fe(II) produced by corrosion was more effective
in increasing the removal rate; under alkaline conditions, the reactivity of
nZVI was suppressed, while the function of Fe(II) was stabilized. In this study,
nZVI has a greater potential for application under neutral conditions, when a
large percentage of unused active sites are not destroyed and the potential
exists for prolonged pollutant removal.
Finally, the whole reaction process was divided into three stages
based on the experimental results and characterization analysis. The first
stage is the adsorption stage, where the active sites adsorb the
pollutants, and the change in pH affects the pollutant removal process by
influencing the electrostatic adsorption. The second stage is the
electron transfer stage. This includes the transfer of electrons from the
iron core through the nZVI shell and the electron transfer process from
Fe(II), but the specific part that dominates depends on the reaction
conditions. The third stage is the mass transfer stage. At this point
precipitates form in the water, co-precipitate, and transfer to the nZVI
surface.
Outlook:
42
Conclusion
s and
outlook
The focus of this study was on the modeling of nZVI removal, and
the response of the modified materials was not examined. Modeling for
different modification modes needs to be further investigated. The choice of
modification method will largely affect the reactivity of different
mechanisms under different conditions.
Corresponding simplifications were made in the pollutant adsorption
stage and co-precipitation part of the model, specifically the combined
treatment of electrostatic adsorption and complex adsorption as well as the
simplification of co-precipitation reaction equation coefficients. This
simplification reduces the complexity of the model construction to a certain
extent, but a more complex theoretical support is required to further describe the
reaction process precisely. Only then can it be applied to the field study,
combining the model with the field study from the mechanism in
exploring the
The mechanism of the nZVI reaction was developed to provide guidance
on the optimal conditions for the nZVI reaction. The idea is as follows.
Determine the pollution condition: first, make a comprehensive
assessment of the pollution condition, including the type, concentration
and distribution of pollutants; select the suitable nZVI modification method
and commercial nZVI; design the nZVI use program: including the
dosage, dosage concentration, dosage method, dosage location and
depth, etc.; monitoring and evaluation, after dosage, we need to monitor
and evaluate the nZVI treatment effect, which may require regular
collection of soil or groundwater samples for laboratory tests; post-
management, according to the results of monitoring and evaluation, post-
management may be required, such as the collection of soil or
groundwater samples for laboratory tests. Monitoring and evaluation,
after the application of nZVI, it is necessary to monitor and evaluate the
treatment effect of nZVI, which may require regular collection of soil or
groundwater samples for laboratory tests; Post-management, according
to the results of monitoring and evaluation, it may be necessary to carry
out post-management, such as adjusting the amount of NZVI application.
Based on the main conclusions of this study, fully utilizing the
adsorption properties of nZVI's continuously forming shell is one of the
keys to enhance the potential applicability of nZVI. The related
- 43 -
modifications are load modification and sulfide modification. The
former does not destroy the original structure of nZVI, and the latter
forms a sulfide shell with stronger electron selectivity. In the future,
these two modifications may be the key direction for field applications.
44
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51
52
Academic papers published during
the master's degree program
Academic papers published during the master's degree program

[1] Wei Du, Yongxiang Zhang*, Yajun Li Chonghui Zhao et al. A model for the
removal of Cr(VI) in water by nanoscale zero-valent iron: quantify reaction processes
and calculate electron efficiencie[J]. Journal of Nanoparticle Research
[2] ZHANG Yongxiang, DU Wei, LI Yajun, et al. A review on the application
of nano zero-valent iron in water treatment[J].
Chinese Environmental Science, 2022,42(11): 5163-5178.
[3] Li Yajun, Zhang Yongxiang*, Lin Yuhui, Yang Wenjing, Du Wei, Zhao
Chonghui. Efficient removal of Cr(VI) by sulfide nanoscale zero valent iron:
characterization, aging and mechanism. Characterization, aging and mechanism.
Desalination and water treatment.
[4] ZHANG Yongxiang,ZHAO Chonghui,LI Yajun,DU Wei. Dynamics of 2,4-
dichlorophenol removal by nano zero-valent iron/peroxysulfate
Mechanical research. Applied Chemical Engineering.
- 51 -
52
a
than
k-
you
a thank-you note
note
The time between not wanting to go to graduate school and wishing for a PhD
always puts me in a trance. Time seems to be a fine arrow that pierces through a
section of thoughts. As I write this acknowledgement, I can't help but
think about what I gained during graduate school. What made me by such
a shift in thinking. Can I get the life I dreamed of?
Reading, learning and thinking have been my main memories and my
main task since I can remember. From being forced, to actively choosing
with understanding; from being ignorant, to being enlightened; from
questioning myself, to choosing to believe. I believe that graduate school
has realistically given me tremendous gains. But where did the above
doubts and these gains come from?
When I really took a moment to think about the content. I realized
that the bits and pieces along the way came from all of you around me.
Mr. Yongxiang Zhang Zhang, my mentor, the one who made me have
a shift in my thinking. To have a goal to work towards, to choose what I
want to do and to fight for it. This is what Mr. Chang always conveyed
throughout graduate school. Receiving this kind of thinking, I realized
that having something to pursue is a happy thing. Laying flat my heart
seemed to run through my entire adult years, and when I really realized it,
I was really afraid that it would be too late. It's always been said that when
you think it's late it's really not. But I don't know if it's too late now. I'm not
a prophet, so I can only choose to believe that it's not too late. Now is
exactly where Mr. Zhang wanted to convey the essence of his thoughts: to
work hard, to face all stages of life, to do what you choose, to do what you
believe. With the gain in thinking, I really feel that this trip is worthwhile.
What's more, Mr. Zhang guided me in my thesis research and modeled my
behavioral habits. I am really afraid that I can't do enough to thank Mr.
Zhang, and it is difficult to express my gratitude to him with my clumsy
words. I just wish Mr. Zhang a peaceful life, good health, and all the best.
In addition, I would like to thank my brothers and sisters in the group
for their great help in my research and life. I often asked Ms. Li Yajun
about nano zero-valent iron; I worked with Mr. Jia Ruitao on the project
and changed the report; I went to the sewage plant with Mr. Hu Yongfeng
- 53 -
to collect water samples; I made a Teacher's Day video with Ms. Yang
Wenjing, Mr. Ding Wenhua, and Ms. Guo Tong for Mr. Zhang; and I was
inseparable from Zhao Chonghui every day. I am very grateful for the
kindness of my colleagues, and I would also like to thank my girlfriend,
Xiaopang, for doing her best for me and treating me like herself. The
biggest thank you is not for your help, but for your company and
participation. Thank you again.
Finally, I would like to thank NIT for giving me this opportunity.
Enhancing my education is only incidental, walking the road of life and
feeling the bitterness, sweetness, sourness, and yin, yang, and yin are the
real gains at this stage.
So the very first questions, what have I gained, what is my future, how
am I going to gain, etc. are all answered.
Thanks to all of you for clearing up my confusion, thanks thanks thanks
thanks.
54
a
than
k-
you
note
- 55 -
app
endi
ce
appendice
PyQt5 for GUI interface design. xlrd for data reading and rewriting.
matplotlib for plotting.
The main window design idea is to create a QWidget class, add
QPushButton to activate the sub-window, and generate the window design
code as follows:
1. class MainWindow(QWidget).
2. def init (self).
3. super(). init ()
4. self.initUI()
5. def initUI(self).
6. # Set window title and size
7. self.setWindowTitle('Concentration change prediction')
8. self.resize(300, 300)
9. self.N1 = QPushButton('Experiment data change', self)
10. self.N1.setGeometry(100,50,100,50)
11. self.N2 = QPushButton('Parameter change and run', self)
13. self.N1.clicked.connect(self.newone1)
14. self.N2.clicked.connect(self.newone2)
Sub-window design, including the Replace Parameter button and Generate Preview
Chart button, sub-window design code:
1. class NewWindow2(QWidget).
2. def init (self).
3. super(). init ()
4. self.initUIK1()
5. self.initUIK_1()
6. self.initUIK2()
7. self.initUIK_2()
8. self.initUIK3()
9. self.initUIK_3()
10. self.initUIK4()
11. self.initUIK5()
12. self.initUIK6()
13. self.initUIK7()
14. self.initUISHH()
15. self.initUISHCr()
16. self.initUICr6() 55
17. self.initUICr3()
18. self.initUIFe3()
19. self.initUIFe2()
20. self.initUIH()
21. self.initUIdelatT()
22. self.initUIalltime()
23. self.action_data()
24. label2=QLabel(self)
25. label2.setText('Initial run parameters')
26. label2.setStyleSheet('font-size:15px')
27. label2.setGeometry(15,5,100,30)
Button design to change the code of K1 as an example:
1. def initUIK_1(self)::
2. label22=QLabel(self)
3. label22.setText('K_1')
4. label22.setStyleSheet('font-size:15px')
5. label22.setGeometry(15,90,30,30)
6. self.Shuru22=QLineEdit(self)
7. self.Shuru22.setGeometry(40,90,100,30)
8. value22=worksheet.cell_value(1,1)
9. self.Shuru22.setPlaceholderText('Now %s'%value22)
10. self.N22 = QPushButton('Change', self)
12. self.N22.clicked.connect(self.change_k_1)
The time advancement is done using the fourth-order Lungkuta method,

using the computational code for Cr(III) as an example:
1. def cr3_d(k4,k6,k7,h,shcr,C_fe2,C_cr3).
2. a=2*k4*shcr*h+2*k6*shcr*h*C_fe2-k7*C_cr3*C_fe2
3. return a
4. def cr3(k4,k6,k7,h,shcr,delatT,C_fe2,C_cr3).
5. s1=cr3_d(k4,k6,k7,h,shcr,C_fe2,C_cr3)
6. s2=cr3_d(k4,k6,k7,h,shcr,C_fe2,C_cr3+delatT/2*s1)
7. s3=cr3_d(k4,k6,k7,h,shcr,C_fe2,C_cr3+delatT/2*s2)
8. s4=cr3_d(k4,k6,k7,h,shcr,C_fe2,C_cr3+delatT*s3)
9. a=C_cr3+delatT/6*(s1+2*s2+2*s3+s4)
10. return a
The data is stored in excel tables and the data is read from the code:
56
app
endi
1. workbook1=xlrd.open_workbook('original_data.xls')
ce
57
2. worksheet=workbook1.sheet_by_index(0)
3. delatT=eval(worksheet.cell_value(5,0)) #units min
4. all_time=eval(worksheet.cell_value(5,1)) #units min
5. hw=10**-14
6. k1=eval(worksheet.cell_value(1,0));k_1=eval(worksheet.cell_value(1,1))
The final result is shown below
Attachment 1 Programming results display diagram (not simulation results)
58

EN S202064346-Du Wei - Modélisation Et Étude Du Mécanisme D'élimination Du Chrome Hexavalent Par Les Nanoparticules de Fer À Valence Zéro

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Chinese Book Classification Number: X523

op Kan sur Objective: Modeling and Mechanism

Master of Engineering Thesis,

Title Modeling and Mechanism of Hexavalent Chromium

theory Essay :: Du Wei (1982-), Chinese

Note on authorization to use the paper

I am fully aware of the regulations of Beijing Institute of Technology

Signed: Date Period: 2023 May 25 May 2023

Signature of Mentor: Date: 2023 May 25 May 2023

5.2.1 characterization ................................................................................ 31

Preparat Method comple Methodol specificities parti morphol surface literat

Green synthesis methods are mostly used to prepare nZVI by reducing

modification, bimetallic modification, vulcanization modification, and

Load modification is to load nZVI onto the surface of the material in

The appearance of spherical or

The surface of the material

rice husk Approx. Good shape Treatment [29]

100 temperature 256 at

The composites are in the form of

framework temperature 800°C is

Bimetallic modification is a modification that combines nZVI with

(⋅OH, H* ) + organic compound →

The potential role of sulfide nano-zero-valent iron (S-nZVI) in pollutant

H2 S → 2H+ + S2− (10)

Fe2+ + S2− → FeS (11)

Fe0 + 2H 2O → Fe(OH) +2 H (12)

Na 2S + H O → 2Na+ + HS− + OH− (14)

Fe2+ + 2HS− → FeS + H 2S (15)

2FeS + 2H+ → FeS +2 Fe2+ + H (16)

Surface modification is an effective method for the dispersion and

concentrations, the surface coating, on the one hand, reduces contaminant

manifested in the blockage of active sites, reduction of diffusion channels,

1.1.4 A field study of nano zero-valent iron

reactive walls, e.g., Eijamal et al.[38] used bimetallic-modified nZVI as a

2 of the ylene (1.92 surface generated chlorides

200m2 of the test 1m, 2m, 3m Input 50~99%.

Osan, Wonju, The monitoring Most nZVI particles remain in the

mig 2, 4m into the modification strength

abandoned chlorine in the

sodium carboxymethylcellulose pressure injection in the presence of CMC polymer. [50]

As shown in Figure 1-2, the nZVI suspension is injected into the

and restricting the in situ remediation effect[53]

Men+ + me− → Me(n−m)+ / Me0 (17)

Men + -me− → Me(n+m)+ (18)

Men+ + Iron oxides and hydroxides→ Me − Fe − OOH (21)

The most important mechanism of action of nZVI is reductive,

and magnetite [60]. While

Fe0 → Fe2+ + 2e− (22)

Nitrate, phosphate, bromate and other anions in water can also be

by nZVI, while the reduction of nitrate by nZVI reduces nitrate to NH+ .

mechani nitrate phosphat bromate perchlor

1.2 Overview of hexavalent

Figure 1-7 Technology Roadmap

impact on the environmental system. nZVI, as one of the most commonly

sodium borohydride NaBH4 AR Tianjin Dingshengxin Chemical Co.

caustic soda NaOH AR Tianjin Dingshengxin Chemical Co.

hydrochloric acid HCl AR Tianjin Dingshengxin Chemical Co.

common salt NaCl AR Tianjin Fuchen Chemical Reagent

Table 2-2 Main Instruments

Flow type peristaltic pumps BT100-1L Baoding Lange Constant

Benchtop Thermostatic Oscillator DSHZ-300A Nanjing Xinyi Biotechnology