Development of Graphitic Carbon Nitride

based Semiconductor Photocatalysts for

Organic Pollutant Degradation

Jing Wang

Doctoral Thesis 2015

Division of Applied Process Metallurgy

Department of Materials Science and Engineering
School of Industrial Engineering and Management
KTH Royal Institute of Technology
SE-100 44 Stockholm
Sweden

Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan i Stockholm,

Framlägges för offentlig granskning för avläggande av Teknologie Doktorsexamen,
Onsdag den 30 september 2015, kl. 10.00 i Sal F3, Lindstedtsvägen 26,
Kungliga Tekniska Högskolan, Stockholm.

ISBN 978-91-7595-675-6
Jing Wang. Development of Graphitic Carbon Nitride based Semiconductor
Photocatalysts for Organic Pollutant Degradation

Department of Materials Science and Engineering

School of Industrial Engineering and Management
KTH Royal Institute of Technology
SE-100 44 Stockholm
Sweden

ISBN 978-91-7595-675-6

© Jing Wang (王静), August, 2015

To my beloved family
Abstract
As a potential solution to the global energy and environmental pollution, design and synthesis

of artificial photocatalysts with high activities have attracted increasing scientific interests

worldwide. In recent years, the graphitic carbon nitride (g-C3N4) has shown new possible

applications in the photocatalytic field due to its unique properties. However, the

photocatalytic efficiency of the pristine g-C3N4 is greatly limited by the high recombination

rate of the photo-induced electron-hole pairs. In this thesis, the aim is to design and fabricate

efficient g-C3N4 based photocatalysts with enhanced photocatalytic activities under a visible

light irradiation.

In order to achieve this goal, two strategies have been employed in the present thesis. First,

the as-obtained g-C3N4 was used as the host material to construct staggered-aligned composite

photocatalysts by selecting semiconductors with suitable band positions. By this method,

three kinds of g-C3N4-based composite photocatalysts such as g-C3N4/ZnS nanocage,

g-C3N4/m-Ag2Mo2O7 and g-C3N4/MIL-88A were successfully fabricated. Second, the

microstructure of the g-C3N4 was modified by the H2O2-treatment at an elevated temperature

and ambient pressure.

In this study, the g-C3N4 was prepared by a simple pyrolysis of urea. As for all the

as-synthesized phtocatalysts, the structures, morphologies and the optical properties were

carefully characterized by the following techniques: XRD, SEM, TEM, FT-IR and DRS. Also,

the band edge positions of m-Ag2Mo2O7 and MIL-88A were studied by the Mott-Schottky

methods. Thereafter, the photocatalytic activities were evaluated by using a solution of

rhodamine B (RhB) as a target pollutant for the photodegradation experiments performed

under a visible light irradiation. The results showed that all the aforementioned g-C3N4-based

photocatalysts exhibited enhanced photocatalytic activities in comparison with the pristine

g-C3N4. For the case of the g-C3N4-based composite photocatalysts, the enhancement factor

over the pristine g-C3N4 can achieve values ranging from 2.6 to 3.4. As for the H2O2-treated

g-C3N4, the degradation rate constant can be 4.6 times higher than that of the pristine g-C3N4.

To understand the key factors in new materials design, we also devote a lot of efforts to
I
elucidate the basic mechanisms during the photocatalytic degradation of organic pollutant.

Based on the results of the active species trapping (AST) experiments, the main active species

in each photocatalytic system were determined. In the g-C3N4/m-Ag2Mo2O7 and the

g-C3N4/MIL-88A system, three kinds of active species of ·O2-, h+ and ·OH were found to be

involved in the photocatalytic reaction. Among them, the ·O2- and h+ were the main active

species. In the g-C3N4/ZnS and H2O2-treated g-C3N4 photocatalytic systems, the main active

species was determined as the ·O2-. The reaction pathways of these active species were also

demonstrated by comparing the band edge positions with the potentials of the redox couple.

In addition, the relationship between the active species and the photocatalytic behaviors of

N-de-ethylation and conjugated structure cleavage were studied. Finally, possible mechanisms

to explain the enhanced photocatalytic activities were proposed for each photocatalytic

system.

The results in this thesis clearly confirm that the photocatalytic activity of the g-C3N4 based

photocatalyst can efficiently be enhanced by constructions of staggered-aligned composites

and by modification of the microstructure of the g-C3N4. The enhanced photocatalytic

performance can mainly be ascribed to the efficient separation of the photo-induced

electron-hole pairs and the increase of the active sites for the photocatalytic reaction.

Keywords: graphitic carbon nitride, visible light-driven photocatalyst, staggered band

alignment, electron-hole pair separation, band edge position

II
Supplements

The present thesis is based on the following supplements:

I Jing Wang, Peng Guo, Qiangsheng Guo, Pär G. Jönsson and Zhe Zhao, “Fabrication of

novel g-C3N4/nanocage ZnS composites with enhanced photocatalytic activities under

visible light irradiation”, CrystEngComm, 2014, 16, 4485-4492.

II Jing Wang, Peng Guo, Maofeng Dou, Jing Wang, Yajuan Cheng, Pär G. Jönsson and

Zhe Zhao, “Visible light-driven g-C3N4/m-Ag2Mo2O7 composite photocatalysts:

synthesis, enhanced activity and photocatalytic mechanism”, RSC Adv., 2014, 4,

51008-51015.

IV Jing Wang, Yajuan Cheng, Peng Guo, Pär G. Jönsson and Zhe Zhao, “Construction of

heterostructured g-C3N4/MIL-88A with enhanced photocatalytic activity under

visible-light irradiation”, submitted to RSC Adv.

IV Jing Wang, Yajuan Cheng, Peng Guo, Pär G. Jönsson and Zhe Zhao, “Investigation of

the photocatalytic mechanism of the H2O2-treated g-C3N4 derived from urea with

superior visible-light photocatalytic activity”, in manuscript.

V Jing Wang, Pär G. Jönsson and Zhe Zhao, “A study of the photocatalytic N-de-ethylation

and chromophore cleavage of RhB over four different g-C3N4 based phtocatalysts”, in

manuscript.

Contribution Statement

I. literature survey, experimental work, data analysis and a major part of writing

II. literature survey, experimental work, a major part of data analysis and writing

III
III. literature survey, experimental work, data analysis and a major part of writing

IV. literature survey, experimental work, data analysis and a major part of writing

V. literature survey, data analysis and a major part of writing

Parts of this work have been presented at the following conference:

Jing Wang, Yajuan Cheng, Peng Guo, Pär G. Jönsson and Zhe Zhao, “Investigation of the

Photocatalytic Mechanism of the H2O2-treated g-C3N4 with Enhanced Activity under Visible

Light Irradiation”, 12th International Conference on Materials Chemistry (MC12) Conference,

York, UK, July 20-23, 2015.

Other work not included

I. Jing Wang, Chenyuan Li, Patrick Diehle, Qiangsheng Guo, and Zhe Zhao, “Controlled

Scalable Synthesis, Morphology Evolution and Catalytic Property of CeO2 Hierarchical

Structures Fabricated via Facile Precipitation Method”, in manuscript.

IV
Acknowledgements
First of all, I would like to express my sincere gratitude to my supervisor Associate Professor

Zhe Zhao. Thank you for giving me the opportunity to conduct this research work at KTH.

Thank you for your guidance, support and fruitful discussions throughout this research work.

Millions of thanks are given to my supervisor Professor Pär Jönsson. Thank you for your

incredible patience, continuous encouragement and solid support during my study. I really

admire your positive altitude and great passion on your work and life. I learned a lot from

you.

I am very grateful to Professor Sichen Du at KTH for his sincere suggestions for the work and

future life.

Thanks Zoltan at SU-MMK for training me to use FT-IR, DRS and BET, which made my

experiments go smoothly. Thanks to Kjell Jansson, Lars Eriksson and Cheuk-Wai Tai for their

help on SEM, XRD and TEM characterizations. Thanks all the cooperators of this research

work. Dr. Maofeng Dou, thank you for your helpful and pleasant discussions regarding the

theoretical calculations.

All the friends and colleagues at KTH-MSE are greatly acknowledged. Thank you for all your

kind help during my study in Stockholm. I will cherish these memorable days with you

forever. In particular, I would like to thank Yajuan. Every moment we spent together in the

labs and after work witnesses our friendship. I am grateful to Junfu for his help and nice

suggestions for the experiments and research work. Also, I would like to thank all my friends

at Stockholm University. I will always remember the happy time we spent together.

I am grateful to all the people who helped me a lot during my stay in Sweden, especially

when I just arrived in Sweden. Your kindness made me feel warm and made the life in

Sweden much easier. I would like to thank Ms. Wenli Long for her kind help for the daily life.

Special thanks to my master supervisors, Professor Xiaoyan Jing and Professor Jun Wang at

Harbin Engineering University. Thank you for guiding me into the research field of Material

V
Chemistry. With your help, I have the opportunity to further study in Sweden. You are not

only my respectable teachers but also my good friends. Thank you.

Thanks to the China Scholarship Council for the financial support during my PhD study. The

Olle Eriksson Foundation is acknowledged for the financial support to the short-term research

stay in Shanghai and the conference in UK.

Very special gratitude goes to my husband Peng Guo. Thank you for your care, unconditional

love and strong support during all my good and bad times. You gave me the courage to face

up all the challenges in life.

Last but not least, I would like to express my deepest gratitude to my dearest parents. Thank

you for your endless love and constant encouragement all the time. Your love is the source of

my happiness. I would also like to thank my parents-in-law for your love, understandings and

support!

Jing Wang

Stockholm, August 2015

VI
Table of Contents
Chapter 1 Introduction ............................................................................................................ 1

1.1 Background .................................................................................................................. 1

1.2 Motivations and objectives ........................................................................................... 3

Chapter 2 Experimental Work ............................................................................................... 6

2.1 Sample Preparation....................................................................................................... 6

2.2 Characterization............................................................................................................ 8

2.3 Photocatalytic activity measurements .......................................................................... 9

2.4 N-de-ethylation and conjugated structure cleavage of RhB ......................................... 9

Chapter 3 Construction of the g-C3N4 based composites ................................................... 11

3.1 Crystal structure and morphology .............................................................................. 12

3.1.1 The CNZS composites ..................................................................................... 12

3.1.2 CNAMO composites ....................................................................................... 14

3.1.3 CNMIL composites.......................................................................................... 15

3. 2 Band structures .......................................................................................................... 16

3.2.1 Bandgap Energy ............................................................................................... 17

3.2.2 Band edge positions ......................................................................................... 19

3.3 Photocatalytic performance of the composites ........................................................... 21

3.4 Photocatalytic mechanisms ........................................................................................ 23

3.4.1 Separation efficiencies of the electron-hole pairs ............................................ 23

3.4.2 Main active species .......................................................................................... 24

3.4.3 Proposed mechanisms ...................................................................................... 26

Chapter 4 Modification of g-C3N4 by H2O2-treatment ....................................................... 30

4.1 Structure and morphology of H2O2-treated g-C3N4 .................................................... 30

4.2 Band structures of H2O2-treated g-C3N4 ..................................................................... 33

4.3 Photocatalytic performance of H2O2-treated g-C3N4 .................................................. 34

4.4 Photocatalytic mechanism of H2O2-treated g-C3N4 .................................................... 34

Chapter 5 Photocatalytic behaviors of the g-C3N4 based photocatalysts .......................... 37

VII
 5.1 N-de-ethylation and conjugated structure cleavage of RhB ....................................... 37

5.2 Relationship between the active species and photocatalytic routes ........................... 38

Chapter 6 Conclusions ........................................................................................................... 42

Chapter 7 Future Work ......................................................................................................... 46

References ............................................................................................................................... 47

VIII
Abbreviations and Symbols
2-MI 2-methylimidazole

ATS Active species trapping

BQ p-Benzoquinone

CB Conduction band

CNZS g-C3N4/ZnS system

CNAMO g-C3N4/m-Ag2Mo2O7

CNMIL g-C3N4/MIL-88A

DRS Diffuse reflection spectra

FA Fumaric acid

FT-IR Fourier transform infrared spectroscopy

LMCT Ligand to metal charge transfer

MOFs Metal organic frameworks

Na2-EDTA Disodium ethylenediaminetetraacetate

PL Photoluminescence

SEM Scanning electron microscopy

TBA tert-butyl alcohol

TEM Transmission electron microscope

VB Valence band

XRD X-ray diffraction

ZA Zinc acetate dehydrate

e- Electron

ECB Conduction band edge potential

Eg Bandgap energy

EVB Valence band edge potential

ɛ Molar absorption coefficient

g-C3N4 Graphitic carbon nitride

h+ Hole

R Weight ratio

IX
Chapter 1 Introduction

1.1 Background

With the development of modern industry and population growth, the environment pollution

caused by hazardous wastes is becoming a global serious problem. Organic dye represents an

important kind of these organic pollutants. Nowadays, there are more than 10 000 types of

commercially-used dyes and the annual production is over 0.7 billion tons.1 More seriously,

about 1-20% of these dyes are lost during the dyeing process and they are released as textile

effluents.2 The organic pollutants in the wastewater are highly toxic and they can produce

some potential carcinogens, which will be harmful to the humans and animals as well as the

whole ecosystems.3

Among many potential solutions to this problem, the photocatalysis has emerged as a

fascinating technique because it is economic, nontoxic, safe and renewable. In the

photocatalytic process, the sunlight illumination can be utilized as the energy source. As we

all know, the sunlight is abundant, clean and safe. Annually, the sun delivers about 3×1024 J of

energy to the surface of the earth. This is four orders of magnitude larger than the energy

demand for the humans all over the world. Therefore, the question of how to utilize the solar

energy is a hot topic in the energy field. As one of the important topics in this field, the design

and synthesis of artificial photocatalysts with high activities have attracted great scientific

interests worldwide.4-7

To date, the most widely used photocatalyst is TiO2, which is reported in 1972 by

Fujishima and Honda for photoelectrochemical water splitting.8 This is a milestone in the

photocatalyst field. However, the traditional TiO2 catalyst need to be excited under an

ultraviolet irradiation, which only accounts for less than 5% of the whole solar spectrum. This

has stimulated researchers to develop novel materials with a reduced bandgap energy (Eg) to

enhance the response to the more abundant visible light photons. Various modified-TiO2 or

non-TiO2 materials have been fabricated as the visible light-driven photocatalyst.9-12

In recent years, the graphitic carbon nitride (g-C3N4) has become a rising star in the
1
photocatalytic field, which is reported as a metal-free photocatalyst for hydrogen evolution by

Wang et al. in 2009.13 As reported previously, the g-C3N4 is constructed by the building blocks

of tri-s-triazine rings bridged with the trigonal N atoms to the 2D layer structure, as is shown

in Figure 1-1.14

Figure 1-1. The crystal structure of the g-C3N4. The color code used
in chemical structures: C, black; N, red.

In general, the g-C3N4 can be fabricated by a polycondensation or a pyrolysis of various

nitrogen-rich precursors, such as cyanamide,13, 15

dicyandiamide,16 melamine,17 melamine

derivatives,18 thiourea,19 urea20-25 and so on.26 The physicochemical properties of the g-C3N4

can be greatly affected by the type of the precursors and the reaction parameters. For example,

the bandgap of the g-C3N4 derived from different precursors varies from 2.58 to 2.89 eV.27

Very recently, urea, which is a common and low-cost material suitable for large scale

production, is found to be a superior precursor to be used for g-C3N4 synthesis. The g-C3N4

can be obtained from the pyrolysis of urea by using a self-supported NH3 gas. The

microscopic mechanism of the reaction paths of the g-C3N4 using urea as precursor is

illustrated in Figure 1-2.19

As the most stable allotrope among the carbon nitrides materials, the g-C3N4 can remain

stable with respect to the thermal (up to 600°C in air) and chemical attacks due to the

tri-s-triazine ring structure and its high condensation degree. Moreover, the g-C3N4 possesses

medium bandgap and proper band edge positions. All these features show that g-C3N4 is a

promising candidate for visible-light driven photocatalysis. Nevertheless, the photocatalytic

efficiency of the pristine g-C3N4 is greatly limited due to the high recombination rate of
2
photogenerated electron-hole pairs.17, 28 Therefore, the development of g-C3N4 based visible

light-driven photocatalysts with enhanced activities for environmental applications has drawn

increasing research attentions during the recent years.23, 27-43

Figure 1-2. Microscopic mechanism of the reaction paths of polymeric carbon nitride.

1.2 Motivations and objectives

This thesis aims to develop novel g-C3N4 based photocatalysts with enhanced photocatalytic

activities under a visible light irradiation. The photocatalysis generally involves three

processes, including (1) the photon absorption; (2) the transfer, migration and separation of

the photo-induced electron-hole pairs; and (3) the photocatalytic reaction on the surface of the

photocatalyst. Correspondingly, the photocatalytic activities can be enhanced from these

aspects. In this thesis, the g-C3N4 has been modified by two approaches. To understand the

key factors in new materials design, we also devote a lot of efforts to elucidate the basic

mechanisms during the photocatalytic degradation of organic pollutant.

(1) Construction of g-C3N4 based composite photocatalysts

As introduced previously, the pristine g-C3N4 usually exhibits low photocatalytic efficiency

due to its fast recombination rate of the photo-induced charge carriers. In order to improve the

separation efficiency of the electron-hole pairs, an option is to develop composites

photocatalysts with matching band structures. According to the band offsets of the two

semiconductors, the band alignment of the composites can be classified into the following

three types: i) a straddling gap (type-I), ii) a staggered gap (type-II) and iii) a broken gap

(type-III), as is illustrated in Figure 1-3. As for the staggered type gap alignment, the charge

carriers can be efficiently separated due to the band offset, while the electrons are

accumulated at the lower conduction band (CB) and the holes at the higher valence band (VB).
3
The recombination of the electron-hole pairs can be inhibited by this process and thus this

will improve the photocatalytic performances.

Based on this consideration, g-C3N4 based composites with well aligned band structures

can be constructed by selecting semiconductors with suitable band positions. In this thesis, the

composites of g-C3N4/ZnS, g-C3N4/m-Ag2Mo2O7 and g-C3N4/MIL-88A were constructed and

studied.

Figure 1-3. Schematic energy band diagram of semiconductor-based heterojunctions.

(2) Fine tuning of the g-C3N4 structure

By the H2O2-treatment at higher temperature, O2 bubbles can be generated and be used as soft

template to introduce some extra pores, terminal edges and defects in the g-C3N4. By using

this method, the microstructure of g-C3N4 can be adjusted. Thereafter, the separation

efficiency of the electron-hole pairs and the light harvesting capability of g-C3N4 can be

improved. In addition, the surface terminations of the edges can act as the real active sites in

the photocatalysis for a higher photocatalytic activity.

For each photocatalytic system, the g-C3N4 based photocatalysts will be investigated with

respect to the following aspects:

☆ To evaluate the photocatalytic activities towards a photodegradation of RhB in the

aqueous solution under a visible light irradiation;

☆ To determine the main active species during the photocatalytic processes;

☆ To study and propose the photocatalytic mechanisms;

☆ To study the photocatalytic behaviors of N-de-ethylation and conjugated structure

cleavage of RhB in each system;

☆ To study the relationship between the active species and the photocatalytic behavior.

4
This thesis is a summary of 5 supplements as shown in the list of papers in the thesis, and the

outline of this thesis is illustrated in Figure 1-4. There are seven chapters in this thesis.

Chapter 1 gives a brief introduction about the background of this research and presents the

motivations and objectives. Then the details about the experiments, including the samples

synthesis, characterizations and properties evaluations, will be presented in chapter 2. Chapter

3 will discuss the results of three kinds of g-C3N4 based composite photocatalysts, including

g-C3N4/ZnS, g-C3N4/Ag2Mo2O7 and g-C3N4/MIL-88A. In chapter 4, the results of

H2O2-treated g-C3N4 will be discussed. Chapter 5 will present some results of these four

g-C3N4-based photocatalysts from a different perspective: to study the N-de-ethylation and

conjugated structure cleavage behaviors. Based on these results, chapter 6 and chapter 7 will

give the main conclusions of this thesis and some suggestions for future work. Overall, the

result from this research work will provide some guidance to fabricate efficient g-C3N4 based

photocatalysts in the future.

Figure 1-4. Framework of this thesis.

5
Chapter 2 Experimental Work

2.1 Sample Preparation

Synthesis of pure g-C3N4

The polymeric g-C3N4 was prepared by a simple pyrolysis of urea without any assistance of a

template. In a typical synthesis, 20 g of urea powder was put into an alumina crucible and

dried at 80 °C. Then, the urea was heated to 550 °C in a Muffle Furnace at a heating rate of

10 °C min-1. Thereafter, it was kept in the furnace for 3 hrs. After the experiment, the resultant

light yellow product was collected and ground into powder for further use. The yield was

comparably low, about 3% - 5%.

It is worth noting that the property of the pure g-C3N4 can greatly be affected by various

factors, such as the precursor kind, reaction temperature, the heating rate, reaction atmosphere

and so on.15, 17, 19 In our study, it is found that the electronic structure (such as the bandgap,

band position) and the properties of the pure g-C3N4 will vary from different series, even

when using the same synthesis procedure. This is because g-C3N4 is not single crystal but a

family of layered graphitic carbon nitride compounds with a C/N ratio close to 0.75.

Therefore, the property of the g-C3N4 is to some extent flexible. In our study, we always use

the same batch g-C3N4 for the each series of composite system. The g-C3N4 in different

photocatalytic systems are denoted as CN-1, CN-2, CN-3 and CN-4 for g-C3N4/ZnS,

g-C3N4/Ag2Mo2O7, g-C3N4/MIL-88A and H2O2-treated g-C3N4, respectively.

Synthesis of the g-C3N4/ZnS nanocage

As a new class of inorganic-organic hybrid porous material, the metal-organic frameworks

(MOFs) have received an increasing research attention due to their potential applications in

the fields of catalysis, gas storage, drug delivery and so on.44-49 Typically, the MOFs are

composed of metal ions or small metal clusters connected by organic linkers through strong

chemical bonds. By tuning these building units, the MOFs can be rationally and easily

functionalized at a molecular level with diverse structures and topologies. The well-defined

6
morphologies facilitate the MOFs as the self-sacrificing template to synthesize the metal

oxides, metal sulfides and so on. In Supplement I, ZIF-8 was employed as an ideal

self-sacrificing template to synthesize hollow polyhedra ZnS. This is due to its non-toxicity,

thermal and chemical stability, low energy consumption and efficient zinc cations supplier.

The g-C3N4/ZnS nanocage composite was fabricated by a template-assistant method.

First, the g-C3N4/ZIF-8 was synthesized at the ambient conditions. In a typical procedure, the

g-C3N4 powder was dispersed in the methanol solvent and treated in an ultrasonic bath for 2

hrs to obtain a uniform suspension. Subsequently, desired amounts of zinc acetate dehydrate

(ZA) and 2-methylimidazole (2-MI) were added into the suspension and stirred for 5 min.

Then, the suspension was aged at room temperature for 24 hrs. After that, the solid was

collected by centrifugation and washed with methanol and dried at 60°C for 12 hrs. Thereafter,

the as-prepared g-C3N4/ZIF-8 precursor was refluxed in the thioacetamide ethanol solution

with trace water at 85°C for 1 h. Finally, the product was collected by centrifugation, washed

with anhydrous ethanol and dried at 60°C for 12 hrs. According to this method, the

g-C3N4/ZnS composites at different weight ratios of 60:1, 12:1, 6:1 and 1:1 were prepared and

denoted as 60CNZS, 12CNZS, 6CNZS and 1CNZS, respectively.

Synthesis of g-C3N4/m-Ag2Mo2O7 composite

First, a desired amount of the as-prepared g-C3N4 was dispersed into 80 mL water and treated

in an ultrasonic bath for 3 hrs. Then, AgNO3 and MoO3 were added to the suspension with the

molar ratio of 2:1. Subsequently, the suspension was reflux under vigorous stirring for 5 hrs.

Finally, the yellow product was collected by centrifugation, washed with water and anhydrous

ethanol several times, and dried at 60°C for 12 hrs. By changing the amounts of the AgNO3

and MoO3, CNAMO composites at different weight ratios of 50:1, 12:1, 6:1 and 1:1 were

prepared and denoted as 50CNAMO, 12CNAMO, 6CNAMO and 1CNAMO, respectively.

The pure m-Ag2MO2O7 was synthesized under the same conditions without the addition of a

g-C3N4 powder.

Preparation of the g-C3N4/MIL-88A composites

First, a desired amount of FeCl3·6H2O was dissolved in the mixture of 20 mL water and 20

7
mL ethanol. Then, the powder of g-C3N4 was dispersed in the dark orange solution in an

ultrasonic bath for 1h. Subsequently, the fumaric acid (FA) of the equal molar as FeCl3·6H2O

was added into the suspension and magnetically stirred for 30 min. After that, the suspension

was transferred into a 100 mL Teflon-lined stainless steel autoclave and heated to 65 °C for

14 hrs. After cooling to room temperature, the product was washed with water and ethanol

repeatedly and it was dried at 65 °C for 12 hrs. By changing the amounts of the g-C3N4 and

FeCl3·6H2O/FA compounds, the CNMIL composites with different weight ratios of 10:1, 6:1,

5:1, 4:1 and 2:1 were prepared and labelled as 10CNMIL, 6CNMIL, 5CNMIL, 4CNMIL and

2CNMIL, respectively. Without the g-C3N4, the pure MIL-88A was synthesized under the

same condition.

Preparation of the H2O2-treated g-C3N4

In typical, the as-obtained g-C3N4 was dispersed in H2O2 solution (30 wt%) and stirred

magnetically. Subsequently, the suspension was heated on the hot plate to 150 °C and

maintained for 30min in the ambient atmosphere. Thereafter, the suspension was naturally

cooled down to the room temperature. Finally, the product was collected by centrifugation,

washed with water and ethanol for three times and dried at 60 °C for 12 hrs.

2.2 Characterization

The crystalline phases of the samples were examined by means of X-ray Powder Diffraction

(XRD, PANalytical powder X-ray diffractometer with Cu Kα1 radiation, λ=0.15406 nm). The

morphologies and sizes of the products were determined by Scanning Electron Microscopy

(SEM, JSM-7000F). Transmission electron microscopy (TEM) images were recorded on a

JEOL-2100F with an accelerating voltage of 200 kV. Fourier transform infrared (FT-IR)

spectra of the samples were recorded using a Varian 670-IR FT-IR spectrometer with an

attenuated total reflectance (ATR) accessory (a Golden Gate accessory with a diamond-based

ATR element). UV-vis diffuse reflectance spectra of the samples were measured in the range

of 200-800 nm using a Shimadzu UV-3600 apparatus and using BaSO4 as the reference.

Photoluminescence spectroscopy data were recorded on a Varian Cary

8
Eclipse Photoluminescence spectrophotometer. Also, Mott-Schottky curves were measured

using a three-electrode system on the CHI604E electrochemistry workstation. A Pt wire and

an Ag/AgCl electrode were used as the counter and reference electrode, respectively. An

aqueous solution of 0.1 M of Na2SO4 was used as the electrolyte solution.

2.3 Photocatalytic activity measurements

The photocatalytic activities of the composite photocatalysts were evaluated by the

degradation of RhB in an aqueous solution under a visible light irradiation. An aqueous

solution of RhB (5mg·L-1) was placed in a glass beaker. Thereafter, a desired amount of

photocatalyst was added. Also, the suspension was stirred and ultrasonically treated in dark

for 30 min to establish an adsorption-desorption equilibrium. The photocatalytic activities of

the samples were tested under a Xe lamp and using a UV cutoff filter (λ> 400nm or 420nm).

In order to avoid the evaporation of the aqueous solution, the cooling water was recycled

outside of the beaker during the whole photocatalytic process. At the given irradiation time

intervals, 0.5 mL of the mixture was collected and then the slurry sample was centrifuged to

separate the photocatalyst particles. The concentration of RhB was analyzed by measuring the

maximum absorbance at 553 nm using a Shimadzu UV-3600 spectrophotometer.

2.4 N-de-ethylation and conjugated structure cleavage of

RhB

The fully N,N,N’,N’-tetraethylated rhodamine molecule can be N-de-ethylated in a stepwise

manner. The spectral peaks of the de-ethylated intermediates are located at different positions:

RhB, 553 nm; N,N,N’-tri-ethylated rhodamine, 539 nm; N,N’-di-ethylated rhodamine, 522

nm; N-ethylated rhodamine, 510nm; and rhodamine, 498 nm. The molar absorption

coefficients ɛmax of these five compounds are 11.5 × 10-4, 5.5 × 10-4, 7.2 × 10-4, 6.1 × 10-4 and

8.4 × 10-4 M-1 cm-1.50, 51 In chapter 5, the yield of the product ( ) from the photocatalytic

degradation of RhB can be calculated using the following equation

( ) /ɛ( )
( ) = (1)
/ɛ( )

9
where ( ) is the intensity of the absorption peak of the de-ethylated product degraded from

RhB, ɛ( ) is the molar absorption coefficient of the main product as determined by the

absorption maximum, is the initial intensity of RhB, and ɛ( ) is the molar absorption

coefficient of RhB. Also, the cleavage degree ( ) is defined as follows:

=1− ( ) (2)

10
Chapter 3 Construction of the g-C3N4 based
composites
In this chapter, a novel g-C3N4/nanocage ZnS composite is firstly fabricated via an anion

exchange route using ZIF-8 as a self-sacrificing template. The ZnS nanocage is selected to

construct composite photocatalysts with the g-C3N4, by considering two main aspects: (1) The

band position of ZnS matches with that of g-C3N4 to form a staggered band alignment and to

improve the separation efficiency of the photo-induced electron-hole pairs; (2) An intimate

interface between the flat surface of polyhedral nanocage of ZnS and the g-C3N4 layer can be

obtained. It can provide a “highway” for the charge carriers transfer and separation. The main

results of the g-C3N4/ZnS nanocage composites are shown and discussed.

However, the ZnS cannot be excited by the visible light due to its wide bandgap. In the

following part, we select m-Ag2Mo2O7, a visible light active semiconductor, to construct

composite photocatalyst with g-C3N4. By this way, the photocatalytic activity can be expected

to be improved by the synergetic effect from two aspects: (1) an improvement of the light

harvesting capability, (2) an enhancement of the separation efficiency of the electron-hole

pairs. The results are presented and discussed below.

In the first two parts, both ZnS (metal sulfide) and m-Ag2Mo2O7 (composite oxide) are

traditional semiconductor photocatalysts. In order to explore more possibilities to construct

g-C3N4-based composite photocatalysts, the MIL-88A, a kind of MOFs material, is selected to

construct a composite photocatalyst with g-C3N4 to enhance the photocatalytic activity. As for

the MOFs materials, when using the transition metals as the structural nodes and selecting

proper organic linkers, the analogous conduction bands can be formed by mixing the empty d

metal orbitals with the lowest unoccupied molecular orbitals of the organic linker.52 Therefore,

the MOFs can behave as semiconductors and be applied in the photocatalytic field for an

organic pollutant degradation or hydrogen evolution from water splitting. Recently, large

efforts have been devoted to develop new photocatalytic materials based on MOFs.53-56 The

11
MIL-88A exhibits a 3D structure built up on trimers of iron(III) octahedra linked to fumarate

dianions to create a 3D framework.57 The MIL-88A could be a promising visible light

photocatalysts, due to its small bandgap which enables visible light excitation. It is worth

pointing out that this is the first time a visible light-driven composite photocatalyst is

constructed between g-C3N4 and MOF.

In this chapter, the results of these three g-C3N4 based composites photocatalysts with

enhanced photocatalytic activities are presented and discussed. For each photocatalyst, the

crystal structures, morphologies, band structures and the photocatalytic performance for a

RhB degradation are presented. Moreover, the main active species involved in the

photocatalytic process are discussed. Based on the results and analysis, possible

photocatalytic mechanisms are discussed and proposed.

3.1 Crystal structure and morphology

3.1.1 The CNZS composites

As confirmed by the XRD analysis, the pure g-C3N4 and ZnS were obtained. In the case of the

pure g-C3N4, two characteristic peaks at 13.7° and 27.4° in the pure g-C3N4 sample can be

indexed as the (100) and (002) diffractions for graphitic materials. These can be ascribed to

the in-plane structural packing motif and interlayer stacking of aromatic segments,

Figure 3-1. XRD patterns of the pure g-C3N4 (a), 6CNZS composite (b) and ZnS (c).

12
respectively.13 When coupling these two semiconductors, the diffraction peaks of the

composites are similar to the pure g-C3N4 pattern. However, a broad band located between 47°

and 58° appeared in the 6CNZS composite, which can be assigned to the (110) and (118)

diffraction peaks of wurtzite ZnS. This indicates that the CNZS composites were successfully

synthesized.

The lamellar structure of the pure g-C3N4 can clearly be observed in Figure 3-2(a). As

shown in Figure 3-2(b), the hollow structure of the dodecahedral ZnS can be confirmed by

cracked nanocages from the SEM observations. The average size of the nanocages is about

750nm. Moreover, the tight contact between the ZnS and g-C3N4 in the sample of 6CNZS is

observed, which is inherited from the 6CNZIF-8. Such a feature is highly desirable for an

efficient separation of photoinduced electron-hole pairs in composites materials and further

enhances the photocatalytic activities.

Figure 3-2. SEM images of the pure g-C3N4 (a) and the 6CNZS composite (b).

In order to further verify the formation of the g-C3N4/ZnS heterojunction, the FT-IR

technique was employed. The top curve shows the spectrum of pure ZnS nanocages and the

inset in Figure 3-3 depicts the detailed information of the wavenumbers between 1800 and

Table 1 FT-IR bands of g-C3N4 and the corresponding vibration modes

-1
Sample Band (cm ) Functional group Vibration mode
806 triazine and tri-s-triazine Out-of-plane bending
1315 C-N of Full condensed C-N(-C)-C Stretching
g-C3N4
1226 C-N of Partial condensed C-NH-C Stretching
3186 N-H and O-H Stretching

13
 Figure 3-3. FT-IR spectra of pure g-C3N4, pure ZnS and CNZS composites.

600 cm-1 for ZnS. The band at 647 cm-1 is ascribed to the characteristic vibrations of ZnS,

which confirm the formation of the ZnS.58 As for the pure g-C3N4, the detailed informations

about the typical bands location and the corresponding vibration modes are illustrated in

Table 1. When coupling the ZnS with g-C3N4, the main peaks of the g-C3N4 are maintained.

However, it is worth noting that the peaks at 1315 and 1226 cm-1 for the pure g-C3N4

respectively shift to higher wavenumbers of 1322 and 1239 cm-1. These results indicate that

interactions between the Zn2+ and the N atoms in the CN heterocycle rings exist. Furthermore,

they suggest that heterojunctions of g-C3N4/ZnS have successfully been achieved.

3.1.2 CNAMO composites

As shown in Figure 3-4(a), the XRD results indicate that the pure phases of g-C3N4 and

monoclinic Ag2Mo2O7 have been successfully synthesized. In the case of the 6CNAMO

composite, all the diffraction peaks of m-Ag2Mo2O7 are maintained well. Meanwhile, a broad

peak at 27.6 ° belonging to the (002) peak of g-C3N4 is also present. By the SEM observation,

the g-C3N4 shows the characteristic layered morphology while the m-Ag2Mo2O7 displays the

nanowires with an average diameter of about 250 nm. As shown in Figure 3-4(b), the

m-Ag2Mo2O7 nanowires are embedded in the g-C3N4 and form a tightly-connected interface

with g-C3N4. This feature can facilitate the efficient separation of the electron-hole pairs and

14
further improve the photocatalytic performance.

Figure 3-4. The XRD pattern of the pure g-C3N4, m-Ag2Mo2O7 and 6CNAMO (a) and the SEM image of the
6CNAMO (b).

3.1.3 CNMIL composites

As confirmed by the XRD analysis, the characteristic peaks of both g-C3N4 and

MIL-88A are presented in the XRD pattern of the g-C3N4/MIL-88A composite

(5CNMIL). The SEM observation displays the typical layered morphology of the

g-C3N4 in Figure 3-5(a). In this study, the MIL-88A was synthesized using the

water-ethanol solution as the solvent. The MIL-88A possesses hexagonal microrods

morphology with a size of 400 nm in length and 150 nm in diameter (see Figure

3-5(b)). Compared to the previous reports,59 the size of the microrods is reduced and

the size distribution is more uniform. As illustrated in Figure 3-5(c) and (d), the

Figure 3-5. The SEM images of the pure g-C3N4 (a), pure MIL-88A microrods
(b) and the 5CNMIL composite (c, d).

15
MIL-88A microrods are attached to the surface of the g-C3N4 layer or wrapped by the

g-C3N4 sheets to form an intimate interface in the CNMIL composite. This

well-developed interface can allow the photo-induced charge carriers transfer and

separate more efficiently.

In addition, the FT-IR spectra for the g-C3N4, MIL-88A and the CNMIL

composites are recorded in Figure 3-6. The typical bands of g-C3N4 are shown in Table

1. The main bands and the corresponding vibration modes of the MIL-88A are

illustrated in Table 2. In the CNMIL composites, all the characteristic features of the

g-C3N4 and MIL-88A are retained. It is found that the intensity of the peak at 984 cm-1,

belonging to the out-of-plane vibration of the carboxylate group, gradually increases

with the increased MIL-88A content. These results validated the formation of the

g-C3N4/MIL-88A hybrid material.

Figure 3-6. FT-IR spectra of pure g-C3N4, pure MIL-88A and

CNMIL composites.

Table 2 FT-IR bands of MIL-88A and the corresponding vibration modes

-1
Sample Band (cm ) Functional group Vibration mode
984 Out-of-plane vibration
MIL-88A 1388 carboxylate Symmetric vibration
1596 Asymmetric vibration

3. 2 Band structures

The photocatalytic performance greatly depends on the band structure of the semiconductor

16
catalysts. On the one hand, the wavelength of the photons that can be absorbed by the

photocatalyst is dependent on the value of the bandgap energy (Eg). On the other hand, the

band edge positions of the VB and CB is another critical factor that affects the photocatalytic

performance. The band edge positions indicate the thermodynamic limitations for the

photoreactions. This parameter can determine the redox capability of the photo-induced e- and

h+. When the position of the CB is more negative than the potential of the redox couple, the

corresponding reduction reaction can occur. Similarly, when the position of the VB is more

positive than the potential of the redox couple, an oxidation reaction will occur.

3.2.1 Bandgap Energy

In order to determine the bandgap energy (Eg) of the photocatalysts, the technique of UV-vis

diffuse reflectance spectrum (DRS) was employed. The results of the ZnS, CN-1 and CNZS

composites are displayed in Figure 3-7. The pure ZnS holds an absorption edge of ca. 340 nm,

which can be ascribed to a wide bandgap with an Eg value of ~ 3.6 eV. As for the g-C3N4 and

CNZS composites, all the samples exhibit strong visible light absorptions with an edge at

around 460 nm. The results imply that the CNZS composites can be utilized as visible

light-driven photocatalysts.

The bandgap energy of semiconductor can be calculated from the formula:

(αhν)n=k(hν-Eg) (3)

where hν is the photon energy, α is the absorption coefficient and k is a constant relative to the

material. Moreover, n is a value that depends on the nature of the transition, which is either 2

for a direct transition or 1/2 for an indirect transition. By this method, the direct bandgap of

2
Figure 3-7. UV-vis diffuse reflectance spectra of pure g-C3N4, ZnS and CNZS samples (a), plot of (αhv)
1/2
versus the photon energy of ZnS (b), and (αhv) versus the photon energy of g-C3N4 and CNZS samples.

17
the ZnS can be estimated to be 3.64 eV. Furthermore, the indirect bandgap of the g-C3N4 can

be determined to be 2.72 eV.60, 61 After combining these two semiconductors, the values of the

bandgap of CNZS composite photocatalysts remain at around 2.72 eV.

Similarly, the electronic band structures of the CN-2, m-Ag2Mo2O7 and the CNAMO

composites are studied in detail. As shown in Figure 3-8, the absorption edges for the g-C3N4

and m-Ag2Mo2O7 are respectively estimated to be 443 nm and 431 nm. As for the CNAMO

composites, they exhibit absorption edges between 443 nm and 431 nm. Moreover, the

indirect bandgap energy of the semiconductors can be evaluated from the plot of (αhν)1/2

versus the photon energy hν by extrapolating the straight line to the axis intercept. Following

this method, the estimated Eg of the samples are about 2.66 and 2.71 eV for CN-2 and

m-Ag2Mo2O7. Correspondingly, the bandgaps of the CNAMO composites range between 2.71

and 2.66 eV. This result indicates that both g-C3N4 and m-Ag2Mo2O7 can be activated by

using a visible light.

Figure 3-8. UV-vis diffuse reflectance spectra of pure g-C3N4, m-Ag2Mo2O7 and CNAMO composite
1/2
photocatalysts (a), plots of (αhv) versus the photon energy of g-C3N4, m-Ag2Mo2O7 and CNAMO
samples (b).

18
 The MIL-88A is a novel material as a photocatalyst. In order to investigate its

semiconductor-based property, the DRS and Mott-Schottky techniques are employed. As

shown in Figure 3-9, the MIL-88A shows several distinct absorption peaks in the visible light

region with the absorption edge at around 620nm. The visible light response can be ascribed

to the ligand-to-metal charge transfer (LMCT) between the O atoms of the coordinating

ligand and the empty orbital of Fe3+ ions. The value of Eg for MIL-88A can be estimated to be

~2.0 eV by using the equation of Eg = 1240/λ. In comparison with the pure CN-3, the CNMIL

composites show more intensive absorptions within the visible light range. This result clearly

indicates that the CNMIL composites can be used as photocatalysts under a visible-light

Figure 3-9 UV-vis diffuse reflectance spectrum of pure MIL-88A.

irradiation.

3.2.2 Band edge positions

The band positions of VB and CB for the m-Ag2Mo2O7 can be estimated according to the

electronegativity by using the equations as follows:

=X− + 1⁄2 (4)

= − (5)

where ECB is the CB edge potential and X is the electronegativity of the semiconductor. X is

defined as the geometric mean of the absolute electronegativity of the constituent atoms. Ee is

the energy of the free electrons on the hydrogen scale, approximately 4.5 eV. Eg is the
19
bandgap of the semiconductor. The X value for m-Ag2Mo2O7 can be calculated as 6.08 eV.

Based on equation (4) and (5), the top of the VB and the bottom of the CB for m-Ag2Mo2O7

are 2.94 V and 0.23 V, respectively.

Further, the results of the band edge positions are confirmed by the Mott-Schottky

technique. Figure 3-10(a) shows the MS plots of the pure m-Ag2Mo2O7 measured under

various frequencies in dark. The positive slopes of the linear MS plots indicate that

m-Ag2Mo2O7 is an n-type semiconductor. The ECB can be determined as the x-intercept in the

MS plot, which is -0.01 V versus Ag/AgCl electrode and 0.19V versus SHE. Combined with

the Eg value of m-Ag2Mo2O7 (2.71 eV), the VB can be calculated to be 2.9 V versus SHE

from equation (5). The values of the band edge positions determined by these two methods

are consistent with each other. Moreover, the CB and VB positions of g-C3N4 are estimated as

-1.25 V and 1.41V versus SHE by using the same method.

Figure 3-10. Mott-Schottky plots of the m-Ag2Mo2O7 (a) and the pure g-C3N4 (b).

Figure 3-11 shows the typical Mott-Schottky plots of MIL-88A recorded at

different frequencies in dark. The positive slope of the linear plots indicates that the

MIL-88A is an n-type semiconductor. The CB position of the MIL-88A is

approximately derived to be -0.34 V versus Ag/AgCl electrode. Combined with the Eg

value of 2.0 eV, the VB position of the MIL-88A can be calculated to be 1.66 V versus

Ag/AgCl.

20
 Figure 3-11. The Mott-Schottky plots of pure MIL-88A.

3.3 Photocatalytic performance of the composites

The photocatalytic activities of the pure CN-1, pure ZnS and the CNZS composites with

different weight ratios were evaluated by the photodegradation of RhB in solution under a

visible light irradiation (λ>400 nm). As shown in Figure 3-12(a), the degradation of RhB over

the pure ZnS can be ignored. This is due to its wide bandgap and the inertness under the

visible light irradiation. The pure g-C3N4 can degrade RhB by 75% within 90 min. In order to

elucidate the effect of the weight ratio (R) of g-C3N4 to ZnS on the photocatalytic activity of

CNZS photocatalysts, a set of parallel experiments were conducted by using CNZS

composites with different R values. All the CNZS composite samples performed enhanced

photocatalytic activities compared to the pristine g-C3N4 and the pure ZnS. When the R value

is decreased from 60:1 to 6:1, the corresponding photocatalytic performance is improved

gradually. However, while further increasing the ZnS amount to the weight ratio of 1:1, the

Figure 3-12. Photocatalytic degradation of RhB over the pure g-C3N4, ZnS and CNZS composites under a visible
light irradiation (a), first-order kinetics plots (b) and their corresponding rate constant k (c).

21
photocatalytic activity is decreased. As illustrated in Figure 3-12(b), the degradation process

can be fitted to pseudo-first-order kinetics by the equation of –ln(C/C0) = kt. Herein, k is the

rate constant (min-1), C0 is the initial concentration of RhB, and C is the actual concentration

of RhB at time t. The values of the rate constant k are shown in Figure 3-12(c). Among all

these photocatalysts, the 6CNZS sample exhibits the highest activity, showing that 94% was

degraded within 90 min with a rate of 0.034 min-1.

The photocatalytic activities of the CNAMO composites are evaluated by the RhB

degradation under visible light irradiation (λ>420nm). As shown in Figure 3-13, all the

CNAMO composites exhibit higher activities as compared with the pure CN-2 and the

m-Ag2Mo2O7. When the weight ratio of g-C3N4 to m-Ag2Mo2O7 is 6:1, the 6CNAMO is the

optimal photocatalyst with a degradation efficiency of 89% after 90 min. The

pseudo-first-order rate constant k of 6CNAMO can be estimated to be 0.021 min-1, which is

3.4 times higher than that of the pure CN-2. The rate constants of the other photocatalysts are

depicted in Figure 3-13(b).

Figure 3-13. Photocatalytic degradation of RhB over the pure g-C3N4, m-Ag2Mo2O7 and CNAMO composites
under a visible light irradiation (a) and their corresponding rate constant k (b).

To evidence the photocatalytic efficiency of the CNMIL composites, a series of

experiments of the photocatalytic degradation of RhB are performed as a test reaction. As

depicted in Figure 13-14(a), the photocatalytic activity of the MIL-88A is negligible due to its

high recombination rate of the photo-induced electron-hole pairs. In the case of the pure CN-3,

around 59% of RhB is degraded within 90min. As combining these two semiconductors, all

22
the CNMIL composites perform better photocatalytic activities. When the weight ratio of

g-C3N4 to MIL-88A varies from 6:1 to 4:1, about 90% of RhB can be decomposed within 90

min under the visible light illumination. Thereafter, the pseudo-first-order rate constants for

these samples are calculated and illustrated in Figure 3-14(b). Higher degradation rates with

the constants of 0.0223, 0.0242 and 0.0247 min-1 are obtained for the 6CNMIL, 5CNMIL and

4CNMIL, respectively. Take 5CNMIL as a reference, the photocatalytic degradation rate of

5CNMIL is 2.6 times higher than that of the pure CN-3.

Figure 3-14. Photocatalytic degradation of RhB over the pure g-C3N4, MIL-88A and CNMIL composites
under a visible light irradiation (a) and their corresponding rate constant k (b).

3.4 Photocatalytic mechanisms

3.4.1 Separation efficiencies of the electron-hole pairs

In the semiconductor photocatalysts, the signals of photoluminescence (PL) spectra arise

from the recombination of the photo-induced electron-hole pairs. Therefore, the PL technique

can be usefully applied to investigate the migration, transfer and separation of the

photo-induced charge carriers.62, 63

As shown in the Figure 3-15, the emission peaks of pure g-C3N4 and 6CNZS appear at

about 456 nm, which can be assigned to the electron-hole pairs recombination of band

transition (ca. 2.7 eV). Compared to the pure g-C3N4, the 6CNZS possess a much weaker

emission peak. In order to exclude the possibility that the PL intensity decreased when the

g-C3N4 was diluted with ZnS in the composite, the intensity was normalized to the mass of
23
g-C3N4. Therefore, the fluorescence quenching implies that the ZnS modification to the

g-C3N4 can efficiently inhibit the recombination of the photogenerated electron-hole pairs.

In the cases of CNAMO and CNMIL, the intensities of the band-band emission PL peaks

of 6CNAMO (Supplement II) and 5CNMIL (Supplement III) are both remarkably reduced

compared to that of the pure g-C3N4. These results indicate that the modification of

m-Ag2Mo2O7 or MIL-88A to g-C3N4 improves the separation efficiency of the photo-induced

electron-hole pairs. In this way, the photocatalytic activity can be enhanced efficiently.

Figure 3-15. Photoluminescence spectra of the g-C3N4 and 6CNZS.

3.4.2 Main active species

The reactive species involved in the photocatalytic process are detected using the active

species trapping (AST) experiments. In our study, tert-butyl alcohol (TBA), disodium

ethylenediaminetetraacetate (Na2-EDTA) and p-benzoquinone (BQ) were employed as

scavengers for hydroxyl radicals (·OH), photogenerated holes (h+) and superoxide radicals

(·O2-), respectively.

As shown in Figure 3-16, when the hole-scavenger or the hydroxyl radical-scavenger is

added into the photocatalytic system, the photocatalytic activity is enhanced. This result

reveals that neither h+ nor ·OH is the main active species for the photocatalytic degradation

over the CNZS photocatalyst. In contrast, the introduction of a scavenger for ·O2- resulted in a

24
remarkable deactivation of the 6CNZS composite photocatalyst. This result clearly implies

that superoxide radicals ·O2- mainly contribute to the photocatalytic reaction.

Figure 3-16. Photocatalytic degradation of RhB over 6CNZS

composite with and without the addition of BQ, Na2-EDTA and TBA.

In comparison with the 6CNZS, different reactive species are detected in the CNAMO

and CNMIL systems. As shown in Figure 3-17, the results of the AST experiments

demonstrate that the active radicals of ·OH, h+ and ·O2- are involved in the photocatalytic

processes for both 6CNAMO and 5CNMIL. Among them, it is found that the h+ and ·O2- are

the main active species.

Figure 3-17. The photocatalytic degradation of RhB over composite photocatalysts of 6CNAMO (a) and
5CNMIL (b) with and without the addition of BQ, Na2-EDTA and TBA.

25
3.4.3 Proposed mechanisms

Based on the results and the analysis above, the photocatalytic mechanisms to explain the

enhanced activities for each composite photocatalyst is proposed and illustrated. In the CNZS

system as shown in Figure 3-18, the g-C3N4 can be excited and generate the electron-hole

pairs under the visible light irradiation, while the ZnS is inert owing to its wide bandgap.

Thereafter, the electrons in the CB of g-C3N4 can be transferred to the CB of ZnS through the

well-developed interface due to their potential difference. In this way, the separation

efficiency of the electron-hole pairs is improved. Further, the electrons can migrate to the

surface of the photocatalyst and combine with the absorbed O2 molecules to form the ·O2-

radicals. The active superoxide radicals have a high oxidation activity, which can

subsequently degrade the RhB.

Figure 3-18. Proposed mechanism for the photodegradation of RhB on CNZS composite.

26
 In case of the CNAMO system, a staggered band alignment between the g-C3N4 and

m-Ag2Mo2O7 can be formed. Such a band configuration can facilitate the efficient separation

of the photo-induced charge carriers and further enhance the photocatalytic activity. A

plausible photocatalytic mechanism is proposed and it is illustrated in Figure 3-19. Under the

visible light irradiation, the g-C3N4 and m-Ag2Mo2O7 can simultaneously be excited and

generate the electron-hole pairs. Due to the potential difference and the staggered band

alignment, a part of the e- in the CB of g-C3N4 can be transferred to the CB of the

m-Ag2Mo2O7. Meanwhile, the h+ in the VB of m-Ag2Mo2O7 can be transferred to the VB of

g-C3N4. Through this cycle, the separation efficiency of the electron-hole pairs can be

Figure 3-19. A schematic diagram of the band structures, electron-hole transport and
separation in the g-C3N4/m-Ag2Mo2O7 composite under a visible light irradiation.

promoted.

By comparing the band positions with the potentials of the redox couple, the generation

routes of the active species can be determined as the following equations (6)-(9). The

photo-induced e- in the CB of the g-C3N4 (eCN-, -1.25V) with a strong reduction capability can

react with the absorbed O2 molecules to form the superoxide radical (O2/·O2-, -0.16V).64 The

as-obtained ·O2- plays a critical role in the photocatalytic degradation of the RhB. Meanwhile,

the hAMO+ (2.9 V) can directly oxidize RhB (0.95 V)65, 66due to the strong oxidation ability of

hAMO+. Moreover, owing to the VB position of m-Ag2Mo2O7 (hAMO+, 2.9V) is more positive

than the redox potential of ·OH /OH- (1.99V),67, 68 the hAMO+ can react with OH- to generate

the hydroxyl radical (·OH).

27
 C N h +e (6)

Ag Mo O h +e (7)

O +e →∙ O (8)

OH + h →∙ OH (9)

Based on the results and analysis, the photocatalytic mechanism of the CNMIL

system is proposed, which is similar as the CNAMO system. As shown in Figure 3-20,

under the visible light illumination, both g-C3N4 (Eg = 2.66 eV) and MIL-88A (Eg =

2.0 eV) can be excited and generate the electron-hole pairs. The potential difference

between the g-C3N4 and MIL-88A allows an e- transfer from the CB of g-C3N4 to that

of MIL-88A. Simultaneously, the h+ in the VB of MIL-88A can migrate to that of the

g-C3N4. By this cycle, the photo-induced electron-hole pairs can be separated

efficiently and improve the photocatalytic activity.

Figure 3-20. Diagrams of the band positions and the photogenerated

electron-hole pair transfer between the g-C3N4 and MIL-88A.

As shown in the equations (10)-(14), the photo-excited eCN- in the CB of g-C3N4

with strong reduction ability (-1.25 V) can react with the adsorbed O2 molecules to

form the main active species of ·O2- radicals. Meanwhile, the hMIL+ can directly oxidize

the RhB owing to its strong oxidation ability (1.86 V). From the AST results, it is

found that the ·OH also play a role in degrading the RhB. However, the ·OH in this

28
CNMIL system is produced in a different way from the g-C3N4/Ag2Mo2O7 composite

system. Due to the weak oxidation ability of the holes in the VB of g-C3N4 (hCN+, 1.4V)

and MIL-88A (hMIL+, 1.86V), the ·OH is produced as a consequence of the reduction of

oxygen rather than due to the oxidation of the OH-(·OH/OH-, 1.99V), as illustrated in

equations (12) - (14).

C N h +e (10)

MIL − 88A h +e (11)

O +e →∙ O (12)

2H + O + 2e →H O (13)

H O +∙ O →∙ OH + OH + O (14)

29
Chapter 4 Modification of g-C3N4 by
H2O2-treatment
In the last chapter, three kinds of g-C3N4 based composite photocatalysts with the staggered

band alignments are constructed successfully. In comparison with the pure g-C3N4, the

photocatalytic activities of these composite photocatalysts are enhanced toward the RhB

degradation. Besides of this method, it is proposed that the photocatalytic performance can be

modified by tuning the microstructure of the g-C3N4. In this chapter, the g-C3N4 is heated in

the H2O2 solution at the ambient pressure. This method is facile and can easily be scaled up.

4.1 Structure and morphology of H2O2-treated g-C3N4

The characteristic lamellar morphology of the g-C3N4 is displayed in the SEM images in

Figure 4-1. As shown in Figure 4-1 (a) and (b), the surface of the pristine g-C3N4 is smooth.

After the H2O2-treatment, the surface of the H2O2-treated g-C3N4 presents porous-like

morphology. At the elevated temperature, the H2O2 can be decomposed to H2O and O2. The

O2 bubbles can be used as the soft template to partially “damage” the surface of the g-C3N4

and generate pores on it. These pores can introduce more edges in the H2O2-treated g-C3N4,

which provide more active sites for the photocatalytic reactions.

30
 Figure 4-1. The SEM images of the pristine g-C3N4 with low magnification (a) and high
magnification (b) and the images of the H2O2-treated g-C3N4 with low magnification (c) and
high magnification.

In addition, the crystal structure of the H2O2-treated g-C3N4 is also investigated by the

XRD analysis. Contrary to the pure g-C3N4, the peak of the (100) at 13.7° is absent in the

XRD pattern of the H2O2-treated g-C3N4. It is indicated that the in-plane structural packing

motif of the H2O2-treated g-C3N4 becomes disordered to some extent. In addition, the

broadening and the decreased intensity of the (002) peak for the H2O2-treated g-C3N4 suggest

the crystallinity of the H2O2-treated g-C3N4 is reduced compared to that of the pristine g-C3N4.

This result is further confirmed by the XPS analysis (Supplement IV). The relative intensity

of the N1s peak at 399.7 eV decreased compared to that of the pristine g-C3N4. Since this

peak is ascribed to the N-(C)3 group used to bridge the structural motif of C6N7, the result

indicates that part of the trigonally bridging N atoms sites were broken and formed some

structural defects by the H2O2-treatment.

31
 Figure 4-2. The XRD patterns of the pristine g-C3N4 and the H2O2-treated g-C3N4.

As shown in Figure 4-3, the pure g-C3N4 and the H2O2-treated g-C3N4 exhibit identical

FT-IR spectra. The characteristic bands and their vibration modes are illustrated in Table 1. In

previous report, the oxygen-doped g-C3N4 can be obtained in a H2O2 solution via

hydrothermal method. The C-O and N-C-O species were detected in the FT-IR spectrum of

the O-doped g-C3N4.69 However, the O-containing functional groups are not detected in the

H2O2-treated g-C3N4 sample in our experiments. Compared to the reaction environment of a

high temperature and a high pressure in the hydrothermal condition, we conducted our

experiment at an elevated temperature but at the ambient pressure. The oxygen cannot enter

the crystal structure of the g-C3N4 in such an open system.

Figure 4-3. FT-IR spectra of the pristine g-C3N4 and H2O2-treated

g-C N .

32
4.2 Band structures of H2O2-treated g-C3N4

The band structure of the H2O2-treated g-C3N4 is characterized by the DRS and MS

techniques. Compared to the pure g-C3N4, the light response region of the H2O2-treated

g-C3N4 extends to longer wavelength of 525 nm. This probably can be ascribed to the extra

defects in the H2O2-treated g-C3N4. Similar phenomenon was observed in the previous

report.17 By calculation, the values of Eg are 2.66 eV and 2.61 eV for the pristine g-C3N4 and

H2O2-treated g-C3N4, respectively. The narrower bandgap of the H2O2-treated g-C3N4 can

improve the capability of the light absorption and thus enhance the photocatalytic

performance. From the positive slope of the MS plots, it is revealed the H2O2-treated g-C3N4

remains as the n-type semiconductor. The CB position of the H2O2-treated g-C3N4 can be

determined as -1.4 V versus an Ag/AgCl electrode. Combined with the bandgap value of 2.61

eV, the VB position of the H2O2-treated g-C3N4 can be calculated as 1.21V versus an

Ag/AgCl electrode. Compared with the pristine g-C3N4, the CB position of the H2O2-treated

g-C3N4 moved to a lower position while the VB position remained the same.

Figure 4-4. UV-vis diffuse reflectance spectra of the pristine- and H2O2-treated g-C3N4 (a) and the
Mott-Schottky plots of the H2O2-treated g-C3N4 (b).

33
4.3 Photocatalytic performance of H2O2-treated g-C3N4

The photocatalytic performance of the catalysts was evaluated by the RhB degradation

under a visible light irradiation (λ>420nm). As shown in the Figure 4-5(a), approximately 97%

of RhB is degraded within 90min in the presence of the H2O2-treated g-C3N4, while ca. 52%

of RhB is decomposed in the presence of the pure CN-4. Moreover, the degradation rate

constant k for the H2O2-treated g-C3N4 is 0.0365 min-1, which is 4.6 times higher than that of

the pristine CN-4 (0.0079 min-1). It is revealed that the photocatalytic activity of the g-C3N4 is

significantly enhanced by the H2O2-treatment.

Figure 4-5. Photocatalytic degradation of RhB over the pristine- and H2O2-treated g-C3N4 under visible light
irradiation (a), first-order kinetics plots for the photodegradation of RhB by pure- and H2O2-treated g-C3N4 (b).

4.4 Photocatalytic mechanism of H2O2-treated g-C3N4

As illustrated in Figure 4-6, the PL spectra of the pure g-C3N4 and H2O2-treated g-C3N4

reveal the transfer and the separation of the photo-excited electron-hole pairs. Under the same

condition, the weaker band-band PL peak of H2O2-treated g-C3N4 indicates that the separation

of the electron-hole pairs in the H2O2-treated g-C3N4 is more efficiently than that in the

pristine g-C3N4. This can be ascribed to some defect states introduced by the H2O2-treatment,

because that the defect can used as the trapping center of the photo-induced charge carrier and

inhibit the recombination of the electron-hole pairs.

34
 Figure 4-6. Photoluminescence spectra of pristine and H2O2-treated g-C3N4.

As shown in Figure 4-7, the AST results confirmed that the ·O2- is the main active

species involved in the photocatalytic process over the H2O2-treated g-C3N4. In the case of

pristine g-C3N4, besides the main active species of ·O2-, the ·OH also play role in degrading

the RhB. The difference can be explained by the following reasons. Under the visible light

irradiation, the pristine g-C3N4 or H2O2-treated g-C3N4 can be excited and generate the

electron-hole pairs. Both the electrons in the CB of g-C3N4 (-1.25V versus SHE) and the

electrons in the CB of the H2O2-treated g-C3N4 can strongly reduce the adsorbed O2 molecules

to form the main active ·O2- radicals. In the case of the g-C3N4, the ·OH is produced as a

consequence of the reduction of oxygen, as is shown in equations (16)-(18). As for the

H2O2-treated g-C3N4, more edges can act as the active sites for the following photocatalytic

reaction. Therefore, more obtained ·O2- radicals can directly degrade the RhB rather than

produce ·OH.

Figure 4-7. Photogenerated carrier trapping in the system of photodegradation of RhB by pure
g-C3N4 (a) and H2O2-treated g-C3N4 (b).

35
 C N h +e (15)

O +e →∙ O (16)

2H + O + 2e →H O (17)

H O +∙ O →∙ OH + OH + O (18)

H O −C N h +e (19)

O +e →∙ O (20)

In conclusion, the H2O2-treated g-C3N4 with an enhanced photocatalytic activity for

degradation of RhB was successfully fabricated. The degradation rate constant of the

H2O2-treated g-C3N4 is 0.0365 min-1, which is 4.6 times higher than that of the pristine g-C3N4

0.0079 min-1. In addition, the main reactive radical involved in the photocatalytic process is

determined as ·O2- based on the AST experiments. The enhanced photocatalytic activity of the

H2O2-treated g-C3N4 can be ascribed to the following reasons:

(1) The H2O2 treatment introduces more pores and edges in the g-C3N4, which can act as the

active sites for the photocatalytic reactions;

(2) The bandgap was narrowed in H2O2-treated g-C3N4 and thus it will improve the capability

of the light absorption;

(3) The defect can probably act as the trapping center for the photo-induced charge carrier

and inhibit the recombination of the electron-hole pairs.

36
Chapter 5 Photocatalytic behaviors of the
g-C3N4 based photocatalysts
In the above mentioned results, the photocatalytic activities are evaluated by the degradation

of the characteristic absorption peak of RhB at 553 nm. In order to give more insight into the

photocatalytic processes over these four g-C3N4 based photocatalysts, the temporal evolution

of the spectral changes during the degradation of RhB are studied in detail. As reported by

Watanabe and co-workers, the gradual hypsochromic shift of the absorption maximum is

attributed to the N-de-ethylation of RhB.51, 70 Different N-de-ethylated intermediates possess

absorption peaks at different positions with different molar absorption coefficients ɛmax. The

data are present in Chapter 2. As for the chromophore cleavage, it can be determined by the

peak intensity decrease. In this chapter, the behaviors of N-de-ethylation and chromophore

cleavage of RhB for the four g-C3N4 based photocatalysts are studied based on a temporal

UV-visible absorption spectra.

5.1 N-de-ethylation and conjugated structure cleavage of

RhB

On one hand, the intensities of the absorption peaks gradually decreased with an increased

irradiation time in these four photocatalytic systems. These results indicate the degradation of

the RhB molecules, especially the cleavages of the conjugated structure of the molecules. On

the other hand, the blue shifts of the spectral peaks were also observed, which is indicative of

the de-ethylation of the fully N,N,N’,N’-tetraethylated rhodamine molecule in a stepwise

manner.

As shown in Figure 5-1 (a) and (b), the absorption peaks of RhB in the photocatalytic

systems of 6CNAMO and 5CNMIL shift from 553 nm to about 526 nm by the photocatalytic

degradation within 90min. It is indicated that the N,N’-di-ethylated rhodamine become the

major constituent in these two systems. The cleavage degrees of RhB were estimated to be 44%

37
and 68% in the presence of 6CNAMO and 5CNMIL, respectively. In contrast, as illustrated in

Figure 5-1 (c) and (d), the hypochromic shift in the presence of 6CNZS or H2O2-treated

g-C3N4 become more pronounced. The saturated shift from 553 nm to about 498 nm indicates

the complete de-ethylation of RhB to rhodamine (Rh). The yields of Rh from RhB were

estimated to be around 66% and 74% for 6CNZS and H2O2-treated g-C3N4, respectively.

Correspondingly, the cleavage degrees are calculated to be 34% and 26%.

Figure 5-1. Temporal UV-visible absorption spectral changes for the RhB solution for the 6CNAMO (a),
5CNMIL (b), 6CNZS (c) and H2O2-treated g-C3N4 (d) under visible light irradiation. Data are given for
experimental times ranging from 0 min to 90 min.

5.2 Relationship between the active species and

photocatalytic routes

As discussed in Chapter 3 and 4, all these three active species, ·O2-, h+ and ·OH, were

involved in the photocatalytic reactions in the of CNAMO and CNMIL systems. On the

contrary, the main active species in the 6CNZS and H2O2-treated g-C3N4 are superoxide
38
radical ·O2-. It is found that the photocatalytic systems with the same active species exhibit

similar photocatalytic behaviors. For this reason, the relationships between the active species

and photocatalytic degradation processes are discussed.

When the ·O2- acts as the main active species in photocatalytic reactions, the

N-de-ethylation is the dominant procedure at the initial stage of the photocatalytic

degradation of RhB. In order to further validate the role of ·O2-, the irradiation time was

further prolonged to 120 min in the H2O2-treated g-C3N4 system. As shown in Figure 5-2,

after 60 min, the absorption peak shifted to 498 nm and remained steady at this position.

Meanwhile, the intensities of peaks gradually decreased. It can be concluded that both

de-ethylation and chromophore structure cleavage can occur in the presence of ·O2-.

Compared to the cleavage of the conjugated structure, the N-de-ethylation for RhB has the

priority in the presence of ·O2-. In the case of 5CNMIL, when h+ and ·OH also participate the

photocatalytic process, the conjugated structure cleavage becomes more efficient, as shown in

Figure 5-2. Even when the irradiation time was prolonged to 120 min, the absorption peaks

shift to 503 nm. It indicates that only partial N-de-ethylation of RhB was obtained.

Figure 5-2. Temporal UV-visible absorption spectral changes for the RhB solution for the (a) H2O2-treated
g-C3N4 and (b) 5CNMIL under a visible light irradiation. Data are given for experimental times ranging from 0
min to 120 min.

Furthermore, the temporal UV-visible absorption spectral changes during the RhB

degradation with the addition of scavengers for the photo-induced charge carriers are studied,

as shown in Figure 5-3. In the case of H2O2-treated g-C3N4 system, when the scavenger for h+

was added, the separation efficiency of the e--h+ pairs can be enhanced and more active ·O2-

can be generated. The saturated shift of the absorption peak was obtained in shorter time of 45

39
min. Within 90 min, the high cleavage degree of RhB was achieved as 92%. It confirms

that ·O2- plays important roles in the N-de-ethylation and the chromophore structure cleavage.

As for the 5CNMIL, when the scavenger for ·O2- was added, the generation of both ·O2-

and ·OH were inhibited greatly, Therefore, h+ will act as the main active species to degrade

the RhB. The absorption peaks are kept at 553nm while their intensities gradually decrease.

Thus, it can be concluded that the photo-excited h+ can split the chromophore structure, but

not de-ethylate the RhB.

Figure 5-3. Temporal UV-visible absorption spectral changes for the RhB solution for (a) H2O2-treated g-C3N4
+ -
with the addition of active species scavenger for h and (b) 5CNMIL with the addition of scavenger for ·O2 .
Data are given for experimental times ranging from 0 min to 90 min.

It is well known that the photocatalytic properties are greatly influenced by the band

structures of the catalysts. The band positions of these four g-C3N4 based photocatalysts are

summarized in Figure 5-4. Compared with traditional semiconductor photocatalysts, the CB

of g-C3N4 is located at a more negative potential. Such a feature enables the photo-induced e-

in the CB of g-C3N4 of strong reduction capability. Therefore, the O2 can be reduced to

generate active species of ·O2- to degrade the RhB. As discussed above, the species of ·O2-

plays more important role in the N-de-ethylation of RhB in comparison with the cleavage of

the conjugated chromophore structure. When the active species of h+ and ·OH participate in

the degradation reaction of RhB, the cleavage of the conjugated structure tends to be more

efficient, which is a significant step for the complete mineralization of RhB. However, due to

the medium bandgap of g-C3N4, the VB of g-C3N4 is also located at a more negative potential

compared with traditional semiconductor photocatalyst. For this reason, the photo-generated

h+ in the VB of g-C3N4 can neither directly decompose the RhB nor produce ·OH from OH-
40
due to its weak oxidation capability. In this case, the VB position of the material, which

determines the oxidation capability of the photo-excited h+, should be considered as another

important factor for selecting proper material to construct efficient composite photocatalyst

with g-C3N4. For example, the lower VB positions of Ag2Mo2O7 and MIL-88A at 2.9 and 1.86

V vs. SHE make the h+ and ·OH as efficient active species for RhB photo-degradation.

Correspondingly, the cleavage degrees in these two systems are higher than that in the

photocatalytic systems of CNZS and H2O2-treated g-C3N4.

Figure 5-4. Summary of the band positions of the photocatalysts of H2O2-treated g-C3N4, CNZS, CNAMO
and CNMIL.
* The data of the band positions in the CNZS system are from the previous literatures. The data in the other
systems are from the Mott-Schottky experimental results.

41
Chapter 6 Conclusions
In the present thesis, four different kinds of g-C3N4 based photocatalysts with enhanced

photocatalytic activities were successfully developed. For each photocatalytic system, the

photocatalysts were investigated from three aspects. First, the photocatalytic activities were

evaluated towards the RhB degradation under the visible light irradiation. In addition, the

active species involved in the photocatalytic processes were determined based on the active

species trapping (AST) experiments. Moreover, the mechanism for the enhancement of the

photocatalytic performance was studied. The main conclusions can be summarized as follows

and as is illustrated in Table 3:

I. Enhanced performance in each photocatalytic system:

(1) For the g-C3N4/ZnS composite photocatalyst, the sample of 6CNZS exhibits the highest

activity that 94% can be degraded within 90 min under a visible light irradiation

(λ>400nm). The optimal photocatalytic degradation rate of 0.034 min-1 is 2.8 times

higher than that of the pure g-C3N4;

(2) The g-C3N4 can construct an efficient composite photocatalyst with multi-metal oxide

m-Ag2Mo2O7. When the weight ratio of g-C3N4 and m-Ag2Mo2O7 is 6:1, the 6CNAMO

composite exhibits the optimal photocatalytic activity under the visible light illumination

(λ>420nm). The first order rate constant k is 0.0208 min-1, which is 3.4 times higher than

for pure g-C3N4 (0.0062 min-1);

(3) A composite photocatalyst with an improved photocatalytic performance is fabricated

between the g-C3N4 and the MIL-88A. It is the first time to construct a g-C3N4 based

composite with a kind of MOFs material. The photocatalytic degradation rate of

5CNMIL (0.0242 min-1) is 2.6 times higher than that of the pure g-C3N4;

(4) Under the visible light illumination (λ>420nm), the degradation rate constant of the

H2O2-treated g-C3N4 is 0.0365 min-1, which is 4.6 times higher than that of the pure

g-C3N4 0.0079 min-1.

42
II. Active species involved in the photocatalytic reactions:

(1) In the g-C3N4/m-Ag2Mo2O7 and the g-C3N4/MIL-88A system, three kinds of active species

of ·O2-, h+ and ·OH are involved in the photocatalytic reaction. Among them, the ·O2-

and h+ are the main active species.

(2) In the g-C3N4/ZnS and H2O2-treated g-C3N4 photocatalytic systems, the main active

species is determined as the super oxide radicals ·O2-.

The ·O2- can be formed from the reduction of the adsorbed O2 molecules by the electrons

in the CB with a strong reduction capability. When the VB edge locates at much lower

position, the photo-induced h+ can directly decompose the organic pollutant or strongly

oxidize the OH- to form the ·OH. Besides, the ·OH can also be generated from as a

consequence of the reduction of oxygen molecules.

III. Mechanism for the enhanced photocatalytic activities:

Each photocatalytic reaction basically involves three processes: i) photon absorption; ii)

generation and separation of the electron-hole pairs; iii) catalytic surface reactions. Thus, the

improvement of the photocatalytic performance can be analyzed from the aforementioned

three aspects.

(1) Due to the narrow bandgap of MIL-88A (2.0eV), the capabilities of the light absorption

of the CNMIL composite photocatalysts are enhanced. In the case of the H2O2-treated

g-C3N4, the photon absorption ability of is enhanced due to its narrower bandgap induced

by the defect state.

(2) On one hand, the separation efficiency of the electron-hole pairs in the g-C3N4 based

composite photocatalysts (CNZS, CNAMO and CNMIL) can be enhanced by the

staggered band alignment through the well-developed interface; On the other hand, the

defect can probably act as the trapping center of the photo-induced charge carrier and

inhibit the recombination of the electron-hole pairs in the H2O2-treated g-C3N4.

(3) In the H2O2-treated g-C3N4, more edges and pores are generated by the O2 bubbles, which

provide more active sites for the photocatalytic reactions and enhance the photocatalytic
43
 activity.

IV. photocatalytic behaviors of N-de-ethylation and conjugated structure cleavage of

RhB

(1) Two kinds of photocatalytic approaches could be observed in these four g-C3N4

photocatalytic systems. In the case of the CNZS and H2O2-treated g-C3N4 systems, the

N-de-dethylation was found to be the dominant process. As for the case of the CNAMO

and CNMIL systems, both a de-ethylation and a chromophore structure cleavage were

found to occur simultaneously.

(2) The presence of active species of ·O2- can induce a de-ethylation and a chromophore

structure cleavage of RhB. The results show that N-de-ethylation has the priority in the

presence of ·O2-.

(3) The presence of photo-excited holes led to a splitting of the chromophore structure for

RhB.

44
 Table 3. Summary of the thesis work.

Photocatalyst Optimal activity How to improve

Visible light Active species
(g-C3N4/) Efficiency within 90min Rate constant Enhancement factor e--h+ separation light absorption Active sites

ZnS 94% 0.034 min-1 2.8 ü λ> 400nm ·O2-

m-Ag2Mo2O7 89% 0.021 min-1 3.4 ü

·O2-, h+, ·OH
MIL-88A 90% 0.024 min-1 2.6 ü ü λ> 420nm

H2O2 97% 0.036 min-1 4.6 ü ü ü ·O2-

45
Chapter 7 Future Work
The following work is suggested for the future research:

(1) In this thesis, the RhB is selected as a target pollutant to evaluate the photocatalytic

activities of the catalysts. In the future, the photocatalytic performance can be further

evaluated to degrade more organic pollutant, such as MB, MO and 4-chlorophenol.

(2) The technique of Total Organic Carbon (TOC) should be employed to investigate the

mineralization of RhB. By this method, the yields of the final products of CO2 and H2O

can be calculated.

(3) The techniques of HPLC, LC/MS/MS and GC/MS can be utilized to further study the

intermediate products and monitor the temporal course of the reaction in detail during the

photocatalytic degradation.

(4) In this research work, we focus on exploring the possibility of promising g-C3N4-based

photocatalysts with enhanced activity under visible light irradiation. As for the practical

application in future, the stability of the photocatalysts is another key factor to be

considered. During the photocatalytic procedure, the redox capability of the

photo-induced electron-hole pairs plays a critical role for the pollutant degradation.

However, the photo-induced electron-hole pairs also can reduce or oxidize the cations or

anions of the photocatalysts. In this case, the stability of the photocatalysts will be

weakened. For example, the ZnS is easily photo-corroded due to the oxidation of S2- by

the photo-induced h+, as shown in the following equation: ZnS + 2h → Zn + S.

Taking into account the fact that the g-C3N4 shows excellent stability, the stability of the

g-C3N4-based photocatalyst can be improved by optimizing the morphology or structure

of the composites materials, such as core-shell morphology.31

46
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