Research Progress on the Construction of Defective Titanium Dioxide and Its Application in Photocatalysis/Photoelectrocatalysis

doi:10.19894/j.issn.1000-0518.240243

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (2): 149-167.DOI: 10.19894/j.issn.1000-0518.240243

• Review •

Research Progress on the Construction of Defective Titanium Dioxide and Its Application in Photocatalysis/Photoelectrocatalysis

Nian JIN¹^,², Chun-Li GAO¹^,², Quan-Qian GE¹^,², Mai XU²(), Xian LIANG², Chuan-Gao ZHU², Feng-Wu WANG²()

^1.School of Materials Science and Engineering，Anhui University of Science and Technology，Huainan 232001，China
^2.School of Chemistry and Material Engineering，Huainan Normal University，Huainan 232038，China

Received:2024-08-01 Accepted:2025-01-20 Published:2025-02-01 Online:2025-03-14
Contact: Mai XU,Feng-Wu WANG
About author:xumai2215@163.com
fengwuwang@163.com；
Supported by:
the National Natural Science Foundation of China(22078121);the Key Project of Natural Science Foundation of Universities of Anhui Province(KJ2021A0963)

Abstract

Abstract:

Photocatalysis/photoelectrocatalysis has attracted great attentions from researchers around the world because of its application in water treatment， water splitting and organic synthesis to solve energy and environmental problems. Many researchers are interested in titanium oxide （TiO₂） nanomaterial as catalytic nanomaterials used in energy and environmental fields. However， the main bottleneck is that it has comparatively big bandgap. The application of photocatalytic materials based on defected TiO₂ is a promising strategy to improve the catalytic performance. The modification of TiO₂ defects can broaden the photoelectric response and improve charge separation efficiency. In this review， we first start with the photocatalysis/photoelectrocatalysis reaction mechanism， propose that the introduction of defective TiO₂ can improve its photocatalysis/photoelectrocatalysis activity， systematically summarize some common synthesis methods and defect engineering strategies for the preparation of defective or black TiO₂， and then elaborate the latest progress of defective TiO₂ in photocatalysis/photoelectrocatalysis applications. Finally， the research on the photocatalysis/photoelectrocatalysis of defective TiO₂ is briefly summarized， and the potential development prospects are proposed.

Key words: Defective titanium dioxide, Photocatalysis/photoelectrocatalysis, Nanomaterials, Modification

CLC Number:

O643

Nian JIN, Chun-Li GAO, Quan-Qian GE, Mai XU, Xian LIANG, Chuan-Gao ZHU, Feng-Wu WANG. Research Progress on the Construction of Defective Titanium Dioxide and Its Application in Photocatalysis/Photoelectrocatalysis[J]. Chinese Journal of Applied Chemistry, 2025, 42(2): 149-167.

Figures/Tables 18

Fig.1 Basic principles of photocatalysis （A） and photoelectrocatalysis （B）［18］

Fig.2 Schematic diagram of TiO2-based photocatalysts with different morphologies［19］

Fig.3 TiO2 in different colors［29］

Fig.4 The types of defects commonly found in TiO2 crystals are：（A） no defects，（B） surface substitution of impurity atoms （dopant），（C） surface vacancies，（D） interstitial impurity atoms，（E） substitution of impurity atoms （dopant），（F） vacancies，（G） self-interstitial atoms，（H） precipitation of impurity atoms （clusters），（I） vacancy clusters［37］

Fig.5 （A） Schematic diagram of the structure of the black defect TiO2 of the core-shell structure ［42］，（B） the structural simulation diagram and （B） the TEM image［43］

Table 1 Preparation method of defective TiO2

Preparation method	Classification	Morphology	Advantages	Drawbacks	Ref.
High-temperature hydrogen reduction	Reduction	Nanoparticles	Controlled hydrogenation reaction	High temperature and high pressure	［61］
Solid-phase reaction method	Reduction	Nanoparticles	Chemical reaction is more rapid and complete	High temperature and high pressure	［62-63］
Plasma method	Reduction	TiO₂ film	Avoid the high pressure and high temperature	-	［30］
Electrochemical reduction	Reduction	TiO₂ film	Precise control of the reaction	Needs a substrate to form the electrode	［64］
Hydrothermal method	Oxidation	Nanoparticles	The reaction conditions are mild	Long reaction time	［65］
Vacuum sintering	Other	Nanoparticles	Good reusability and stability	High temperature and high pressure	［66］
Microwave method	Other	Nanoparticles	The response is quick and easy	-	［67］
Ultraviolet irradiation	Other	Nanoparticles	High efficiency and environmental friendliness	High energy consumption	［68］
Ultrasonic-induced surface disordering	Other	Nanoparticles	The response is thorough	-	［69］
Decomposition/condensation of titanium isopropoxide	Other	Nanoparticles	The reaction conditions are mild and quick	-	［70］

Fig.6 （A） Schematic diagram of the preparation process of self-floating， bi-affinity， large mesoporous structure black defective TiO2 foam；（B） SEM images，（C） physical images and （D） photodegradation［72］

Fig.7 （A） Schematic diagram of the preparation of black mesoporous defect Ti3+/N-TiO2 particles，（B） SEM images of Ti3+/N-TiO2 particles， and （C） photocatalytic mechanism schematic of black Ti3+/N-TiO2［75］

Fig.8 Schematic diagram of the preparation of defective TiO2 by liquid-phase plasma method［80］

Table 2 Study on the preparation of defective TiO2 by electrochemical reduction method

Morphology	Counter electrode	Reference electrode	Electrolyte	Applied voltage， time	Ref.
Film	Pt	Ag/AgCl	NaOH（concentration： 1 mol/L）	2 V， 20 s	［82］
Nanotubes	Pt	Ag/AgCl	（NH₄）₂SO₄（concentration： 1 mol/L）	1.5 V， 150 s	［83］
Nanotubes	-	-	Na₂SO₄（solvents： water， ethylene glycol）	10 V； 20 V； 40 V； 3 min	［84］
Nanotubes	-	Ag/AgCl	K₂SO₄（concentration： 0.5 mol/L）	0.8 V， 30 s	［85］
Nanotubes	-	-	KH₂PO₄ （concentration： 0.1 mol/L）	16.7 mA/cm²（current density）， 90 s	［86］

Fig.9 Schematic diagram of the principle of different methods to modify defective TiO2

Fig.10 Preparation process for chiral defects TiO2-x /Cu x O deposited by single atom Pt［88］

Fig.11 Schematic diagram of the possible band structure of N，P-BTNAs photoanodes and their synergistic PEC activation of sulfate［101］

Fig.12 Schematic diagram of carrier transport of type Ⅰ （A）， type Ⅱ （B）， Z （C） and S （D） heterojunctions［102-105］

Fig.13 （A） Preparation flow of Co2P/PC-black defective TiO2 catalyst，（B） particle size distribution of the product and （C） TEM image of the product［105］

Fig.14 Preparation process of defective TiO2-x /TpPa-1-COF［119］

Fig.15 （A） Flow chart for the preparation of black defective TiO2 nanotubes loaded with MOFs；（B） SEM image of black defective TiO2 nanotubes；（C） SEM image of black TiO2 nanotubes loaded with MOF and hollow Cu1.8S nanospheres；（D） Band gap calculation of the prepared sample；（E） Photocurrent-time curves of prepared samples；（F） The impedance set of the prepared sample；（G） Degradation of 2，4-dichlorophenol by prepared samples［83］

Table 3 A summary of the research on photoelectric catalysis of black TiO2 modified doping

Modified substances	Modification method	Application	Ref.
Carbon quantum dots	Alkali-assisted ultrasound	Photoelectrocatalytic performance testation	［82］
NH₂-La MOFs	Hydrothermal method	Photoelectrocatalytic degradation of 2，4-dichlorophenol	［83］
Polyaniline	Electrochemical method	Photoelectrocatalytic degradation of tetrabromobisphenol A	［120］
N	High-temperature calcination	Photoelectrocatalytic degradation of sulfadidiumdimethylpyrimidine	［121］
MIL-100（Fe）	Pulse deposition， self-assembly	Photoelectrocatalytic degradation of antibiotics	［122］
Ti₃CN MXene	Hydrothermal method	Photoelectrocatalytic CO₂ reduction	［123］
Peryl molecules， Pt	Spin coating method， spin magnetron sputtering	Photoelectrocatalytic water oxidation	［124］
rGO	Liquid phase method	Photoelectrocatalytic water splitting	［125］
RuO， BiVO₄	Sedimentation	Photoelectrocatalytic degradation of acetaminophen	［126］

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Research Progress on the Construction of Defective Titanium Dioxide and Its Application in Photocatalysis/Photoelectrocatalysis

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