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Photocatalytic applications and modification methods of two-dimensional nanomaterials: a review

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Abstract

Due to its unique electronic structure and special size effect, two-dimensional (2D) nanomaterials have shown great potential far beyond bulk materials in the field of photocatalysis. How to deeply explore the photocatalytic mechanism of 2D nanomaterials and design more efficient 2D semiconductor photocatalysts are research hotspots. This review provides a comprehensive introduction to typical 2D nanomaterials and discusses their current application status in the field of photocatalysis. The effects of material properties such as band structure, morphology, crystal face structure, crystal structure and surface defects on the photocatalytic process are discussed. The main modification methods are highlighted, including doping, noble metal deposition, heterojunction, thickness adjustment, defect engineering, and dye sensitization in 2D material systems. Finally, the future development of 2D nanomaterials is prospected. It is hoped that this paper can provide systematic and useful information for researchers engaged in the field of photocatalysis.

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Fig. 1
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Reproduced with permission from Ref. [22]. Copyright 2018, Royal Society of Chemistry. Reproduced with permission from Ref. [23]. Copyright 2020, Elsevier. Reproduced with permission from Ref. [24]. Copyright 2017, ACS Publications. Reproduced with permission from Ref. [25]. Copyright 2020, Elsevier

Fig. 4
Fig. 5

Reproduced with permission from Ref. [48].Copyright 2021, Elsevier

Fig. 6

Reproduced with permission from Ref. [69]. Copyright 2020, Royal Society of Chemistry. d The schematic diagram of the synthesis processes of TiO2/NiO. e The schematic diagram of the photocatalytic mechanism of TiO2/NiO. Reproduced with permission from Ref. [58] Copyright 2020, Elsevier. Degradation curves of MB by MnO2/Fe3O4 at different pH values f in the dark and g with UV−Vis light, h the speculated reaction principle of MnO2/Fe3O4 and MB under different pH values. Reproduced with permission from Ref. [71]. Copyright 2014, ACS Publications

Fig. 7

Reproduced with permission from Ref. [84]. Copyright 2023, John Wiley and Sons. c Evolution of the band structure of 2H‑MoS2 calculated for samples of decreasing thickness. Reproduced with permission from Ref. [96]. Copyright 2017, Springer Nature. d Schematic diagram of direct band gap and indirect band gap. Reproduced with permission from Ref. [97]. Copyright 2020, ACS Publications. e Scanning electron microscope image of U-CN/MoS2-3. f Histograms of hydrogen production for different ratios of U-CN/MoS2. g Heterojunction mechanism of U-CN/MoS2 photocatalyst. Reproduced with permission from Ref. [106]. Copyright 2019, Elsevier

Fig. 8

Reproduced with permission from Ref. [114]. Copyright 2016, Royal Society of Chemistry

Fig. 9

Reproduced with permission from Ref. [135]. Copyright 2019, Royal Society of Chemistry

Fig. 10

Reproduced with permission from Ref. [147]. Copyright 2019, John Wiley and Sons

Fig. 11

Reproduced with permission from Ref. [163]. Copyright 2022, ACS Publications. b Structural diagrams of the four kinds of MXenes. Reproduced with permission from Ref. [165]. Copyright 2022, Elsevier. c The charge-transfer process in the Ti3C2/TiO2 system. Reproduced with permission from Ref. [166]. Copyright 2020, Elsevier. d Schematic diagram of the reaction mechanism of 2D-Bi2MoO6@2D-Mxene. (NSs: nanosheets) Reproduced with permission from Ref. [169]. Copyright 2020 Elsevier

Fig. 12
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Reproduced with permission from Ref. [177]. Copyright 2023, Elsevier

Fig. 14

Reproduced with permission from Ref. [185]. Copyright 2023, Elsevier. f Schematic illustration of the crystal orientation of the nanosheet. g The high resolution transmission electron microscopy (HRTEM) images of the ultrathin BiOCl nanosheet. h The atomic force microscopic image of the ultrathin BiOCl nanosheet. i The RhB degradation curve. j The positron annihilation spectroscopy. k The positron lifetime spectrum. Reproduced with permission from Ref. [188]. Copyright 2013, ACS Publications

Fig. 15

Reproduced with permission from Ref. [193]. Copyright 2019, Elsevier

Fig. 16
Fig. 17

Reproduced with permission from Ref. [209]. Copyright 2015, Elsevier. c The Tauc plots of different samples. d Photo-induced temperature rise rates of different samples. e The electron paramagnetic resonance (EPR) spectra of 2,2,6,6-tetramethylpiperidinyl (TEMP-1O2) for Co1Zn19-ZIF. f The EPR spectra of 5,5-dimethyl-1-pyrroline N-oxide (DMPO-O2-) for Co1Zn19-ZIF. Reproduced with permission from Ref. [214]. Copyright 2023, Elsevier

Fig. 18

Reproduced with permission from Ref. [219]. Copyright 2014, ACS Publications. b Schematic illustration of the hot-electron-injection effect: excitation of the electrons from thermal equilibrium to a high-energy state upon absorbing photons and injection of the electrons to the CB of the semiconductor (I). Redistribution of electron energy and formation of a Fermi–Dirac distribution at a high-temperature Fermi level after the injection of the electrons (II). Restoration of the standard electron distribution with electrons and holes flowing to different regions in the semiconductor (III). Reproduced with permission from Ref. [220]. Copyright 2015, John Wiley and Sons. c The absorption spectra of different BiVO4 samples. d The absorption spectrum of the Ag NPs and the reflectance spectrum of the io-BiVO4 sample. e The IPCE spectra of different BiVO4 samples. f The schematic diagram of Schottky junction of Ag/BiVO4. Reproduced with permission from Ref. [221]. Copyright 2016, AIP Publishing. (FTO: F-doped tin oxide) g The HRTEM images of different Ag/TiO2 samples. h The schematic diagram of the formation mechanism of Ag NPs different sizes. Reproduced with permission from Ref. [226]. Copyright 2020, Royal Society of Chemistry

Fig. 19

Reproduced with permission from Ref. [231]. Copyright 2016, Elsevier. d SEM images of pure TiO2 nanofibers and TiO2/MoS2 composite nanofibers. e The band structures of TiO2/MoS2 heterostructure. Reproduced with permission from Ref. [232]. Copyright 2020, Elsevier. f TEM images of WO3 nanosheets, g-C3N4 nanosheets and WO3/g-C3N4 samples. g The band structures of pure g-C3N4 and WO3 before bonding (left), the internal electric field and band-edge bending of the WO3/g-C3N4 interface after bonding (middle), and the schematic diagram of the S-heterojunction charge-transfer process between WO3 and g-C3N4 under illumination (right). h the Schematic illustration of type II heterojunction and S-scheme heterojunction. Reproduced with permission from Ref. [233]. Copyright 2019, Elsevier. i Schematic illustration of NMS/SCN S-scheme heterojunction. (TEOA: Triethanolamine) Reproduced with permission from Ref. [234]. Copyright 2021, Elsevier

Fig. 20

Reproduced with permission from Ref. [236]. Copyright 2022, Elsevier. d AFM images and height cutaway views of different CdS samples. e Kubelka–Munk function vs. photon energy curves of different CdS samples. f Rates of photocatalytic produced hydrogen of different CdS samples. Reproduced with permission from Ref. [237]. Copyright 2018, Elsevier

Fig. 21

Reproduced with permission from Ref. [239]. Copyright 2019, Elsevier. d The typical TEM images of CN and CNQ680 and the schematic diagram of the morphology change from CN to CNQ. e The converted Kubelka–Munk vs. light energy plots of CN and CNQs. f Schematic diagram of band structure change from CN to CNQ680. g The FTIR spectra of CN and CNQs. h the (N2c)/(N3c) ratio of CN and CNQs. i The C/N ratio of CN and CNQs. Reproduced with permission from Ref. [240]. Copyright 2017, Elsevier. j The total and atomic projected DOS analyses of different h-BN samples. Reproduced with permission from Ref. [241]. Copyright 2021, ACS Publications

Fig. 22

Reproduced with permission from Ref. [242]. Copyright 2018, Elsevier. b energy bandgaps of different samples. Reproduced with permission from Ref. [243]. Copyright 2019, Academic Press Inc. c M − S plots of MIL-53 (Fe). d LSV curve of MIL-53 (Fe) for HER. e Illustration of band structure of MIL-53 (Fe). f M − S plots of EY-sensitized MIL-53 (Fe). g Photocatalytic hydrogen evolution activity of different samples. Reproduced with permission from Ref. [244]. Copyright 2022, Elsevier. h The photoexcited charge-transfer processes that may occur in the Bi2MoO6@RhB samples: 1. direct bandgap transition; 2. intrinsic charge recombination; 3. electron trapping/detrapping; 4. intramolecular photoexcitation; 5. interfacial electron injection; 6. interfacial electron recombination; 7. radiationless decay. i sacrificial agent experiments over Bi2MoO6@RhB under LED light irradiation. (TBA: tert-Butanol) Reproduced with permission from Ref. [245]. Copyright 2023, Elsevier

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Acknowledgements

This work was supported by the National Natural Science Foundation of China Youth Program (52204399), the Postdoctoral Research Foundation of China (2021MD703866), the Scientific and Technological Innovation Team Project of Shaanxi Innovation Capability Support Plan (2022TD-30), Youth Innovation Team of Shaanxi Universities (2019-2022), Fok Ying Tung Education Foundation (171101), Natural Science Basic Research Program of Shaanxi Province (2022JQ-478), the Scientific Research Program of Youth Innovation Team of Shaanxi (22JP037), the Science and Technology Project of Universities and Institutes Staff Serving Enterprises in Xi'an (22GXFW0059) and Top Young Talents Project of “Special Support Program for High Level Talents” in Shaanxi Province (2018-2023).

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  1. School of Metallurgy Engineering, Xi’an University of Architecture and Technology, Xi’an, 710055, China

    Fan Yang, Ping Hu, Fan Yang, Xing-Jiang Hua, Bo Chen, Lili Gao & Kuai-She Wang

  2. National and Local Joint Engineering Research Center for Functional Materials Processing, Xi’an University of Architecture and Technology, Xi’an, 710055, China

    Fan Yang, Ping Hu, Fan Yang, Xing-Jiang Hua, Bo Chen & Kuai-She Wang

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Author 1: Yang Fan is currently studying for a master’s degree in Xi’an University of Architecture and Technology; Author 3: Yang Fan is currently working as a postdoctoral researcher in Xi’an University of Architecture and Technology.

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Yang, F., Hu, P., Yang, F. et al. Photocatalytic applications and modification methods of two-dimensional nanomaterials: a review. Tungsten 6, 77–113 (2024). https://doi.org/10.1007/s42864-023-00229-x

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