Acta Phys. -Chim. Sin. ›› 2025, Vol. 41 ›› Issue (7): 100071.doi: 10.1016/j.actphy.2025.100071
Special Issue: S-scheme heterojunction in photocatalysis
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Hollow structured photocatalysts
Fangxuan Liu1, Ziyan Liu1, Guowei Zhou1,*(
), Tingting Gao1, Wenyu Liu3, Bin Sun1,2,*()
- 1 Key Laboratory of Fine Chemicals in Universities of Shandong, Jinan Engineering Laboratory for Multi-Scale Functional Materials, School of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, Shandong Province, China
2 Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai, Yantai 264006, Shandong Province, China
3 Faculty of Mechanical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, Shandong Province, China
-
Received:2025-01-25Revised:2025-02-19Accepted:2025-02-24Published:2025-05-22 -
Contact:Email: gwzhou@qlu.edu.cn (Guowei Zhou)binsun@qlu.edu.cn (Bin Sun) -
Supported by:National Natural Science Foundation of China(52202102); National Natural Science Foundation of China(52472215); National Natural Science Foundation of China(52202007); the National Natural Science Foundation of China(51972180); the Natural Science Foundation of Shandong Province(ZR2019BB030); the Natural Science Foundation of Shandong Province(ZR2021QE282); Key Research & Development Project of Shandong Province(2024TSGC0222); Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province(2021KJ056); Science Fund of Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(AMGM2023F13); Science Fund of Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai(AMGM2021F05); Science, Education and Industry Integration Innovation Pilot Project from Qilu University of Technology (Shandong Academy of Sciences)(2024ZDZX13)
Cite this article
Fangxuan Liu, Ziyan Liu, Guowei Zhou, Tingting Gao, Wenyu Liu, Bin Sun. Hollow structured photocatalysts[J]. Acta Phys. -Chim. Sin. 2025, 41(7), 100071. doi: 10.1016/j.actphy.2025.100071
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Fig 1
The structure and light propagation route of (a) solid photocatalyst and (b-d) hollow structured photocatalysts with different number of shells."
Fig 2
Synthesis and applications of hollow structured photocatalysts."
Fig 3
Synthetic strategies of hollow structured photocatalyst: (a) hard template method, (b) soft template method, and (c) template free method (Kirkendall effect)."
Fig 4
(a) Synthesis process of NG/CdS hollow sphere, FESEM images of (b) SiO2, (c) CdS/SiO2, (d) NG/CdS/SiO2, and (e) NG/CdS. Reprinted with permission from Ref. [81], Copyright 2019, Wiley-VCH GmbH. (f) Synthesis process of α-Fe2O3 nanosphere with different shell structures, TEM images of (g) single-shell, (h) double-shell, and (i) triple-shell. Reprinted with permission from Ref. [42], Copyright 2021, Springer Nature."
Fig 5
(a) Synthesis process of Ni-ZnO@C/g-C3N4 hollow microsphere. Reprinted with permission from Ref. [70], Copyright 2023, Elsevier. (b) Synthesis process of NiCo2O4 with different morphologies, TEM images of (c) porous spheres, (c) single-shell, and (e) double-shell. Reprinted with permission from Ref. [56], Copyright 2021, Elsevier."
Fig 6
(a) Synthesis process of ZnO@Co3O4 hollow cube, (b) FESEM and (c) TEM images of ZnO@Co3O4 hollow cube. Reprinted with permission from Ref. [94], Copyright 2023, Elsevier. (d) Synthesis process of hollow CdS with different morphologies by using Cu2O as a sacrificial template, FESEM and TEM images of (e, f) CdS nanooctahedron, (g, h) CdS nanobox, and (i, j) CdS nanosphere. Reprinted with permission from Ref. [93], Copyright 2024, Elsevier."
Fig 7
(a) Synthesis process of hollow ZIF-8 nanosphere, SEM and corresponding TEM images of ZIF-8 with the (b) 0, (c) 3, (d) 5, and (e) 9 v/v % n-hexane concentrations, respectively. Reprinted with permission from Ref. [110], Copyright 2023, American Chemical Society."
Fig 8
(a) Synthesis process of ZIF-8-HS, (b) structure feature of ZIF-8-HS with different shell thickness prepared by adjusting the concentrations of 2-methylimidazole and Zn2+ and corresponding TEM images. Reprinted with permission from Ref. [114], Copyright 2023, Elsevier. (c) Synthesis process of hollow mesoporous UiO-66 (Ce), (d) the micelle structure obtained by adjusting the ratio of F127/P123 and corresponding TEM images of UiO-66 (Ce). Reprinted with permission from Ref. [30], Copyright 2023, Wiley-VCH GmbH."
Fig 9
(a) Synthesis process of hollow porous TiO2 nanosphere, (b) FESEM and (c) TEM images of TiO2. Reprinted with permission from Ref. [105], Copyright 2023, The Royal Society of Chemistry."
Fig 10
(a) Synthesis process of Cu-Zn DA/HNC, (b) TEM image of Cu-Zn DA/HNC. Reprinted with permission from Ref. [29], Copyright 2024, Elsevier. (c) Synthesis process of four-shell hollow Zn0.5Mn0.5Co2O4 and Zn0.5Mn0.5Co2O4/RGO composite, TEM images of (d) Zn0.5Mn0.5Co2O4 and (e) Zn0.5Mn0.5Co2O4/RGO. Reprinted with permission from Ref. [130], Copyright 2023, Elsevier."
Fig 11
(a) Preparation process of hollow structured VO, Zn-ZnO/ZnS, (b) TEM images of ZnO with different structures. Reprinted with permission from Ref. [22], Copyright 2024, Elsevier. (c) Schematic illustration of OMHS-COF-H at different time intervals, (d) corresponding TEM images. Reprinted with permission from Ref. [55], Copyright 2023, Wiley-VCH GmbH."
Fig 12
(a) Synthesis process of hollow Fe3O4@HMCCS, FESEM images of (b) HMCCS, (c) Fe3O4@HMCCS with low Fe3O4 content, and (d) Fe3O4@HMCCS with high Fe3O4 content. Reprinted with permission from Ref. [125], Copyright 2023, Elsevier."
Fig 13
(a) Synthesis process of hollow rod-like NiCoMn-S ternary metal sulfide, (b) FESEM and (c) TEM images of NiCoMn-S. Reprinted with permission from Ref. [126], Copyright 2022, Elsevier. (d) Synthetic process of CoMn-PBA HSs, FESEM and TEM images of (e, f) CoMn-glycerate SSs and (g, h) CoMn-PBA HSs. Reprinted with permission from Ref. [138], Copyright 2021, Wiley-VCH GmbH."
Fig 14
FESEM and TEM images of (a, b) TiO2 hollow microspheres and (c, d) SnO2 hollow microspheres. Reprinted with permission from Ref. [139], Copyright 2006, Wiley-VCH GmbH. (e) Synthesis process of NiCo2O4 double-walled hollow nanotube, (f) FESEM and (g) TEM images of NiCo2O4. Reprinted with permission from Ref. [43], Copyright 2023, Elsevier. (h) Synthesis process of single-shell, double-shell, and triple-shell hollow MIL-101 crystals, TEM images of MIL-101: (i) solid, (j) single-shell, (k) double-shell, and (l) triple-shell. Reprinted with permission from Ref. [140], Copyright 2017, Wiley-VCH GmbH."
Table 1
Overview of hollow structured photocatalysts."
| Material | Structure | Method | Specific surface area/(m2∙g−1) | Ref. |
| NG/CdS | Single-shell hollow sphere | SiO2 hard template | 27.00 | [ |
| α-Fe2O3 | Triple-shell hollow sphere | SiO2 hard template | 92.00 | [ |
| Ni-ZnO@C | Core-double-shell hollow sphere | Carbon sphere hard template | 23.01 | [ |
| NiCo2O4 | Double-shell hollow sphere | Carbon sphere hard template | 93.50 | [ |
| ZnO@Co3O4 | Single-shell hollow cube | ZIF template | 51.90 | [ |
| ZIF-8 | Single-shell hollow sphere | Microemulsion template | 1325.00 | [ |
| Ce1−xCuxO2 | Single-shell hollow sphere | Microemulsion template | 127.40 | [ |
| Cu2O | Single-shell hollow sphere | Supramolecular micelles template | 22.60 | [ |
| ZIF-8 | Single-shell hollow sphere | Supramolecular micelles template | 1195.00 | [ |
| UiO-66(Ce) | Single-shell hollow hexagon | Supramolecular micelles template | 1061.00 | [ |
| TiO2 | Single-shell hollow sphere | Gas bubble template | 297.00 | [ |
| Fe2(MoO4)3 | Single-shell hollow sphere | Gas bubble template | 24.00 | [ |
| Cu-Zn DA/HNC | Single-shell hollow lozenge | Kirkendall effect | 744.00 | [ |
| ZnO | Single-shell hollow sphere | Ostwald ripening | 16.00 | [ |
| OMHS-COF-H | Single-shell hollow sphere | Ostwald ripening | 193.35 | [ |
| Fe3O4@HMCCS | Single-shell hollow sphere | Spray drying | 294.00 | [ |
| Cr2O3 | Triple-shell hollow sphere | Spray drying | 56.90 | [ |
| NiCoMn-S | Single-shell hollow rod | Ion exchange | 94.90 | [ |
| CoMn-PBA | Single-shell hollow sphere | Ion exchange | 89.80 | [ |
| TiO2 | Single-shell hollow sphere | Chemically induced self-transformation | 15.30 | [ |
| NiO | Triple-shell hollow sphere | Self-assembly | 51.60 | [ |
| CeO2 | Single-shell hollow sphere | SiO2 hard template | 78.00 | [ |
| NC/Pt/TiO2 | Single-shell hollow sphere | SiO2 hard template | 73.80 | [ |
| TiO2-x | Single-shell hollow sphere | Carbon sphere hard template | 64.28 | [ |
| CdS/NiS | Single-shell hollow sphere | SiO2 hard template | 303.10 | [ |
| Cu2−xS@ZnxCd1−xS | Single-shell hollow nanobox | Ion exchange | 18.65 | [ |
| CuMn2O4 | Single-shell hollow sphere | Self-assembly | 15.00 | [ |
| ZnS/CoS2 | Five-shell hollow sphere | Self-assembly | 121.60 | [ |
| OCN@In2S3 | Single-shell hollow sphere | Self-assembly | 83.78 | [ |
| P-NC@CNHS | Single-shell hollow sphere | MCM-41 template | 92.00 | [ |
| TB-COF | Single-shell hollow sphere | Self-assembly | 818.00 | [ |
| MnIn2S4@In2S3 | Single-shell hollow nanotube | MOF template | 215.30 | [ |
| ZnCdS | Single-shell hollow nanocage | ZIF template | 178.58 | [ |
| In2O3/PDA | Single-shell hollow tube | MIL-68 template | 42.00 | [ |
| Ag-CdS1−x@ZnIn2S4−x | Single-shell hollow nanobox | vulcanization | 41.60 | [ |
| C-NiO | Single-shell hollow sphere | Carbon sphere hard template | 131.79 | [ |
| CdS | Single-shell hollow sphere | SiO2 hard template | 65.00 | [ |
| Mn, C-ZnO | Core-triple shell hollow spheres | Self-assembly | 15.00 | [ |
| P-CoSx/ZnS | Single-shell hollow dodecahedron | MOF template | 42.40 | [ |
| Au/ZnO | Single-shell hollow sphere | Sodium citrate-assisted alkali precipitation | 13.10 | [ |
| N-TiO2 | Single-shell hollow sphere | Phenolic resin hard template | 124.44 | [ |
Table 2
Overview of the performance of hollow structured photocatalysts for pollutant degradation."
| Hollow photocatalyst | Application | Degradation efficiency | Ref. |
| TiO2 | Tetracycline | 98.2%/60 min | [ |
| Cu2O | Methyl orange | 95.8%/240 min | [ |
| NiO | Bisphenol A | 100.0%/60 min | [ |
| CeO2 | Tetracycline | 100.0%/50 min | [ |
| TiO2−x | Methylene blue | 92.5%/420 min | [ |
| Au/ZnO | Rhodamine B | 73.0%/20 min | [ |
| MoS2/PANI/PAN@BiFeO3 | Tetracycline Methyl orange | 99.5%/60 min 99.9%/60 min | [ |
| Au-FePO4 mYSNCs | Methylene blue Tetracycline | 99.0%/50 min 95.0%/100 min | [ |
Fig 15
The FEM simulated concentration gradient distribution and degradation intermediate of BPA: (a) NiO nanoparticle, (b) double-shell and (c) triple-shell NiO nanospheres, (d) the mineralization efficiency of BPA on different NiO structures. Reprinted with permission from Ref. [143], Copyright 2023, Elsevier. (e) UV-Vis diffuse reflectance spectra and (f) photocatalytic tetracycline hydrochloride degradation of MoS2/PANI/PAN@BiFeO3 with different morphologies. Reprinted with permission from Ref. [167], Copyright 2023, Elsevier. (g) The mechanism diagram of Au-FePO4 mYSNCs in photocatalysis. Reprinted with permission from Ref. [168], Copyright 2023, Wiley-VCH GmbH."
Table 3
Overview of the performance of hollow structured photocatalysts for H2 production."
| Hollow photocatalyst | Sacrificial agent | H2 production rate/(mmol∙g−1∙h–1) | AQY | Ref. |
| UiO-66(Ce) | TEOA | 0.36 | − | [ |
| NC/Pt/TiO2 | Methanol | 25.70 | 13.20% (365 nm) | [ |
| CeO2/ZnxCd1−xIn2S4 | Na2SO3, Na2S | 4.09 | 9.50% (400 nm) | [ |
| VO, Zn-ZnO/ZnS | Na2SO3, Na2S | 160.91 | 15.40% (365 nm) | [ |
| CdS/NiS | Na2SO3, Na2S | 2.18 | − | [ |
| Cu2−xS@ZnxCd1−xS | Na2SO3, Na2S | 8.17 | 10.20% (420 nm) | [ |
| CdS | Na2SO3, Na2S | 3.42 | 28.90% (450 nm) | [ |
| CuMn2O4 | TEOA | 1.59 | − | [ |
| Ni-ZnO@C/g-C3N4 | TEOA | 0.34 | − | [ |
| ZnS/CoS2 | Na2SO3, Na2S | 8.00 | 54.60% (290 nm) | [ |
Fig 16
(a) Photocatalytic H2 evolution rates of multi-shell ZnS/CoS2 with different heating rate, (b) photocatalytic H2 evolution mechanism of multi-shell ZnS/CoS2 under light irradiation. Reprinted with permission from Ref. [149], Copyright 2020, Wiley-VCH GmbH. (c–e) Side and top views of charge density differences over CdS/NiS HNS, (f) adsorption free energy of H2 on CdS and NiS. Reprinted with permission from Ref. [146], Copyright 2024, Elsevier. (g) The comparison of multiple light reflection in the solid and hollow structure of Cu2−xS@ZnCdS. Reprinted with permission from Ref. [147], Copyright 2024, Wiley-VCH GmbH."
Fig 17
(a) Schematic illustration of the energy band structure and charge transfer of P, N−C@CNHS. Reprinted with permission from Ref. [151], Copyright 2023, American Chemical Society. (b) Photocatalytic H2O2 production of Ag-CdS1−x, ZnIn2S4−x, and Ag-CdS1−x@ZnIn2S4−x under visible light irradiation, (c) cyclic performance and (d) photocatalytic mechanism of H2O2 production over Ag-CdS1−x@ZnIn2S4−x. Reprinted with permission from Ref. [156], Copyright 2023, Elsevier. (e) Photocatalytic H2O2 production of CN, HCN, and CHCN-0.02 under visible light irradiation, (f) apparent quantum efficiency of CHCN-0.02. Reprinted with permission from Ref. [177], Copyright 2023, Elsevier."
Table 4
Overview of the performance of hollow structured photocatalysts for H2O2 production."
| Hollow photocatalyst | Reaction system | Yield | AQY/(420 nm) | Ref. |
| OCN@In2S3 | Ethanol | 0.63 (mmol∙g−1∙h−1) | – | [ |
| P-NC@CNHS | Isopropanol | 4.57 (mmol∙g−1∙h−1) | – | [ |
| TB-COF | Ethanol | 6.07 (mmol∙g−1∙h−1) | 7.83% | [ |
| MnIn2S4@In2S3 | Ethanol | 2.57 (mmol∙g−1∙h−1) | 10.52% | [ |
| ZnCdS@PDA | H2O | 45.50 (mmol∙g−1∙h−1) | 0.89% | [ |
| In2O3/PDA | Ethanol | 0.37 (mmol∙g−1∙h−1) | – | [ |
| Ag-CdS1−x@ZnIn2S4−x | Ethanol | 1.18 (mmol∙g−1∙h−1) | – | [ |
| g-C3N4 | Ethanol | 1.58 (mmol∙g−1∙h−1) | 28.10% | [ |
| CdS/RF | Ethanol | 0.80 (mmol∙g−1∙h−1) | – | [ |
Table 5
Overview of the performance of hollow-structured photocatalysts for CO2 reduction."
| Hollow photocatalyst | Reaction system | Reduction product | Yield/(µmol∙g−1∙h−1) | AQY | Ref. |
| NG/CdS | H2SO4/NaHCO3 | CO, CH4 | 2.59, 0.33 | 0.90% (420 nm) | [ |
| OMHS-COF-H | TIPA | CO, H2 | 15874.00, 1298.00 | 1.01% (420 nm) | [ |
| C-NiO | H2O/TEOA | CO, CH4 | 6.64, 3.77 | – | [ |
| ZnxCd1−xS-Co | H2O/acetonitrile/TEOA | CO | 7629.70 | – | [ |
| CdS | H2O | CO, CH4, CH3 | 4.59, 0.19, 2.22 | – | [ |
| Mn, C-ZnO | – | CO, O2 | 0.54, 0.46 | 0.03% (365 nm) | [ |
| CeO2@CeO2/A-TiO2 | TEOA | CO, CH4 | 97.63, 15.00 | – | [ |
| CuxO/CeO2 | Ethanol/H2O | CO, CH4 | 124.90, 9.10 | – | [ |
Fig 18
(a) AQE and UV-visible absorption spectra of Mn, C-ZnO core-triple shell hollow sphere, (b) UV-Vis diffuse reflectance spectra of different Mn, C-ZnO, C-ZnO, ZnO and the multiple reflection effect of the incident light inside the hollow cavity, (c) schematic illustration of CO2 activation and reduction on Mn, C-ZnO. Reprinted with permission from Ref. [158], Copyright 2021, Springer. (d) CO2 photoreduction activity over ZnxCd1−xS with different shell number and Co atom loading amount. Reprinted with permission from Ref. [178], Copyright 2024, American Chemical Society. (e) Schematic illustration of heterogeneous hollow multi-shell CeO2@CeO2/A-TiO2 for photocatalytic CO2 reduction into CH4. Reprinted with permission from Ref. [183], Copyright 2022, Wiley-VCH GmbH."
Table 6
Overview of the performance of hollow structured photocatalysts for N2 fixation."
| Hollow photocatalyst | Reaction system | Yield | AQY | Ref. |
| P-CoSx/ZnS | H2O | 1175.37 μmol∙g−1∙h−1 | 7.56% (365nm) | [ |
| BiOBr/Bi4O5Br2 | H2O | 66.87 μmol∙g−1∙h−1 | 0.15% (365nm) | [ |
| Au-Ag2O | H2O | 28.20 mg∙m−2∙h−1 | 1.20% (685nm) | [ |
| InVO4 | H2O | 66.18 µmol∙g−1∙h−1 | 0.50% (385nm) | [ |
| N-TiO2 | H2O | 80.09 μmol∙g−1∙h−1 | 0.07% (375nm) | [ |
| Yb3+: Tm3+: CeF3 | H2O | 15.06 μmol∙g−1∙h−1 (NH4+) | – | [ |
Fig 19
(a) NH3 production rate of NTO-0.5, TiO2, and P25 under different light irradiation, (b) cyclic performance for NH3 production over NTO-0.5. Reprinted with permission from Ref. [161], Copyright 2022, Elsevier. (c) Schematic illustration of scattering, reflecting, and photocatalytic process of Yb3+: Tm3+: CeF3 for N2 fixation. Reprinted with permission from Ref. [189], Copyright 2022, Elsevier. (d–f) The SPV images of InVO4 with different morphologies under light irradiation and darkness, (g) SPV change before and after light irradiation. Reprinted with permission from Ref. [188], Copyright 2020, Wiley-VCH GmbH."
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