Defect engineering and 2D/2D coupling in Mn- and B-doped BiVO4 and Ti3C2 nanostructures

Bidueinezhad, Mahjoobeh; Fathirad, Fariba

doi:10.61882/CNJ.3.2.602

Defect engineering and 2D/2D coupling in Mn- and B-doped BiVO4 and Ti3C2 nanostructures

Document Type : Original Article

Authors

Mahjoobeh Bidueinezhad

Fariba Fathirad

Department of Nanotechnology, Graduate University of Advanced Technology, Kerman, Iran

10.61882/CNJ.3.2.602

Abstract

Doping is an effective method that modulates the electronic and optical properties of semiconductor nanomaterials through the addition of foreign atoms. In this work, bismuth vanadate (BiVO4) and titanium carbide (Ti3C2) MXene nanosheets were synthesized through facile solution processes. To elucidate the roles of defect engineering and 2D/2D interfacial coupling, a series of systems including Mn-BiVO4, B-Ti3C2, Ti₃C₂/BiVO4, Mn-BiVO4/Ti3C2, BiVO4/B-Ti3C2, and Mn-BiVO4/B-Ti3C2 were synthesized and characterized by XRD, FTIR, FESEM, and EDX. DRS results reveal that Mn and B doping, as well as the construction of the heterostructure, lower the optical band gap from 2.6 eV (pristine BiVO4/Ti3C2) to 2.4 eV (Mn-BiVO4/B-Ti3C2) and cause a redshift of ~30 nm in the absorption edge. XRD analysis confirms a lattice contraction of 0.41 Å in BiVO4 due to Mn doping and an expansion of 2.87 Å in Ti3C2 layers upon B doping. These controlled defect states and 2D/2D interfaces enhance charge separation and photoactivity, demonstrating the potential of Mn-BiVO4/B-Ti3C2 for photo-driven redox applications such as hydrogen evolution.

Graphical Abstract

Defect engineering and 2D/2D coupling in Mn- and B-doped BiVO4 and Ti3C2 nanostructures

Keywords

Ti3C2 MXene

Doping

Heterostructures

Photoactivity

[1] V. Mohammadi, J. Rosen, Y. Gogotsi, The world of two-dimensional carbides and nitrides (MXenes), Science, 372 (2021) 1581. https://doi.org/10.1126/science.abf158

[2] Z. Chen, X. Duan, W. Wei, S. Wang, B.-J. Ni, Recent advances in transition metal-based electrocatalysts for alkaline hydrogen evolution, J. Mater. Chem. A, 7(25) (2019) 14971–15005. https://doi.org/10.1039/C9TA03220G

[3] Y. Vasseghian, E.N. Dragoi, F. Almomani, A comprehensive review on MXenes as new nanomaterials for degradation of hazardous pollutants: Deployment as heterogeneous sonocatalysis, Chemosphere, 287 (2022) 132387. https://doi.org/10.1016/j.chemosphere.2021.132387

[4] N. Devi, R. Kumar, R. Kumar Singh, S.A. Moshkalev, Recent development of MXenes and their composites in electrochemical energy storage: Current status, challenges and future prospects, J. Power Sources, 636 (2025) 236538. https://doi.org/10.1016/j.jpowsour.2025.236538

[5] F. Fathirad, E. Sadeghi, NiFe₂O₄/Ti₃C₂ nanocomposite as an efficient catalyst for methanol electro-oxidation reaction: Investigating annealing temperature and synergetic effect, Fuel, 358 (2024) 130130. https://doi.org/10.1016/j.fuel.2023.130130

[6] Z. Chen, J. Cao, X. Wu, D. Cai, M. Luo, S. Xing, X. Wen, Y. Chen, Y. Jin, D. Chen, Y. Cao, B/N Co-doping sequence: An efficient electronic modulation of the Pd/MXene interface with enhanced electrocatalytic properties for ethanol electrooxidation, ACS Appl. Mater. Interfaces, 14(10) (2022) 12223–12233. https://doi.org/10.1021/acsami.1c23718

[7] J. Chen, X. Yuan, F. Lyu, Q. Zhong, H. Hu, Q. Pan, Q. Zhang, Integrating MXene nanosheets with cobalt-tipped carbon nanotubes for an efficient oxygen reduction reaction, J. Mater. Chem. A, 7(3) (2019) 1281–1286. https://doi.org/10.1039/C8TA10574J

[8] I.A. Alsafari, S. Munir, S. Zulfiqar, M.S. Saif, M.F. Warsi, M. Shahid, Synthesis, characterization, photocatalytic and antibacterial properties of copper ferrite/MXene (CuFe₂O₄/Ti₃C₂) nanohybrids, Ceram. Int., 47(20) (2021) 28874–28883. https://doi.org/10.1016/j.ceramint.2021.07.048

[9] Z. Wang, K. Yu, Y. Feng, R. Qi, J. Ren, Z. Zhu, Stabilizing Ti₃C₂Tx-MXenes with TiOF2 nanospheres intercalation to improve hydrogen evolution reaction and humidity-sensing performance, Appl. Surf. Sci., 496 (2019) 143729. https://doi.org/10.1016/j.apsusc.2019.143729

[10] A. Kudo, K. Omori, H. Kato, A novel aqueous process for preparation of crystal form-controlled and highly crystalline BiVO₄ powder from layered vanadates at room temperature and its photocatalytic and photophysical properties, J. Am. Chem. Soc., 121(49) (1999) 11459–11467. https://doi.org/10.1021/ja992541y

[11] S. Tokunaga, H. Kato, A. Kudo, Selective preparation of monoclinic and tetragonal BiVO₄ with scheelite structure and their photocatalytic properties, Chem. Mater., 13(12) (2001) 4624–4628. https://doi.org/10.1021/cm0103390

[12] S. Kohtani, A.S. Makino, A. Kudo, K. Tokumura, Y. Ishigaki, Photocatalytic degradation of 4-n-nonylphenol under irradiation from solar simulator: Comparison between BiVO₄ and TiO₂ photocatalysts, Chem. Lett., 31 (2002) 660–661. https://doi.org/10.1246/cl.2002.660

[13] X. Du, T. Zhao, Z. Xiu, Z. Xing, Li Z., Pan K., Yang S., Zhou W., BiVO₄@ZnIn₂S₄/Ti₃C1111000 MXene quantum dots assembly all-solid-state direct Z-Scheme photocatalysts for efficient visible-light-driven overall water splitting, Appl. Mater. Today, 20 (2020) 100719. https://doi.org/10.1016/j.apmt.2020.100719

[14] P. Dagar, S. Kumar, A.K. Ganguli, Effect of Mn²⁺ incorporation on the photoelectrochemical properties of BiVO4, J. Chem., 46(6) (2022) 2875–2886. https://doi.org/10.1039/D1NJ05292F

[15] J. Joy, J. Mathew, S.C. George, Nanomaterials for photoelectrochemical water splitting–review, Int. J. Hydrogen Energy, 43(10) (2018) 4804-4817. https://doi.org/10.1016/j.ijhydene.2018.01.099

[16] Y. Peng, Y. Shi, S. Yan, G. Li, Photocarrier behavior and photocatalytic H₂O₂ synthesis performance of amorphous/crystalline SrTiO₃/BiVO₄ layered heterostructures, Renew. Energy, 237 (2024) 121686. https://doi.org/10.1016/j.renene.2024.121686

[17] B. Alshahrani, S. Saad Fares, R. Saleh Alqurashi, M. Salman, A.H. Korna, Effect of gamma irradiation on the structural, optical, and electronic properties of PVC/BiVO₄/ZnO nanocomposite films, Phys. Open, 23 (2025) 100252. DOI: 10.1016/j.physo.2025.100252

[18] H. Wang, Y. Bai, R. Wang, Y. Fu, Q. Mei, B. Bai, Q. Wang, Boosting photoelectrochemical water splitting: Enhanced hole transport in BiVO4 photoanodes via interfacial coupling, Catal. Sci. Technol., 15 (2024) 405–415. https://doi.org/10.1039/D4CY01284D

[19] Z. Fu, Y. Zhu, D. Qin, Y. Yang, S. Han, Z. Dong, Functional coupling hole transport and extraction units over BiVO₄ for efficient solar-to-hydrogen conversion, Energy Convers. Manag., 322 (2024) 119153. https://doi.org/10.1016/j.enconman.2024.119153

[20] C. Feng, X. Jia, X. Shao, X. Cheng, F. Zhan, Y. Zhang, Z. Bian, K. Zhao, F. Yu, Z. Wang, Doping engineering achieves BiVO₄ and hematite band matching accelerating photoelectrochemical water splitting, Fuel, 387 (2025) 134457. https://doi.org/10.1016/j.fuel.2025.134457

[21] D. Afzali, B. Bahadori, F. Fathirad, Ultrasound-assisted emulsification/microextraction based on solidification of trace amounts of thallium prior to graphite furnace atomic absorption spectrometry determination, Toxicol. Environ. Chem., 95(7) (2013) 1080–1089. https://doi.org/10.1080/02772248.2013.856912

[22] C. Zhou, Y. Hu, Z. Zhang, T. Shen, J. Song, R. Guan, Y. Guan, B-doped BiVO₄/Bi nanocomposites activated persulfate for efficient photocatalytic degradation of levofloxacin, Sep. Purif. Technol., 359 (2025) 130557. https://doi.org/10.1016/j.seppur.2024.130557

[23] X. Fan, H. Liang, Y. Song, Z. Xing, J. Bai, Development of a novel beads-like In/Fe co-doped BiVO₄ composite for enhanced photocatalytic degradation of tetracycline in water, Colloids Surf. A: Physicochem. Eng. Aspects, 687 (2024) 133477. https://doi.org/10.1016/j.colsurfa.2024.133477

[24] T. Iqbal, M. T. Qureshi, R. Shahzad, S. Afsheen, S. Kausar, G. Yunus, M.S. Mansha, L. Aamir, R. M. Munir, H.A. El-Serehy, M.Y. Khan, B.M. Al-Maswari, Synergistic impacts of novel tantalum doping in BiVO4 for effective photocatalytic applications, antimicrobial activity, and antioxidant aspect, Inorg. Chem. Commun., 170 (2024) 113365. https://doi.org/10.1016/j.inoche.2024.113365

[25] W. Wang, M. Fan, Z. Zhang, L. Wu, Y. Liu, Y. Cao, W. Peng, In-situ nanofication of Cu-doped BiVO₄ on montmorillonite nanosheets with enhanced photocatalytic efficiency for phenolic degradation, Sep. Purif. Technol., 361 (2025) 131341. https://doi.org/10.1016/j.seppur.2024.131341

[26] J. Zheng, Z. Zhao, J. Liang, B. Liang, H. Huang, G. Huang, M. Junaid, J. Wang, K. Huang, Simultaneous photocatalytic removal of tetracycline and hexavalent chromium by BiVO₄/0.6CdS photocatalyst: Insights into the performance, evaluation, calculation and mechanism, J. Colloid Interface Sci., 667 (2024) 650–662. https://doi.org/10.1016/j.jcis.2024.04.127

[27] V. Balakumar, C. Chuaicham, K. Sasaki, K. Sekar, Fabrication of BiVO₄/reduced graphene oxide photocatalyst for hexavalent chromium reduction under visible region, Mater. Today, 50 (2022) 400–405. https://doi.org/10.1016/j.matpr.2021.11.381

[28] D. Afzali, F. Fathirad, S. Ghaseminezhad, Z. Afzali, Determination of trace amounts of zirconium in real samples after microwave digestion and ternary complex dispersive liquid–liquid microextraction, Environmental monitoring and assessment, 186 (6) (2014) 3523-3529. https://doi.org/10.1007/s10661-014-3635-7

[29] Y. Liu, R. Zhao, D. Yu, Efficient detection and degradation of hexavalent chromium wastewater in tourist attractions using dual-fluorescent UiO-66-NH₂ stabilized polysulfone Pickering emulsions, Colloids Surf. A: Physicochem. Eng. Aspects, 706 (2025) 135812. https://doi.org/10.1016/j.colsurfa.2024.135812

[30] A. Raja, P. Rajasekaran, B. Vishnu, K. Selvakumar, J.Y. Do, M. Swaminathan, M. Kang, Fabrication of effective visible-light-driven ternary Z-scheme ZnO-Ag-BiVO₄ heterostructured photocatalyst for hexavalent chromium reduction, Sep. Purif. Technol., 252 (2020) 117446. https://doi.org/10.1016/j.seppur.2020.117446

[31] F. Qureshi, M. Tahir, Photoelectrochemical water splitting with engineering aspects for hydrogen production: Recent advances, strategies and challenges, Int. J. Hydrogen Energy, 69 (2024) 760–776. https://doi.org/10.1016/j.ijhydene.2024.05.039