In situ Synthesis of 2D Bismuth/Graphitic Carbon Nitride Heterojunctions for the Visible Light-Driven Organic Dye Degradation

Buse Sündü; Ayben Türkkan; Zafer EROĞLU; Onder Metin

doi:10.5281/zenodo.10372139

Authors

Buse Sündü Koç University https://orcid.org/0000-0003-0922-2104
Ayben Türkkan Koç University https://orcid.org/0009-0004-9222-6695
Zafer EROĞLU Koç University https://orcid.org/0000-0002-0601-2526
Onder Metin Koç University https://orcid.org/0000-0003-1622-4992

DOI:

https://doi.org/10.5281/zenodo.10372139

Keywords:

Graphitic carbon nitride, 2D Bismuth, heterojunction, Photodegradation, Sustainable chemistry

Abstract

In this study, highly efficient photocatalysts were developed by synthesizing binary heterojunctions of 2D Bismuth/Graphitic Carbon Nitride (2D Bi/gCN) in various ratios through a facile in situ synthesis method. Advanced analytical techniques were used to characterize the yielded heterojunctions, and their photocatalytic performance was evaluated in the Methyl Orange (MO) degradation under visible light irradiation. The 2D Bi/gCN heterojunctions provided exceptional photoactivity under visible light illumination, leading to the significantly higher degradation efficiency compared to pristine gCN. To clarify the high photocatalytic dye degradation activity of 2D Bi/gCN heterojunctions, a band diagram that depicts the dynamics of electron-hole migration between the gCN and 2D Bi in the heterojunction structure revealed the formation of a type-I heterojunction. The photophysical and structural characteristics of the 2D Bi/gCN heterojunctions were assessed by utilizing different approaches to authenticate the effective integration of 2D Bi into gCN layers. The 2D Bi/gCN heterojunctions exhibit enhanced light absorption and improved charge separation, with the 2D Bi_0.06/gCN composition exhibiting the highest photocatalytic performance, achieving 61% MO photodegradation efficiency in 30 min. Kinetic analysis demonstrated that the 2D Bi_0.06/gCN composition degraded MO at a rate 2.04 times higher than pristine gCN. Overall, the 2D Bi/gCN heterojunctions showed promising photocatalytic properties with the 2D Bi_0.06/gCN heterojunctions emerging as an exceptionally efficient photocatalyst for MO degradation under visible light illumination. This research contributes to the understanding and application of 2D Bi/gCN heterojunctions as photocatalysts in the development of other sustainable chemical processes.

References

Ukaogo, P. O.; Ewuzie, U.; Onwuka, C. V. Environmental Pollution: Causes, Effects, and the Remedies. In Microorganisms for Sustainable Environment and Health; Elsevier, 419–429 (2020).

Shang, Y.; Xu, A. An Evaluation of the Impact of Natural Ecotourism on Environmental Pollution. Environ. Sci. Pollut. Res 28 (26), 33764–33770 (2021).

Lu, G.; Li, X.; Li, W.; Liu, Y.; Wang, N.; Pan, Z.; Zhang, G.; Zhang, Y.; Lai, B. Thermo-Activated Periodate Oxidation Process for Tetracycline Degradation: Kinetics and Byproducts Transformation Pathways. J. Hazard. Mater. 461, 132696 (2024).

Dey, P. C.; Das, R. Enhanced Photocatalytic Degradation of Methyl Orange Dye on Interaction with Synthesized Ligand Free CdS Nanocrystals under Visible Light Illumination. Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 231, 118122 (2020).

Mittal, A.; Malviya, A.; Kaur, D.; Mittal, J.; Kurup, L. Studies on the Adsorption Kinetics and Isotherms for the Removal and Recovery of Methyl Orange from Wastewaters Using Waste Materials. J. Hazard. Mater. 148 (1–2), 229–240 (2007).

Combes, R. D.; Haveland-Smith, R. B. A Review of the Genotoxicity of Food, Drug and Cosmetic Colours and Other Azo, Triphenylmethane and Xanthene Dyes. Mutat. Res. Genet. Toxicol. 98 (2), 101–243 (1982).

Prival, M. J.; Davis, V. M.; Peiperl, M. D.; Bell, S. J. Evaluation of Azo Food Dyes for Mutagenicity and Inhibition of Mutagenicity by Methods Using Salmonella Typhimurium. Mutat. Res. Toxicol. 206 (2), 247–259 (1988).

Zou, Y.; Wang, X.; Khan, A.; Wang, P.; Liu, Y.; Alsaedi, A.; Hayat, T.; Wang, X. Environmental Remediation and Application of Nanoscale Zero-Valent Iron and Its Composites for the Removal of Heavy Metal Ions: A Review. Environ. Sci. Technol. 50 (14), 7290–7304 (2016).

Yang, S.; Tian, D.; Wang, X.; Zhou, P.; Xiong, Z.; Zhang, H.; Liu, Y.; Yao, G.; Lai, B. The Enhanced Mechanism of Fe(III)/H2O2 System by N, S-Doped Mesoporous Nanocarbon for the Degradation of Sulfamethoxazole. Sep. Purif. Technol. 308, 122900 (2023).

Yin, K.; Wu, R.; Shang, Y.; Chen, D.; Wu, Z.; Wang, X.; Gao, B.; Xu, X. Microenvironment Modulation of Cobalt Single-Atom Catalysts for Boosting Both Radical Oxidation and Electron-Transfer Process in Fenton-like System. Appl. Catal. B Environ. 329, 122558 (2023).

Yin, K.; Peng, L.; Chen, D.; Liu, S.; Zhang, Y.; Gao, B.; Fu, K.; Shang, Y.; Xu, X. High-Loading of Well Dispersed Single-Atom Catalysts Derived from Fe-Rich Marine Algae for Boosting Fenton-like Reaction: Role Identification of Iron Center and Catalytic Mechanisms. Appl. Catal. B Environ. 336, 122951 (2023).

Shang, Y.; Kan, Y.; Xu, X. Stability and Regeneration of Metal Catalytic Sites with Different Sizes in Fenton-like System. Chinese Chem. Lett. 34 (8), 108278 (2023).

Yang, M.; Hou, Z.; Zhang, X.; Gao, B.; Li, Y.; Shang, Y.; Yue, Q.; Duan, X.; Xu, X. Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N 4 –C Intensified Radical and Nonradical Pathways. Environ. Sci. Technol. 56 (16), 11635–11645 (2022).

Ahmad, R.; Ahmad, Z.; Khan, A. U.; Mastoi, N. R.; Aslam, M.; Kim, J. Photocatalytic Systems as an Advanced Environmental Remediation: Recent Developments, Limitations and New Avenues for Applications. Journal of Environmental Chemical Engineering. Elsevier Ltd December 1, 4143–4164 (2016).

Fujishima, A., Honda, K. Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature 238 (5358), 37–38 (1972).

Hunge, Y. M. Basics and Advanced Developments in Photocatalysis – a Review (Mini Review). Int. J. Hydrol. 2 (4) (2018).

Sun, R.; Wang, Z.; Saito, M.; Shibata, N.; Ikuhara, Y. Atomistic Mechanisms of Nonstoichiometry-Induced Twin Boundary Structural Transformation in Titanium Dioxide. Nat. Commun. 6 (1), 7120 (2015).

Yano, M.; Koike, K.; Ogata, K.; Nogami, T.; Tanabe, S.; Sasa, S. Zinc Oxide‐based Biosensors. Phys. status solidi c 9 (7), 1570–1573 (2012).

Zhu, M.; Hu, Y.; Li, Y.; Jin, H.; Zhu, Z. Effect of Magnetic Field on Phase Morphology Transformation of MnO 2 Nanostructures in a Hydrothermal Process. Phys. status solidi c 9 (1), 122–127 (2012).

Pandey, K.; Jeong, H. K. Synthesis of Tungsten Disulfide for Electrochemical Energy Applications. Mater. Sci. Eng. B 295, 116601 (2023).

Sakthivel, T.; Huang, X.; Wu, Y.; Rtimi, S. Recent Progress in Black Phosphorus Nanostructures as Environmental Photocatalysts. Chem. Eng. J. 379, 122297 (2020).

Jiang, L.; Yuan, X.; Pan, Y.; Liang, J.; Zeng, G.; Wu, Z.; Wang, H. Doping of Graphitic Carbon Nitride for Photocatalysis: A Review. Appl. Catal. B Environ. 217, 388–406 (2017).

Wang, X.; Blechert, S.; Antonietti, M. Polymeric Graphitic Carbon Nitride for Heterogeneous Photocatalysis. ACS Catal. 2 (8), 1596–1606 (2012).

Cao, S.; Low, J.; Yu, J.; Jaroniec, M. Polymeric Photocatalysts Based on Graphitic Carbon Nitride. Adv. Mater. 27 (13), 2150–2176 (2015).

Zhou, L.; Zhang, H.; Sun, H.; Liu, S.; Tade, M. O.; Wang, S.; Jin, W. Recent Advances in Non-Metal Modification of Graphitic Carbon Nitride for Photocatalysis: A Historic Review. Catal. Sci. Technol. 6 (19), 7002–7023 (2016).

Nasir, M. S.; Yang, G.; Ayub, I.; Wang, S.; Wang, L.; Wang, X.; Yan, W.; Peng, S.; Ramakarishna, S. Recent Development in Graphitic Carbon Nitride Based Photocatalysis for Hydrogen Generation. Appl. Catal. B Environ. 257, 117855 (2019).

Zhou, J.; Chen, W.; Sun, C.; Han, L.; Qin, C.; Chen, M.; Wang, X.; Wang, E.; Su, Z. Oxidative Polyoxometalates Modified Graphitic Carbon Nitride for Visible-Light CO 2 Reduction. ACS Appl. Mater. Interfaces 9 (13), 11689–11695 (2017).

Zhang, N.; Wen, L.; Yan, J.; Liu, Y. Dye-Sensitized Graphitic Carbon Nitride (g-C3N4) for Photocatalysis: A Brief Review. Chem. Pap. 74 (2), 389–406 (2020).

Wudil, Y. S.; Ahmad, U. F.; Gondal, M. A.; Al-Osta, M. A.; Almohammedi, A.; Sa’id, R. S.; Hrahsheh, F.; Haruna, K.; Mohamed, M. J. S. Tuning of Graphitic Carbon Nitride (g-C3N4) for Photocatalysis: A Critical Review. Arab. J. Chem. 16 (3), 104542 (2023).

Li, H.; Liu, Y.; Gao, X.; Fu, C.; Wang, X. Facile Synthesis and Enhanced Visible‐Light Photocatalysis of Graphitic Carbon Nitride Composite Semiconductors. ChemSusChem 8 (7), 1189–1196 (2015).

Wang, J.; Xu, M.; Tremblay, P.-L.; Zhang, T. Improved Polyhydroxybutyrate Production by Cupriavidus Necator and the Photocatalyst Graphitic Carbon Nitride from Fructose under Low Light Intensity. Int. J. Biol. Macromol. 203, 526–534 (2022).

Le, S.; Jiang, T.; Zhao, Q.; Liu, X.; Li, Y.; Fang, B.; Gong, M. Cu-Doped Mesoporous Graphitic Carbon Nitride for Enhanced Visible-Light Driven Photocatalysis. RSC Adv. 6 (45), 38811–38819 (2016).

Lin, H.; Wu, J.; Zhou, F.; Zhao, X.; Lu, P.; Sun, G.; Song, Y.; Li, Y.; Liu, X.; Dai, H. Graphitic Carbon Nitride-Based Photocatalysts in the Applications of Environmental Catalysis. J. Environ. Sci. 124, 570–590 (2023).

Liu, X.; Zhang, S.; Guo, S.; Cai, B.; Yang, S. A.; Shan, F.; Pumera, M.; Zeng, H. Advances of 2D Bismuth in Energy Sciences. Chem. Soc. Rev. 49 (1), 263–285 (2020).

Zhang, K.; Jin, B.; Park, C.; Cho, Y.; Song, X.; Shi, X.; Zhang, S.; Kim, W.; Zeng, H.; Park, J. H. Black Phosphorene as a Hole Extraction Layer Boosting Solar Water Splitting of Oxygen Evolution Catalysts. Nat. Commun. 10 (1), 2001 (2019).

R., S.; Kainthla, I.; Dongre S., S.; D’Souza, L.; Balakrishna, R. G. Recent Advances in Ecofriendly 2D Monoelemental Bismuthene as an Emerging Material for Energy, Catalysis and Biomedical Applications. J. Mater. Chem. C 11 (21), 6777–6799 (2023).

Ozer, M. S.; Eroglu, Z.; Yalin, A. S.; Kılıç, M.; Rothlisberger, U.; Metin, O. Bismuthene as a Versatile Photocatalyst Operating under Variable Conditions for the Photoredox C H Bond Functionalization. Appl. Catal. B Environ. 304, 120957 (2022).

Yilmazer, A.; Eroglu, Z.; Gurcan, C.; Gazzi, A.; Ekim, O.; Sundu, B.; Gokce, C.; Ceylan, A.; Giro, L.; Unal, M. A.; Arı, F.; Ekicibil, A.; Ozgenç Çinar, O.; Ozturk, B. I.; Besbinar, O.; Ensoy, M.; Cansaran-Duman, D.; Delogu, L. G.; Metin, O. Synergized Photothermal Therapy and Magnetic Field Induced Hyperthermia via Bismuthene for Lung Cancer Combinatorial Treatment. Mater. Today Bio 23, 100825 (2023).

Eroglu, Z.; Ozer, M. S.; Metin, O. Black Phosphorus Quantum Dots/Carbon Nitride-Reduced Graphene Oxide Ternary Heterojunction as a Multifunctional Metal-Free Photocatalyst for Photooxidation Reactions. ACS Sustain. Chem. Eng. 11 (19), 7560–7572 (2023).

Cao, S.; Low, J.; Yu, J.; Jaroniec, M. Polymeric Photocatalysts Based on Graphitic Carbon Nitride. Adv. Mater. 27 (13), 2150–2176 (2015).

Zhang, W.; Hu, Y.; Ma, L.; Zhu, G.; Zhao, P.; Xue, X.; Chen, R.; Yang, S.; Ma, J.; Liu, J.; Jin, Z. Liquid-Phase Exfoliated Ultrathin Bi Nanosheets: Uncovering the Origins of Enhanced Electrocatalytic CO2 Reduction on Two-Dimensional Metal Nanostructure. Nano Energy 53, 808–816 (2018).

Kong, L.; Wang, J.; Ma, F.; Sun, M.; Quan, J. Graphitic Carbon Nitride Nanostructures: Catalysis. Appl. Mater. Today 16, 388–424 (2019).

Zhu, Y.; Wu, Y.; Li, S.; Yuan, X.; Shen, J.; Luo, S.; Wang, Z.; Gao, R.; Wu, J.; Ge, L. Photocatalytic and Photothermal Bismuthene Nanosheets as Drug Carrier Capable of Generating CO to Improve Drug Sensitivity and Reduce Inflammation for Enhanced Cancer Therapy. Chem. Eng. J. 446, 137321 (2022).

Liu, C.; Zhang, Y.; Dong, F.; Reshak, A. H.; Ye, L.; Pinna, N.; Zeng, C.; Zhang, T.; Huang, H. Chlorine Intercalation in Graphitic Carbon Nitride for Efficient Photocatalysis. Appl. Catal. B Environ. 203, 465–474 (2017).

Fang, X.; Gao, R.; Yang, Y.; Yan, D. A Cocrystal Precursor Strategy for Carbon-Rich Graphitic Carbon Nitride toward High-Efficiency Photocatalytic Overall Water Splitting. iScience 16, 22–30 (2019).

Eroglu, Z.; Sündü, B.; Metin, O. Tailoring the Redox Ability of Carbon Nitride Quantum Dots/Reduced Graphene Oxide-Black Phosphorus (CNQDs@rGOBP) Ternary Heterojunctions for Photodegradation of Organic Pollutants. Mater. Today Sustain. 23, 100418 (2023).

Kılıç, D.; Sevim, M.; Eroğlu, Z.; Metin, Ö.; Karaca, S. Strontium Oxide Modified Mesoporous Graphitic Carbon Nitride/Titanium Dioxide Nanocomposites (SrO-Mpg-CN/TiO2) as Efficient Heterojunction Photocatalysts for the Degradation of Tetracycline in Water. Adv. Powder Technol. 32 (8), 2743–2757 (2021).

Altan, O.; Eroğlu, Z.; Küçükkeçeci, H.; Metin, Ö. Black Phosphorus-Based Photocatalysts for Energy and Environmental Applications. In Nanostructured Photocatalysts; Elsevier, 421–449 (2021).

Eroglu, Z.; Ozer, M. S.; Kubanaliev, T.; Kilic, H.; Metin, Ö. Synergism between Few-Layer Black Phosphorus and Graphitic Carbon Nitride Enhances the Photoredox C–H Arylation under Visible Light Irradiation. Catal. Sci. Technol. 12 (17), 5379–5389 (2022).

Eroglu, Z.; Metin, O. Internal Interactions within the Complex Type-II Heterojunction of a Graphitic Carbon Nitride/Black Phosphorus Hybrid Decorated with Graphene Quantum Dots: Implications for Photooxidation Performance. ACS Appl. Nano Mater. 6 (9), 7960–7974 (2023).