Interfacial charge transfer and photocatalytic activity in a reverse designed Bi₂O₃/TiO₂ core-shell

Abstract

In this study, the electronic and photocatalytic properties of core-shell heterojunctions photocatalysts with reversible configuration of TiO₂ and Bi₂O₃ layers were studied. The core-shell nanostructure, obtained by efficient control of the sol-gel polymerization and impregnation method of variable precursors of semiconductors, makes it possible to study selectively the role of the interfacial charge transfer in each configuration. The morphological, optical, and chemical composition of the core-shell nanostructures were characterized by high-resolution transmission electron microscopy, UV-visible spectroscopy and X-ray photoelectron spectroscopy. The results show the formation of homogenous TiO₂ anatase and Bi₂O₃ layers with a thickness of around 10 and 8 nm, respectively. The interfacial charge carrier dynamic was tracked using time resolved microwave conductivity and transition photocurrent density. The charge transfer, their density, and lifetime were found to rely on the layout layers in the core-shell nanostructure. In optimal core-shell design, Bi₂O₃ collects holes from TiO₂, leaving electrons free to react and increase by 5 times the photocatalytic efficiency toward H₂ generation. This study provides new insight into the importance of the design and elaboration of optimal heterojunction based on the photocatalyst system to improve the photocatalytic activity.

Graphical abstract

Keywords

photocatalysis / core-shell / heterojunction / H₂ / TiO₂ / Bi₂O₃

References

[1] Kumaravel V, Mathew S, Bartlett J, . Photocatalytic hydrogen production using metal doped TiO₂: a review of recent advances. Applied Catalysis B: Environmental, 2019, 244: 1021–1064

[2] Reza Gholipour M, Dinh C T, Béland F, . Nanocomposite heterojunctions as sunlight-driven photocatalysts for hydrogen production from water splitting. Nanoscale, 2015, 7(18): 8187–8208

[3] Ghazzal N M, Chaoui N, Aubry E, . A simple procedure to quantitatively assess the photoactivity of titanium dioxide films. Journal of Photochemistry and Photobiology A Chemistry, 2010, 215(1): 11–16

[4] Gesesse G D, Wang C, Chang B K, . A soft-chemistry assisted strong metal–support interaction on a designed plasmonic core–shell photocatalyst for enhanced photocatalytic hydrogen production. Nanoscale, 2020, 12(13): 7011–7023

[5] Gesesse G D, Le Neel T, Cui Z, . Plasmonic core-shell nanostructure as an optical photoactive nanolens for enhanced light harvesting and hydrogen production. Nanoscale, 2018, 10(43): 20140–20146

[6] Liu M, Inde R, Nishikawa M, . Enhanced photoactivity with nanocluster-grafted titanium dioxide photocatalysts. ACS Nano, 2014, 8(7): 7229–7238

[7] Liu G, Du K, Haussener S, . Charge transport in two-photon semiconducting structures for solar fuels. ChemSusChem, 2016, 9(20): 2878–2904

[8] Naldoni A, Altomare M, Zoppellaro G, . Photocatalysis with reduced TiO₂: from black TiO₂ to cocatalyst-free hydrogen production. ACS Catalysis, 2019, 9(1): 345–364

[9] Moniz S J A, Shevlin S A, Martin D J, . Visible-light driven heterojunction photocatalysts for water splitting – a critical review. Energy & Environmental Science, 2015, 8(3): 731–759

[10] Yi S, Zhang X, Wulan B, . Non-noble metals applied to solar water splitting. Energy & Environmental Science, 2018, 11(11): 3128–3156

[11] Wang C, Li J, Paineau E, Laachachi A, . A sol-gel biotemplating route with cellulose nanocrystals to design a photocatalyst for improving hydrogen generation. Journal of Materials Chemistry A, 2020, 8(21): 10779–10786

[12] Wei L, Yu C, Zhang Q, . TiO₂-based heterojunction photocatalysts for photocatalytic reduction of CO₂ into solar fuels. Journal of Materials Chemistry A, Materials for Energy and Sustainability, 2018, 6(45): 22411–22436

[13] Li J, Jiménez-Calvo P, Paineau E, . Metal chalcogenides based heterojunctions and novel nanostructures for photocatalytic hydrogen evolution. Catalysts, 2020, 10(1): 89

[14] Bessekhouad Y, Chaoui N, Trzpit M, . UV-vis versus visible degradation of Acid Orange II in a coupled CdS/TiO₂ semiconductors suspension. Journal of Photochemistry and Photobiology A Chemistry, 2006, 183(1–2): 218–224

[15] Xu D, Hai Y, Zhang X, . Bi₂O₃ cocatalyst improving photocatalytic hydrogen evolution performance of TiO₂. Applied Surface Science, 2017, 400: 530–536

[16] Lopes O F, Carvalho K T G, Avansi W Jr, . Growth of BiVO₄ nanoparticles on a Bi₂O₃ surface: effect of heterojunction formation on visible irradiation-driven catalytic performance. Journal of Physical Chemistry C, 2017, 121(25): 13747–13756

[17] Wu Y, Lu G, Li S. The doping effect of Bi on TiO₂ for photocatalytic hydrogen generation and photodecolorization of rhodamine B. Journal of Physical Chemistry C, 2009, 113(22): 9950–9955

[18] Zhang L, Ye X, Boloor M, . Significantly enhanced photocurrent for water oxidation in monolithic Mo: BiVO₄/SnO₂/Si by thermally increasing the minority carrier diffusion length. Energy & Environmental Science, 2016, 9(6): 2044–2052

[19] Xie M, Fu X, Jing L, . Long-lived, visible-light-excited charge carriers of TiO₂/BiVO₄ nanocomposites and their unexpected photoactivity for water splitting. Advanced Energy Materials, 2014, 4(5): 1300995

[20] Ho C H, Chan C H, Huang Y, . The study of optical band edge property of bismuth oxide nanowires α-Bi₂O₃. Optics Express, 2013, 21(10): 11965–11972

[21] Bessekhouad Y, Robert D, Weber J V. Photocatalytic activity of Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions. Catalysis Today, 2005, 101(3–4): 315–321

[22] Ayekoe P Y, Robert D, Goné D L. Preparation of effective TiO₂/Bi₂O₃ photocatalysts for water treatment. Environmental Chemistry Letters, 2016, 14(3): 387–393

[23] Reddy N L, Emin S, Valant M, . Nanostructured Bi₂O₃@TiO₂ photocatalyst for enhanced hydrogen production. International Journal of Hydrogen Energy, 2017, 42(10): 6627–6636

[24] Meng S, Sun W, Zhang S, . Insight into the transfer mechanism of photogenerated carriers for WO₃/TiO₂ heterojunction photocatalysts: Is it the transfer of band-band or Z-scheme? Why? Journal of Physical Chemistry C, 2018, 122(46): 26326–26336

[25] Gesesse G D, Li C, Paineau E, . Enhanced photogenerated charge carriers and photocatalytic activity of biotemplated mesoporous TiO₂ films with a chiral nematic structure. Chemistry of Materials, 2019, 31(13): 4851–4863

[26] Chen M, Li Y, Wang Z, . Controllable synthesis of core-shell Bi@amorphous Bi₂O₃ nanospheres with tunable optical and photocatalytic activity for NO removal. Industrial & Engineering Chemistry Research, 2017, 56(37): 10251–10258

[27] Ghazzal M N, Kebaili H, Joseph M, . Photocatalytic degradation of Rhodamine 6G on mesoporous titania films: combined effect of texture and dye aggregation forms. Applied Catalysis B: Environmental, 2012, 115–116: 276–284

[28] Ghazzal M N, Wojcieszak R, Raj G, . Study of mesoporous CdS-quantum-dot-sensitized TiO₂ films by using X-ray photoelectron spectroscopy and AFM. Beilstein Journal of Nanotechnology, 2014, 5: 68–76

[29] Sanna S, Esposito V, Andreasen J W, . Enhancement of the chemical stability in confined δ-Bi₂O₃. Nature Materials, 2015, 14(5): 500–504

[30] Jiang H Y, Cheng K, Lin J. Crystalline metallic Au nanoparticle-loaded α-Bi₂O₃ microrods for improved photocatalysis. Physical Chemistry Chemical Physics, 2012, 14(35): 12114–12121

[31] Ghazzal M N, Chaoui N, Genet M, . Effect of compressive stress inducing a band gap narrowing on the photoinduced activities of sol–gel TiO₂ films. Thin Solid Films, 2011, 520(3): 1147–1154

[32] Nam H J, Amemiya T, Murabayashi M, . Photocatalytic activity of sol-gel TiO₂ thin films on various kinds of glass substrates: the effects of Na⁺ and primary particle size. Journal of Physical Chemistry B, 2004, 108(24): 8254–8259

[33] Xu Y, Schoonen M A A. The absolute energy positions of conduction and valence bands of selected semiconducting minerals. American Mineralogist, 2000, 85(3–4): 543–556

[34] Savenije T J, Ferguson A J, Kopidakis N, . Revealing the dynamics of charge carriers in polymer: fullerene blends using photoinduced time-resolved microwave conductivity. Journal of Physical Chemistry C, 2013, 117(46): 24085–24103

Acknowledgments

This work was supported by the public grant overseen by the French National Research Agency (ANR) as part of the “Investissements d’Avenir” program (Labex NanoSaclay, reference: ANR-10-LABX-0035) through project “Z-scheme,” the “Agence Nationale de la Recherche (ANR)” through the UpPhotoCat project, and the “Département de Chimie de la Faculté des Sciences d'Orsay de l'Université Paris-Saclay” through young researcher grant.

RIGHTS & PERMISSIONS

2021 Higher Education Press