Photocatalytic applications of layered niobates and their composites

• Ano de defesa: 2022
• Autor(a) principal: Nunes, Barbara Nascimento
• Orientador(a): Patrocinio, Antonio Otavio de Toledo , Bahnemann, Detlef
• Banca de defesa: Beutel, Sascha , Wark, Michael , Feldhoff, Armin
• Tipo de documento: Tese
• Tipo de acesso: Acesso aberto
• Idioma: eng
• Instituição de defesa: Universidade Federal de Uberlândia
• Programa de Pós-Graduação: Programa de Pós-graduação em Química
• País: Brasil
• Palavras-chave em Português: 2D materials; niobium oxide; niobates; thin films; photoactive surface; photocatalysis; hydrogen; water splitting; Materiais 2D; óxido de nióbio; niobatos; filmes finos; fotoativos Superfície; fotocatálise; hidrogênio; separação de água; estudos mecanísticos
• Área do conhecimento CNPq: CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA::FOTO-QUIMICA INORGANICA
• Link de acesso: https://repositorio.ufu.br/handle/123456789/34943; http://doi.org/10.14393/ufu.te.2022.217

Photocatalytic applications of two-dimensional (2D) materials have called great interest due to several electronic and structural advantages. Among these materials, layered niobates are well-known photocatalysts for H2 evolution with a rich surface chemistry. Taking into account the highly exposed active sites of its 2D structure and the morphological flexibility, the properties of the exfoliated hexaniobate as a heterogeneous photocatalyst has been explored in this work, with particular attention to the electronic and interfacial processes involved in the H2 evolution. Firstly, highly efficient photocatalytic surfaces were obtained through the layer-by-layer (LbL) deposition of hexaniobate nanoscrolls on conductive glasses. These films were deposited by using poly(allylamine hydrochloride) as a polyelectrolyte and further thermal treatment leading to films composed of a fuzzy assembly of hexaniobate nanoscrolls. This configuration favored the diffusion of water and methanol molecules thus facilitating an efficient H2 evolution. Moreover, pre-adsorption of [Pt(NH3)4]2+ cations on the niobate layers allowed the production of metallic Pt nanoclusters within the nanoscrolls. The Pt-modified films exhibited apparent quantum yields of (4.0 ± 0.5) % for H2 evolution from water/methanol mixtures under UV-A irradiation. Then, in order to induce novel electronic processes without changing the bulk properties of the hexaniobate, surface modification was performed by grafting with metallic nanoclusters. Exfoliated hexaniobate (K4−xHxNb6O17) composites with metal ions such as Co2+, Fe3+ and Cu2+ were prepared and their photocatalytic properties were fully investigated. Morphological characterization showed that the grafting ions are attached to the hexaniobate surface forming amorphous clusters. These species induce an additional absorption feature in the UV-A region, which is attributed to an interfacial charge transfer from the niobate valence band to the metal ion centers. In the case of Co2+ and Fe3+, enhanced UV-driven photoactivity in plain water was observed for 0.1 wt.% grafted samples, especially for those modified with Co2+ ions, while smaller H2 evolution rates are observed as the concentration of the grafting ions increased. When Pt was added to the photocatalyst, the H2 evolution rate for the 0.1% Co-grafted sample in plain water was 70% higher than that observed for the nongrafted Pt-hexaniobate. For Cu2+-grafted hexaniobates, Cu2+ clusters provided an expressive improvement in the photocatalytic H2 evolution under UV-vis irradiation from methanolic aqueous solution and promising results for partial water splitting, in comparison to the hexaniobate with photodeposited Pt. These species on the hexaniobate surface present a high redox reversibility, being easily reduced to Cu1+/Cu0 and reoxidized to Cu2+. Cu2+ ions work as electron scavenger following band gap excitation while the resulting reduced species act as active sites to produce H2. Thus, the presence of different ions at different concentrations can directly affect the fate of the photogenerated carriers thus triggering the photocatalytic activity in different ways. Overall, the grafted ions contribute to a more efficient charge separation and to higher photocatalytic performances.