Ruthenium-modified TiO2 photocatalysts for hydrogen generation from water splitting and simultaneous CO2 photoreduction

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-05-01 DOI:10.1016/j.jphotochem.2025.116477

Joanna Kapica-Kozar , Ewelina Kusiak-Nejman , Konrad Sobczuk , Agnieszka Wanag , Waldemar Bednarski , Katarzyna Ćmielewska , Ewa Ekiert , Iwona Pełech , Daniel Sibera , Piotr Staciwa , Marcin Gano , Urszula Narkiewicz , Antoni W. Morawski

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Abstract

TiO₂ modification with Ruthenium red heated at 400 °C as an effective method of obtaining chlorine-free photocatalysts for CO₂ reduction to valuable chemicals with higher photoactivity then commercial TiO₂ P25 was presented. The results showed an influence of Ru modification on significant decrease of the E_g of TiO₂ samples (with the Ru increase). The created by ruthenium some oxygen defects and the of Ti³⁺ sites are crucial for photoactivity in H₂ generation and CO₂ reduction. The relative free electron concentrations in the oxygen vacancies in TiO₂ samples were influenced by Ru. The highest concentration of unpaired electrons in oxygen vacancies and oxygen radicals occurs for samples containing 0.1 and 0.25 % Ru. Very weak signals attributed to Ti³⁺ were recorded for Ru 0.5 % and Ru 1 % samples. All modified samples exhibit high selectivity to hydrogen and TiO₂+0.25%Ru sample was the most effective in photocatalytic water splitting producing H₂, as well as CO and CH₄ production. Additionally, good reproducibility was found for this sample.

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钌修饰TiO2光催化剂用于水裂解制氢和同时光还原CO2

采用400℃加热钌红改性TiO2，获得了光活性高于商用TiO2 P25的无氯光催化剂。结果表明，Ru改性对TiO2样品的Eg有显著的降低作用（随Ru的增加）。钌产生的氧缺陷和Ti3+位点对H2生成和CO2还原的光活性至关重要。TiO2样品中氧空位的相对自由电子浓度受Ru的影响。在含有0.1%和0.25% Ru的样品中，氧空位和氧自由基中不成对电子的浓度最高。在0.5% Ru和1% Ru样品中记录到Ti3+的微弱信号。改性后的样品对氢均有较高的选择性，其中TiO2+0.25%Ru的样品在光催化水裂解生成H2、CO和CH4方面效果最好。此外，该样品具有良好的重现性。

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来源期刊

Journal of Photochemistry and Photobiology A-chemistry 化学-物理化学

CiteScore

7.90

自引率

7.00%

发文量

580

审稿时长

48 days

期刊介绍： JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds. All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor). The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.