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Visible-light H2 production using self-doped CaTiO3 derived from marble Waste: Synthesis, mechanism, modelling and energy assessment

Author

Listed:
  • Ragab, Safaa
  • Elkatory, Marwa R.
  • Hassaan, Mohamed A.
  • Şenol, Halil
  • El-Nemr, Mohamed A.
  • El Nemr, Ahmed

Abstract

This study developed a novel method to synthesize self-doped CaTiO3 (SD-CaTiO3) from Triesta Marble (TM) waste. HNO3 treatment of the marble powder yielded a sustainable calcium nitrate precursor, Ca(NO3)2·(H2O)x. In situ Mg2+ doping from TM impurities during perovskite synthesis was made possible by the subsequent addition of TiO2 and carefully regulated calcination. Chemical interactions during synthesis are essential to creating a stable and effective photocatalyst. Acidic treatment of TM facilitates Ca2+ leaching and complexation with nitrate ions. A strong perovskite lattice is formed during calcination by solid-state interactions involving Ca2+, Ti2+, and Mg2+. Lattice deformation and oxygen vacancies are created when Mg2+ partially replaces Ti4+. These flaws improve charge carrier separation and stabilize the perovskite structure. Mg2+ ions from TM impurities integrate into the CaTiO3 lattice during perovskite crystallization (at 850 °C), as demonstrated by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Ultraviolet–Visible Spectroscopy (UV–Vis). Using Fourier Transform Infrared Spectroscopy, UV–Vis, Brunauer–Emmett–Teller Surface Area Analysis, Scanning Electron Microscopy, XRD, and XPS, the physicochemical characteristics of the generated SD-CaTiO3 were comprehensively described. The crystallite phase was orthorhombic (COD 9002801), and most of the nanoparticles were between 52.43 and 126.52 nm in size, according to the XRD test. The visible-light response of SD-CaTiO3 with a band gap of 2.393 eV was confirmed by the redshifted absorption edge towards longer wavelengths produced by adding TiO2 to TM nitrate. Using 900 mg/L of SD-CaTiO3 at a pH of 10 and a 1200-W metal halide lamp as the visible light source without any sacrificial agents, a maximum H2 generation rate of 11,778 μmol/L was attained under visible light. Using XRD and XPS, the suggested mechanism of H2 generation was validated. Using artificial neural networks and the Box-Behnken architecture, H2 productions were effectively predicted. According to the energy balance study, high-energy inputs for synthesis and calcination result in a considerable net energy deficit (−128,246 kJ). This emphasizes the necessity of optimization to increase the process's economic and energy efficiency.

Suggested Citation

  • Ragab, Safaa & Elkatory, Marwa R. & Hassaan, Mohamed A. & Şenol, Halil & El-Nemr, Mohamed A. & El Nemr, Ahmed, 2026. "Visible-light H2 production using self-doped CaTiO3 derived from marble Waste: Synthesis, mechanism, modelling and energy assessment," Renewable Energy, Elsevier, vol. 256(PD).
    • Handle: RePEc:eee:renene:v:256:y:2026:i:pd:s0960148125018348
    DOI: 10.1016/j.renene.2025.124170
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