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<p>Solar-driven photoelectrocatalytic (PEC) technology has been widely recognized as a green and sustainable alternative to fossil fuel energy production. In this work, Mn<sup>2+</sup> doped CdS/TiO<sub>2</sub> nanorods (Mn–CdS/TiO<sub>2</sub>) photoanodes were prepared by a modified two-step hydrothermal method for green hydrogen production under simulated solar illumination. The effect of Mn doping on the PEC performance of CdS/TiO<sub>2</sub> photoanode was systematically investigated. The UV–Vis diffuse reflectance spectrum, Mott–Schottky analysis and electrochemical impedance spectra demonstrate that Mn doping improves the visible light absorption, carrier density and charge separation of CdS/TiO<sub>2</sub>. The cyclic voltammetry (CV) measurements reveal that the electrochemical active surface area (ECSA) of the Mn–CdS/TiO<sub>2</sub> electrode is higher than that of the undoped TiO<sub>2</sub>/CdS, exhibiting more surface active sites. The PEC measurements show that the optimized Mn–CdS/TiO<sub>2</sub> photoanode with Mn/Cd atomic ratio as 9:1000 achieves the highest photocurrent density of 16.00&#xa0;mA&#xa0;cm<sup>−2</sup> among the investigated ones. By analyzing the oxidation products of glycerol, it is found that the main products are formic acid and lactic acid with a total production rate of 719.87&#xa0;mmol&#xa0;m<sup>−2</sup>&#xa0;h<sup>−1</sup> and a total selectivity of 80.17%. Simultaneously, a hydrogen production rate of 1517.56&#xa0;mmol m<sup>−2</sup> h<sup>−1</sup> is obtained at the cathode within 2&#xa0;h at 0.9&#xa0;V versus RHE under AM 1.5G illumination (100&#xa0;mW&#xa0;cm<sup>−2</sup>). This work provides a versatile strategy for the preparation of high-performance TiO<sub>2</sub>-based photoanodes for both biomass upgrading into value-added chemicals and green hydrogen production.</p> Graphical abstract <p>An increased photoelectrochemical glycerol oxidation performance is achieved over ternary Mn–CdS/TiO<sub>2</sub> after Mn doping and the corresponding mechanism is investigated.</p>

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Selective photoelectrocatalytic glycerol oxidation over a ternary Mn–CdS/TiO2 photoanode with simultaneous hydrogen evolution

  • 期刊论文

  • 发表日期：

    2025年8月25日

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  • Chenfeng Jiang,
  • Jin Fang,
  • Jiayu Lin,
  • Yi Sun,
  • Wei Zhou,
  • Xiaoyan Zhang,
  • Weimin Cao,
  • Danhong Cheng

摘要

Solar-driven photoelectrocatalytic (PEC) technology has been widely recognized as a green and sustainable alternative to fossil fuel energy production. In this work, Mn2+ doped CdS/TiO2 nanorods (Mn–CdS/TiO2) photoanodes were prepared by a modified two-step hydrothermal method for green hydrogen production under simulated solar illumination. The effect of Mn doping on the PEC performance of CdS/TiO2 photoanode was systematically investigated. The UV–Vis diffuse reflectance spectrum, Mott–Schottky analysis and electrochemical impedance spectra demonstrate that Mn doping improves the visible light absorption, carrier density and charge separation of CdS/TiO2. The cyclic voltammetry (CV) measurements reveal that the electrochemical active surface area (ECSA) of the Mn–CdS/TiO2 electrode is higher than that of the undoped TiO2/CdS, exhibiting more surface active sites. The PEC measurements show that the optimized Mn–CdS/TiO2 photoanode with Mn/Cd atomic ratio as 9:1000 achieves the highest photocurrent density of 16.00 mA cm−2 among the investigated ones. By analyzing the oxidation products of glycerol, it is found that the main products are formic acid and lactic acid with a total production rate of 719.87 mmol m−2 h−1 and a total selectivity of 80.17%. Simultaneously, a hydrogen production rate of 1517.56 mmol m−2 h−1 is obtained at the cathode within 2 h at 0.9 V versus RHE under AM 1.5G illumination (100 mW cm−2). This work provides a versatile strategy for the preparation of high-performance TiO2-based photoanodes for both biomass upgrading into value-added chemicals and green hydrogen production.

Graphical abstract

An increased photoelectrochemical glycerol oxidation performance is achieved over ternary Mn–CdS/TiO2 after Mn doping and the corresponding mechanism is investigated.