4.8 Article

Energy Platform for Directed Charge Transfer in the Cascade Z-Scheme Heterojunction: CO2 Photoreduction without a Cocatalyst

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 38, Pages 20906-20914

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202106929

Keywords

charge lifetime; charge modulation; heterojunctions; photocatalysis; Z-Scheme heterojunctions

Funding

  1. National Natural Science Foundation of China [U1805255]
  2. UK EPSRC [EP/S018204/2]
  3. Royal Society Newton Advanced Fellowship grant [NAF\R1\191163, NA170422]
  4. Leverhulme Trust [RPG-2017-122]
  5. EPSRC [EP/S018204/2] Funding Source: UKRI

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A universal strategy was developed to construct a cascade Z-Scheme system using an effective energy platform as the core to direct charge transfer and separation. The experimental results and DFT calculations based on van der Waals structural models revealed that the introduced platform prolonged the lifetimes of spatially separated electrons and holes without compromising their reduction and oxidation potentials. The optimized cascade Z-Scheme showed significant improvement in photoactivity for CO2 reduction to CO under visible-light irradiation, surpassing other reported Z-Scheme systems even with noble metals as mediators.
A universal strategy is developed to construct a cascade Z-Scheme system, in which an effective energy platform is the core to direct charge transfer and separation, blocking the unexpected type-II charge transfer pathway. The dimension-matched (001)TiO2-g-C3N4/BiVO4 nanosheet heterojunction (T-CN/BVNS) is the first such model. The optimized cascade Z-Scheme exhibits approximate to 19-fold photoactivity improvement for CO2 reduction to CO in the absence of cocatalysts and costly sacrificial agents under visible-light irradiation, compared with BVNS, which is also superior to other reported Z-Scheme systems even with noble metals as mediators. The experimental results and DFT calculations based on van der Waals structural models on the ultrafast timescale reveal that the introduced T as the platform prolongs the lifetimes of spatially separated electrons and holes and does not compromise their reduction and oxidation potentials.

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