Unconventional Substitution for BiVO4 to Enhance Photoelectrocatalytic Performance by Accelerating Polaron Hopping,ACS Applied Materials & Interfaces

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Unconventional Substitution for BiVO4 to Enhance Photoelectrocatalytic Performance by Accelerating Polaron Hopping
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-03-07 , DOI: 10.1021/acsami.2c23169
Jiachen Wang ₁ , Jing Bai ₁ , Yan Zhang ₁ , Lei Li ₁ , Changhui Zhou ₁ , Tingsheng Zhou ₁ , Jinhua Li ₁ , Hong Zhu ₂ , Baoxue Zhou _{1,

3}

Affiliation

Bismuth vanadate (BiVO₄) as a fascinating semiconductor for photoelectrocatalytic (PEC) water oxidation with suitable band gap (E_g) has been limited by the issue of poor separation and transportation of charge carriers. Herein, we propose an unconventional substitution of V⁵⁺ sites by Ti⁴⁺ in BiVO₄ (Ti:BiVO₄) for the similar ionic radii and accelerated polaron hopping. Ti:BiVO₄ increased the photocurrent density 1.90 times up to 2.51 mA cm^–2 at 1.23 V vs RHE and increased the charge carrier density 1.81 times to 5.86 × 10¹⁸ cm^–3. Compared with bare BiVO₄, Ti:BiVO₄ improves the bulk separation efficiency to 88.3% at 1.23 V vs RHE. The DFT calculations have illustrated that Ti-doping modification could decrease the polaron hopping energy barrier, narrow the E_g, and decrease the overpotential of the oxygen evolution reaction (OER) concurrently. With further spin-coated FeOOH cocatalyst, the photoanode has a photocurrent density of 3.99 mA cm^–2 at 1.23 V vs RHE. The excellent PEC performance of FeOOH/Ti:BiVO₄ is attributed to the synergistic effect of the FeOOH layer and Ti doping, which could promote charge carrier separation and transfer by expediting polaron migration.

中文翻译：

BiVO4 的非常规替代通过加速极化子跳跃来增强光电催化性能

钒酸铋（BiVO ₄ ）作为一种具有合适带隙（ E _g ）的用于光电催化（PEC）水氧化的迷人半导体，一直受到电荷载流子分离和传输不良问题的限制。在此，我们提出在BiVO ₄ (Ti:BiVO ₄ ) 中用Ti ⁴⁺非常规地取代V ⁵⁺位点，以获得相似的离子半径和加速极化子跳跃。 Ti:BiVO ₄在1.23 V vs RHE下将光电流密度提高1.90倍，达到2.51 mA cm ^–2 ，并将载流子密度提高1.81倍，达到5.86 × 10 ¹⁸ cm ^–3 。与裸BiVO ₄相比，Ti:BiVO ₄在1.23 V vs RHE下将体分离效率提高至88.3%。 DFT计算表明Ti掺杂改性可以降低极化子跳跃能垒，缩小E _g ，同时降低析氧反应（OER）的过电势。通过进一步旋涂 FeOOH 助催化剂，光电阳极在 1.23 V vs RHE 下的光电流密度为 3.99 mA cm ^–2 。 FeOOH/Ti:BiVO ₄优异的PEC性能归因于FeOOH层和Ti掺杂的协同效应，它可以通过加速极化子迁移来促进载流子分离和转移。

更新日期：2023-03-07

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