Built-in Electric Fields Enhancing Photocarrier Separation and H2 Evolution

IF 13.5 2区化学 Q1 CHEMISTRY, PHYSICAL 物理化学学报 Pub Date : 2024-11-01 Epub Date: 2023-12-25 DOI:10.3866/PKU.WHXB202311001

Peipei Sun , Jinyuan Zhang , Yanhua Song , Zhao Mo , Zhigang Chen , Hui Xu

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Abstract

The construct of the internal electric field (IEF) is recognized as an effective driver for promoting charge migration and separation to enhance photocatalytic performance. In this study, one-dimensional nanorods of Mn_0.2Cd_0.8S (MCS) co-doped with interstitial chlorine (Cl_int) and substitutional chlorine (Cl_sub) were designed and synthesized using a one-step solvothermal method. The incorporation of Cl_int and Cl_sub led to an unbalanced charge distribution and the formation of IEF in the MCS nanorods, contributing to the improvement of photogenerated carrier kinetic behavior. Through density functional theory (DFT) calculations, the effect of Cl_int and Cl_sub doping on the activity of the MCS was visually explained by examining differences in electronic structure, charge distribution and H₂ adsorption/desorption balance. Interestingly, the modulation of the energy band structure of MCS primarily resulted from the contribution of Cl_int, while Cl_sub playing a negligible role. Moreover, the Cl_sub further facilitated the optimization of Cl_int concerning the H₂ adsorption-desorption Gibbs free energy

(Δ G_{H *})

of MCS. Ultimately, the

Δ G_{H *}

of 0.9 Cl-MCS favored H₂ production (1.14 vs. 0.17 eV), leading to a 9 times increase in photocatalytic H₂ production activity compared to MCS. This investigation presents a valuable approach for constructing IEF in bimetallic sulfide photocatalysts.

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内置电场增强光载流子分离和H2演化

内部电场（IEF）的构建是促进电荷迁移和分离以提高光催化性能的有效驱动因素。本研究采用一步溶剂热法设计并合成了Mn0.2Cd0.8S （MCS）与间隙氯（Clint）和取代氯（Clsub）共掺杂的一维纳米棒。Clint和Clsub的掺入导致MCS纳米棒中的电荷分布不平衡，并形成IEF，有助于改善光生载流子的动力学行为。通过密度泛函理论（DFT）计算，从电子结构、电荷分布和H2吸附/解吸平衡的差异上直观地解释了Clint和Clsub掺杂对MCS活性的影响。有趣的是，MCS的能带结构的调制主要是由于Clint的贡献，而Clsub的作用可以忽略不计。此外，Clsub进一步促进了MCS对H2吸附-解吸Gibbs自由能（ΔGH*）的Clint优化。最终，0.9 Cl-MCS的ΔGH*有利于H2生成（1.14 vs. 0.17 eV），导致光催化H2生成活性比MCS提高9倍。本研究为在双金属硫化物光催化剂中构建IEF提供了一条有价值的途径。下载：下载高清图片（91KB）下载：下载全尺寸图片

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