第一作者：贵州大学 Yuhui Liu
通讯作者：贵州大学 陈鹏、Xiaoxu Deng，湖南大学 尹双凤
DOI：https://doi.org/10.1021/acscatal.4c05031
构建紧凑的直接Z和S型异质结构是实现高效电荷分离和光催化性能的有效策略。然而，界面取向的随机性和晶格失配往往导致有效内部电荷转移的盲区，这阻碍了紧凑异质结的逻辑设计。实验结果和理论研究表明，在紧凑的S-scheme异质结构中，复杂的内部电荷可以直接转移到中间共晶平面进行电子-空穴复合，这有助于建立一个驱动电荷转移的固有电场。此外，这些Bone-Joint结构调节了内在的化学和能量相互作用，从而操纵了反应物的吸附模式和表面反应能。结果表明，合成的催化剂具有良好的过氧化氢生产性能和稳定性。这为异质结构内电荷传递动力学提供了一种范式，并为设计高效的异质结构提供了指导思想。
Figure 1. (a) Comparison of the charge transfer pathways of S-scheme heterojunction mechanisms. (b) HR-TEM images of ZIS-2 and (c) schematic models of the observed HR-TEM images. The blue and orange balls are the atoms of Zn2In2S5 and ZnIn2S4, respectively. (d, e) HAADFSTEM images of the ZIS-2 phase interface. (f) Zn EXAFS spectra in R space for ZnS, ZIS-2, and ZIS-R. Morlet wavelet transform contour plots for the k3-weighted EXAFS spectra for ZIS-R (g) and ZIS-2 (h).
Figure 2. Three-dimensional plots of the differences in the potentials of (a) ZIS-2 and (d) ZIS-R in the dark compared to (b) ZIS-2 and (e) ZIS-R in light illumination environments. Distribution of the differences in the potentials of (c) ZIS-2 and (f) ZIS-R in light illumination and dark environments. (g) Differential charge density and work functions of ZIS. Pseudocolor TA spectra of (h) ZIS-R and (i) ZIS-2 in the initial time window of 100 ps. Typical TA kinetics probed at 700 nm for (j) ZIS-R and (k) ZIS-2. (l) Decay pathways of photogenerated electrons in ZIS-R and ZIS-2.
Figure 3. (a) Performance of photocatalytic H2O2 production. (b) AQY of H2O2 production over ZIS-2. (c) Amount of H2O2 generated by ZIS-2 under AM 1.5 G simulated sunlight irradiation (100 mW cm−2) and the corresponding SCC efficiency. (d) RRDE polarization curves over the catalyst in an O2-saturated 0.1 M KOH solution at 1600 rpm with ring current (upper part) and disk current (bottom part). (e) Inset shows the calculated average number of transferred electrons (n) (upper part). H2O2 selectivity as a function of the applied potential (bottom part). (f) Comparison of the photocatalytic production of H2O2 of different catalysts. (g) Stability of ZIS-2 during the photocatalytic production of H2O2.
Figure 4. (a) In situ FT-IR spectroscopy was utilized to study the reaction of ZIS-2. (b) Comparison of chemical bond lengths and charge densities before and after O2(−O−O−) adsorption of ZIS. (c) Comparison of the Gibbs free energies of the two reaction pathways. (d) Comparison of Gibbs free energies in the formation of H2O2 from several materials.
Unveiling Intrinsic Charge Transfer Dynamics in Bone-Joint S‑Scheme Heterostructures To Promote Photocatalytic Hydrogen Peroxide Generation
https://doi.org/10.1021/acscatal.4c05031
