第一作者：广东石油化工学院 Xiaolong Tang
通讯作者：广东石油化工学院 余长林，清华大学 朱永法
DOI：https://doi.org/10.1021/acscatal.4c04341
目前光催化H2O2生产系统中载流子重组率高的限制，极大地抑制了H2O2的生成速度。本研究通过原位聚合葡萄糖在In2S3上成功制备了In-S-C键桥接的In2S3/HTCC致密异质结。该界面In-S-C键为界面上的电子提供了快速转移通道，实现了高效的界面电荷转移效率，从而在In2S3和HTCC之间形成了增强的内置电场，从而大大加快了电荷分离的速度，有效延长了光生载流子的寿命。HTCC的覆盖增强了In2S3对可见光的吸收和对O2的吸收，同时降低了其双电子氧还原反应（ORR）的能垒。值得注意的是，研究表明，In2S3/HTCC不仅可以通过两步单电子ORR生成H2O2，还可以通过利用1O2作为中间体的替代途径生成H2O2，从而提高H2O2的产量。利用这些优势，In2S3/HTCC-2在纯水体系中产生H2O2的速率高达1392 μmol g-1 h-1，分别是纯In2S3和HTCC的18.2和5.2倍。该工作不仅提供了一种新的基于HTCC的有机/无机异质结光催化剂的合成方法，而且为异质结构的界面键合调节光催化产生H2O2活性的潜在机制提供了新的见解。
Figure 1. (a) Scheme of the synthesis of In2S3/HTCC. (b) SEM images of In2S3, (c) HTCC, and (d) In2S3/HTCC. (e, f) HRTEM images of In2S3/HTCC.
Figure 2. (a) XRD spectra of all samples. (b) Raman spectra of In2S3, In2S3/HTCC, and HTCC. High-resolution XPS spectra of In2S3, HTCC, and In2S3/HTCC: (c) In 3d, (d) S 2p, (e) C 1s, (f) O 1s.
Figure 3. (a) Photocatalytic production of H2O2 under visible light irradiation for all samples. (b) Kd and Kf values for photocatalytic production of H2O2 for 1 h of photocatalysis for all samples. (c) UV−vis DRS spectra and AQY values under monochromatic light irradiation of In2S3/HTCC-2. (d) Cyclic testing of H2O2 photocatalytic production by In2S3/HTCC-2. (e) Comparison of the H2O2 yields of In2S3/HTCC-2 with those of other photocatalysts reported in the last two years.
Figure 4. (a) Charge density difference between the heterogeneous structures of In2S3/HTCC. The brown, red, pink, purple, and yellow colors correspond to the C, O, H, In, and S atoms, respectively. (b) schematic illustration of the band structures for In2S3/HTCC, (c) photocurrent densities, and (d) EIS maps of all samples. (e) TRPL spectra of In2S3, HTCC, and In2S3/HTCC. (f) SPV values of different photocatalysts and photocatalytic H2O2 yield for each sample.
Figure 5. (a) ESR plots of In2S3/HTCC for DMPO-·O2−, DMPO-·OH, and TEMPO−1O2. (b) H2O2 yields of In2S3/HTCC reacted for 1 h in different sacrificial systems. (c) In situ FTIR spectra of In2S3/HTCC. (d) Schematic diagram of the mechanism of In2S3/HTCC photocatalytic production of H2O2. (e) Free energy profiles of 2e−ORR processes on In2S3 and In2S3/HTCC; and O2 adsorption on (f) HTCC, (g) In2S3, and (h) In2S3/HTCC. The brown, red, pink, purple, and yellow colors correspond to the C, O, H, In, and S atoms.
Furan-Based HTCC/In2S3 Heterojunction Achieves Fast Charge Separation To Boost the Photocatalytic Generation of H2O2 in Pure Water
https://doi.org/10.1021/acscatal.4c04341
