Department of Environmental Science and Engineering, Fuzhou University, Minhou, Fujian, 350108, P. R. China.
State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Minhou, Fujian, 350108, P. R. China.
ChemSusChem. 2022 Sep 20;15(18):e202201107. doi: 10.1002/cssc.202201107. Epub 2022 Aug 3.
It is of pivotal significance to explore robust photocatalysts to promote the photoreduction of CO into solar fuels. Herein, an intelligent metal-insulator-semiconductor (MIS) nano-architectural photosystem was constructed by electrostatic self-assembly between cetyltrimethylammonium bromide (CTAB) insulator-capped metal Ni nanoparticles (NPs) and covalent triazine-based frameworks (CTF-1). The metal-insulator-CTF composites unveiled a substantially higher CO evolution rate (1254.15 μmol g h ) compared with primitive CTF-1 (1.08 μmol g h ) and reached considerable selectivity (98.9 %) under visible-light irradiation. The superior photocatalytic CO conversion activity over Ni-CTAB-CTF nanoarchitecture could be attributed to the larger surface area, reinforced visible-light response, and CO capture capacity. More importantly, the Ni-CTAB-CTF nanoarchitecture endowed the photoexcited electrons on CTF-1 with the ability to tunnel across the thin CTAB insulating layer, directionally migrating to Ni NPs and thereby leading to the efficient separation of photogenerated electrons and holes in the photosystem. In addition, isotope-labeled ( CO ) tracer results verified that the reduction products come from CO rather than the decomposition of the photocatalysts. This study opens a new avenue for establishing a highly efficient and selective artificial photosystem for CO conversion.
探索稳健的光催化剂以促进 CO 光还原为太阳能燃料具有重要意义。在此，通过在具有介电常数的金属 Ni 纳米粒子（NPs）和共价三嗪基框架（CTF-1）之间的静电自组装，构建了智能金属-绝缘体-半导体（MIS）纳米结构光系统。与原始 CTF-1（1.08 μmol·g -1 ·h -1 ）相比，金属-绝缘体-CTF 复合材料表现出更高的 CO 析出率（1254.15 μmol·g -1 ·h -1 ），并且在可见光照射下达到了相当高的选择性（98.9%）。Ni-CTAB-CTF 纳米结构在 CO 转化活性方面的优异性能可归因于更大的比表面积、增强的可见光响应和 CO 捕获能力。更重要的是，Ni-CTAB-CTF 纳米结构赋予了 CTF-1 上的光激发电子穿过薄的 CTAB 绝缘层的能力，定向迁移到 Ni NPs，从而导致光系统中光生电子和空穴的有效分离。此外，同位素标记（ CO ）示踪结果验证了还原产物来自 CO 而不是光催化剂的分解。这项研究为建立高效和选择性的人工 CO 转化光系统开辟了新途径。
