Zhang Xiaohan, Li Tong, Hu Chun, Yan Xiutong, Qiao Kai, Chen Zhihong
Institute of Environmental Research at Greater Bay, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou University, Guangzhou 510006, China.
School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China.
Nanomaterials (Basel). 2022 Aug 25;12(17):2929. doi: 10.3390/nano12172929.
Graphitic CN-based materials are promising for photocatalytic H evolution applications, but they still suffer from low photocatalytic activity due to the insufficient light absorption, unfavorable structure and fast recombination of photogenerated charge. Herein, a novel anion-cation co-doped g-CN porous nanotube is successfully synthesized using a self-assembly impregnation-assisted polymerization method. Ni ions on the surface of the self-assembly nanorod precursor can not only cooperate with HP gas from the thermal cracking of NaHPO as an anion-cation co-doping source, but, more importantly, suppress the shape-collapsing effect of the etching of HP gas due to the strong coordinate bonding of Ni-P, which leads to a Ni and P co-doped g-CN porous nanotube (PNCNT). Ni and P co-doping can build a new intermediate state near the conduction band in the bandgap of the PNCNT, and the porous nanotube structure gives it a higher BET surface area and light reflection path, showing a synergistic ability to broaden the visible-light absorption, facilitate photogenerated charge separation and the light-electron excitation rate of g-CN and provide more reaction sites for photocatalytic H evolution reaction. Therefore, as expected, the PNCNT exhibits an excellent photocatalytic H evolution rate of 240.91 μmol·g·h, which is 30.5, 3.8 and 27.8 times as that of the pure g-CN nanotube (CNT), single Ni-doped g-CN nanotube (NCNT) and single P-doped g-CN nanotube (PCNT), respectively. Moreover, the PNCNT shows good stability and long-term photocatalytic H production activity, which makes it a promising candidate for practical applications.
基于石墨相氮化碳的材料在光催化析氢应用方面具有潜力,但由于光吸收不足、结构不理想以及光生电荷快速复合,其光催化活性仍然较低。在此,采用自组装浸渍辅助聚合方法成功合成了一种新型的阴离子 - 阳离子共掺杂石墨相氮化碳多孔纳米管。自组装纳米棒前驱体表面的镍离子不仅可以与磷酸氢二钠热裂解产生的磷化氢气体协同作为阴离子 - 阳离子共掺杂源,更重要的是,由于镍 - 磷之间的强配位键,抑制了磷化氢气体蚀刻导致的形状坍塌效应,从而得到镍和磷共掺杂的石墨相氮化碳多孔纳米管(PNCNT)。镍和磷共掺杂可以在PNCNT的带隙中靠近导带处构建一个新的中间态,并且多孔纳米管结构赋予其更高的比表面积和光反射路径,显示出协同拓宽可见光吸收、促进光生电荷分离以及提高石墨相氮化碳的光电子激发速率的能力,并为光催化析氢反应提供更多反应位点。因此,正如预期的那样,PNCNT表现出优异的光催化析氢速率,为240.91 μmol·g·h -1,分别是纯石墨相氮化碳纳米管(CNT)、单镍掺杂石墨相氮化碳纳米管(NCNT)和单磷掺杂石墨相氮化碳纳米管(PCNT)的30.5倍、3.8倍和27.8倍。此外,PNCNT表现出良好的稳定性和长期光催化产氢活性,这使其成为实际应用中有前景的候选材料。