Li Yanbing, Jin Zhiliang, Tsubaki Noritatsu
Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan; School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, PR China.
School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, PR China.
J Colloid Interface Sci. 2023 Jul;641:861-874. doi: 10.1016/j.jcis.2023.03.068. Epub 2023 Mar 15.
Although Prussian blue and its analogs (PB/PBAs) have open framework structures, large surface areas, uniform metal active sites, and tunable compositions, and have been investigated for a long time, owing to their unfavorable visible light responsiveness, they rarely been reported in photocatalysis. This largely limits their applications in solar-to-chemical energy conversion. Here, a continuous-evolution strategy was conducted to convert the poor-performance NiCo PBA (NCP) toward high-efficiency complex photocatalytic nanomaterials. First, chemical etching was performed to transform raw NCP (NCP-0) to hollow-structured NCP (including NCP-30, and NCP-60) with enhanced diffusion, penetration, mass transmission of reaction species, and accessible surface area. Then, the resultant hollow NCP-60 frameworks were further converted into advanced functional nanomaterials including CoO/3NiO, NiCoP nanoparticles, and CoNiS nanorods with a considerably improved photocatalytic H evolution performance. The hollow-structured NCP-60 particles exhibit an enhanced H evolution rate (1.28 mol gh) compared with the raw NCP-0 (0.64 mol gh). Furthermore, the H evolution rate of the resulting NiCoP nanoparticles reached 16.6 mol gh, 25 times that of the NCP-0, without any cocatalysts.
尽管普鲁士蓝及其类似物（PB/PBAs）具有开放框架结构、大表面积、均匀的金属活性位点和可调节的组成，并且已经被研究了很长时间，但由于其可见光响应性不佳，它们在光催化方面鲜有报道。这在很大程度上限制了它们在太阳能到化学能转换中的应用。在此，采用连续演化策略将性能不佳的镍钴PBA（NCP）转化为高效的复合光催化纳米材料。首先，进行化学蚀刻，将原始NCP（NCP-0）转化为具有增强的反应物种扩散、渗透、传质和可及表面积的中空结构NCP（包括NCP-30和NCP-60）。然后，将所得的中空NCP-60框架进一步转化为具有显著改善的光催化析氢性能的先进功能纳米材料，包括CoO/3NiO、NiCoP纳米颗粒和CoNiS纳米棒。与原始NCP-0（0.64 μmol g⁻¹ h⁻¹）相比，中空结构的NCP-60颗粒表现出更高的析氢速率（1.28 μmol g⁻¹ h⁻¹）。此外，所得NiCoP纳米颗粒的析氢速率达到16.6 μmol g⁻¹ h⁻¹，是NCP-0的25倍，且无需任何助催化剂。
