Watanabe Shinta, Inaba Yusuke, Harigai Miki, Takeshita Kenji, Onoe Jun
Department of Energy Science and Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-8603, Japan.
Laboratory for Zero-Carbon Energy, Tokyo Institute of Technology, 2-12-1-N1-16, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
Sci Rep. 2022 Mar 24;12(1):5135. doi: 10.1038/s41598-022-08838-1.
We have examined the uptake mechanisms of platinum-group-metals (PGMs) and molybdenum (Mo) ions into Prussian blue nanoparticles (PBNPs) in a nitric acid solution for 24-h sorption test, using inductively coupled plasma atomic emission spectroscopy, powder XRD, and UV-Vis-NIR spectroscopy in combination with first-principles calculations, and revealed that the Ru and Pd ions are incorporated into PBNPs by substitution with Fe and Fe ions of the PB framework, respectively, whereas the Rh ion is incorporated into PBNPs by substitution mainly with Fe and minorly with Fe ion, and Mo ion is incorporated into PBNPs by substitution with both Fe and Fe ions, with maintaining the crystal structure before and after the sorption test. Assuming that the amount of Fe elusion is equal to that of PGMs/Mo substitution, the substitution efficiency is estimated to be 39.0% for Ru, 47.8% for Rh, 87% for Pd, and 17.1% for Mo. This implies that 0.13 g of Ru, 0.16 g of Rh, 0.30 g of Pd, and 0.107 g of Mo can be recovered by using 1 g PBNPs with a chemical form of KFe(III)[Fe(II)(CN)].
我们通过电感耦合等离子体原子发射光谱法、粉末X射线衍射法和紫外-可见-近红外光谱法，并结合第一性原理计算，研究了在硝酸溶液中进行24小时吸附试验时铂族金属（PGMs）和钼（Mo）离子进入普鲁士蓝纳米颗粒（PBNPs）的摄取机制，结果表明，Ru和Pd离子分别通过取代PB骨架中的Fe和Fe离子而掺入PBNPs中，而Rh离子主要通过取代Fe并少量取代Fe离子而掺入PBNPs中，Mo离子通过同时取代Fe和Fe离子而掺入PBNPs中，吸附试验前后晶体结构保持不变。假设Fe的溶出量等于PGMs/Mo的取代量，则Ru的取代效率估计为39.0%，Rh为47.8%，Pd为87%，Mo为17.1%。这意味着使用1 g化学形式为KFe(III)[Fe(II)(CN)]的PBNPs可以回收0.13 g的Ru、0.16 g的Rh、0.30 g的Pd和0.107 g的Mo。
