Voytovich Vladimir V, Kurnosenko Sergei A, Silyukov Oleg I, Rodionov Ivan A, Minich Iana A, Zvereva Irina A
Institute of Chemistry, Saint Petersburg State University, Saint Petersburg, Russia.
Front Chem. 2020 Apr 23;8:300. doi: 10.3389/fchem.2020.00300. eCollection 2020.
A series of hybrid niobates HCaNbO×RNH, containing -alkylamines (R = Me, Et, Pr, Bu, Hx, Oc) intercalated into the interlayer space, has been thoroughly studied concerning the photocatalytic hydrogen production from a model aqueous solution of methanol for the first time. All the hybrid photocatalysts were synthesized by the conventional ceramic technique followed by protonation and intercalation of -alkylamines. The products were characterized using XRD, Raman, IR and diffuse reflectance spectroscopy, TGA, CHN-analysis and SEM. Photocatalytic measurements were conducted according to an advanced scheme taking into account possible changes in the photocatalyst concentration because of sedimentation, pH shifts and exfoliation of the samples into nanoplatelets. Special attention was also paid to the feasible improvement of the photocatalytic activity of the samples via their modification with Pt nanoparticles as a cocatalyst. In the series of amine derivatives, the highest rate of hydrogen generation was demonstrated by the Pt-loaded HCaNbO×BuNH reaching apparent quantum efficiency of 13% in the 220-340 nm range. The initial HCaNbO showed comparable efficiency of 8.3% that is greater than for other amine derivatives. It was demonstrated that for the investigated samples the photocatalytic activity correlates with their ability of water intercalation.
首次对一系列层间插入了含 - 烷基胺（R = 甲基、乙基、丙基、丁基、己基、辛基）的混合铌酸盐HCaNbO×RNH进行了深入研究，考察其在甲醇模型水溶液中的光催化产氢性能。所有混合光催化剂均采用传统陶瓷技术合成，随后进行 - 烷基胺的质子化和插层。通过X射线衍射（XRD）、拉曼光谱、红外光谱和漫反射光谱、热重分析（TGA）、元素分析（CHN分析）和扫描电子显微镜（SEM）对产物进行了表征。根据一种先进的方案进行光催化测量，该方案考虑了由于样品沉降、pH值变化以及样品剥落为纳米片而导致的光催化剂浓度的可能变化。还特别关注了通过用铂纳米颗粒作为助催化剂对样品进行改性来切实提高其光催化活性。在一系列胺衍生物中，负载铂的HCaNbO×BuNH表现出最高的产氢速率，在220 - 340 nm范围内表观量子效率达到13%。初始的HCaNbO表现出8.3%的可比效率，高于其他胺衍生物。结果表明，对于所研究的样品，光催化活性与其水插层能力相关。
