Simon Zoe C, Paterno Ann Marie N, McHugh Kaitlyn M, Moncure Paige J, Sen Riti, Patton Samuel T, Lopato Eric M, Talledo Savannah, Bernhard Stefan, Millstone Jill E
Department of Chemistry, University of Pittsburgh Pittsburgh Pennsylvania 15260 USA
Department of Chemistry, Carnegie Mellon University Pittsburgh Pennsylvania 15213 USA.
Chem Sci. 2023 Feb 15;14(11):2860-2865. doi: 10.1039/d2sc06980f. eCollection 2023 Mar 15.
Whether in organic synthesis or solar energy conversion, light can be a powerful reagent in chemical reactions and introduce new opportunities for synthetic control including duration, intensity, interval, and energy of irradiation. Here, we report the use of a molecular photosensitizer as a reducing agent in metallic nanoparticle syntheses. Using this approach, we report three key findings. (1) Nanoparticles produced by photocatalytic reduction form a continuous nucleation mechanism, as opposed to burst and burst-like nucleation processes typically observed in metal nanoparticle syntheses. (2) Because nucleation is continuous, as long as the solution is irradiated (and there remains excess reagents in solution), nanoparticle nucleation can be turned on and off by controlling the timing and duration of irradiation, with no observable particle growth. (3) This synthetic method extends to the formation of bimetallic nanoparticles, which we show also form a continuous nucleation pathway, and follow predicted patterns of metal incorporation as a function of the magnitude of the difference between the reduction potentials of the two metals. Taken together, these results establish a versatile synthetic method for the formation of multimetallic nanoparticles using visible light.
无论是在有机合成还是太阳能转换中,光都可以成为化学反应中的一种强大试剂,并为合成控制带来新的机会,包括照射的持续时间、强度、间隔和能量。在此,我们报告了在金属纳米颗粒合成中使用分子光敏剂作为还原剂的情况。通过这种方法,我们报告了三个关键发现。(1)光催化还原产生的纳米颗粒形成连续成核机制,这与金属纳米颗粒合成中通常观察到的爆发式和成核样成核过程相反。(2)由于成核是连续的,只要溶液受到照射(并且溶液中仍有过量试剂),通过控制照射的时间和持续时间,纳米颗粒成核就可以开启和关闭,而没有可观察到的颗粒生长。(3)这种合成方法扩展到双金属纳米颗粒的形成,我们表明双金属纳米颗粒也形成连续成核途径,并遵循预测的金属掺入模式,该模式是两种金属还原电位之差大小的函数。综上所述,这些结果建立了一种使用可见光形成多金属纳米颗粒的通用合成方法。