Pujari Sidharam P, Driss Hafedh, Bannani Fatma, van Lagen Barend, Zuilhof Han
Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708 WE Wageningen, The Netherlands.
Department of Chemical and Materials Engineering and Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia.
Chem Mater. 2018 Sep 25;30(18):6503-6512. doi: 10.1021/acs.chemmater.8b03113. Epub 2018 Sep 10.
Silicon nanoparticles (Si NPs) are highly attractive materials for typical quantum dots functions, such as in light-emitting and bioimaging applications, owing to silicon's intrinsic merits of minimal toxicity, low cost, high abundance, and easy and highly stable functionalization. Especially nonoxidized Si NPs with a covalently bound coating serve well in these respects, given the minimization of surface defects upon hydrosilylation of H-terminated Si NPs. However, to date, methods to obtain such H-terminated Si NPs are still not easy. Herein, we report a new synthetic method to produce size-tunable robust, highly crystalline H-terminated Si NPs (4-9 nm) using microwave irradiation within 5 min at temperatures between 25 and 200 °C and their further covalent functionalization. The key step to obtain highly fluorescent (quantum yield of 7-16%) green-red Si NPs in one simple step is the reduction of triethoxysilane and (+)-sodium l-ascorbate, yielding routinely ∼1 g of H-Si NPs via a highly scalable route in 5-15 min. Subsequent functionalization via hydrosilylation yielded Si NPs with an emission quantum yield of 12-14%. This approach can be used to easily produce high-quality H-Si NPs in gram-scale quantities, which brings the application of functionalized Si NPs significantly closer.
硅纳米颗粒(Si NPs)因其具有低毒性、低成本、高丰度以及易于且高度稳定地进行功能化等固有优点,对于典型的量子点功能,如发光和生物成像应用而言,是极具吸引力的材料。特别是具有共价键合涂层的非氧化Si NPs在这些方面表现出色,因为氢终止的Si NPs进行硅氢化反应时表面缺陷得以最小化。然而,迄今为止,获得此类氢终止的Si NPs的方法仍然不容易。在此,我们报告了一种新的合成方法,该方法使用微波辐射,在25至200°C的温度下5分钟内即可制备出尺寸可调的、坚固的、高度结晶的氢终止Si NPs(4 - 9纳米)及其进一步的共价功能化。在一个简单步骤中获得高荧光性(量子产率为7 - 16%)的绿 - 红Si NPs的关键步骤是三乙氧基硅烷和(+)-l - 抗坏血酸钠的还原反应,通过高度可扩展的路线在5 - 15分钟内常规产出约1克氢硅纳米颗粒。随后通过硅氢化反应进行功能化,得到发射量子产率为12 - 14%的Si NPs。这种方法可用于轻松地以克级规模生产高质量的氢硅纳米颗粒,这使得功能化Si NPs的应用大大向前推进。