Scalable and sustainable manufacturing of ultrathin metal-organic framework nanosheets (MONs) for solar cell applications
Scalable and sustainable manufacturing of ultrathin metal-organic framework nanosheets (MONs) for solar cell applications
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DOI：
10.1016/j.cej.2023.146871
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发表时间：
2023-10
影响因子：
15.1
通讯作者：
David J. Ashworth;Justin Driver;Kezia Sasitharan;Ram R.R. Prasad;Joshua Nicks;Benedict J. Smith;
中科院分区：
文献类型：
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作者：
David J. Ashworth;Justin Driver;Kezia Sasitharan;Ram R.R. Prasad;Joshua Nicks;Benedict J. Smith;
金属有机骨架纳米片（MONs）是一类新兴的2D材料，其可调化学使其成为广泛的传感，催化，电子和分离应用的理想选择。然而，创建可扩展的路线来合成高质量的纳米片仍然具有挑战性，并且很少考虑制造这些材料的经济性。在这里，我们展示了用于有机太阳能电池的锌卟啉基纳米片Zn 2（H2 TCPP）的可扩展合成，并对其中试规模生产进行了技术经济分析。对溶剂热合成的工艺化学的彻底研究使得能够减少反应时间、增加固体含量和批量放大反应。值得注意的是，三乙胺的加入加速了反应动力学，这使得合成温度能够从> 80 °C降至室温。在连续搅拌釜反应器中应用这些新的反应条件直接形成单层MON，产率为99%，时空产率为16 kg m-3天-1，与采用文献方法相比，产率增加约20倍。技术经济分析表明，与文献反应条件相比，生产成本降低了94%，并表明生产成本主要由配体价格决定。通过合成相关的Cu 2（H2 TCPP）MONs和通过金属化的卟啉单元与六种不同的金属离子的可调谐性证明了该方法的普遍适用性。最后，纳米片的价值通过有机光伏器件的功率转换效率在MONs被纳入到活性层时的近一倍来证明。总的来说，这项工作展示了第一个可扩展和可持续的路线，以生产高价值应用的单层纳米片。
Metal-organic framework nanosheets (MONs) are an emerging class of 2D materials whose tunable chemistry make them ideal for a wide range of sensing, catalytic, electronics and separation applications. However, creating scalable routes to the synthesis of high quality, ultrathin nanosheets remains challenging and little consideration has been given to the economics of making these materials. Here, we demonstrate a scalable synthesis of zinc-porphyrin based nanosheets, Zn2(H2TCPP), for use in organic solar cells and conduct a techno-economic analysis of their pilot-plant scale manufacture. A thorough investigation of the process chemistry of the solvothermal synthesis enabled reduction of reaction time, increased solid content and scale-up of the reaction in batch. Significantly, the addition of triethylamine accelerated the reaction kinetics, which enabled the synthesis temperature to be dropped from > 80 °C to room temperature. Application of these new reaction conditions in a continuous stirred-tank reactor directly formed monolayer MONs at 99 % yield with a space–time yield of 16 kg m−3day−1, an approximately 20-fold increase in yield compared to adapting the literature procedure. Techno-economic analysis showed a 94 % reduction in the production costs compared to the literature reaction conditions and indicated that the production cost was dominated by ligand price. The general applicability of the method was demonstrated through synthesis of related Cu2(H2TCPP) MONs and tunability through metalation of the porphyrin units with six different metal ions. Finally, the value of the nanosheets was demonstrated through a near doubling in the power conversion efficiency of organic photovoltaic devices when the MONs were incorporated into the active layer. Overall, this work demonstrates the first scalable and sustainable route to producing monolayer nanosheets for high value applications.