Solar-driven Plasmonic Catalysis

该项目解决了与精确操纵催化和能量转换中原子/电荷转移的界面相关的主要挑战，其中的优先目标包括可见光等离子体催化和高选择性，例如将二氧化碳转化为甲醇。由多金属氧酸盐稳定的金属纳米粒子(POM@MNP)和聚碳氮化物(PCN)制备的一系列新的二元和三元催化材料将建立在POM@Ru在热催化、光催化和电催化方面的显著协同作用的基础上。该项目的基础是合成可调的单原子分子金属氧化物催化剂。它们将被用来制备POM@AuNP和POM@CuNP二元系统，以便在金属-氧化物/金属界面上精确地定位活性金属位置(例如，钛、锆、钒、铬、锰、铁、钴、镍、锌)。通过将这些POM@MNP支撑在PCN上而获得的三元材料将提供来自光活性和电活性PCN的附加功能。POM/MnP界面将用高分辨率电子显微镜进行分析，NPs在PCN上的分布将用电子断层扫描来确定。热和光催化实验将通过时间分辨光谱进行研究，并辅之以超快电荷提取动力学的研究。POM/MNP、POM/PCN、MNP/PCN和POM@MNP/PCN界面上的电荷转移将是开发新型可见光等离子体催化材料独特的光物理特性的关键。微调这些多组分催化剂的性质需要对这些体系有更深入的了解，这将得到DFT计算模型研究的帮助。在原子水平上精确地操纵界面将提高活性和选择性，并能够为新工艺设计催化剂，为二氧化碳的利用以及相关的能量转换和储存提供更好的能力。

This project addresses the major challenges associated with precise manipulation of interfaces for atom/charge transfer in catalysis and energy conversion, where high priority goals include visible-light plasmonic catalysis and high selectivity in e.g. CO2 conversion to MeOH. A range of new binary and ternary catalytic materials prepared from polyoxometalate-stabilised metal nanoparticles (POM@MNP) and polymeric carbon nitride (PCN) will build on previous work of the remarkable synergy in POM@Ru thermal, photo- and electro-catalysis.Underpinning the project is the synthesis of heterometal-substituted polyoxometalates (POMs) as tunable, single-atom, molecular metal oxide catalysts. These will be used to prepare POM@AuNP and POM@CuNP binary systems in order to precisely locate reactive metal sites (e.g. Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Zn) at the metal-oxide/metal interface. Ternary materials obtained by supporting these POM@MNP on PCN will provide additional functionality derived from the photo- and electro-active PCN. POM/MNP interfaces will be analysed by high resolution electron microscopy and the distribution of NPs on PCN will be determined using electron tomography. Thermal and photocatalytic experiments will be studied by time-resolved spectroscopy and supplemented by studies of ultrafast charge extraction dynamics. Charge transfer at POM/MNP, POM/PCN, MNP/PCN and POM@MNP/PCN interfaces will be key to exploiting the unique photo physics of the new binary and ternary materials for visible light plasmonic catalysis. Fine tuning the properties of these multicomponent catalysts will require a deeper understanding of these systems, and this will be aided by DFT computational modelling studies.Precise manipulation of interfaces at the atomic level will improve activity and selectivity and enable catalyst design for new processes, providing better capabilities for CO2 utilisation and related energy conversion and storage.