Solar-driven Plasmonic Catalysis

该项目解决了与催化和能量转换中原子/电荷转移界面的精确操作相关的主要挑战，其中高优先级目标包括可见光等离子体催化和高选择性，例如CO2转化为MeOH。一系列新的二元和三元催化材料由多金属氧酸稳定的金属纳米颗粒（POM@MNP）和聚合氮化碳（PCN）制备，将建立在先前在POM@Ru热、光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异质金属取代多金属氧酸盐（pom）作为可调的单原子分子金属氧化物催化剂。这些将用于制备POM@AuNP和POM@CuNP二元体系，以便精确定位金属-氧化物/金属界面上的活性金属位点（例如Ti， Zr， V, Cr, Mn, Fe, Co, Ni, Zn）。通过在PCN上支持这些POM@MNP获得的三元材料将提供来自光和电活性PCN的额外功能。POM/MNP界面将通过高分辨率电子显微镜进行分析，NPs在PCN上的分布将通过电子断层扫描确定。热催化和光催化实验将通过时间分辨光谱进行研究，并辅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利用新型二元和三元材料独特的光物理特性进行可见光等离子体催化的关键。微调这些多组分催化剂的性质将需要对这些系统有更深入的了解，这将有助于DFT计算建模研究。在原子水平上对界面的精确操作将提高活性和选择性，并使催化剂能够设计新的工艺，为二氧化碳利用和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.