RUI: Modulation of cation exchange using oxidation/reduction to design plasmonic nanoheterostructures

RUI摘要：通过氧化/还原调节阳离子交换来设计等离子体纳米异质结构DMR-2003337第1部分：非技术摘要制造下一代纳米材料的一种方法是将单个纳米颗粒转化为更复杂的结构。这个过程从一种形式的纳米颗粒开始，然后用一种类型的原子交换另一种类型的原子。这使得纳米颗粒具有最初的大小和形状，但具有更多的化学成分。这一有用但尚未完全了解的过程称为阳离子交换。该项目由材料研究部的固态和材料化学计划支持，揭示了如何通过改变起始纳米颗粒的特征来改变阳离子交换的结果。预计这将影响粒子在化学上的变化程度以及新成分的去向。它还将改变粒子吸收光线的方式。通过这些实验获得的对阳离子交换如何工作的洞察力将使人们能够控制纳米级的化学和结构。这最终将使设计和创造复杂的纳米设备成为可能，这些设备具有对社会重要的广泛应用，特别是在传感和太阳能转换方面。除了直接来自科学的好处外，材料化学的培训将通过本科生研究和主要是本科机构的实验室与R1大学的实验室之间的创新伙伴关系来加强。宾夕法尼亚州中部地区的研究基础设施将得到支持，广泛参与化学和材料的障碍将减少。第二部分：技术综述从硫化铜纳米颗粒开始，通过阳离子交换选择性地引入新的组分，形成了设计的纳米异质结构。初步数据表明，沸石纳米颗粒的碘氧化改变了与镉和锌离子的阳离子交换倾向，因为它同时改变了硫化铜颗粒的局域表面等离子体共振。提出了氧化/还原过程可以作为调控部分阳离子交换的化学和空间选择性的工具。该项目由材料研究部的固态和材料化学计划支持，旨在揭示硫化铜纳米颗粒通过氧化还原过程的变化所影响的结构-性质关系，并利用这些关系设计新型的等离子体纳米异质结构。该项目研究了各种氧化和还原方法，并阐明了对硫化铜纳米颗粒的结构、铜离子空位浓度、等离子体行为和阳离子交换倾向的影响。拟议中的工作揭示的基本见解将提高我们在纳米尺度上控制化学和结构的能力。所研究的颗粒有可能用作催化剂、光伏或太阳水蒸发中的太阳能吸收剂、光热癌症治疗中的近红外吸收剂或传感器。材料化学方面的培训将通过本科生研究和密切的师生互动以及主要是本科生机构的实验室和R1大学的实验室之间的创新伙伴关系来加强。宾夕法尼亚州中部地区的研究基础设施将得到支持，广泛参与化学和材料研究的障碍将减少。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Abstracts for RUI: Modulation of cation exchange using oxidation/reduction to design plasmonic nanoheterostructures DMR-2003337 PART 1: NON-TECHNICAL SUMMARYOne route to create next-generation nanomaterials is by taking single nanoparticles and transforming them into more complex structures. The process starts with one form of nanoparticle and trades out one type of atom for another. This leaves the nanoparticle with the same size and shape it started with, but with additional chemical components. This useful, but not yet fully understood, process is called cation exchange. This project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, uncovers how one can change the outcome of cation exchange by altering the features of the starting nanoparticle. It is expected that this will affect how much the particle changes in chemistry and where the new components go. It will also change the way the particles absorb light. The insights into how cation exchange works gained through these experiments will allow control over chemistry and structure on the nanoscale. This will eventually make it possible to design and create complex nanodevices that have a broad range of applications that are important to society, particularly in sensing and solar energy conversion. In addition to the benefits that come from directly from the science, training in materials chemistry will be strengthened through undergraduate research and an innovative partnership between laboratories at a primarily undergraduate institution and at an R1 university. Research infrastructure in the Central Pennsylvania region will be supported and barriers to broad participation in chemistry and materials will be reduced. PART 2: TECHNICAL SUMMARYStarting with copper sulfide nanoparticles, designed nanoheterostructures are created through selective introduction of new components through cation exchange. Preliminary data show that iodine oxidation of roxbyite nanoparticles alters the propensity for cation exchange with cadmium and zinc ions as it simultaneously alters the localized surface plasmon resonance of copper sulfide particles. It is proposed that oxidation/reduction processes can be employed as tools to modulate chemical and spatial selectivity of partial cation exchange. This project, supported by the Solid State and Materials Chemistry program within the Division of Materials Research, seeks to reveal structure-property relationships affected by the alteration of copper sulfide nanoparticles through redox processes and to utilize these relationships to design novel plasmonic nanoheterostructures. The project examines various means of oxidation and reduction and elucidates the effects on structure, Cu-ion vacancy concentration, plasmonic behavior, and propensity for cation exchange in copper sulfide nanoparticles. The fundamental insights uncovered by the proposed work will advance our ability to control chemistry and structure on the nanoscale. The particles investigated have the potential to act as catalysts, solar energy absorbers in PV or solar water evaporation, NIR absorbers in photothermal cancer treatment, or sensors. Training in materials chemistry will be strengthened through undergraduate research with close student-faculty interaction and an innovative partnership between laboratories at a primarily undergraduate institution and at an R1 university. Research infrastructure in the Central Pennsylvania region will be supported and barriers to broad participation in chemistry and materials research will be reduced.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.