Thermodynamic studies of the Pt-Cu-P and Pt-Ni-P systems as a basis for systematic alloy development.

近20年来，与Ni和/或Cu合金化的磷化铂一直是电催化剂开发的许多研究的主题。它们在结晶的、结晶稳定的状态和非晶的、亚稳态中都显示出有前途的电化学行为。然而，由于缺乏对Pt-Cu-Ni-P四元体系所基于的Pt-Cu-P和Pt-Ni-P三元体系的基本热力学描述，因此缺乏系统合金开发所需的基本知识。此外，磷（P）的实验工作不是无害的，这是由于其有毒的改性（白色P），此外，其低升华温度（约300°C）使实验工作大大复杂化。这些条件使得以前的高通量方法来研究金属磷化物是不可能的。本研究项目的目的是简要描述的三元系统Pt-Cu-P和Pt-Ni-P和模型的四元系统Pt-Cu-Ni-P的熔化平衡，以使系统的合金开发应用特定的要求。除了热力学平衡的描述，低熔点的玻璃形成所需的组合物可以确定在一个更有针对性的方式比经典的系统测试系列。为了实现这一目标，该研究项目设想通过高通量实验、已建立的计算机辅助方法和随后的有针对性的关键实验的巧妙组合，有效地解锁上述系统。实验工作包括采用温度梯度法制备样品，并对样品进行热分析（DTA、DSC、Flash DSC）。此外，还进行了微观结构研究（SEM/EDX/WDX）和结构研究（XRD），目的是确定各个相的化学成分和晶体结构。

Platinum phosphides, to which Ni and/or Cu are alloyed, have been the subject of much research for the development of electrocatalysts for almost 20 years. They show promising electrochemical behavior both in the crystalline, thermodynamically stable state and in the amorphous, metastable state. However, due to the lack of a fundamental thermodynamic description of the Pt-Cu-P and Pt-Ni-P ternary systems, on which the Pt-Cu-Ni-P quaternary system is founded, the fundamental knowledge necessary for systematic alloy development is lacking. Moreover, experimental work with phosphorus (P) is not harmless due to its toxic modification (white P), and in addition, its low sublimation temperature (about 300°C) greatly complicates experimental work. These conditions make previous high-throughput approaches to the study of metal phosphides impossible. The present research project aims to describe thermodynamically the ternary systems Pt-Cu-P and Pt-Ni-P and to model the melting equilibria of the quaternary system Pt-Cu-Ni-P in order to enable systematic alloy development for application-specific requirements. In addition to the description of the thermodynamic equilibria, the low-melting compositions required for glass formation can be identified in a more targeted manner than by classical systematic test series. To achieve the goal, the research project envisions efficiently unlocking the aforementioned systems through a clever combination of high-throughput experiments, established computer-aided methods, and subsequent targeted key experiments. The experimental work includes sample preparation by temperature gradient method, and the samples are investigated by thermal analysis (DTA, DSC, Flash DSC). In addition, microstructure investigations (SEM/EDX/WDX) and structural investigations (XRD) are performed with the aim of determining the chemical compositions and crystal structures of the respective phases.