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

铂磷化物是镍和/或铜的合金，近20年来一直是电催化剂开发的研究课题。它们在结晶、热力学稳定状态和无定形、亚稳态状态下都表现出良好的电化学行为。然而，由于建立Pt-Cu-Ni-P四元体系的Pt-Cu-P和Pt-Ni-P三元体系缺乏基本的热力学描述，因此缺乏系统合金开发所需的基础知识。此外，磷(P)的实验工作由于其有毒修饰（白色P）而不是无害的，并且其低升华温度（约300℃）大大增加了实验工作的复杂性。这些条件使得以前研究金属磷化物的高通量方法变得不可能。目前的研究项目旨在对三元体系Pt-Cu-P和Pt-Ni-P进行热力学描述，并对四元体系Pt-Cu-Ni-P的熔化平衡进行建模，以便能够针对特定应用要求进行系统的合金开发。除了热力学平衡的描述之外，玻璃形成所需的低熔点成分可以用比经典系统测试系列更有针对性的方式来识别。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结合，有效地解锁上述系统。实验工作包括用温度梯度法制备样品，并用热分析（DTA， DSC, Flash DSC）对样品进行研究。此外，还进行了微观结构研究（SEM/EDX/WDX）和结构研究（XRD），以确定各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.