Facile Solvent-Free Synthesis of Metal Thiophosphates and Their Examination as Hydrogen Evolution Electrocatalysts

Nathaniel Coleman; Ishanka A. Liyanage; Matthew D. Lovander; Johna Leddy; Edward G. Gillan

doi:10.3390/molecules27165053

Back

Facile Solvent-Free Synthesis of Metal Thiophosphates and Their Examination as Hydrogen Evolution Electrocatalysts

Journal article

Open access

Peer reviewed

Facile Solvent-Free Synthesis of Metal Thiophosphates and Their Examination as Hydrogen Evolution Electrocatalysts

Nathaniel Coleman, Ishanka A. Liyanage, Matthew D. Lovander, Johna Leddy and Edward G. Gillan

Molecules (Basel, Switzerland), Vol.27(5053), p.5053

08/01/2022

DOI: 10.3390/molecules27165053

Files and links (1)

url

https://doi.org/10.3390/molecules27165053View

Published (Version of record) Open Access

Abstract

The facile solvent-free synthesis of several known metal thiophosphates was accomplished by a chemical exchange reaction between anhydrous metal chlorides and elemental phosphorus with sulfur, or combinations of phosphorus with molecular P2S5 at moderate 500 °C temperatures. The crystalline products obtained from this synthetic approach include MPS3 (M = Fe, Co, Ni) and Cu3PS4. The successful reactions benefit from thermochemically favorable PCl3 elimination. This solvent-free route performed at moderate temperatures leads to mixed anion products with complex heteroatomic anions, such as P2S64−. The MPS3 phases are thermally metastable relative to the thermodynamically preferred separate MPx/ MSy and more metal-rich MPxSy phases. The micrometer-sized M-P-S products exhibit room-temperature optical and magnetic properties consistent with isolated metal ion structural arrangements and semiconducting band gaps. The MPS3 materials were examined as electrocatalysts in hydrogen evolution reactions (HER) under acidic conditions. In terms of HER activity at lower applied potentials, the MPS3 materials show the trend of Co > Ni >> Fe. Extended time constant potential HER experiments show reasonable HER stability of ionic and semiconducting MPS3 (M = Co, Ni) structures under acidic reducing conditions.

electrocatalyst

hydrogen evolution reaction

metal thiophosphates

solvent-free metathesis

Details

Title: Subtitle: Facile Solvent-Free Synthesis of Metal Thiophosphates and Their Examination as Hydrogen Evolution Electrocatalysts
Creators: Nathaniel Coleman - University of Iowa
Ishanka A. Liyanage - University of Iowa
Matthew D. Lovander - University of Iowa
Johna Leddy - University of Iowa
Edward G. Gillan - University of Iowa
Resource Type: Journal article
Publication Details: Molecules (Basel, Switzerland), Vol.27(5053), p.5053
DOI: 10.3390/molecules27165053
eISSN: 1420-3049
Publisher: MDPI AG
Grant note: DOI: 10.13039/100000001, name: National Science Foundation, award: 15276400, 0957555
Language: English
Date published: 08/01/2022
Academic Unit: Chemistry
Record Identifier: 9984285497102771

Metrics

10 Record Views

10 Times Cited - Web of Science